CA1050381A - Amine polyphosphates - Google Patents
Amine polyphosphatesInfo
- Publication number
- CA1050381A CA1050381A CA210,447A CA210447A CA1050381A CA 1050381 A CA1050381 A CA 1050381A CA 210447 A CA210447 A CA 210447A CA 1050381 A CA1050381 A CA 1050381A
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- amine
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- polyphosphate
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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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Novel organic polyphosphate mixtures comprising a plurality of polyphosphate salts of one or more primary, secondary or tertiary amines are obtained by a process comprising 1) forming an aqueous polyphosphoric acid solution comprising from 80 to 88% by weight of phosphorus pentoxide and 2) reacting said polyphosphoric acid solution with a primary, secondary or tertiary amine in such a way as to avoid hydrolysis of the polyphosphate species.
Such mixtures are useful as builders in liquid cleaning compositions comprising surface active agents or alkali metal hydroxides or silicates with which they are more compatible in aqueous solution than previously used polyphosphate builder salts.
Novel organic polyphosphate mixtures comprising a plurality of polyphosphate salts of one or more primary, secondary or tertiary amines are obtained by a process comprising 1) forming an aqueous polyphosphoric acid solution comprising from 80 to 88% by weight of phosphorus pentoxide and 2) reacting said polyphosphoric acid solution with a primary, secondary or tertiary amine in such a way as to avoid hydrolysis of the polyphosphate species.
Such mixtures are useful as builders in liquid cleaning compositions comprising surface active agents or alkali metal hydroxides or silicates with which they are more compatible in aqueous solution than previously used polyphosphate builder salts.
Description
~05~3~3~
This invention relates to liquid cleaning composi-tions comprising a polyphosphate builder. Such compositions include both liquid detergent solutions comprising a surface active agent such as are currently employed as dishwashing and textile detergents and also highly alkaline solu~ions comprising little or no surface active agent such as are used for cleaning hard surfaces, e.g. the insides of ovens and for machine dishwashing bottle washing and beer keg washing. The present compositions may have various degrees of aqueous dilution and in the extreme case may be stable suspensions or gels. The polyphosphate solutions may al50 be dried by suitable means to provide a solid builder com-position. In the gel or suspension form the compositions may be used in cosmetic detergents, e.g. shaving creams.
Polyphosphate huilders are useful in all such compositions both for their sequestering effect on heavy metal ions, notably calcium ions, ana for their detergent builder proper-ties additional to this sequestering effect.
Considerable efforts have been made to provide satisfactorily built cleaning compositions of the types instanced above but as yet a number of problems xemain.
The primary difficulty in the case of liquid cleaning compositions arises from the variegated nature of the necessaxy ingredients coupled with the properties which the liquid cleaning composition must possess. In the case - Qf compositions comprising sur~ace active agents in solu-~ion the primary problem may be expressed as that of pro-viding a composition which has a sufficient concentration of surface active agénts and builder in the same solution to give a satisfactory cleaning performance but which at the same time is homogeneous, has a chill point well below room temperature and a short reliquifaction time at room ~.
~5~38~
temperature after storage at low temperature. In addition in order to gain acceptance the solution should be sufficient-}y concentrated that a container of moderate siz~ containing the solution will provide an acceptable number of washings -about as many washings as an equivalent sized container of solid detergent. All these requirements are onerous in that they increase the necessity of the builder and sur~ace active agents having a high compatibility. Compatibility limita-tions are o~ten further aggravated by the need for further ingredients such as a silicate (as a corrosion inhibitor) suds builders, and organic solvents. In the case of highly al~aline liquid cleaning compositions comprising little or no surface active agent similar problems arise in relation to the compatibilities in aqueous solution of the phosphate builder and the alkaline ingredient which is nQrmally a caustic alkali or a sodium silicate or a mixture of the two.
Attempts to mitigate these problems have been concentrated on varying the nature of the surace active agent and the builder so as to discover a combination having a large degree of compatibility or in incorporating a further ingredient into the composition which is designed to homogenise the solution. Combinations of these approach-es have also been used.
However, the scope for variation is limited by the desired properties of the composition and the success in alleviating the above problems has been limited.
The scope for varying the nature of the surface active ingredients (where used) is limited by the required detergency characteristics of the composition, that is not all surface active agents possess the foaming properties (either high or low foaming ability may be desired) mild-~ S03t~1 ness washing ability and low cost which are required for use in liquid detergents. A notable difficulty arises in the case of the non-ionic surface active agents having the low foaming pr~perties essential in liquid detergents for use in automatic dishwashing machines as well as other desirable washing properties. Such non ionic surfactants may be dissolved only with difficulty in concentrated alkaline builder solutions-unless certain specialised ingredients are added to bring about compatibility (see for example B.P. 991980).
A variet~ of homogenising agents designedto in-crease the compatibility of the vaxious ingredi~nts are also widely used in many types of cleaning compositions. Most widespread among these are the so-called "hydrotropes", notably sodium or potassium, salts of benzene, toluene or xylene sulphonic acids and triamyl phosphate. Various organic copolymers have also been suggested (see for examplç
B.P. 943353) and the incorporation of "assistant solubilizers"
such as ethanol or ethylene glycol has also been proposed.
The disadvantage of all these additional ingredients is that they contribute little or nothing to the actual cle~n-ing properties of the composition so that the expense of their incorporation must be weighed solely against their ability to enable the c~ncentration of the builder or surface active agent in the solution to be increased. Moreover the dilution o the cleansing effect resulting from the use of such homo-genizers lessens the effectiveness of the composition.
The third major possibility of increasing the com patibility of the ingredients of the compositions lies in the variation of the nature of the builder. The scope for such variation is however limited. The condensed phosphates are the most widely accepted Idetergent builders and many of these ~ _ 4 :~61 503~
have been examined. The ma]or commercially accepted poly-phosphate builder salts are the alkali metal pyrophosphates and the alkali metal tripolyphosphates and the alkali metal hexametaphosphates. For liquid detergent compositions the most widely accepted builder is potassium pyrophosphate.
Whilst this compound is acknowledged to be a less effective builder than other compounds such as sodium tripolyphosphate potassium pyrophosphate is relatively free from the dis-advantag s of limited compatibiliky with other ingredients in detergent solutions and of hydrolysis in aqueous solutions which attach to the tripolyphosphates. Even so potassium pyrophosphate is I
- 4~ -~0sa~38:~
not as compatible with surface active agents as might be desired and the problems outlined above still hinder the development of liquid detergents.
We have now discoverecl a ranye of polyphosphate builder salts suitable for use in liquid cleansingcompositions which considerably reduce the aforesaid disadvantages in com-parison with the aforementioned known polyphosphate builders.
The invention provides a cleaning composition which comprises from 4 to 25~ by weight expressed as the weight of P2O5 on the total weight of the composition of a mixture of a plu-rality of polyphosphate salts of one or more primary, secondary or tertiary amines which mixtura has been obtained by forming an aqueous polyphosphoric acid solution comprising from 80 to 88% by weight of phosphorus pentoxide which has been allowed to reach equilibrium and subsequently reacting the said polyphosphoric acid solution with a primary r secondary or tertiary amine without causing any substantial hydrolysis of the polyphosphate species present in the acid;
from 0.1 to 50~ by weight of a water-soluble surfactant.
~0 The following advantageous properties ~or the compositions of the invention may be listed:
(1) High se~uestering ability for calcium and magnesium ions;
12) Exceptionally good detergent builder properties in addition to sequestering ability;
(3) Compatibility in aqueous solution with highly alkaline reagents and surface active agent substantially better than that of the conven-tional builder solutions;
(4) Satisfactory viscosi~ies over a broad range of solids contents leading to convenient ,. ~, :.
1~03~3~
handling. Such properties are desirable in the formuiation of liquid cleansing products.
It is to be understood that whilst the mixtures are not necessarily superior to conventional builders in all the above respects, they are nevert!heless uniquely valuable in the combination of these properties which they possess.
The builder solutions are obtained by neutralisation of aqueous polyphosphoric acid solutions comprising from 80 to 88% by weight of phosphorus pentoxide. The polyphosphoric acid species present in such solutions are in equilibrium with one another and the over-all composition is governed solely by the P205 content o~ the acid as is illustrated in the Canadian Journal of Chemistry, Vol34 (1956) p.790, where the compositions of a number of acids which are useful according to our invention are detailed. These species are primarily the straight chain polyphosphoric acids.
Useful aqueous polyphosphoric acid solutions may be made by conventional means such as by concentration of orthophosphoric acid solutions or by dilution of polyphosphoric acid solutions having greater than the desired P205 content with water. Whilst the presence of other materials in the polyphosphoric acid solutions is not excluded, it is desirable that these solutions be substantially unadulterated and poly-phosphoric acid solutions derived by any of the above mentioned procedures from phosphorus pentoxide obtained by the burning of electrothermally produced phosphorus are preferred.
Polyphosphoric acid solutions derived by the solution of P205 in so-called "wet process" phosphoric acid ob~ained by acidification of phosphate rock are also useful according to the invention. The e~uilibria detailed above between ~OSi~3~
the various polyphosphate acid species contained in a poly-phosphoric acid having a particular P205 content are set up virtually immediately in that acid but preferably the acid is allowed to equilibrate before the neutralisation stPp, e.g. by allowing them to stand for a period of time at room temperature before neutralisation commences. Suitable times are from one minute upwards.
The mixtures in aqueous solution may be obtained by the reaction of the polyphosphoric acid solutions with a primary, secondary or tertiary ~mine. In the term 'amine' as used herein are included all compounds having an amino grouping which are capable of neutralising phosphoric acid, i.e. all compounds having an amino grouping other than one at~ached to a carboxyl group, regardless of the other con-stituents of the molecule so that, for example, this term includes amino acids and substituted amines such as alkanol-amines. Preferred amines have molecular weights below 200, most preferably below 150. Particularly valuable amines include mono-, di- and tri-ethanolamines and propanolamines.
