CA1121690A - Detergent compositions - Google Patents
Detergent compositionsInfo
- Publication number
- CA1121690A CA1121690A CA000336795A CA336795A CA1121690A CA 1121690 A CA1121690 A CA 1121690A CA 000336795 A CA000336795 A CA 000336795A CA 336795 A CA336795 A CA 336795A CA 1121690 A CA1121690 A CA 1121690A
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- Prior art keywords
- alkali metal
- weight
- composition according
- detergent composition
- orthophosphate
- Prior art date
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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
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
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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)
Abstract
Abstract of the Disclosure Particulate fabric washing detergent compositions are made with mixed phosphate detergency builders which comprise at least 5%
of a water-soluble alkali metal polymer phosphate and at least 2% of an alkali metal orthophosphate in the ratio of 10:1 - 1:5 parts by weight, the total amount of these phosphates being from 10%
to 40% of the composition and not more than 10%
of other phosphate builders being present, together with 0.01% to 10% of an anti-deposition agent which is preferably an anionic polyelectrolyte.
of a water-soluble alkali metal polymer phosphate and at least 2% of an alkali metal orthophosphate in the ratio of 10:1 - 1:5 parts by weight, the total amount of these phosphates being from 10%
to 40% of the composition and not more than 10%
of other phosphate builders being present, together with 0.01% to 10% of an anti-deposition agent which is preferably an anionic polyelectrolyte.
Description
~ 1690 ~ 1 - cC,1035 DETERGENT COMPOSITIONS
The present invention relates to powdered detergent compositions which are adapted for fabric washing, and which contain synthetic detergent active compounds together with : mixed phosphate detergency builders. The invention concerns in particular the production of detergent compositions which contain levels of the mixed phosphate detergency builders which can be lower than conventional phosphate builder levels, but which still retain good detergency properties..
~ccording to the present invention, a particulate detergent composition based on mixed phosphate detergency builders comprises a synthetic anionic, nonionic, amphoteric or zwitterionic detergent compound or mixture thereo~, an alkali metal orthophosphate, an alkali metal or a~nmoniwn :
, . - 2 - cC.1035 polymer phosphate and an antideposition agent as de.t'ined below.
In UK patent No, 1,530,799 we described and claimed powdered alkaline fabric washing detergent compositions which essentially contain mixed alkali metal tripolyphosphate and alkali metal or-thophosphate detergency builders in the ratio of from 10:~ to 1:5 parts by weight. ~hese compositions were found to have surprisingly good detergency properties though con-taining - 10 lower levels of the phosphate detergency builders than in conventional sodium tripolyphosphate-based detergent compositions. This development enabled either a reduct~on iIl manul'acturing cost because the differencc iIl phosphate content could be made up with a cheaper filler, or an improvement in overall detergency by adding ex-tra bleach or other additive instead. ~dditionally, this development facilitated tlle achievement of decreased phosphorus levels in d~tergent products to meet present or expected le~islation.
Products of the type described in our aforcmentioned patent have already met with appreciable commercial success, especially as economy brands. Xowever, one potential problem which has been found with the detergent compositions based on ; mixed alkali metal tripolyphosphate and orthophosphate builders, is the level of inorganic deposits which are some-times found on washed fabrics and to a lesser extent surfaces in washing machines, especially heater elements, ~he present invention is directed to decreasing the level o~ such ,. . _. .. ..... . .. . ... _,.. .. , .. .~ . . . . ,.. . . ., . . .. . . . .. _, . . . . .~. .. _ . .. .. .. ... .. ., , . . . . .. _ ., _ _ 3 _ cC.1035 deposits whil~t retaining benefits oL good detergency buildirlg properties.
Whilst not wishing to be bound by theory, it appears that the partial or complete replacement of the sodium tripolyphosphate in the detergent compositions of our afore-mentioned patent by the alkali metal or ammonium polymer phosphate gives less inorganic deposition on the washed fabrics, because the polymer phosphate has a decreased tendency to degrade to alkali metal pyropho~phate during the washing process. Also, by adding some and preferably all or at least a major part of thepolymer phosphate to the detergent composition in discrete particul~te form, as distinct from including tlle polymer phosphate in a spray dried base powder, the degradation of the polymer phosphate during spray drying which would form more alkali metal pyrophosphate can be avoided. ~e have found that the presence in the detergent composition of any such alkali metal pyrophosphate contributes particularly to inorganic deposits on the wa~hing machines. Thus, by hindering the formation of alkali metal pyrophosphate during the washing process, and preferably also avoiding or substantially decreasing initial presence of the pyrophosphate in the detergent compositions, a major step forward is taken to control inorganic deposition on fabrics and washing machine surfaces better than hitherto, and yet still achieve good detergency building at relatively low phosphate levels.
. ~
_ ~ _ cC.1035 In addition, the p~esence of an antideposition agent al~ces possiblc n further reduction in the level of inorganic depo~ition, especially on washed fabric~
appears that the antideposition agents stabilise the suspended insoluble calcium orthophosphate particles, and hence inhibit their deposition on the fabrics. Thus, in accordance with the invention steps are taken to control the inorganic deposition caused by both precipitated calci~o pyrophosphate and orthophosphate, giving substantial technical and hence commercial benefit.
The alkali metal polymer phosphate used in the compo-sitions of the invention is preferably sodium polymer phos-phate, but if desired the potassium or ammonium salts can be used. ~or convenience the term alkali metal polymer phos-phate is used hereinafter and in the claims to include ~hesodium,~potassium and ammonium salts. The alkali metal polymer phosphates are generally represented as having the formula M20(MP03)n, where M is sodium, potassium or ammonium and n is an integer which is at least 4 and up to about ~00 or more, preferably from about 6 to about 50~ In the case of the preferred sodium polymer phosphates, t-hese figures correspond to a P205 content of at least about 60.4% by weight up to a theoretical maximum of about 69.6%, preferably about 63% to about 69% P205 by weight of the polymer phosphate. ~o be effective the polymer phosphates must of course be water-soluble.
It should be app~eciated th~t the chemical : ' -`
- 5 - cC.10~5 structures o~ the polymer phosphates are not precisely defined, and some degree of ring formation or branching may be present in the otherwise normally linear polymer structure~ especially with the shorter polymer 5 chain lengths. lhe polymer phosphates are sometimes also known as glassy phosphates or Graham~s salt.
It is preferred that all or at least a major part of the alkali metal polymer phosphate should be admixed with a detergent base powder, ie postdosed, to obtain the most lO benefit of lower alkali metal pyrophosphate content in the product. Eowever, some or all of the alkali metal polymer phosphate can be included in the base powder if desired, and this can help to improve the powder properties, particularly when relatively low alkali metal orthophosphate 15 levels are used. Any alkali metal polymer phosphate which is postdosed should, of course, ha~e a suitable particulate form for postdosing, that is to say it should have an appropriate particle size range and powder density for uniform mixing with the base powder, so as to avoid undue 20 segregation in the finished product.
Detergent compositions which are based on mixed phosphate builders and incorporate an alkali metal ortho-phosphate and discrete particles of alkali metal polymer B phosphate, which can be made by postdosing t~he ~latter 25 ingredient, a3r3eG d7e~cribed in our co-pending UE patent application ,90,3,~, of even date.
11'~1690 - 6 - c~.10~5 ~ he alkali metal orthophosphate used is either potassium or preferably sodium orthophosphate, as the latter is cheaper and more readily available. Normally the tri-alkali metal salts are used~ but orthophosphoric acid or the di- or mono-alkali metal salts, e.g. disodium hydrogen orthophosphate or mo~osodium dihydrogen orthophosphate could be used if desired in the production of the compositions. In the latter event other more alkaline salts should also be present to maintain a high pH in the end product, i.e. with full neutralisation to the trialkali metal orthophosphate salts. ~he use of a mixture of the monosodium dihydrogen and disodium hydrogen orthophosphates in the ratio of 1:3 to 2:3, especially about 1:2, is particularly advantageoùs, as such a ~ixture (known as kiln-feed) is made in the production of sodium tripoly-phosphate and is readily available. It is preferred to have all the alkali metal orthophosphate present in the detergent base powder, eg by inclusion in an aqueous detergent slurry ~nd then spray dried~ but part of the orthophosphate can be po9tdosed if desired, either separately or together with the alkali metal polymer phosphate.