Other amines which may be used include morpholine, mono-, di-and tri-ethyl, n-propyl, iso~propyl and n-, iso- and sec-butylamines, N,N-dimethyl-ethanolamine, aminoethylethanolamine, N-2-aminoethylethanolamine, N-methyldiethanolamine, N-methyl-morpholine, N-ethylmorpholine, N,N-diethylethanolamine, N-methylethanolamine.
It may be desirable to effect the reaction step simultaneously with a dilution to bring about the desired final concentration of the builder solution, provided that such dilution does not bring about hydrolysis of the poly-phosphate anion species present. It is characteristic of the builder solutions for present use that the spectrum of polyphosphate anions present, substantially corresponds to ~0~6338~
that present in the original polyphosphoric acid solution.
Hydrolysis of polyphosphate anions is preferably avoided by maintaining the pH of the reaction medium in the-range 4-12, preferably 6-12i most preferably 7-10, and the temperature below 70C, preferably below 40C, say 15C to 70c, or 15C
to 40C.
Previous attempts to neutralise polyphosphoric acid solutions having a P2O5 content in the range 80-88~ by weight have failed to appreciate the necessity of avoiding the hydro lysis o~ the polyphosphate species during the neutralisation step. For example B.P.919,249 describes the neutralisation of a phosphoric acid solution containing 84% by weight of P2O~
u~ing a mixture of diethanolamine and potassium hydroxide.
The resulting polyphosphate is claimed to be a useful builder in liquid detergents however in order to incorporate suffi-cient builder in a liquid detergent solution the presence of a water miscible organic cosolvent such as ethanol is essen-tial. The amine builder salts of our invention made under the conditions outlined above are sufficiently compatible with detergent solutions to enable the use of such an organic co~
soIvent to be avoided if desired. However the presence of such cosolvents in the compositions of our invention is not excluded.
In B.P.1066234 there is described a solid detergent builder which is produced by the neutralisation of a poly-phosph~ric acid solution containing 83~ by weight of P2O5 with an excess of an alkali metal salt, preferably the carbonate. Although this patent teaches the desirability of avoiding the hydrolysis of the polyphosphate anions present it is only concerned with the alkali-metal salts and their use in admixture with alkali-metal carbonates as solid detergent builders.
~S03~
The mixtures for present use are preferably those obtainable by reaction of the said phosphoric acids and the said amines in a 1:1 ratio of c~cidic hydrogen atoms in the polyphosphoric acid(s) to hydrogen atoms bonded to nitrogen in the amine but compounds obtainable by partial neutralisa-tion of the polyphosphoric acids by the amines also have utility. In the general case of builders will be compounds obtainable by the reaction of the said polyphosphoric acids with amine in a ratio of from 1:10 to 10:1 say 1:5 to 5:1 prefPrably 1:1 to 3:1 expressed as the ratio of amine groups to phosphorus atoms.
- In any case reaction be~ween the amine and the poly~
phosphori~ acia mixture preferably proceeds to a final pH of from 4 to 12 preferably from 4 ko 10 most preferably from 7 to 1~.
The builder salts are conveniently obtained b~ the straightforward addition of the polyphosphoric acid to the amine or the aqueous solution thereof fQllowed by concentra-tion or dilution as required for the proposed use.
In the case of the salts derived from amines which contain an hydroxy substituent on their carbon chain it is necessary to maintain the water content of the system at a sufficient level so as to ensure the desired salt formation occurs rather than esterification such as is described in USP 3728419, a water level of above 15% by weight is normally sufficient. In general we prefer to maintain the water con-tent in the builder salt solution in the range 20-40% by weight si~ce this facilitates the handling o~ the product.
In the case of amines which do not contain a hydroxyl group and therefore cannot be esterified this restriction is not essential although it is preferred to maintain the water content of the system above 25% by weight. Decrease in this g 1~5~3~
water content results in a progressive tendency to form a solid product and such processes are less preferred.
A particularly valuable and unlooked for property is that aqueous solutions of the mixtures may, within certain proportion ranges, depending upon the amine involved, comprise concentrations of the said polyphosphate salt mixture in excess of the solubility limit for a true solution whilst remaining as stable suspensions or gels which are useful as builders for paste type cleaning agents such as oven ~leaners and other highly alkaline hard surface cleaners as well as cosmetic cleaners in paste form such as shaving creams. ~he aqueous cleaning compositions of the invention are according-ly defined 3~3~
herein as including solutîons wherein the polyphosphate mix-tures are in sol and suspension form as well as in true solu-tions. Mixtures as hereinbefore defined which are in the form of stable aqueous suspensions constitute a preferred aspect of this invention. In general, such suspension-type solutions will comprise from 35 to 60% by weight of poly-phosphate mixture expressed as weight of P205 on the total weight of polyphosphate mixture plus-water present. However, the minimum concentration at which the suspensions are formed varies somewhat with the nature of the cation and suspensions of the invention may variously comprise from 40 to 60, 40 to 50 and 45 to 60% by weight of the polyphosphate mixture (on the aforementioned basis) depending upon the amine concerned.
Solutions of the builders thus formed may provide a solid builder for incorporation into solid detergent formula-tions with other conventional ingredients. Preferably they are sprayed as solutions onto preformed solid detergent com-positions. Such solid detergent formulations constitute a ~urther aspect o~ the invention.
The mixtures are used in the novel cleaning composi-tions in a wide ra~ge of concentrations depending upon the envisaged application and upon the solubility of the mixture.
They will be present in concentrations of from 4 to 25% by weight, more usually ~rom 6 to 18%, e.g. from 10 to 15% by weight (all these percentages being expressed as percentages of P2O5 from the respective polyphosphates~ on the total weights of the compositions. Aqueous solutions of the poly-phosphate mixtures as hereinbefore defined comprising at least 4%, preferably at least 10~ thereof, on the aforesaid basis constitute a further aspect of this invention. Preferred such solutions comprise from 6 to 18%, more specially from 10 to 16% by weight of the mixture on the aforesaid basis.
. . _ . . _ ~S(~31~1L
The proportion of surface active agent in the novel compositions may vary within wide limits just as with known such compositions, depending upon the use in question. Novel compositions will comprise from 0.1 to 50~ by weight of sur-face active agent and in particular cases may comprise say from 0.1 to 5%, e.g. 0.5 to 3% by weight in the case of a hard surface cleaner and from 10 to 50%, e.g~ 20 to 30% in the case of a heavy duty liquid detergent.
The surface active agents which may be employed in the novel compositions include non-ionic, anionic, cationic and amphoteric surface active agents, generally such as these mentioned in Volume 19, pages 507-566 of the Encyclo-paedia of Chemical Technology, Second Edition by Kirk- Othmer published by Interscience 1969.
Particular surface active agents which may find use in the novel compositions include: alkyl aryl sulphonates such as lithium, sodium, potassium, ammonium or other water-soluble salts of sulphonic acids of alkyl-substituted benzenes such as decyl toluene, dodecyl-x~ylene, octylbenzene, nonyl-benzene~ decylbenzene, tridecylbenzene, tetradecylbenzene, pentadecylbenzene, dodecylbenzene and hexadecylbenzene;
Olefin sulphonates such as water-soluble alkali metal and alkaline earth metal mono- or di-olefin sulphonic acids comprising from 8 to 24 carbon atoms;
Alkali metal or ammonium alkyl sulphates in which the alkyl groups have from 10 to 18 carbon atoms and polyoxy-ethylenated and polyoxypropylenated derivatives thereof;
Alkali metals or ammonium salts of alkane sulphonates;
Alkali metal or ammonium salts of sulphosuccinated materials of the average general formula:
l2 C (OCH2 C~n OR2 ` `
1 ~05~38~
wherein n is from 0 to 25, R is hydrogen or a methyl group and R2 an alkyl group having f:rom 8 to 25 carbon atoms.
- Amine oxides such as those described ~n B.P.943,353 having the formula RlR2R3NO, w:herein Rl is an alkyl radical having from 9 to 25, preferably 10 to 16 carbon atoms and R
and R2 are methyl or ethyl groups:
Betaines of the general formula + R~
Rl - N - R3 . R4 - CO2 wherein R2 and R3 are alkyl or alkenyl groups cvntaining from 1 to 6 carbon atoms and are preferably methyl groups, R4 is an~alkyl group containing from 1 to 6 carbon atoms and Rl is an alkyl or alkenyl group containing from 8 to 18 carbon atoms:
. Amido-amine derivatives having the formula ~ Rl . I
N(CH2~n N
. where R represents an alkyl or alkenyl group having from 8 to 20 carbon atoms, Rl and R2 are the same or different groups selected from hydrogen atoms, methyl or ethyl groups and n is an integer in the range 1 to 4 and corresponding amines and betaine derivatives.
Polyoxethylene compounds of the general formula RO(CHCHRlO)xH where R is an alkyl, aryl, alkaryl, alicyclic, acyl, amino or alkylamino group; Rl is hydrogen or an alkyl group having from 1 to 4 carbon atoms and x is from 3 to 100, usually from 6 to 50. Such compounds include fatty alcohol polyethoxylate~, fatty acid polyethoxylat~s, polyethylene glycol ethers, mixed polyethylene and polypropylene glycol ethers, amine and diamine polyethoxylates~ and ~atty alkyl-olamide ethoxylates:
i(~Sa3~
¦ Fatty alcohol phosphates and polyethoxylated and ¦ polypropyloxylated deriva'es thereof:
Fa~ty acid soaps.
- The novel compositio:ns comprising surface active agents will normally be compou:nded by addition of an aqueous solution of the surface active agent (or agents) used to a solution of the polyphosphate mixture, optionally followed by dilution although other means may also be used.
In the case o highly alkaline cleaners of the in-vention comprising little or no surfactant, the proportion of polyphosphate salt mixture will generally represent from 2 to 20% by weight (expressed as P2O5) in the composition, prefer-ably 5 to 15%, whilst the alkaline component or components, which will normally be sodium hydroxide and/or an alkali - metal silicate salt such as soaium metasilicate will generally be present in a proportion of from half to twice by weight of the weight of the polyphosphate salt mixture (expressed as weight of solid material). In the case of caustic alkalis such as sodium and potassium hydroxide these might typically represent from 10-15% by weight of the total solids content of the composition. Where alkali metal silicate salts are used, these mi~ht typically represent from 25 to 40~ by weight of the total solids content of the composition. Alkali metal ~ilicates ~or present use are preferably those having an M20:SiO2 ratio of from 0.5:1 to 2:1 where M is soaium or potassium, sodium metasilicate being particularly preferred.
The novel compositions may also comprise known adjuvants for liquid cleaning compositions such as antisoil redeposition agen~s, e.g. carboxymethyl cellulose, polyvinyl pyrrolidone, or the sodium salts of a copolymer of di-isobutylene and maleic anhydride, optical brightening agents;
perfumes; dyes; bacteriostats and bacteriocides; opacifying ~OS~3~3 IL
agents; colorants; sudsing agents, e.g. ethanolamides such as coconut ethanolamide and fatty allcohols such as lauryl alcohols; phase stabilisers such as lower aliphatic alcohols and homogenizing agents. Although the polyphosphate builders generally permit less homogeniz:;ng agent to be present than would be necessary with convent:ional phosphate builders, the preferred c~mpositions of the invention are those which in-clude a so-called hydrotope such as an alkali metal, alkaline earth metal or ammonium salt of benzene-, naphthaline-, an alkylbenzene - or an alkyl naphthalene - sulphonic acid having not more than 5 aliphatic carbon atoms. Preferred such hydrotopes are sodium xylene sulphonates ~sold by Albright and Wilson Limited under the registered trade name Eltesol'), sodium toluene sulphonate, sodium benzene sul-phonate and sodium naphthalene sulphonate. Preferably hydro-topes are present in the novel compositions in proportions of from 2 to 20% by weight, more preferably 2 to 10%, most preferably 3 to 5%. In the case of hard surface cleaners of the inventiont it may also be desired to incorporate a chlorine-releasing agent which is preferably sodium hypo-chloride although chlorinated isocyana~es can also be used.
Normally, chlorine-releasing agents, where used, will be - present in a concentration such as to give from 0.5 to 3~, e.g. 1 to 2~ available chlorine ~w/v) which is roughly equivalent in the case of sodium hypochlorite. For 8-12 v~v sodium hypochlorite.
Compositions of the invention may be employed to ¦ advantage in a range of cleaning applicatisns such as the cleaning of textiles, including wool, wood, leather, metal earthenware, china and stone as well as for human use.
The polyphosphate builders of the invention are ~ - 14 ~1~350315~1 particularly applicable in liquid detergent compositions designed for the cleaning of fine fabrics. These compositions will normally contain from 4 to 10~ of the polyphosphate ex-pressed as the weight of P205 and from O to 5% of a suitable surfactant which is preferably a non-ionic surfactant.
.
- 14A ~
~05~3~3~
The invention is illustrated by the following Examples i~l which all parts are expressed on a weight basis and all proportions of proprietary surfactant ingrsdients are expressed in terms of active ingredient (a.i.) any water present in the surfactant as aclded being included in the given proportions of total water.
Example A composition was made up as follows:
Monoethanolamine polyphosphate comprising 36.75% by weight P2O5 and 63.25% by weight 8% expressed P2O5 Monoethanolamine ~ "NANSA" (Trademark) SS 60 15%
This invention relates to liquid cleaning composi-tions comprising a polyphosphate builder. Such compositions include both liquid detergent solutions comprising a surface active agent such as are currently employed as dishwashing and textile detergents and also highly alkaline solu~ions comprising little or no surface active agent such as are used for cleaning hard surfaces, e.g. the insides of ovens and for machine dishwashing bottle washing and beer keg washing. The present compositions may have various degrees of aqueous dilution and in the extreme case may be stable suspensions or gels. The polyphosphate solutions may al50 be dried by suitable means to provide a solid builder com-position. In the gel or suspension form the compositions may be used in cosmetic detergents, e.g. shaving creams.
Polyphosphate huilders are useful in all such compositions both for their sequestering effect on heavy metal ions, notably calcium ions, ana for their detergent builder proper-ties additional to this sequestering effect.
Considerable efforts have been made to provide satisfactorily built cleaning compositions of the types instanced above but as yet a number of problems xemain.
The primary difficulty in the case of liquid cleaning compositions arises from the variegated nature of the necessaxy ingredients coupled with the properties which the liquid cleaning composition must possess. In the case - Qf compositions comprising sur~ace active agents in solu-~ion the primary problem may be expressed as that of pro-viding a composition which has a sufficient concentration of surface active agénts and builder in the same solution to give a satisfactory cleaning performance but which at the same time is homogeneous, has a chill point well below room temperature and a short reliquifaction time at room ~.
~5~38~
temperature after storage at low temperature. In addition in order to gain acceptance the solution should be sufficient-}y concentrated that a container of moderate siz~ containing the solution will provide an acceptable number of washings -about as many washings as an equivalent sized container of solid detergent. All these requirements are onerous in that they increase the necessity of the builder and sur~ace active agents having a high compatibility. Compatibility limita-tions are o~ten further aggravated by the need for further ingredients such as a silicate (as a corrosion inhibitor) suds builders, and organic solvents. In the case of highly al~aline liquid cleaning compositions comprising little or no surface active agent similar problems arise in relation to the compatibilities in aqueous solution of the phosphate builder and the alkaline ingredient which is nQrmally a caustic alkali or a sodium silicate or a mixture of the two.
Attempts to mitigate these problems have been concentrated on varying the nature of the surace active agent and the builder so as to discover a combination having a large degree of compatibility or in incorporating a further ingredient into the composition which is designed to homogenise the solution. Combinations of these approach-es have also been used.
However, the scope for variation is limited by the desired properties of the composition and the success in alleviating the above problems has been limited.
The scope for varying the nature of the surface active ingredients (where used) is limited by the required detergency characteristics of the composition, that is not all surface active agents possess the foaming properties (either high or low foaming ability may be desired) mild-~ S03t~1 ness washing ability and low cost which are required for use in liquid detergents. A notable difficulty arises in the case of the non-ionic surface active agents having the low foaming pr~perties essential in liquid detergents for use in automatic dishwashing machines as well as other desirable washing properties. Such non ionic surfactants may be dissolved only with difficulty in concentrated alkaline builder solutions-unless certain specialised ingredients are added to bring about compatibility (see for example B.P. 991980).
A variet~ of homogenising agents designedto in-crease the compatibility of the vaxious ingredi~nts are also widely used in many types of cleaning compositions. Most widespread among these are the so-called "hydrotropes", notably sodium or potassium, salts of benzene, toluene or xylene sulphonic acids and triamyl phosphate. Various organic copolymers have also been suggested (see for examplç
B.P. 943353) and the incorporation of "assistant solubilizers"
such as ethanol or ethylene glycol has also been proposed.
The disadvantage of all these additional ingredients is that they contribute little or nothing to the actual cle~n-ing properties of the composition so that the expense of their incorporation must be weighed solely against their ability to enable the c~ncentration of the builder or surface active agent in the solution to be increased. Moreover the dilution o the cleansing effect resulting from the use of such homo-genizers lessens the effectiveness of the composition.
The third major possibility of increasing the com patibility of the ingredients of the compositions lies in the variation of the nature of the builder. The scope for such variation is however limited. The condensed phosphates are the most widely accepted Idetergent builders and many of these ~ _ 4 :~61 503~
have been examined. The ma]or commercially accepted poly-phosphate builder salts are the alkali metal pyrophosphates and the alkali metal tripolyphosphates and the alkali metal hexametaphosphates. For liquid detergent compositions the most widely accepted builder is potassium pyrophosphate.
Whilst this compound is acknowledged to be a less effective builder than other compounds such as sodium tripolyphosphate potassium pyrophosphate is relatively free from the dis-advantag s of limited compatibiliky with other ingredients in detergent solutions and of hydrolysis in aqueous solutions which attach to the tripolyphosphates. Even so potassium pyrophosphate is I
- 4~ -~0sa~38:~
not as compatible with surface active agents as might be desired and the problems outlined above still hinder the development of liquid detergents.
We have now discoverecl a ranye of polyphosphate builder salts suitable for use in liquid cleansingcompositions which considerably reduce the aforesaid disadvantages in com-parison with the aforementioned known polyphosphate builders.
The invention provides a cleaning composition which comprises from 4 to 25~ by weight expressed as the weight of P2O5 on the total weight of the composition of a mixture of a plu-rality of polyphosphate salts of one or more primary, secondary or tertiary amines which mixtura has been obtained by forming an aqueous polyphosphoric acid solution comprising from 80 to 88% by weight of phosphorus pentoxide which has been allowed to reach equilibrium and subsequently reacting the said polyphosphoric acid solution with a primary r secondary or tertiary amine without causing any substantial hydrolysis of the polyphosphate species present in the acid;
from 0.1 to 50~ by weight of a water-soluble surfactant.
~0 The following advantageous properties ~or the compositions of the invention may be listed:
(1) High se~uestering ability for calcium and magnesium ions;
12) Exceptionally good detergent builder properties in addition to sequestering ability;
(3) Compatibility in aqueous solution with highly alkaline reagents and surface active agent substantially better than that of the conven-tional builder solutions;
(4) Satisfactory viscosi~ies over a broad range of solids contents leading to convenient ,. ~, :.
1~03~3~
handling. Such properties are desirable in the formuiation of liquid cleansing products.
It is to be understood that whilst the mixtures are not necessarily superior to conventional builders in all the above respects, they are nevert!heless uniquely valuable in the combination of these properties which they possess.
The builder solutions are obtained by neutralisation of aqueous polyphosphoric acid solutions comprising from 80 to 88% by weight of phosphorus pentoxide. The polyphosphoric acid species present in such solutions are in equilibrium with one another and the over-all composition is governed solely by the P205 content o~ the acid as is illustrated in the Canadian Journal of Chemistry, Vol34 (1956) p.790, where the compositions of a number of acids which are useful according to our invention are detailed. These species are primarily the straight chain polyphosphoric acids.