The alkali metal orthophosphate oan be used in the form of the anhydrou~ or hydrated salts, but in the former case it is preferred to promote hydration during processing, eg by adding the anhydrous orthophosphate to a detergent slurry and spray drying to form the base powder. The alkali metal polynner phosphates do not form hydrated salts as such, and 69~3 - 7 - cC.10~5 are normally used in ~nhydrous form, but they arc hygroscopic ~Id t~nd to absorb atmosplleric moisture. The ~llounts of the salts used are expressed iIl ;UlhydrOU9 ~Orl~.
The total ~nounts of the essential alkali l~etal polymer phosphate and alkali metal orthop~osphate, and any otller pl~osphates which may be present in the detergent compositions, are cllosen according to the overall detergency builder level w~lich is desired in the detergent compositions or according to the maximum permitted phosphorus content.
Normally the total phospllate builder level, which i9 preferably derived solely from alkali metal polymer phosphate and alkali metal orthophosphate, is between about 10% and about 4~/o~by weight of the composition, preferably with an amount of at least about 5% and at least about 2% up to about 20% each of the alkali metal polymer phosphate and orthophosphate, respectively. Preferabl~ the amounts of the alkali metal polymer phosphate and alkali metal ortho-phosphate are each from about 5% to about 15%, especially -; about 5% to 10%, by weight of the composition. The total 20 amount of alkali metal polymer phosphate and alkali metal - orthophosphate is preferably from about 10% to about 25%, especially about 15% to about 20%~ by weight of the composition.
Generally speaking, it is preferred to have amounts of 25 the alkali metal polymer phosphate and the alkali metal orthophosphate generally within the ratio of from about ~:1 to about 1:3, especially about 2:1 to about 1:2, parts by ~lZ1690 - 8 - cc . '1 035 weight, respectively. ~hese ratios of polymer phosphate to orthophosphate are par-ticularly suitable for detergent compositions used at relatively high product concentrations, i.e. 0.3% to 0.8% by weight, as is common practice in Europe, especially in front-loading automatic washing machines, and where moderate levels of phosphates are allowed in the products, i.e. equivalent to 3% to 7% P.
It is preferable that the only phosphate detergenc~
builders used to make the compositions of the invention should be the alkali metal polymer phosphate and alkali metal orthophosphate. In particular, it is desirable to add no alkali metal, ie sodium or potassium, pyrophos-phates to the compositions as they tend to increase inorganic deposition as mentioned above. It is also preferred not to have any alkali metal tripolyphosphate present because of the relative ease with which it hydrolyses to form the alkali metal pyrophosphate. However, some alkali metal tripoly-phosphate may be present if desire~ either in the base powder or postdosed thereto, ior example because oi its beneficial effect on the base powder properties or because Or its relative cheapness. But ior optimum detergency in - relation to total phosphate content, it is preierred to have not more than about 10% by weight of other alkali metal phosphate builders, and especiially not more than about 5% of tripolyphosphate present in the detergent composition.
Some tripolyphosphate and pyrophosphate are also generally found as impurities at low levels in other , .
.'''' ' 6 ~
- 9 - cC.10~5 commercial alkali metal phosphates, and some tripoly-pho~phate and pyrophosphate may be formed by any hydrolysis of the pol~mer phosphate during processing, especially if some of it is present in the slurry r~ther -than being all postdosed~ Hence, total absence of alkali metal tripoly- -phosphate and pyropho3phate is generally unattainable in the detergent compositions. It is particularly pre~erred to have not more than about 2.5% of alkali metal p~rophosphate present in the compositions, as at higher levels the amounts of inorganic deposits on the washing machine parts become significantl~ more noticeable.
~ he detergent compositions of the invention essentially contain one or more antideposition agents to decrease the tendency to form inorganic deposits on washed fabrics. The antideposition agents appear to be effective by stabilising -insoluble calcium orthophosphate particles in suspension.
However, the best test for determining whether or not an antidepo~ition agent is effective in a detergent composition according to the invention i9 to determine the level of inorganic deposits on fabric washed with and without the antideposition agent present. The most effective antidepo-sition agents are generally anionic polyèlectrolytes, ; especially polymeric aliphatic carboxylates. The amount of any such antideposition agent can be from about 0.01~ to about 10% of the compositions, but is normally from about 0.1% to about 5~ by weight, preferably from about 0.2~ to about 2% by weight of the compositions.
~ 10 - cC.10~5 Speci:ric preferr~d ~ltidtpo~ition a~onts aro the alk~li metal or ~lunontulll, pr~era~ly tl~c sodiulll, snlts Or llolllo~
co-polyluers ol acrylic acid or substitllt~d .~crylic acids, such as sodium polyacryla-tc, the sodiulll salt of copolymeth-acryl~nide/acrylic acid and sodiwu poly-alpha-llydroxyacrylate, salts of copolyme~s of ~ leic anhydri.de with ethylene, acrylic acid, ~inylmethylether or styrene,especially 1:1 copolymers, and optionally with partial esterification of the carbox~l groups. Such copol.ymers preferably have relatively low molecular weights, eg in the range of about 1,000 to 50,000.
Other ~ntideposition agents include the sodiu~l salts of poly-maleic acid, polyitaconic acid and polyaspartic acid, phos-phate esters of ethoxylated aliphatic alcohols, polyethylene glycol phosphate esters, and certain organic phosphonic acids or salts thereof such as sodium ethane-1-hydroxy-1,1-diphosphonate, sodium ethylenediamine tetramethylene phos-phonate, and sodium 2-phosphonobutane tricarbox~late.
Mixtures of organic phosphonic acids or substituted acrylic acids or their salts with protective colloids such as gelatin may also be used. ~he most preferred.anti-deposition agents are sQdîum polyacrylates having a ~ of about 10,000 to 50,000, for example about 20,000 to 30,000.
The detergent compositions of the invention necessarily include from about 2.5% to about 50~/o, preferably about 5%
to about 30%, and especially about ~0% to about 25%, by weight of a synthetic anionic, nonionic, amphoteric or - zwitterionic detergent compou~d or mixture thereof. Many ~ cC.10~5 suitcible detergent compounds are commerciall~ available and are Eully described in the literature, for example ir.
"Surface ~ctive Agents and Detergents", Volumes I and II, by ~chwar-tz, Perry & Berch.
~he preferred detergent compounds which can be used are ~ynthetic anionic and nonionic compounds. The former are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alk~l portion of higher acyl radicals~ ~xamples of suitable synthetic anionic detergen-t compounds are sodium and potassiu~ alkyl sulphates, especially those obtained by ! sulphating higher (C8 Cl8) alcohols procluced lor exa~ple from tallow or COCOllUt oil; sodiu~l and potassium alkyl tCg-C20) ben~ene sulphonates, particularly sodium linear secondary alkyl (Cl0-Cl5) benzene sulphonates; sodi~n alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or COCO}lUt oil and synthetic alcohols derived from petroleum; sodium COCOIIUt oil fatty monoglyceride sulphates and sulphonates; sodiu~ and potassium salts of sulphuric acid esters of higher (Cg_C
fatty alcohol-alkylene oxide, particularly ethylene. o.~ide, reaction products; the reaction products of fat-ty acids such as coconut fatty acids esterified witll isethionic acid and neutralised with sodium hydroxide; sodiulIl and potassium salts of fatty acid amides of methyl tallrine; alkane mono~
sulphonates such as those derived by r~actiIlg alpha-olefins :
- 12 - cC.1035 (C8-C20) wlth sodium bisulphite and those deriv~cI by renctin~ paraffiIls with S02 ~l~l Cl2 a~lll t~1e~ ydrolysillg with a base to produce a randolll sulphon~te; and olefin slllpllonates, which term is used to describe tlle material Illade by reacting olefins, particularly Clo-C20 alpha-ole~ins, witl~ S03 and then neutralising ~Id hydrolysing the reaction product. The preferred anionic dotergent col~pounds are sodium (Cll-C15) alkyl ben~ene sulphoIlates ~ld sodium ~Cl6-cl8) alkyl Sulphates.