Useful aqueous polyphosphoric acid solutions may be made by conventional means such as by concentration of orthophosphoric acid solutions or by dilution of polyphosphoric acid solutions having greater than the desired P205 content with water. Whilst the presence of other materials in the polyphosphoric acid solutions is not excluded, it is desirable that these solutions be substantially unadulterated and poly-phosphoric acid solutions derived by any of the above mentioned procedures from phosphorus pentoxide obtained by the burning of electrothermally produced phosphorus are preferred.
Polyphosphoric acid solutions derived by the solution of P205 in so-called "wet process" phosphoric acid ob~ained by acidification of phosphate rock are also useful according to the invention. The e~uilibria detailed above between ~OSi~3~
the various polyphosphate acid species contained in a poly-phosphoric acid having a particular P205 content are set up virtually immediately in that acid but preferably the acid is allowed to equilibrate before the neutralisation stPp, e.g. by allowing them to stand for a period of time at room temperature before neutralisation commences. Suitable times are from one minute upwards.
The mixtures in aqueous solution may be obtained by the reaction of the polyphosphoric acid solutions with a primary, secondary or tertiary ~mine. In the term 'amine' as used herein are included all compounds having an amino grouping which are capable of neutralising phosphoric acid, i.e. all compounds having an amino grouping other than one at~ached to a carboxyl group, regardless of the other con-stituents of the molecule so that, for example, this term includes amino acids and substituted amines such as alkanol-amines. Preferred amines have molecular weights below 200, most preferably below 150. Particularly valuable amines include mono-, di- and tri-ethanolamines and propanolamines.
Other amines which may be used include morpholine, mono-, di-and tri-ethyl, n-propyl, iso~propyl and n-, iso- and sec-butylamines, N,N-dimethyl-ethanolamine, aminoethylethanolamine, N-2-aminoethylethanolamine, N-methyldiethanolamine, N-methyl-morpholine, N-ethylmorpholine, N,N-diethylethanolamine, N-methylethanolamine.
It may be desirable to effect the reaction step simultaneously with a dilution to bring about the desired final concentration of the builder solution, provided that such dilution does not bring about hydrolysis of the poly-phosphate anion species present. It is characteristic of the builder solutions for present use that the spectrum of polyphosphate anions present, substantially corresponds to ~0~6338~
that present in the original polyphosphoric acid solution.
Hydrolysis of polyphosphate anions is preferably avoided by maintaining the pH of the reaction medium in the-range 4-12, preferably 6-12i most preferably 7-10, and the temperature below 70C, preferably below 40C, say 15C to 70c, or 15C
to 40C.
Previous attempts to neutralise polyphosphoric acid solutions having a P2O5 content in the range 80-88~ by weight have failed to appreciate the necessity of avoiding the hydro lysis o~ the polyphosphate species during the neutralisation step. For example B.P.919,249 describes the neutralisation of a phosphoric acid solution containing 84% by weight of P2O~
u~ing a mixture of diethanolamine and potassium hydroxide.
The resulting polyphosphate is claimed to be a useful builder in liquid detergents however in order to incorporate suffi-cient builder in a liquid detergent solution the presence of a water miscible organic cosolvent such as ethanol is essen-tial. The amine builder salts of our invention made under the conditions outlined above are sufficiently compatible with detergent solutions to enable the use of such an organic co~
soIvent to be avoided if desired. However the presence of such cosolvents in the compositions of our invention is not excluded.
In B.P.1066234 there is described a solid detergent builder which is produced by the neutralisation of a poly-phosph~ric acid solution containing 83~ by weight of P2O5 with an excess of an alkali metal salt, preferably the carbonate. Although this patent teaches the desirability of avoiding the hydrolysis of the polyphosphate anions present it is only concerned with the alkali-metal salts and their use in admixture with alkali-metal carbonates as solid detergent builders.
~S03~
The mixtures for present use are preferably those obtainable by reaction of the said phosphoric acids and the said amines in a 1:1 ratio of c~cidic hydrogen atoms in the polyphosphoric acid(s) to hydrogen atoms bonded to nitrogen in the amine but compounds obtainable by partial neutralisa-tion of the polyphosphoric acids by the amines also have utility. In the general case of builders will be compounds obtainable by the reaction of the said polyphosphoric acids with amine in a ratio of from 1:10 to 10:1 say 1:5 to 5:1 prefPrably 1:1 to 3:1 expressed as the ratio of amine groups to phosphorus atoms.
- In any case reaction be~ween the amine and the poly~
phosphori~ acia mixture preferably proceeds to a final pH of from 4 to 12 preferably from 4 ko 10 most preferably from 7 to 1~.
The builder salts are conveniently obtained b~ the straightforward addition of the polyphosphoric acid to the amine or the aqueous solution thereof fQllowed by concentra-tion or dilution as required for the proposed use.
In the case of the salts derived from amines which contain an hydroxy substituent on their carbon chain it is necessary to maintain the water content of the system at a sufficient level so as to ensure the desired salt formation occurs rather than esterification such as is described in USP 3728419, a water level of above 15% by weight is normally sufficient. In general we prefer to maintain the water con-tent in the builder salt solution in the range 20-40% by weight si~ce this facilitates the handling o~ the product.
In the case of amines which do not contain a hydroxyl group and therefore cannot be esterified this restriction is not essential although it is preferred to maintain the water content of the system above 25% by weight. Decrease in this g 1~5~3~
water content results in a progressive tendency to form a solid product and such processes are less preferred.
A particularly valuable and unlooked for property is that aqueous solutions of the mixtures may, within certain proportion ranges, depending upon the amine involved, comprise concentrations of the said polyphosphate salt mixture in excess of the solubility limit for a true solution whilst remaining as stable suspensions or gels which are useful as builders for paste type cleaning agents such as oven ~leaners and other highly alkaline hard surface cleaners as well as cosmetic cleaners in paste form such as shaving creams. ~he aqueous cleaning compositions of the invention are according-ly defined 3~3~
herein as including solutîons wherein the polyphosphate mix-tures are in sol and suspension form as well as in true solu-tions. Mixtures as hereinbefore defined which are in the form of stable aqueous suspensions constitute a preferred aspect of this invention. In general, such suspension-type solutions will comprise from 35 to 60% by weight of poly-phosphate mixture expressed as weight of P205 on the total weight of polyphosphate mixture plus-water present. However, the minimum concentration at which the suspensions are formed varies somewhat with the nature of the cation and suspensions of the invention may variously comprise from 40 to 60, 40 to 50 and 45 to 60% by weight of the polyphosphate mixture (on the aforementioned basis) depending upon the amine concerned.
Solutions of the builders thus formed may provide a solid builder for incorporation into solid detergent formula-tions with other conventional ingredients. Preferably they are sprayed as solutions onto preformed solid detergent com-positions. Such solid detergent formulations constitute a ~urther aspect o~ the invention.
The mixtures are used in the novel cleaning composi-tions in a wide ra~ge of concentrations depending upon the envisaged application and upon the solubility of the mixture.
They will be present in concentrations of from 4 to 25% by weight, more usually ~rom 6 to 18%, e.g. from 10 to 15% by weight (all these percentages being expressed as percentages of P2O5 from the respective polyphosphates~ on the total weights of the compositions. Aqueous solutions of the poly-phosphate mixtures as hereinbefore defined comprising at least 4%, preferably at least 10~ thereof, on the aforesaid basis constitute a further aspect of this invention. Preferred such solutions comprise from 6 to 18%, more specially from 10 to 16% by weight of the mixture on the aforesaid basis.
. . _ . . _ ~S(~31~1L
The proportion of surface active agent in the novel compositions may vary within wide limits just as with known such compositions, depending upon the use in question. Novel compositions will comprise from 0.1 to 50~ by weight of sur-face active agent and in particular cases may comprise say from 0.1 to 5%, e.g. 0.5 to 3% by weight in the case of a hard surface cleaner and from 10 to 50%, e.g~ 20 to 30% in the case of a heavy duty liquid detergent.
The surface active agents which may be employed in the novel compositions include non-ionic, anionic, cationic and amphoteric surface active agents, generally such as these mentioned in Volume 19, pages 507-566 of the Encyclo-paedia of Chemical Technology, Second Edition by Kirk- Othmer published by Interscience 1969.
Particular surface active agents which may find use in the novel compositions include: alkyl aryl sulphonates such as lithium, sodium, potassium, ammonium or other water-soluble salts of sulphonic acids of alkyl-substituted benzenes such as decyl toluene, dodecyl-x~ylene, octylbenzene, nonyl-benzene~ decylbenzene, tridecylbenzene, tetradecylbenzene, pentadecylbenzene, dodecylbenzene and hexadecylbenzene;
Olefin sulphonates such as water-soluble alkali metal and alkaline earth metal mono- or di-olefin sulphonic acids comprising from 8 to 24 carbon atoms;
Alkali metal or ammonium alkyl sulphates in which the alkyl groups have from 10 to 18 carbon atoms and polyoxy-ethylenated and polyoxypropylenated derivatives thereof;
Alkali metals or ammonium salts of alkane sulphonates;
Alkali metal or ammonium salts of sulphosuccinated materials of the average general formula:
l2 C (OCH2 C~n OR2 ` `
1 ~05~38~
wherein n is from 0 to 25, R is hydrogen or a methyl group and R2 an alkyl group having f:rom 8 to 25 carbon atoms.
- Amine oxides such as those described ~n B.P.943,353 having the formula RlR2R3NO, w:herein Rl is an alkyl radical having from 9 to 25, preferably 10 to 16 carbon atoms and R
and R2 are methyl or ethyl groups:
Betaines of the general formula + R~
Rl - N - R3 . R4 - CO2 wherein R2 and R3 are alkyl or alkenyl groups cvntaining from 1 to 6 carbon atoms and are preferably methyl groups, R4 is an~alkyl group containing from 1 to 6 carbon atoms and Rl is an alkyl or alkenyl group containing from 8 to 18 carbon atoms:
. Amido-amine derivatives having the formula ~ Rl . I
N(CH2~n N
. where R represents an alkyl or alkenyl group having from 8 to 20 carbon atoms, Rl and R2 are the same or different groups selected from hydrogen atoms, methyl or ethyl groups and n is an integer in the range 1 to 4 and corresponding amines and betaine derivatives.
Polyoxethylene compounds of the general formula RO(CHCHRlO)xH where R is an alkyl, aryl, alkaryl, alicyclic, acyl, amino or alkylamino group; Rl is hydrogen or an alkyl group having from 1 to 4 carbon atoms and x is from 3 to 100, usually from 6 to 50. Such compounds include fatty alcohol polyethoxylate~, fatty acid polyethoxylat~s, polyethylene glycol ethers, mixed polyethylene and polypropylene glycol ethers, amine and diamine polyethoxylates~ and ~atty alkyl-olamide ethoxylates:
i(~Sa3~
¦ Fatty alcohol phosphates and polyethoxylated and ¦ polypropyloxylated deriva'es thereof:
Fa~ty acid soaps.
- The novel compositio:ns comprising surface active agents will normally be compou:nded by addition of an aqueous solution of the surface active agent (or agents) used to a solution of the polyphosphate mixture, optionally followed by dilution although other means may also be used.
In the case o highly alkaline cleaners of the in-vention comprising little or no surfactant, the proportion of polyphosphate salt mixture will generally represent from 2 to 20% by weight (expressed as P2O5) in the composition, prefer-ably 5 to 15%, whilst the alkaline component or components, which will normally be sodium hydroxide and/or an alkali - metal silicate salt such as soaium metasilicate will generally be present in a proportion of from half to twice by weight of the weight of the polyphosphate salt mixture (expressed as weight of solid material). In the case of caustic alkalis such as sodium and potassium hydroxide these might typically represent from 10-15% by weight of the total solids content of the composition. Where alkali metal silicate salts are used, these mi~ht typically represent from 25 to 40~ by weight of the total solids content of the composition. Alkali metal ~ilicates ~or present use are preferably those having an M20:SiO2 ratio of from 0.5:1 to 2:1 where M is soaium or potassium, sodium metasilicate being particularly preferred.
The novel compositions may also comprise known adjuvants for liquid cleaning compositions such as antisoil redeposition agen~s, e.g. carboxymethyl cellulose, polyvinyl pyrrolidone, or the sodium salts of a copolymer of di-isobutylene and maleic anhydride, optical brightening agents;
perfumes; dyes; bacteriostats and bacteriocides; opacifying ~OS~3~3 IL
agents; colorants; sudsing agents, e.g. ethanolamides such as coconut ethanolamide and fatty allcohols such as lauryl alcohols; phase stabilisers such as lower aliphatic alcohols and homogenizing agents. Although the polyphosphate builders generally permit less homogeniz:;ng agent to be present than would be necessary with convent:ional phosphate builders, the preferred c~mpositions of the invention are those which in-clude a so-called hydrotope such as an alkali metal, alkaline earth metal or ammonium salt of benzene-, naphthaline-, an alkylbenzene - or an alkyl naphthalene - sulphonic acid having not more than 5 aliphatic carbon atoms. Preferred such hydrotopes are sodium xylene sulphonates ~sold by Albright and Wilson Limited under the registered trade name Eltesol'), sodium toluene sulphonate, sodium benzene sul-phonate and sodium naphthalene sulphonate. Preferably hydro-topes are present in the novel compositions in proportions of from 2 to 20% by weight, more preferably 2 to 10%, most preferably 3 to 5%. In the case of hard surface cleaners of the inventiont it may also be desired to incorporate a chlorine-releasing agent which is preferably sodium hypo-chloride although chlorinated isocyana~es can also be used.
Normally, chlorine-releasing agents, where used, will be - present in a concentration such as to give from 0.5 to 3~, e.g. 1 to 2~ available chlorine ~w/v) which is roughly equivalent in the case of sodium hypochlorite. For 8-12 v~v sodium hypochlorite.
Compositions of the invention may be employed to ¦ advantage in a range of cleaning applicatisns such as the cleaning of textiles, including wool, wood, leather, metal earthenware, china and stone as well as for human use.
The polyphosphate builders of the invention are ~ - 14 ~1~350315~1 particularly applicable in liquid detergent compositions designed for the cleaning of fine fabrics. These compositions will normally contain from 4 to 10~ of the polyphosphate ex-pressed as the weight of P205 and from O to 5% of a suitable surfactant which is preferably a non-ionic surfactant.
.
- 14A ~
~05~3~3~
The invention is illustrated by the following Examples i~l which all parts are expressed on a weight basis and all proportions of proprietary surfactant ingrsdients are expressed in terms of active ingredient (a.i.) any water present in the surfactant as aclded being included in the given proportions of total water.
Example A composition was made up as follows:
Monoethanolamine polyphosphate comprising 36.75% by weight P2O5 and 63.25% by weight 8% expressed P2O5 Monoethanolamine ~ "NANSA" (Trademark) SS 60 15%
2 "EMPINMIN" (Trademark~ KSN 27 8%
Lauric/myristic monoethanolamide 2%
Lauric/myristic monoethanolamide 2%
3 "ELTESOL" ~Trademark~ SX 93 3.7% a~i.
Water to 100%
(I) Trade name for a 60% w/w aqueous paste of sodium dodecylbenzene sulphonate supplied by Albright & Wilson Ltd.
(2) Trade name for a 27% aqueous solution of ethoxylated sodium lauryl sulphate comprising three ethylene oxide groups per molecule supplied by Albright & Wilson Ltd.
- (3) Trade name for a 93% sodium xylene sulphonate supplied by Albright & Wilson Ltd., the balance of the material being sodium sulphate and water.
The product was suitable for use as a dishwashing detergent for manual use, being a clear homogeneous liquid at ambient temperature. By contrast the same formulation wherein the monoethanolamine polyphosphate was replaced by tetrapotassium pyrophosphate at a level of 8% as P2O5 separated into two phases.
Exam~e 2 1~381 \
A composition was made up having the same composition as that of Eample I save that it contained I2~ (expressed P205 ) monoethanolamine pol~phosphate and 4.7% Eltesol SX 9~. Again, the composition was a clear homogeneous liquid at room temperature suitable for use as a dishwashing detergent.
By contrast, the same composition with sodium tripolyphosphate substituted at equivalent P205 content ~or the monoethonolamine polyphosphate separated into two distinct phases at room temp-I0 erature. The same result was obtained when pota~siumpyrophosphate was likewise substituted ~or the monoethanolamine polyphosphate.
Example 3 I5 A composition was made up as ~ollows:
Monoethanolamine polyphosphateI6.8% (expressed as P205) Nansa SS 60 I5~ a.i.
Lauric/myristic monoethanolamide 2%
Eltesol SX 9~ 3.7% a.i.
Water to I00%
This composition was again a clear homogeneous liquid at room temperature suitable ~or use as a dishwashing detergent.
By contrast, replacement o~ the monoethanolamine polyphosphate ~y I6.8% (expressed as P205) of potassium pyrophosphate gave a composition which subsisted as two phases at ambient temperature.
A composition was made up as ~ollows:
Isopropanolamine polyphosphateI2.6%
comprising 3I-82~ by weight P205(expressed as P205) and 68.I8~ by we~ght Isopropanolamine ~5 Nansa SS 60 I2% a.i.
(I) Empimin KSN 60 6% a.i.
Lauric/myristic monoethz~olam~de 2 ~L05~3~
Eltesol SX 93 2.8%
Water to 100%
(I) Trade name for a sodium lauryl ethoxy sulphate comprising 3 ethylene oxide groups per molecule in 60% aqueous solution comprising 10% ethanol as solu-bilizer supplied by Albright & Wilson Ltd.
The composition was a clear, homogeneous liquid at amblent temperature, suitable fbr use as a dishwashing detergent. As in previous examples, replacement of the isopropanolamine polyphosphate by an equivalent amount o~
potassium pyrophosphate expressed as P2O5 gave a two~phase composition at ambient temperature.
Example 5 A composition was made up as follows:
(I) Nansa SSA 3% a.i~
Triethanolamine 2%
Monoethanolamine 1.5%
Coconut fatty acid 8%
- Monoethanolamine polyphosphate 9.6%
as used in example I (expressed as P2O5) (2) Eltesol PCS 93 5% a.i.
(3) "EMæILAN" (Trademark) XA 5 5% a.i.
Water to 100~
(I) Trade name for a ca. 96% dodecylbenzene sulphonic acid supplied by Albright & Wilson Ltd.
(2) Trade name for a 93% potassium cumene sulphonate the balance being potassium sulphate and water, supplied by Albright & Wilson Ltd.
(3) Trade name for lauryl alcohol ethoxylate comprising approximately 60% by weight ethylene oxide supplied by Albright ~ Wilson Ltd.
This composition was a clear, homogeneous liquid at - 17 ~
- lB , ~ os~3l~l ambient temperature and was suitable for use as a heavy duty liquid detergent for mechanical washing appliances.
By contrast, replacement of the monoethanolamine polyphosphate by an equivalent quantity of potassium pyro-phosphate gave a two-phase composition at ambient temperature, Example 6 A composition was made up as follows:
Monoethanolamine polyphosphate 12% (expressed as P2O5) as used in example I
(I) Empilan PPE 2910 1% a.i.
Coconut fatty acid 2%
Triethanolamine 0.4%
Eltesol PCS 93 5% a.i.
Water to 100%
(I) Trade name for a high molecular weight polycondensate of propylene and ethylene oxides supplied by Albright & Wilson Ltd.
- The composition was a clear, homogeneous solution for use as a dishwashing detergent for mechanical washing~
Replacement of the monoethanolamine polyphosphate by an - ~ equivalent amount of potassium pyrophosphate gave a composition which was a thick paste at ambient temperature.
Example 7 Two compositions were made up as follows:
Composition I
Monoethanolamine polyphosphate as 12% (expressed as used in example I P2O5) 30% aqueous solution of ethoxylated potassium lauryl phosphate comprisin~
5 ethylene oxide groups per molecule and consisting essentially of a 1:1 per molar mixture of mono(laurylpen-tethoxy) phosphate and di(laurylpen-tethoxy) Phosphate 3.6% a.i.
Water to 100%
B
~L05038~
Composition 2 As (I) but with isopropanolamine polyphosphate tas used in Example 4) replacing monoethanolamine polyphos-phate.