Suitable nonionic detergerlt compounds WhiCIl may be used include in particular the reaction prodllcts of compounds having a hydrophobic group and a reactive hydrogen atom, for ex ~lple aliphatic alcohols, acids, ~lides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are alkyl (C6_C22) phenol-ethylene oxide condellsates, generally 5 to 25 EO, ie 5 to 25 units of ethylene oxids per molecule, the condensa~ioIl products of aliphatic (C8-Cl8) primary or secondary linear or branched alcohols with ethylene oxide, generally 6 to 30 EO, ~r with both ethylene oxide and propylene oxide~ and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine. Other so-called non-ionic detergent compounds include long chain tertiary amine oxides~ long chain tertiary phosphine oxides and dialkyl sulphoxides.
11'~1690 .
- 13 - cC.10~5 Mixtures of detergent compounds, for example mixed ionic or mixed anionic alld noniollic compounds ~lay ~e used in the detergent compositions, p~ ticulnrly ln the latter case to provide controlled low sudsing pl-operties. This is beneficial for compositions intended for use in suds~ toler-~lt àutolllatic washing ~achines. We have also found that the ? use of some nonionic detergent compounds in the compositi~ns ~ecreases tlle tendency of insoluble phosphato salts to deposit on tlle washed fabrics, especially when used in admixture with some soaps as described below.
~mounts of a~nphoteric or zwitterionic detergent compounds can also be used in the compositions of the invention but this is not normally desired due to their relatively high i cost. If any amphoteric or ~witterionic detergent compounds are used it is generally in small amounts in co~npositions based on the much more commonly used synthetic anionic and/or nonionic detergent compounds. For example, ~lixtures of ; a~ine oxides and ethoxylated nonionic detergent compounds ca bc used.
Soaps may also be present in the detergent compositions ol tlle invention, hut not as the sole detergent compollllds.
The soaps are particularly useful at low levels in billary and ternary mixtures, together with noniollic or mi~Yed synthetic anionic and nonionic detergent compounds, whica1 have low su~sing properties. The soaps which are used are thesodium, or less desira~ly potassi~u~, salts of ~lO-C2~ Iatty acids. It is particularly preferred that the soaps shoul~
, .
,, , ~, . . , . - . .
. ~ . . , ~
, ~. . . . . ~.
so ~ _ cC.10 be based mainly on the longer chain fat-ty acids within this r.~lge, tllat is with at least half of tllc soaps h~ving a carbon chain leng-th of 16 or over. This is most convenient-ly accomplished by using soaps from natural sources such as tallow, palm oil or rapeseed oil, which can be hardened if desired, with lesser ~mounts of other shorter chain soaps, prepared from nut oils such as coconut oil or palm kernel oil. The amount of such soaps can be varied between about 0.5% and about 25~ by weight, with lower amounts of about 0.5% to about 5% being generally su~ficient for lather control. Amounts of soap between about 2% and about 20%~
especially between about 5% and about 15%~ cc~n advantageously be used to give a beneficial effect on detergency.
~part from the essential detergent compounds and detergency builders, the detergent compositions of the invention can contain any of the conventional additives in the amounts in which such materials are no~nally employed in fabric washing detergent compositions. Examples of these additives incluae lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, lather depressants such as alkyl phosphates, waxes and silicones, antiredeposition agents such as sodiw~ carboxylllethylcellulose and polyvinyl pyrrolidone optionally copolymerised with vinyl acetate, oxygell-releasing bleaching agents such as sodium perborate and sodium percarbonate, per-acid bleach precursors, chlorine-releaSing bleaching agents such as trichloroisocyaIl_ 11'~1~90 - 15 - c~.1035 uric acid and alkali metal salts of dichloroisocyanuric acid, fabric sol`tening agents, inorgarlic salts such as sodiwn sulphate, sodium carbonate and n~agnesiuln silicate, and, usually present in very minor ~nounts, fluorescent agents, pelfumes, enzymes such as proteases and amylases, germicides and colourants.
It is particularly beneficial to include in the detergent compositions an ~mount of sodium perborate, preferably between about 1~/o and about 40%, for example about 15% to about 30%, by weight. It has been found that the bleaching action of sodium perborate is boosted under the highly alkaline conditions which also give optimum detergency building action ior the alkali metal orthophosphate. Thus, it becomes possible to achieve improved bleaching properties by using the same levels of sodium perborate as normal; or decreased levels of sodium perborate can be used to give equal bleaching properties to those of conventional products with higher levels of perborate and sodium tripolyphosphate as the sole detergency builder. The latter OptiOIl can also be used to further decrease the r~w materials costs of the compositions,-if a cheap filler is used in place of part of -the sodiwn perborate.
It is also possible to include in the detergent compositions of the invention minor amolmts, preferably not more than about 20% by weight, of oth~r non-phosphate deter-gency builders, which may be either so-called precipita~t builders, ion exchange or sequestrant builders. ~his is of ---`` 1121690 - 16 - cC.10~5 p~rticular bene~it where it is desired to increase deter~ency whilst USillg particularly low levels of the essential alkali metal polymer phosphate and alkali metal orthophosphate builders, so as to achieve especially low phosphorus contents 5 in the detergent compositions. Examples of such other detergency builders are amine carboxylates such as sodium nitrilotriacetate, sodium carbonate, sodium aluminosilicate ion-exchange materials such as zeolites A and X, sodium citrate and soap, which can function as a detergency builder, 10 as discussed above. However, such other builder materials are not essential and it is a particular benefit of using the mixod alkali metal polymer phosphate and orthophosphate that satisfactory detergency properties oan be achieved at lower total phosphate levels than hitherto considered 15 necessary without other detergency builders.
It is generally also desirable to include in the compo-SitiollS an amount of an alkali metal silicate, particularly sodium ortho-, meta- or preferably neutral or alkaline silicate . The presence of such alkal i metal silicates at 20 levels of at least about 1%, and preferably from about 5% to abollt l5'k, by weight of the compositions, is advantageous in decreasing the corrosion of metal parts in washing machi~les, besides giving processing benefits and generally improved powder properties. The more highly alkaline ortho_ and meta-25 silicates would normally only be used at lower amounts withinthis range, in admixture with the neutral or alkaline silicates .
l69() - 17 - cC.1035 ~ he compositions of the inv~ntion are r~quired to be ullcaline, but not too strongly alkaline as this could re4ult in f~bric damage alld also be hn~ardous for do~lestic usage.
In practice the compositions should give a pH of frolo 9 to ll ill use in aqueous wash solution. It is preferred in paxticular for do~estic products to have a mini~um p~ of at least 9.25 and especially a pH of 9.5 or ov.,r, as lower p~s tend to be less effective for optimum detergency building, and a maximum p~ of 10.5, as more highly alkaline products can be hazardous if misused. The plI is measured at the lowest normal usage concentration of 0.1~ ~/v of the product in water o~ 12H (Ca), (French permanent hardness, calci~n only) ~t 50C so that a satisfactory degree of alkalinity can be assured in use at all normal product concentrations.
~he pH of the detergent compositions i~ use is controlled by the amount of alkali metal orthophosphate and any other alkaline salts such as alkali metal silicate~
sodium perborate and sodium carbonate present. The presence of such other alkaline salts, especially the alkali metal silicates, is particularly beneficial, because the alkalinity ~f the alkali metal orthophosphate is dilllinished in hard water due to precipitation Or the calcium salt. In addition the alkali metal polymer phosphate is more stable and resistant to hydrolysis under highly alkaline conditions. The other ingredicnts in the alkaline detergent compositions of the invention should of course be chosen for . : , -,.~ ~ . . .
- ~ , `
l~Z1690 - 18 - cC.1035 alkalin~ stability, especiall~ the pH sensitive materials such as enzymes.
~ he detergent compositions of the invention are normally made in particulate form, for example by slurry making and spray drying, preferably with admixture of the alkali metal polymer phosphate to n spray dried base powder.
~owever, if desired the detergent compositions may be compressed or compacted into tablets or blocks, or otherwise treated for example by granulation, prior to packaging and sale. Because of the hygroscopic nature of the alkali metal polymer phosphates, it may be desirable to use moisture impermeable packaging for the detergent compositions, for example in plastic or fabric sachets containing pre_ measured doses for washing machine usage.
The in~ention is illustrated by the followîng ~xamples in which parts and percentages are by weight except where otherwise indicated.
Examples 1 to 9 ~ series of detergent powders were prepared by firstly spray drying a detergent base powder to the following ` formulation:
, llZ1690 - 19 - cC.1035 Ing~diellt ~ (based oll rinal product) Sodium alkyl benzene 9 sulphoIIate Nonionic detergent compoundl l Sodium orthophosphate 8 Sodium silicate lO
(Na20:SiO2, 1:2) Magnesium silicate 0.5 Sodium sulphate27.2 Water and minor additives ~.3 65.0 l Cl~-Cl5 alcohol - 18 E0 condensate.
~mounts of additives as specified in the Table below were then added ~o this base powder-to make the ~ormula~.ions as ~ollows:
Ingredient Ex: l 2 3 .4 5 6 7 8 g _ Base powder 65 Sodium poly~er lO - - lO - - lO
phosphate Sodium poly~er - lO - - lO - - lO
phosphate Sodium polymer - - 10. - - 10 - - 10 phosphate4 20 Sodium polyacrylate5 - - - 2 2 2 Sodium sulphate 2 2 2 - - ~ 1 1 1 Sodium perborate 20 f Nonionic deter~ent 2 >
(continued overleaf) ,~ . .. . _ .. .... .~ . .
~ 6 ~
- - 20 - cC.10~5 (Con-tinued) %
In~.redient ~x: 1 2 ~ 4 5 6 7 8 9 Enzyme and per~wne , .
Lather controller6 0.6
The present invention relates to powdered detergent compositions which are adapted for fabric washing, and which contain synthetic detergent active compounds together with : mixed phosphate detergency builders. The invention concerns in particular the production of detergent compositions which contain levels of the mixed phosphate detergency builders which can be lower than conventional phosphate builder levels, but which still retain good detergency properties..
~ccording to the present invention, a particulate detergent composition based on mixed phosphate detergency builders comprises a synthetic anionic, nonionic, amphoteric or zwitterionic detergent compound or mixture thereo~, an alkali metal orthophosphate, an alkali metal or a~nmoniwn :
, . - 2 - cC.1035 polymer phosphate and an antideposition agent as de.t'ined below.
In UK patent No, 1,530,799 we described and claimed powdered alkaline fabric washing detergent compositions which essentially contain mixed alkali metal tripolyphosphate and alkali metal or-thophosphate detergency builders in the ratio of from 10:~ to 1:5 parts by weight. ~hese compositions were found to have surprisingly good detergency properties though con-taining - 10 lower levels of the phosphate detergency builders than in conventional sodium tripolyphosphate-based detergent compositions. This development enabled either a reduct~on iIl manul'acturing cost because the differencc iIl phosphate content could be made up with a cheaper filler, or an improvement in overall detergency by adding ex-tra bleach or other additive instead. ~dditionally, this development facilitated tlle achievement of decreased phosphorus levels in d~tergent products to meet present or expected le~islation.
Products of the type described in our aforcmentioned patent have already met with appreciable commercial success, especially as economy brands. Xowever, one potential problem which has been found with the detergent compositions based on ; mixed alkali metal tripolyphosphate and orthophosphate builders, is the level of inorganic deposits which are some-times found on washed fabrics and to a lesser extent surfaces in washing machines, especially heater elements, ~he present invention is directed to decreasing the level o~ such ,. . _. .. ..... . .. . ... _,.. .. , .. .~ . . . . ,.. . . ., . . .. . . . .. _, . . . . .~. .. _ . .. .. .. ... .. ., , . . . . .. _ ., _ _ 3 _ cC.1035 deposits whil~t retaining benefits oL good detergency buildirlg properties.
Whilst not wishing to be bound by theory, it appears that the partial or complete replacement of the sodium tripolyphosphate in the detergent compositions of our afore-mentioned patent by the alkali metal or ammonium polymer phosphate gives less inorganic deposition on the washed fabrics, because the polymer phosphate has a decreased tendency to degrade to alkali metal pyropho~phate during the washing process. Also, by adding some and preferably all or at least a major part of thepolymer phosphate to the detergent composition in discrete particul~te form, as distinct from including tlle polymer phosphate in a spray dried base powder, the degradation of the polymer phosphate during spray drying which would form more alkali metal pyrophosphate can be avoided. ~e have found that the presence in the detergent composition of any such alkali metal pyrophosphate contributes particularly to inorganic deposits on the wa~hing machines. Thus, by hindering the formation of alkali metal pyrophosphate during the washing process, and preferably also avoiding or substantially decreasing initial presence of the pyrophosphate in the detergent compositions, a major step forward is taken to control inorganic deposition on fabrics and washing machine surfaces better than hitherto, and yet still achieve good detergency building at relatively low phosphate levels.
. ~
_ ~ _ cC.1035 In addition, the p~esence of an antideposition agent al~ces possiblc n further reduction in the level of inorganic depo~ition, especially on washed fabric~
appears that the antideposition agents stabilise the suspended insoluble calcium orthophosphate particles, and hence inhibit their deposition on the fabrics. Thus, in accordance with the invention steps are taken to control the inorganic deposition caused by both precipitated calci~o pyrophosphate and orthophosphate, giving substantial technical and hence commercial benefit.
The alkali metal polymer phosphate used in the compo-sitions of the invention is preferably sodium polymer phos-phate, but if desired the potassium or ammonium salts can be used. ~or convenience the term alkali metal polymer phos-phate is used hereinafter and in the claims to include ~hesodium,~potassium and ammonium salts. The alkali metal polymer phosphates are generally represented as having the formula M20(MP03)n, where M is sodium, potassium or ammonium and n is an integer which is at least 4 and up to about ~00 or more, preferably from about 6 to about 50~ In the case of the preferred sodium polymer phosphates, t-hese figures correspond to a P205 content of at least about 60.4% by weight up to a theoretical maximum of about 69.6%, preferably about 63% to about 69% P205 by weight of the polymer phosphate. ~o be effective the polymer phosphates must of course be water-soluble.
It should be app~eciated th~t the chemical : ' -`
- 5 - cC.10~5 structures o~ the polymer phosphates are not precisely defined, and some degree of ring formation or branching may be present in the otherwise normally linear polymer structure~ especially with the shorter polymer 5 chain lengths. lhe polymer phosphates are sometimes also known as glassy phosphates or Graham~s salt.
It is preferred that all or at least a major part of the alkali metal polymer phosphate should be admixed with a detergent base powder, ie postdosed, to obtain the most lO benefit of lower alkali metal pyrophosphate content in the product. Eowever, some or all of the alkali metal polymer phosphate can be included in the base powder if desired, and this can help to improve the powder properties, particularly when relatively low alkali metal orthophosphate 15 levels are used. Any alkali metal polymer phosphate which is postdosed should, of course, ha~e a suitable particulate form for postdosing, that is to say it should have an appropriate particle size range and powder density for uniform mixing with the base powder, so as to avoid undue 20 segregation in the finished product.
Detergent compositions which are based on mixed phosphate builders and incorporate an alkali metal ortho-phosphate and discrete particles of alkali metal polymer B phosphate, which can be made by postdosing t~he ~latter 25 ingredient, a3r3eG d7e~cribed in our co-pending UE patent application ,90,3,~, of even date.