Both compositions (I) and (2) were clear, homo~
geneous liquids at ambient temperature, suitable for use as liquid detergents for hard surface cleaning.
By contrast, a composition wherein 12% (expressed as P2O5) of potassium pyrophosphate replaced the monoethanol-amine (or isopropanolamine) polyphosphate separated into two distinct phases at ambient temperature.
Example_8 A composition was made up as follows:
Monoethanolamine polyphsophate 4%
as used in example I(expressed as P2O5) (I) "EMPICOL" (Trademark) L Q 3 310% a.i.
(2) "EMPIG~N" (Trademark) BB 2~ a.i.
Eltesol SX 93 2 Water to 100%
(I) Trade name for a 33~ aqueous solution of monoethanol-amine lauryl/myristyl sulphate supplied by Albright & Wilson Ltd.
(2) Trade name for a 30% aqueous solution of alkyl dimethyl betaine represented by the ~ormula R - N - Me2CH2CO2 where R is predominately lauryl/myristyl supplied by Albright &
~ilson Ltd.
The composition was a clear homogeneous li~uid at ambient temperature suitable for use as a liquid hand cleanser.
By contrast a composition where potassium pyro-phosphate replaced monoethanolamine polyphosphate at 4~ P2O5 iB
1, .
1()5~3~1 level was heterogeneous paste at ambient temperature.
Example 9 A composition (I) found highly suitable for both machine and hand washing of woollen garme~ts was made up as follows:
Nansa SSA 10% a.i.
Triethanolamine 6%
Monoethanolamine 3%
Empimin KSN 27 2.7%
Coconut fatty acid 4%
Monoethanolamine polyphosphate 6% ~expressed as as used in example I P2O5) Empilan PPE 2910 2% a.i.
Optical brightening agent 0.2%
Bacteriocide 0.1~
Perfume 0.2%
: Water to 100%
A further composition (2) of similar utility was ~ also made to the same formulation save that 2% of "TRITON"
20 (Trademark~ CF32 r~placed the Empilan PPE 2910 (Triton CF32 is a trade name for a non-ionic surface active amine poly~glycol condensate supplied by the Rohm & Haas Company) A composition (3) was also made up as follows:
Nansa SSA 10% a.i.
Triethanolamine 4.4 Monoethanolamine 2.2%
Empicol SDD (~) 4%
Isopropanolamine polyphosphate 6% (expressed as as used in example 4 P2O5 Optical brightening agent 0.3%
Bacteriocide 0.1%
Perfume 0.1 Water to 100%
E~j ~v 1138~
t+) Trade name for a 40% aqueous solution of a disodium alkylethoxy sulphosuccinate halfester where the alkyl group are predominately lauryl/myristyl and the ethoxy group is primarily derived from diethylene glycol (supplied by Albright & Wilson Ltd.) Compositions I and 2 were of the 'low-foam' type incorporating coconut fatty acid soap with either Empilan PPE 2910 or Triton CF32 as foam depressants. All three composi~ions (1) (2) and (3) were clear homogeneous liquids at room temperature.
~ ach of these compositions was compared in standard washing tests to a typical conventional detergent powder of the following compositions:
Sodium do~ecylbenzene sulphon~te 3 ~atty alcohol polyethoxylate 4 ( T I mols. Et2O) Sodium silicate 1:2 5%
Sodium tripolyphosphate 42 Optical brightening agent 0.49 'I-ALCALASE'' (Trademark) P (+) 0.5%
Perfume 0.2%
Moisture 10 - pH (1% solution) ca. 10 (+) a protealytic enzyme supplied by Novo Industria S~
me effectiveness of compositions 1, 2 and 3 and of the re~erence powder was then determined in duplicate standard washing tests. These involved subjecting 40 3" by 3"
swatches of a standard test cloth to the rotating washing action of a "LAUNDER-O-METER" (Trademark) supplied by the Atlas Electrical Device Co. (Chicago).- Swatches were washed in pairs (two swatches per cylinder of the loading table) with 38~L
the addition of 2 g of the composition under test to each cylinder. Washing was at 80C using water of given hardness proceeded for 20 minutes following which the swatches were rinsed, ironed dry between cotton cloths and then compared for light reflectance using Haxrison colour measurements with a white tiIe reference and a light source filtered through a green filter. Results are quoted as percentages calculated from the equation:
~= 100 x ~Reflectance A (washed) - Reflectance A (unwashed)) _ (Refle~tance R (washed) - Reflectance R ~unwashed)) Where reflectance A is the colour scale reading of the swatch washed in the composition under test and reflectance R is the colour scale reading of the swatch washed in the reference composition.
One series of tests was carried out using standard soiled wool swatches reference "EMPA" ~Trademark) 102 (supplied by Empa Laboratories, Switzerland) using both water of hardness 50 ppm (Ca Co3) and water of 300 ppm (Ca Co3) hardness --the atomic ratio of Ca~Mg present in the water being 4:1 in both cases. Results were as follows:
Soft WaterHard Water ~%) ~ (%) Reference Powder 100 100 Composition 1 92.686.8 Composition 2 87.686.8 Composition 3 95.090.0 These results are within the range for a liquid detergent compared with a powder and compare favourably with results obtainable from conventional liquid detergents as is demonstrated below.
Similar tests were also carried out using sOiled ~ - 22 ~
~1 38~
polyester/cotton swatches (60/40 Dacron/Cotton) supplied by Test Fabrics Inc. with the following results:
Soft Water Hard Water (% ) (~) Reference Powder 100 100 Composition 1 89.3 118 Composition 2 75.0 122.7 Composition 3 93.8 124 Here it may be seen that the performances of compositions of the invention actually surpass that of the reference powder under the most testing washing conditions, that is in hard water.
Washing colour stability tests were also carried out on compositions 1, 2 and 3 according to I.W.S. method number 105 using standard dyed woollen fabrics. Assessment of colour change and staining were carried out on the British Standards Institute Grey Scale, the preferred total being 27 points minimum.
r~
22a -038~
Results were:
Reference Powder 23~5 Points Composition I ~0.5 Points Composition 2 ~0.5 Points Composition 3 32.0 Points To further demonstrate the improved effectiveness of the com-position of the invention their per~ormance was compared with IO those of similar compositions made up using conventional poly-phosphate molecules at approximately the highest consentration possible without causing cloudiness or precipitation or phase separation at lower temperatures (i.e.the highest consentration possible ror a commercially acceptable composition). These conventlonal ~ormulations ( a B C and D) were as follows:
I5 A. Nansa SS 60 IO.0%
Empimin KNS 27 IO.0%
Tetrapotassium pyrophosphate 6.5% (expressed as P205) + Empilan CDE 2.5%
Eltesol SX 93 ~.0%
Optical brightening agent 0.2%
Bacteriocide O.I%
Water to I00%
+ Registered trade name for a surfactant active diethanolamide derivati~e of "total" coconut fatty acid supplied by Albright & Wilson Ltd.
B. Nansa SS 60 8.5%
+ Empicol ESB ~ I~.0%
~0 Empilan CDE I.0%
Tetrapotassiu~ pyrophosphate 5~0~ (expressed as P205) Eltesol SX 9~ 5.0%
Optical brightening agent 0.2 Bacteriocide O.I%
~5 Perfume o ~%
Water to IOO~
Re~istered trade name for a 27.5~ aqueous solution of sodium lauryl ethoxy sulphate comprising two ethylene oxide groups per molecule.
C. Triethanolamine dodecylbenzene sulphonate I4% a.i.
~mpimin K~N 27 4.0~
Tetrapotassium pyrophosphate 6.5%
(expressed as P205) Coconut fatty acid .soap 5.0%
Triton CF ~2 4.0%
= Eltesol SCS 9~ 2.0 Optical brightening agent a ~2~
Bacteriocide O.I%
IO Perfume 0.2%
Water to I00%
= Registered trade name for a 93~ sodium cumene sulpho~ate the balance being sodium sulphate and water - supplied by Albri~ht & Wilson Ltd.
I5 D. Empilan KA 5 IO~
Empimin KSN 27 I.35%
Tetrapotassium pyrophosphate 3.5%
(expressed as P205) Eltesol SX 93 5~
Optical brightening agent O.2%
Bacteriocide O.I%
Per~ume 0.2%
Water to I00%
And the washing per~ormance o~ these compositions A - D was compared with those o~ the abo~e compositions I and 2 by the method as before against the same re~erence powder, Standard wool swatches (Empa I02) were used.
Results were as ~ollows (~uoted in the same basls as be~ore):
Composition So~t Water Hard Water ~ (%)~
Re~erence Powder IOO IOO
I 87 89.5 2 ~7 89.0 ~ 85 82 B 85 48.o C - 62.0 D 85.5 56 ~4 ~1)5a 38~
The improved detergent performance o~ the composltlons I and 2 of the invent~on is clear ~rom these results. Thls is especially evident in the tests using hard water where the sequestering ability of the polyphosphate builder is most ¢ritical.
A particularly striking comparison is that between the effect of composition C and those of I and 2. Although the latter contains less Empimin KSN 27 active ingredient~ less coconut fatty acid lass non~ionic surfactant and less "hydrotrope"
~Eltesol SCS 93) they nevertheless exhibit improved detergent I0 in hard water ascribable to the superior building propertles of the polyphosphate builders of the invention over the conventional tetrapotassium pyrophosphate.
Example~I0 I5 572 kilograms of an aqueous solution of a phosphoric acid containing 84% by weight o~ phosphorus pentoxide representing ~2.2 parts by weight of the reaction mixture were added to a solution of 37.9 parts o~ monoethanolamine in 29.9 parts by weight of water in a ~acketed stainless steel vessel equiped with a turbln mixer over a period o~ 2~ hours with efficient cooling and stirring. The temperature was held below 40 C
throughout. The produck monoethanolamine polyphosphate was a straw coloured vlscous liquid comprising 27.0% by weight of P20s having a ~iscosity o~ I500 centistokes at 20C and a density of I.~75. The product was useful according to example No. 4 Example II
To 443g isopropanol in 297g water was added slowly, Wit~l stirring, at between I5 and 40C 260~ of a polyphosphoric acid solution comprising 85% by weight P205 . The pH was between 4 and I0 throu~hout. The product was suitable ~or use according to example No. 4 ~LOSD38~;
Example 12 Isopropanolamine polyphosphate was prepared by an analogous procedure to that used in example 10 using 24~65 parts of a polyphosphoric acid containing 84% by weight of phosphorus pentoxide, 44.3 parts of monoisopropanolamine and 31.05 parts of water. The product was a clear viscous - liquid useful according to example 4.
Example 13 A composition was made up as follows:
Monoethanolamine poIyphosphate 9.6% as P2O5 (as used in example 1) Empilan 2910 3%
Ethylene diamine tetra-acetic acid 0.2%
Phosphoric acid 2.6~
Potassium hydroxide (50%) 9.1%
Sodiu~ metasilicate penthydrate 5.0%
Formalin (40% solution) 0.2%
"ACRYSOL" (Trademark) ASE 108 ( ) 6.25 Water to 100%
(1) Acrysol ASE 108 is a registered trademark for a high molecular weight acid copolymer emulsion supplied by the Rohm & Haas Company.
The product was a homogeneous liquid highly suitable for use in mechanical dishwashers.
n 26 -~',
Water to 100%
(I) Trade name for a 60% w/w aqueous paste of sodium dodecylbenzene sulphonate supplied by Albright & Wilson Ltd.
(2) Trade name for a 27% aqueous solution of ethoxylated sodium lauryl sulphate comprising three ethylene oxide groups per molecule supplied by Albright & Wilson Ltd.
- (3) Trade name for a 93% sodium xylene sulphonate supplied by Albright & Wilson Ltd., the balance of the material being sodium sulphate and water.
The product was suitable for use as a dishwashing detergent for manual use, being a clear homogeneous liquid at ambient temperature. By contrast the same formulation wherein the monoethanolamine polyphosphate was replaced by tetrapotassium pyrophosphate at a level of 8% as P2O5 separated into two phases.
Exam~e 2 1~381 \
A composition was made up having the same composition as that of Eample I save that it contained I2~ (expressed P205 ) monoethanolamine pol~phosphate and 4.7% Eltesol SX 9~. Again, the composition was a clear homogeneous liquid at room temperature suitable for use as a dishwashing detergent.
By contrast, the same composition with sodium tripolyphosphate substituted at equivalent P205 content ~or the monoethonolamine polyphosphate separated into two distinct phases at room temp-I0 erature. The same result was obtained when pota~siumpyrophosphate was likewise substituted ~or the monoethanolamine polyphosphate.
Example 3 I5 A composition was made up as ~ollows:
Monoethanolamine polyphosphateI6.8% (expressed as P205) Nansa SS 60 I5~ a.i.
Lauric/myristic monoethanolamide 2%
Eltesol SX 9~ 3.7% a.i.
Water to I00%
This composition was again a clear homogeneous liquid at room temperature suitable ~or use as a dishwashing detergent.
By contrast, replacement o~ the monoethanolamine polyphosphate ~y I6.8% (expressed as P205) of potassium pyrophosphate gave a composition which subsisted as two phases at ambient temperature.
A composition was made up as ~ollows:
Isopropanolamine polyphosphateI2.6%
comprising 3I-82~ by weight P205(expressed as P205) and 68.I8~ by we~ght Isopropanolamine ~5 Nansa SS 60 I2% a.i.
(I) Empimin KSN 60 6% a.i.
Lauric/myristic monoethz~olam~de 2 ~L05~3~
Eltesol SX 93 2.8%
Water to 100%
(I) Trade name for a sodium lauryl ethoxy sulphate comprising 3 ethylene oxide groups per molecule in 60% aqueous solution comprising 10% ethanol as solu-bilizer supplied by Albright & Wilson Ltd.
The composition was a clear, homogeneous liquid at amblent temperature, suitable fbr use as a dishwashing detergent. As in previous examples, replacement of the isopropanolamine polyphosphate by an equivalent amount o~
potassium pyrophosphate expressed as P2O5 gave a two~phase composition at ambient temperature.
Example 5 A composition was made up as follows:
(I) Nansa SSA 3% a.i~
Triethanolamine 2%
Monoethanolamine 1.5%
Coconut fatty acid 8%
- Monoethanolamine polyphosphate 9.6%
as used in example I (expressed as P2O5) (2) Eltesol PCS 93 5% a.i.
(3) "EMæILAN" (Trademark) XA 5 5% a.i.
Water to 100~
(I) Trade name for a ca. 96% dodecylbenzene sulphonic acid supplied by Albright & Wilson Ltd.
(2) Trade name for a 93% potassium cumene sulphonate the balance being potassium sulphate and water, supplied by Albright & Wilson Ltd.
(3) Trade name for lauryl alcohol ethoxylate comprising approximately 60% by weight ethylene oxide supplied by Albright ~ Wilson Ltd.
This composition was a clear, homogeneous liquid at - 17 ~
- lB , ~ os~3l~l ambient temperature and was suitable for use as a heavy duty liquid detergent for mechanical washing appliances.
By contrast, replacement of the monoethanolamine polyphosphate by an equivalent quantity of potassium pyro-phosphate gave a two-phase composition at ambient temperature, Example 6 A composition was made up as follows:
Monoethanolamine polyphosphate 12% (expressed as P2O5) as used in example I
(I) Empilan PPE 2910 1% a.i.
Coconut fatty acid 2%
Triethanolamine 0.4%
Eltesol PCS 93 5% a.i.
Water to 100%
(I) Trade name for a high molecular weight polycondensate of propylene and ethylene oxides supplied by Albright & Wilson Ltd.
- The composition was a clear, homogeneous solution for use as a dishwashing detergent for mechanical washing~
Replacement of the monoethanolamine polyphosphate by an - ~ equivalent amount of potassium pyrophosphate gave a composition which was a thick paste at ambient temperature.
Example 7 Two compositions were made up as follows:
Composition I
Monoethanolamine polyphosphate as 12% (expressed as used in example I P2O5) 30% aqueous solution of ethoxylated potassium lauryl phosphate comprisin~
5 ethylene oxide groups per molecule and consisting essentially of a 1:1 per molar mixture of mono(laurylpen-tethoxy) phosphate and di(laurylpen-tethoxy) Phosphate 3.6% a.i.
Water to 100%
B
~L05038~
Composition 2 As (I) but with isopropanolamine polyphosphate tas used in Example 4) replacing monoethanolamine polyphos-phate.
Both compositions (I) and (2) were clear, homo~
geneous liquids at ambient temperature, suitable for use as liquid detergents for hard surface cleaning.
By contrast, a composition wherein 12% (expressed as P2O5) of potassium pyrophosphate replaced the monoethanol-amine (or isopropanolamine) polyphosphate separated into two distinct phases at ambient temperature.
Example_8 A composition was made up as follows:
Monoethanolamine polyphsophate 4%
as used in example I(expressed as P2O5) (I) "EMPICOL" (Trademark) L Q 3 310% a.i.
(2) "EMPIG~N" (Trademark) BB 2~ a.i.
Eltesol SX 93 2 Water to 100%
(I) Trade name for a 33~ aqueous solution of monoethanol-amine lauryl/myristyl sulphate supplied by Albright & Wilson Ltd.
(2) Trade name for a 30% aqueous solution of alkyl dimethyl betaine represented by the ~ormula R - N - Me2CH2CO2 where R is predominately lauryl/myristyl supplied by Albright &
~ilson Ltd.
The composition was a clear homogeneous li~uid at ambient temperature suitable for use as a liquid hand cleanser.
By contrast a composition where potassium pyro-phosphate replaced monoethanolamine polyphosphate at 4~ P2O5 iB
1, .
1()5~3~1 level was heterogeneous paste at ambient temperature.
Example 9 A composition (I) found highly suitable for both machine and hand washing of woollen garme~ts was made up as follows:
Nansa SSA 10% a.i.
Triethanolamine 6%
Monoethanolamine 3%
Empimin KSN 27 2.7%
Coconut fatty acid 4%
Monoethanolamine polyphosphate 6% ~expressed as as used in example I P2O5) Empilan PPE 2910 2% a.i.
Optical brightening agent 0.2%
Bacteriocide 0.1~
Perfume 0.2%
: Water to 100%
A further composition (2) of similar utility was ~ also made to the same formulation save that 2% of "TRITON"
20 (Trademark~ CF32 r~placed the Empilan PPE 2910 (Triton CF32 is a trade name for a non-ionic surface active amine poly~glycol condensate supplied by the Rohm & Haas Company) A composition (3) was also made up as follows:
Nansa SSA 10% a.i.
Triethanolamine 4.4 Monoethanolamine 2.2%
Empicol SDD (~) 4%
Isopropanolamine polyphosphate 6% (expressed as as used in example 4 P2O5 Optical brightening agent 0.3%
Bacteriocide 0.1%
Perfume 0.1 Water to 100%
E~j ~v 1138~
t+) Trade name for a 40% aqueous solution of a disodium alkylethoxy sulphosuccinate halfester where the alkyl group are predominately lauryl/myristyl and the ethoxy group is primarily derived from diethylene glycol (supplied by Albright & Wilson Ltd.) Compositions I and 2 were of the 'low-foam' type incorporating coconut fatty acid soap with either Empilan PPE 2910 or Triton CF32 as foam depressants. All three composi~ions (1) (2) and (3) were clear homogeneous liquids at room temperature.