11'~1690 - 6 - c~.10~5 ~ he alkali metal orthophosphate used is either potassium or preferably sodium orthophosphate, as the latter is cheaper and more readily available. Normally the tri-alkali metal salts are used~ but orthophosphoric acid or the di- or mono-alkali metal salts, e.g. disodium hydrogen orthophosphate or mo~osodium dihydrogen orthophosphate could be used if desired in the production of the compositions. In the latter event other more alkaline salts should also be present to maintain a high pH in the end product, i.e. with full neutralisation to the trialkali metal orthophosphate salts. ~he use of a mixture of the monosodium dihydrogen and disodium hydrogen orthophosphates in the ratio of 1:3 to 2:3, especially about 1:2, is particularly advantageoùs, as such a ~ixture (known as kiln-feed) is made in the production of sodium tripoly-phosphate and is readily available. It is preferred to have all the alkali metal orthophosphate present in the detergent base powder, eg by inclusion in an aqueous detergent slurry ~nd then spray dried~ but part of the orthophosphate can be po9tdosed if desired, either separately or together with the alkali metal polymer phosphate.
The alkali metal orthophosphate oan be used in the form of the anhydrou~ or hydrated salts, but in the former case it is preferred to promote hydration during processing, eg by adding the anhydrous orthophosphate to a detergent slurry and spray drying to form the base powder. The alkali metal polynner phosphates do not form hydrated salts as such, and 69~3 - 7 - cC.10~5 are normally used in ~nhydrous form, but they arc hygroscopic ~Id t~nd to absorb atmosplleric moisture. The ~llounts of the salts used are expressed iIl ;UlhydrOU9 ~Orl~.
The total ~nounts of the essential alkali l~etal polymer phosphate and alkali metal orthop~osphate, and any otller pl~osphates which may be present in the detergent compositions, are cllosen according to the overall detergency builder level w~lich is desired in the detergent compositions or according to the maximum permitted phosphorus content.
Normally the total phospllate builder level, which i9 preferably derived solely from alkali metal polymer phosphate and alkali metal orthophosphate, is between about 10% and about 4~/o~by weight of the composition, preferably with an amount of at least about 5% and at least about 2% up to about 20% each of the alkali metal polymer phosphate and orthophosphate, respectively. Preferabl~ the amounts of the alkali metal polymer phosphate and alkali metal ortho-phosphate are each from about 5% to about 15%, especially -; about 5% to 10%, by weight of the composition. The total 20 amount of alkali metal polymer phosphate and alkali metal - orthophosphate is preferably from about 10% to about 25%, especially about 15% to about 20%~ by weight of the composition.
Generally speaking, it is preferred to have amounts of 25 the alkali metal polymer phosphate and the alkali metal orthophosphate generally within the ratio of from about ~:1 to about 1:3, especially about 2:1 to about 1:2, parts by ~lZ1690 - 8 - cc . '1 035 weight, respectively. ~hese ratios of polymer phosphate to orthophosphate are par-ticularly suitable for detergent compositions used at relatively high product concentrations, i.e. 0.3% to 0.8% by weight, as is common practice in Europe, especially in front-loading automatic washing machines, and where moderate levels of phosphates are allowed in the products, i.e. equivalent to 3% to 7% P.
It is preferable that the only phosphate detergenc~
builders used to make the compositions of the invention should be the alkali metal polymer phosphate and alkali metal orthophosphate. In particular, it is desirable to add no alkali metal, ie sodium or potassium, pyrophos-phates to the compositions as they tend to increase inorganic deposition as mentioned above. It is also preferred not to have any alkali metal tripolyphosphate present because of the relative ease with which it hydrolyses to form the alkali metal pyrophosphate. However, some alkali metal tripoly-phosphate may be present if desire~ either in the base powder or postdosed thereto, ior example because oi its beneficial effect on the base powder properties or because Or its relative cheapness. But ior optimum detergency in - relation to total phosphate content, it is preierred to have not more than about 10% by weight of other alkali metal phosphate builders, and especiially not more than about 5% of tripolyphosphate present in the detergent composition.
Some tripolyphosphate and pyrophosphate are also generally found as impurities at low levels in other , .
.'''' ' 6 ~
- 9 - cC.10~5 commercial alkali metal phosphates, and some tripoly-pho~phate and pyrophosphate may be formed by any hydrolysis of the pol~mer phosphate during processing, especially if some of it is present in the slurry r~ther -than being all postdosed~ Hence, total absence of alkali metal tripoly- -phosphate and pyropho3phate is generally unattainable in the detergent compositions. It is particularly pre~erred to have not more than about 2.5% of alkali metal p~rophosphate present in the compositions, as at higher levels the amounts of inorganic deposits on the washing machine parts become significantl~ more noticeable.
~ he detergent compositions of the invention essentially contain one or more antideposition agents to decrease the tendency to form inorganic deposits on washed fabrics. The antideposition agents appear to be effective by stabilising -insoluble calcium orthophosphate particles in suspension.
However, the best test for determining whether or not an antidepo~ition agent is effective in a detergent composition according to the invention i9 to determine the level of inorganic deposits on fabric washed with and without the antideposition agent present. The most effective antidepo-sition agents are generally anionic polyèlectrolytes, ; especially polymeric aliphatic carboxylates. The amount of any such antideposition agent can be from about 0.01~ to about 10% of the compositions, but is normally from about 0.1% to about 5~ by weight, preferably from about 0.2~ to about 2% by weight of the compositions.
~ 10 - cC.10~5 Speci:ric preferr~d ~ltidtpo~ition a~onts aro the alk~li metal or ~lunontulll, pr~era~ly tl~c sodiulll, snlts Or llolllo~
co-polyluers ol acrylic acid or substitllt~d .~crylic acids, such as sodium polyacryla-tc, the sodiulll salt of copolymeth-acryl~nide/acrylic acid and sodiwu poly-alpha-llydroxyacrylate, salts of copolyme~s of ~ leic anhydri.de with ethylene, acrylic acid, ~inylmethylether or styrene,especially 1:1 copolymers, and optionally with partial esterification of the carbox~l groups. Such copol.ymers preferably have relatively low molecular weights, eg in the range of about 1,000 to 50,000.
Other ~ntideposition agents include the sodiu~l salts of poly-maleic acid, polyitaconic acid and polyaspartic acid, phos-phate esters of ethoxylated aliphatic alcohols, polyethylene glycol phosphate esters, and certain organic phosphonic acids or salts thereof such as sodium ethane-1-hydroxy-1,1-diphosphonate, sodium ethylenediamine tetramethylene phos-phonate, and sodium 2-phosphonobutane tricarbox~late.
Mixtures of organic phosphonic acids or substituted acrylic acids or their salts with protective colloids such as gelatin may also be used. ~he most preferred.anti-deposition agents are sQdîum polyacrylates having a ~ of about 10,000 to 50,000, for example about 20,000 to 30,000.
The detergent compositions of the invention necessarily include from about 2.5% to about 50~/o, preferably about 5%
to about 30%, and especially about ~0% to about 25%, by weight of a synthetic anionic, nonionic, amphoteric or - zwitterionic detergent compou~d or mixture thereof. Many ~ cC.10~5 suitcible detergent compounds are commerciall~ available and are Eully described in the literature, for example ir.
"Surface ~ctive Agents and Detergents", Volumes I and II, by ~chwar-tz, Perry & Berch.
~he preferred detergent compounds which can be used are ~ynthetic anionic and nonionic compounds. The former are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alk~l portion of higher acyl radicals~ ~xamples of suitable synthetic anionic detergen-t compounds are sodium and potassiu~ alkyl sulphates, especially those obtained by ! sulphating higher (C8 Cl8) alcohols procluced lor exa~ple from tallow or COCOllUt oil; sodiu~l and potassium alkyl tCg-C20) ben~ene sulphonates, particularly sodium linear secondary alkyl (Cl0-Cl5) benzene sulphonates; sodi~n alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or COCO}lUt oil and synthetic alcohols derived from petroleum; sodium COCOIIUt oil fatty monoglyceride sulphates and sulphonates; sodiu~ and potassium salts of sulphuric acid esters of higher (Cg_C
fatty alcohol-alkylene oxide, particularly ethylene. o.~ide, reaction products; the reaction products of fat-ty acids such as coconut fatty acids esterified witll isethionic acid and neutralised with sodium hydroxide; sodiulIl and potassium salts of fatty acid amides of methyl tallrine; alkane mono~
sulphonates such as those derived by r~actiIlg alpha-olefins :
- 12 - cC.1035 (C8-C20) wlth sodium bisulphite and those deriv~cI by renctin~ paraffiIls with S02 ~l~l Cl2 a~lll t~1e~ ydrolysillg with a base to produce a randolll sulphon~te; and olefin slllpllonates, which term is used to describe tlle material Illade by reacting olefins, particularly Clo-C20 alpha-ole~ins, witl~ S03 and then neutralising ~Id hydrolysing the reaction product. The preferred anionic dotergent col~pounds are sodium (Cll-C15) alkyl ben~ene sulphoIlates ~ld sodium ~Cl6-cl8) alkyl Sulphates.
Suitable nonionic detergerlt compounds WhiCIl may be used include in particular the reaction prodllcts of compounds having a hydrophobic group and a reactive hydrogen atom, for ex ~lple aliphatic alcohols, acids, ~lides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are alkyl (C6_C22) phenol-ethylene oxide condellsates, generally 5 to 25 EO, ie 5 to 25 units of ethylene oxids per molecule, the condensa~ioIl products of aliphatic (C8-Cl8) primary or secondary linear or branched alcohols with ethylene oxide, generally 6 to 30 EO, ~r with both ethylene oxide and propylene oxide~ and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine. Other so-called non-ionic detergent compounds include long chain tertiary amine oxides~ long chain tertiary phosphine oxides and dialkyl sulphoxides.
11'~1690 .
- 13 - cC.10~5 Mixtures of detergent compounds, for example mixed ionic or mixed anionic alld noniollic compounds ~lay ~e used in the detergent compositions, p~ ticulnrly ln the latter case to provide controlled low sudsing pl-operties. This is beneficial for compositions intended for use in suds~ toler-~lt àutolllatic washing ~achines. We have also found that the ? use of some nonionic detergent compounds in the compositi~ns ~ecreases tlle tendency of insoluble phosphato salts to deposit on tlle washed fabrics, especially when used in admixture with some soaps as described below.
~mounts of a~nphoteric or zwitterionic detergent compounds can also be used in the compositions of the invention but this is not normally desired due to their relatively high i cost. If any amphoteric or ~witterionic detergent compounds are used it is generally in small amounts in co~npositions based on the much more commonly used synthetic anionic and/or nonionic detergent compounds. For example, ~lixtures of ; a~ine oxides and ethoxylated nonionic detergent compounds ca bc used.
Soaps may also be present in the detergent compositions ol tlle invention, hut not as the sole detergent compollllds.
The soaps are particularly useful at low levels in billary and ternary mixtures, together with noniollic or mi~Yed synthetic anionic and nonionic detergent compounds, whica1 have low su~sing properties. The soaps which are used are thesodium, or less desira~ly potassi~u~, salts of ~lO-C2~ Iatty acids. It is particularly preferred that the soaps shoul~
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so ~ _ cC.10 be based mainly on the longer chain fat-ty acids within this r.~lge, tllat is with at least half of tllc soaps h~ving a carbon chain leng-th of 16 or over. This is most convenient-ly accomplished by using soaps from natural sources such as tallow, palm oil or rapeseed oil, which can be hardened if desired, with lesser ~mounts of other shorter chain soaps, prepared from nut oils such as coconut oil or palm kernel oil. The amount of such soaps can be varied between about 0.5% and about 25~ by weight, with lower amounts of about 0.5% to about 5% being generally su~ficient for lather control. Amounts of soap between about 2% and about 20%~
especially between about 5% and about 15%~ cc~n advantageously be used to give a beneficial effect on detergency.
~part from the essential detergent compounds and detergency builders, the detergent compositions of the invention can contain any of the conventional additives in the amounts in which such materials are no~nally employed in fabric washing detergent compositions. Examples of these additives incluae lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, lather depressants such as alkyl phosphates, waxes and silicones, antiredeposition agents such as sodiw~ carboxylllethylcellulose and polyvinyl pyrrolidone optionally copolymerised with vinyl acetate, oxygell-releasing bleaching agents such as sodium perborate and sodium percarbonate, per-acid bleach precursors, chlorine-releaSing bleaching agents such as trichloroisocyaIl_ 11'~1~90 - 15 - c~.1035 uric acid and alkali metal salts of dichloroisocyanuric acid, fabric sol`tening agents, inorgarlic salts such as sodiwn sulphate, sodium carbonate and n~agnesiuln silicate, and, usually present in very minor ~nounts, fluorescent agents, pelfumes, enzymes such as proteases and amylases, germicides and colourants.
It is particularly beneficial to include in the detergent compositions an ~mount of sodium perborate, preferably between about 1~/o and about 40%, for example about 15% to about 30%, by weight. It has been found that the bleaching action of sodium perborate is boosted under the highly alkaline conditions which also give optimum detergency building action ior the alkali metal orthophosphate. Thus, it becomes possible to achieve improved bleaching properties by using the same levels of sodium perborate as normal; or decreased levels of sodium perborate can be used to give equal bleaching properties to those of conventional products with higher levels of perborate and sodium tripolyphosphate as the sole detergency builder. The latter OptiOIl can also be used to further decrease the r~w materials costs of the compositions,-if a cheap filler is used in place of part of -the sodiwn perborate.
It is also possible to include in the detergent compositions of the invention minor amolmts, preferably not more than about 20% by weight, of oth~r non-phosphate deter-gency builders, which may be either so-called precipita~t builders, ion exchange or sequestrant builders. ~his is of ---`` 1121690 - 16 - cC.10~5 p~rticular bene~it where it is desired to increase deter~ency whilst USillg particularly low levels of the essential alkali metal polymer phosphate and alkali metal orthophosphate builders, so as to achieve especially low phosphorus contents 5 in the detergent compositions. Examples of such other detergency builders are amine carboxylates such as sodium nitrilotriacetate, sodium carbonate, sodium aluminosilicate ion-exchange materials such as zeolites A and X, sodium citrate and soap, which can function as a detergency builder, 10 as discussed above. However, such other builder materials are not essential and it is a particular benefit of using the mixod alkali metal polymer phosphate and orthophosphate that satisfactory detergency properties oan be achieved at lower total phosphate levels than hitherto considered 15 necessary without other detergency builders.
It is generally also desirable to include in the compo-SitiollS an amount of an alkali metal silicate, particularly sodium ortho-, meta- or preferably neutral or alkaline silicate . The presence of such alkal i metal silicates at 20 levels of at least about 1%, and preferably from about 5% to abollt l5'k, by weight of the compositions, is advantageous in decreasing the corrosion of metal parts in washing machi~les, besides giving processing benefits and generally improved powder properties. The more highly alkaline ortho_ and meta-25 silicates would normally only be used at lower amounts withinthis range, in admixture with the neutral or alkaline silicates .
l69() - 17 - cC.1035 ~ he compositions of the inv~ntion are r~quired to be ullcaline, but not too strongly alkaline as this could re4ult in f~bric damage alld also be hn~ardous for do~lestic usage.
In practice the compositions should give a pH of frolo 9 to ll ill use in aqueous wash solution. It is preferred in paxticular for do~estic products to have a mini~um p~ of at least 9.25 and especially a pH of 9.5 or ov.,r, as lower p~s tend to be less effective for optimum detergency building, and a maximum p~ of 10.5, as more highly alkaline products can be hazardous if misused. The plI is measured at the lowest normal usage concentration of 0.1~ ~/v of the product in water o~ 12H (Ca), (French permanent hardness, calci~n only) ~t 50C so that a satisfactory degree of alkalinity can be assured in use at all normal product concentrations.
~he pH of the detergent compositions i~ use is controlled by the amount of alkali metal orthophosphate and any other alkaline salts such as alkali metal silicate~
sodium perborate and sodium carbonate present. The presence of such other alkaline salts, especially the alkali metal silicates, is particularly beneficial, because the alkalinity ~f the alkali metal orthophosphate is dilllinished in hard water due to precipitation Or the calcium salt. In addition the alkali metal polymer phosphate is more stable and resistant to hydrolysis under highly alkaline conditions. The other ingredicnts in the alkaline detergent compositions of the invention should of course be chosen for . : , -,.~ ~ . . .