~ ach of these compositions was compared in standard washing tests to a typical conventional detergent powder of the following compositions:
Sodium do~ecylbenzene sulphon~te 3 ~atty alcohol polyethoxylate 4 ( T I mols. Et2O) Sodium silicate 1:2 5%
Sodium tripolyphosphate 42 Optical brightening agent 0.49 'I-ALCALASE'' (Trademark) P (+) 0.5%
Perfume 0.2%
Moisture 10 - pH (1% solution) ca. 10 (+) a protealytic enzyme supplied by Novo Industria S~
me effectiveness of compositions 1, 2 and 3 and of the re~erence powder was then determined in duplicate standard washing tests. These involved subjecting 40 3" by 3"
swatches of a standard test cloth to the rotating washing action of a "LAUNDER-O-METER" (Trademark) supplied by the Atlas Electrical Device Co. (Chicago).- Swatches were washed in pairs (two swatches per cylinder of the loading table) with 38~L
the addition of 2 g of the composition under test to each cylinder. Washing was at 80C using water of given hardness proceeded for 20 minutes following which the swatches were rinsed, ironed dry between cotton cloths and then compared for light reflectance using Haxrison colour measurements with a white tiIe reference and a light source filtered through a green filter. Results are quoted as percentages calculated from the equation:
~= 100 x ~Reflectance A (washed) - Reflectance A (unwashed)) _ (Refle~tance R (washed) - Reflectance R ~unwashed)) Where reflectance A is the colour scale reading of the swatch washed in the composition under test and reflectance R is the colour scale reading of the swatch washed in the reference composition.
One series of tests was carried out using standard soiled wool swatches reference "EMPA" ~Trademark) 102 (supplied by Empa Laboratories, Switzerland) using both water of hardness 50 ppm (Ca Co3) and water of 300 ppm (Ca Co3) hardness --the atomic ratio of Ca~Mg present in the water being 4:1 in both cases. Results were as follows:
Soft WaterHard Water ~%) ~ (%) Reference Powder 100 100 Composition 1 92.686.8 Composition 2 87.686.8 Composition 3 95.090.0 These results are within the range for a liquid detergent compared with a powder and compare favourably with results obtainable from conventional liquid detergents as is demonstrated below.
Similar tests were also carried out using sOiled ~ - 22 ~
~1 38~
polyester/cotton swatches (60/40 Dacron/Cotton) supplied by Test Fabrics Inc. with the following results:
Soft Water Hard Water (% ) (~) Reference Powder 100 100 Composition 1 89.3 118 Composition 2 75.0 122.7 Composition 3 93.8 124 Here it may be seen that the performances of compositions of the invention actually surpass that of the reference powder under the most testing washing conditions, that is in hard water.
Washing colour stability tests were also carried out on compositions 1, 2 and 3 according to I.W.S. method number 105 using standard dyed woollen fabrics. Assessment of colour change and staining were carried out on the British Standards Institute Grey Scale, the preferred total being 27 points minimum.
r~
22a -038~
Results were:
Reference Powder 23~5 Points Composition I ~0.5 Points Composition 2 ~0.5 Points Composition 3 32.0 Points To further demonstrate the improved effectiveness of the com-position of the invention their per~ormance was compared with IO those of similar compositions made up using conventional poly-phosphate molecules at approximately the highest consentration possible without causing cloudiness or precipitation or phase separation at lower temperatures (i.e.the highest consentration possible ror a commercially acceptable composition). These conventlonal ~ormulations ( a B C and D) were as follows:
I5 A. Nansa SS 60 IO.0%
Empimin KNS 27 IO.0%
Tetrapotassium pyrophosphate 6.5% (expressed as P205) + Empilan CDE 2.5%
Eltesol SX 93 ~.0%
Optical brightening agent 0.2%
Bacteriocide O.I%
Water to I00%
+ Registered trade name for a surfactant active diethanolamide derivati~e of "total" coconut fatty acid supplied by Albright & Wilson Ltd.
B. Nansa SS 60 8.5%
+ Empicol ESB ~ I~.0%
~0 Empilan CDE I.0%
Tetrapotassiu~ pyrophosphate 5~0~ (expressed as P205) Eltesol SX 9~ 5.0%
Optical brightening agent 0.2 Bacteriocide O.I%
~5 Perfume o ~%
Water to IOO~
Re~istered trade name for a 27.5~ aqueous solution of sodium lauryl ethoxy sulphate comprising two ethylene oxide groups per molecule.
C. Triethanolamine dodecylbenzene sulphonate I4% a.i.
~mpimin K~N 27 4.0~
Tetrapotassium pyrophosphate 6.5%
(expressed as P205) Coconut fatty acid .soap 5.0%
Triton CF ~2 4.0%
= Eltesol SCS 9~ 2.0 Optical brightening agent a ~2~
Bacteriocide O.I%
IO Perfume 0.2%
Water to I00%
= Registered trade name for a 93~ sodium cumene sulpho~ate the balance being sodium sulphate and water - supplied by Albri~ht & Wilson Ltd.
I5 D. Empilan KA 5 IO~
Empimin KSN 27 I.35%
Tetrapotassium pyrophosphate 3.5%
(expressed as P205) Eltesol SX 93 5~
Optical brightening agent O.2%
Bacteriocide O.I%
Per~ume 0.2%
Water to I00%
And the washing per~ormance o~ these compositions A - D was compared with those o~ the abo~e compositions I and 2 by the method as before against the same re~erence powder, Standard wool swatches (Empa I02) were used.
Results were as ~ollows (~uoted in the same basls as be~ore):
Composition So~t Water Hard Water ~ (%)~
Re~erence Powder IOO IOO
I 87 89.5 2 ~7 89.0 ~ 85 82 B 85 48.o C - 62.0 D 85.5 56 ~4 ~1)5a 38~
The improved detergent performance o~ the composltlons I and 2 of the invent~on is clear ~rom these results. Thls is especially evident in the tests using hard water where the sequestering ability of the polyphosphate builder is most ¢ritical.
A particularly striking comparison is that between the effect of composition C and those of I and 2. Although the latter contains less Empimin KSN 27 active ingredient~ less coconut fatty acid lass non~ionic surfactant and less "hydrotrope"
~Eltesol SCS 93) they nevertheless exhibit improved detergent I0 in hard water ascribable to the superior building propertles of the polyphosphate builders of the invention over the conventional tetrapotassium pyrophosphate.
Example~I0 I5 572 kilograms of an aqueous solution of a phosphoric acid containing 84% by weight o~ phosphorus pentoxide representing ~2.2 parts by weight of the reaction mixture were added to a solution of 37.9 parts o~ monoethanolamine in 29.9 parts by weight of water in a ~acketed stainless steel vessel equiped with a turbln mixer over a period o~ 2~ hours with efficient cooling and stirring. The temperature was held below 40 C
throughout. The produck monoethanolamine polyphosphate was a straw coloured vlscous liquid comprising 27.0% by weight of P20s having a ~iscosity o~ I500 centistokes at 20C and a density of I.~75. The product was useful according to example No. 4 Example II
To 443g isopropanol in 297g water was added slowly, Wit~l stirring, at between I5 and 40C 260~ of a polyphosphoric acid solution comprising 85% by weight P205 . The pH was between 4 and I0 throu~hout. The product was suitable ~or use according to example No. 4 ~LOSD38~;
Example 12 Isopropanolamine polyphosphate was prepared by an analogous procedure to that used in example 10 using 24~65 parts of a polyphosphoric acid containing 84% by weight of phosphorus pentoxide, 44.3 parts of monoisopropanolamine and 31.05 parts of water. The product was a clear viscous - liquid useful according to example 4.
Example 13 A composition was made up as follows:
Monoethanolamine poIyphosphate 9.6% as P2O5 (as used in example 1) Empilan 2910 3%
Ethylene diamine tetra-acetic acid 0.2%
Phosphoric acid 2.6~
Potassium hydroxide (50%) 9.1%
Sodiu~ metasilicate penthydrate 5.0%
Formalin (40% solution) 0.2%
"ACRYSOL" (Trademark) ASE 108 ( ) 6.25 Water to 100%
(1) Acrysol ASE 108 is a registered trademark for a high molecular weight acid copolymer emulsion supplied by the Rohm & Haas Company.
The product was a homogeneous liquid highly suitable for use in mechanical dishwashers.
n 26 -~',
Claims (10)
1. A cleaning composition which comprises from 4 to 25% by weight expressed as the weight of P2O5 on the total weight of the composition of a mixture of a plurality of poly-phosphate salts of one or more primary, secondary or tertiary amines which mixture has been obtained by forming an aqueous polyphosphoric acid solution comprising from 80 to 88% by weight of phosphorus pentoxide which has been allowed to reach equilibrium and subsequently reacting the said poly phosphoric acid solution with a primary, secondary or tertiary amine without causing any substantial hydrolysis at a ratio of phosphoric acid to amine from 1:10 to 10:1 expressed as the ratio of phosphorus atoms to amine groups to a final pH of 4 to 12; from 0.1 to 50% by weight of a water soluble surfactant selected from non-ionic, anionic, cationic and amphoteric surface active agents.
2. A composition according to claim 1 wherein the surfactant is anionic.
3. A composition according to claim 2 wherein the surfactant is an alkyl aryl sulphonate.
4. A composition according to any of claims 1 to 3, wherein the polyphosphoric acid solution comprises from 82 to 86% by weight of P2O5.
5. A composition according to claim 1 wherein the reaction between the polyphosphoric acid and the amine takes place at a pH of from 4 to 12 and at a temperature of from 15 to 70°C and in the case of hydroxy substituted amines the water content of the reaction system is maintained at above 15% by weight of the reaction mixture.
6. A composition according to claim 5 wherein the amine has a molecular weight of less than 200.
7. A composition according to claim 6 wherein the amine is a mono, di or tri ethanolamine or propanolamine.
8. A composition according to any of claims 1, or 5 wherein the polyphosphoric acid is reacted with the amine in a molar ratio of from 1:1 to 3:1.
9. A composition according to claim 7 which comprises a mono, di or tri ethanolamine salt of an alkyl benzene sulphonic acid.
10. A composition according to any of claims 1, or 5 which comprises from 6 to 18% by weight (expressed as weight of P2O5 on the total weight of the composition) of the mixture of polyphosphates.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB46657/73A GB1489867A (en) | 1973-10-05 | 1973-10-05 | Detergent compositions comprising amine polyphosphates |
| GB799974 | 1974-02-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1050381A true CA1050381A (en) | 1979-03-13 |
Family
ID=26241807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA210,447A Expired CA1050381A (en) | 1973-10-05 | 1974-10-01 | Amine polyphosphates |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS5078606A (en) |
| AU (1) | AU507654B2 (en) |
| BE (1) | BE820707A (en) |
| BR (1) | BR7408281D0 (en) |
| CA (1) | CA1050381A (