- ~ , `
l~Z1690 - 18 - cC.1035 alkalin~ stability, especiall~ the pH sensitive materials such as enzymes.
~ he detergent compositions of the invention are normally made in particulate form, for example by slurry making and spray drying, preferably with admixture of the alkali metal polymer phosphate to n spray dried base powder.
~owever, if desired the detergent compositions may be compressed or compacted into tablets or blocks, or otherwise treated for example by granulation, prior to packaging and sale. Because of the hygroscopic nature of the alkali metal polymer phosphates, it may be desirable to use moisture impermeable packaging for the detergent compositions, for example in plastic or fabric sachets containing pre_ measured doses for washing machine usage.
The in~ention is illustrated by the followîng ~xamples in which parts and percentages are by weight except where otherwise indicated.
Examples 1 to 9 ~ series of detergent powders were prepared by firstly spray drying a detergent base powder to the following ` formulation:
, llZ1690 - 19 - cC.1035 Ing~diellt ~ (based oll rinal product) Sodium alkyl benzene 9 sulphoIIate Nonionic detergent compoundl l Sodium orthophosphate 8 Sodium silicate lO
(Na20:SiO2, 1:2) Magnesium silicate 0.5 Sodium sulphate27.2 Water and minor additives ~.3 65.0 l Cl~-Cl5 alcohol - 18 E0 condensate.
~mounts of additives as specified in the Table below were then added ~o this base powder-to make the ~ormula~.ions as ~ollows:
Ingredient Ex: l 2 3 .4 5 6 7 8 g _ Base powder 65 Sodium poly~er lO - - lO - - lO
phosphate Sodium poly~er - lO - - lO - - lO
phosphate Sodium polymer - - 10. - - 10 - - 10 phosphate4 20 Sodium polyacrylate5 - - - 2 2 2 Sodium sulphate 2 2 2 - - ~ 1 1 1 Sodium perborate 20 f Nonionic deter~ent 2 >
(continued overleaf) ,~ . .. . _ .. .... .~ . .
~ 6 ~
- - 20 - cC.10~5 (Con-tinued) %
In~.redient ~x: 1 2 ~ 4 5 6 7 8 9 Enzyme and per~wne , .
Lather controller6 0.6
2 Polymer chain length 6_8.
3 Polymer chain length 15-20 (plus 0.36% NaOH for pH
control).
Polymer chain lengtll 25-30 (plus 0.72% NaOH for p~
control).
Versicol E7 (molecular weight 27000).
6 ~lkyl phosphate.
These detergent compositions were evaluated for washing performance, including especially inorganic deposition on fabrics. The tests were accomplished in laundrometer machines using a product concentration of 8 g/l in water o~
40 French hardness at 95C. The levels of deposition on the fabrics were determined after 10 repeat wash cycles using standard fabrics as indicated.
~ inorganic deposition Fabric E~:1 2 3 ~ 5 6 7 8 9 Cotton poplin 0.6 0.5 0.7 0.2 0.2 0.2 0.3 0.1 0.2 Polyester/cotton 0.5 1.0 1.0 0.2 0.2 0.2 0.2 0.2 0.2 blend (50:50) Unsized cotton 1.8 2.0 2.1 0.6 0.3 0.2 0.8 0.3 0.3 ~ hese results are good in comparison with other reduced phosphate builder products, and show especially the benefit of using pol~-acrylate in conjunction with the orthophosphate-: 25 polymer phosphate builder mixture. A comparative product - 21 - cC.1035 with 12% sodium tripolyphosphate instead of the pol~mer phosphate and wi-th no polyacrylate gave 1.8%, 2.9% and 6.0% deposition on the same fabrics, respectively, under the same test conditions.
Examples 10 - 14 ~ series of detergent compositions were prepared by mixing the ingredients to the following formulation:
n~edient %
Sodium alkyl benzene sulphonate 6 10 ~onionic detergent compounds (mixed 4 alcohol - 12 and 18 E0) Sodium polymer phosphate 6 Sodium orthophosphate 6 ...
Sodium silicate 12 Sodium carboxymethylcellulose 15 Sodium polyacr~late 2 Sodium sulphate 33 Sodium perborate 22 Water and minor additives to 100 ~he sodium polymer phosphate used had a chain length(~
of about 18 and the sodium polyacrylates used had molecular weights as follows:
:E~c. 10 - MW '4, 000 ~x. 11 - MW I8,000 Ex. 12 - M~ 30,000 Ex. 13 - MW :50,000 Ex. 14 - MW 210,000 ^' 1~'~1690 - 22 - cC.1035 The compositions were then tested for detergency and inorganic deposition on washed fabrics (ash). Considering the low phosphate builder level the detergency properties were good, and the ash levels were particularly low, being between 0.5% and 0.9% on cotton poplin fabric and between 1.5% and 2.0% on Krefeld cotton after 10 wash cycles.
~he tests were conducted at a product concentration of 8 g/l in an Atlas Baunderometer at 95C in 23GH water. By way o~ comparison, the ash levels for a similar sodium tripoly-phosphate-sodium orthophosphate built formulation were 2.0%
and 5.7% respectively, under the same conditions.
Examples 15 - 18 ~our detergent compositions were made to the --fo~mulation below: -n~redient %
Sodium alkylbenzene sulphonate 7 ~onionic detergent compounds (12-18 ~0) 5 Sodium orthophosphate1 6.0 Sodium polymer phosphate1 (chain length 18) 10.0 20 Sodium silicate 12.0 Sodium sulphate 28.0 Antideposition agent1' 2 2.0 Sodium perborate1 22 Water and minor additives to 100 Added in particulate form to the dry-mixed base powder.
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- 23 - cC.1035 Ih Example 15 - Sodium polyacrylate (MW 27,000) " 16 - ~thylenediaminetetramethylene phosphonic acid " " 17 - Polyhydroxy acrylic acid " " 18 - Polymaleic acid (MW 1,400).
~hese compositions were evaluated for detergency and inorganic fabric deposition, and found to be good in both respects. ~he aver~ge figures for the latter on different cotton types after 10 wash cycles were only 0.3%, 0.65%, o. 75% and 1.3%, respectively, under the same conditions as for Examples 10 to 14.
Similar results were also achieved when sodium ethane-1-hydroxy-1,1-diphosphonate and other molecular weight polyacrylates were used as antideposition agents in the for=ulatio~.
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control).
Polymer chain lengtll 25-30 (plus 0.72% NaOH for p~
control).
Versicol E7 (molecular weight 27000).
6 ~lkyl phosphate.
These detergent compositions were evaluated for washing performance, including especially inorganic deposition on fabrics. The tests were accomplished in laundrometer machines using a product concentration of 8 g/l in water o~
40 French hardness at 95C. The levels of deposition on the fabrics were determined after 10 repeat wash cycles using standard fabrics as indicated.
~ inorganic deposition Fabric E~:1 2 3 ~ 5 6 7 8 9 Cotton poplin 0.6 0.5 0.7 0.2 0.2 0.2 0.3 0.1 0.2 Polyester/cotton 0.5 1.0 1.0 0.2 0.2 0.2 0.2 0.2 0.2 blend (50:50) Unsized cotton 1.8 2.0 2.1 0.6 0.3 0.2 0.8 0.3 0.3 ~ hese results are good in comparison with other reduced phosphate builder products, and show especially the benefit of using pol~-acrylate in conjunction with the orthophosphate-: 25 polymer phosphate builder mixture. A comparative product - 21 - cC.1035 with 12% sodium tripolyphosphate instead of the pol~mer phosphate and wi-th no polyacrylate gave 1.8%, 2.9% and 6.0% deposition on the same fabrics, respectively, under the same test conditions.
Examples 10 - 14 ~ series of detergent compositions were prepared by mixing the ingredients to the following formulation:
n~edient %
Sodium alkyl benzene sulphonate 6 10 ~onionic detergent compounds (mixed 4 alcohol - 12 and 18 E0) Sodium polymer phosphate 6 Sodium orthophosphate 6 ...
Sodium silicate 12 Sodium carboxymethylcellulose 15 Sodium polyacr~late 2 Sodium sulphate 33 Sodium perborate 22 Water and minor additives to 100 ~he sodium polymer phosphate used had a chain length(~
of about 18 and the sodium polyacrylates used had molecular weights as follows:
:E~c. 10 - MW '4, 000 ~x. 11 - MW I8,000 Ex. 12 - M~ 30,000 Ex. 13 - MW :50,000 Ex. 14 - MW 210,000 ^' 1~'~1690 - 22 - cC.1035 The compositions were then tested for detergency and inorganic deposition on washed fabrics (ash). Considering the low phosphate builder level the detergency properties were good, and the ash levels were particularly low, being between 0.5% and 0.9% on cotton poplin fabric and between 1.5% and 2.0% on Krefeld cotton after 10 wash cycles.
~he tests were conducted at a product concentration of 8 g/l in an Atlas Baunderometer at 95C in 23GH water. By way o~ comparison, the ash levels for a similar sodium tripoly-phosphate-sodium orthophosphate built formulation were 2.0%
and 5.7% respectively, under the same conditions.
Examples 15 - 18 ~our detergent compositions were made to the --fo~mulation below: -n~redient %
Sodium alkylbenzene sulphonate 7 ~onionic detergent compounds (12-18 ~0) 5 Sodium orthophosphate1 6.0 Sodium polymer phosphate1 (chain length 18) 10.0 20 Sodium silicate 12.0 Sodium sulphate 28.0 Antideposition agent1' 2 2.0 Sodium perborate1 22 Water and minor additives to 100 Added in particulate form to the dry-mixed base powder.
-.
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- 23 - cC.1035 Ih Example 15 - Sodium polyacrylate (MW 27,000) " 16 - ~thylenediaminetetramethylene phosphonic acid " " 17 - Polyhydroxy acrylic acid " " 18 - Polymaleic acid (MW 1,400).
~hese compositions were evaluated for detergency and inorganic fabric deposition, and found to be good in both respects. ~he aver~ge figures for the latter on different cotton types after 10 wash cycles were only 0.3%, 0.65%, o. 75% and 1.3%, respectively, under the same conditions as for Examples 10 to 14.
Similar results were also achieved when sodium ethane-1-hydroxy-1,1-diphosphonate and other molecular weight polyacrylates were used as antideposition agents in the for=ulatio~.
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Claims (16)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A particulate alkaline detergent composition comprising from about 2.5% to about 50% by weight of a synthetic anionic, nonionic, amphoteric or zwitterionic detergent compound or mixture thereof,at least about 5% by weight of a water-soluble alkali metal polymer phosphate having the formula M2O-(MP°3)n wherein M is alkali metal and n is an integer of at least 4, and at least about 2% by weight of an alkali metal orthophosphate, the ratio of the polymer phosphate to the orthophosphate being from about 10:1 to about 1:5 parts by weight, the total amount of the alkali metal polymer phosphate and alkali metal orthophosphate being from about 10% to about 40% by weight of the composition and not more than about 10% of other alkali metal phosphate builders being in the composition, and from about 0.01% to about 10% by weight of an anti-deposition agent which is an anionic polyelectrolyte.
2. A detergent composition according to Claim 1, wherein the alkali metal polymer phosphate is in sodium salt form.
3. A detergent composition according to Claim 1, wherein in the formula of the alkali metal polymer phosphate n is from about 6 to about 50.
4. A detergent composition according to Claim 1, wherein the amount of alkali metal polymer phosphate is from about 5% to about 15% by weight of the composition.
5. A detergent composition according to Claim 1, wherein the alkali metal orthophosphate is trisodium orthophosphate, disodium monohydrogen orthophosphate, monosodium dihydrogen orthophosphate or a mixture thereof.
6. A detergent composition according to Claim 1, wherein the amount of alkali metal orthophosphate is from about 5% to about 15% by weight of the composition.
7. A detergent composition according to Claim 1, wherein the total amount of the alkali metal polymer phosphate and of the alkali metal orthophosphate is from about 10% to about 25% by weight of the composition.
8. A detergent composition according to Claim 1, wherein the ratio by weight of alkali metal polymer phosphate to alkali metal orthophosphate is from about 3:1 to about 1:3
9. A detergent composition according to Claim 1, comprising not more than about 5% by weight of alkali metal tripolyphosphate.
10. A detergent composition according to Claim 1, comprising not more than about 2.5% by weight Or alkali metal pyrophosphate.
11. A detergent composition according to Claim 1, wherein the anti-deposition agent is a polymeric aliphatic carboxylate.
12. A detergent composition according to Claim 1, wherein the antideposition agent is an organic phosphonic acid or a salt thereof.
13. A detergent composition according to Claim 11, wherein the polymeric aliphatic carboxylate is sodium polyacrylate.
14. A detergent composition according to Claim 1, wherein the amount of the antideposition agent is from about 0.1%
to about 5% by weight of the composition.
to about 5% by weight of the composition.
15. A detergent composition according to Claim 1, comprising from about 0.5% to about 25% by weight of soap.
16. A detergent composition according to Claim 1, comprising from about 10% to about 40% by weight of sodium perborate or percarbonate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7839071 | 1978-10-03 | ||
| GB39071/78 | 1978-10-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1121690A true CA1121690A (en) | 1982-04-13 |
Family
ID=10500075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000336795A Expired CA1121690A (en) | 1978-10-03 | 1979-10-02 | Detergent compositions |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0009954B1 (en) |
| JP (1) | JPS5550095A (en) |
| AT (1) | ATE79T1 (en) |
| AU (1) | AU533316B2 (en) |
| BR (1) | BR7906346A (en) |
| CA (1) | CA1121690A (en) |
| DE (1) | DE2960405D1 (en) |
| ZA (1) | ZA795232B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3035805A1 (en) * | 1980-09-23 | 1982-05-06 | Hoechst Ag, 6000 Frankfurt | METHOD FOR PRODUCING GRANULES OF CONDENSED PHOSPHATES |
| GR76045B (en) * | 1981-04-08 | 1984-08-03 | Procter & Gamble | |
| JPS5821498A (en) * | 1981-07-30 | 1983-02-08 | ダスキンフランチヤイズ株式会社 | Bleaching agent composition and manufacture |
| GB2233338A (en) * | 1989-06-23 | 1991-01-09 | Unilever Plc | Detergent composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4116852A (en) * | 1975-02-14 | 1978-09-26 | The Procter & Gamble Company | Builders and built detergent compositions |
| MX143145A (en) * | 1975-02-20 | 1981-03-25 | Procter & Gamble | IMPROVED GRANULAR DETERGENT COMPOSITION |
| GB1530799A (en) * | 1975-08-28 | 1978-11-01 | Unilever Ltd | Detergent compositions |
| DE2816770C2 (en) * | 1977-04-22 | 1984-10-18 | The Procter & Gamble Co., Cincinnati, Ohio | Textile detergent containing builders |
-
1979
- 1979-10-01 AT AT79302059T patent/ATE79T1/en not_active IP Right Cessation
- 1979-10-01 EP EP79302059A patent/EP0009954B1/en not_active Expired
- 1979-10-01 DE DE7979302059T patent/DE2960405D1/en not_active Expired
- 1979-10-02 CA CA000336795A patent/CA1121690A/en not_active Expired
- 1979-10-02 BR BR7906346A patent/BR7906346A/en unknown
- 1979-10-02 AU AU51360/79A patent/AU533316B2/en not_active Ceased
- 1979-10-02 ZA ZA00795232A patent/ZA795232B/en unknown
- 1979-10-03 JP JP12783779A patent/JPS5550095A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| ATE79T1 (en) | 1981-06-15 |
| AU533316B2 (en) | 1983-11-17 |
| BR7906346A (en) | 1980-05-27 |
| AU5136079A (en) | 1980-04-17 |
| EP0009954A1 (en) | 1980-04-16 |
| DE2960405D1 (en) | 1981-09-17 |
| EP0009954B1 (en) | 1981-06-10 |
| ZA795232B (en) | 1981-05-27 |
| JPS5550095A (en) | 1980-04-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |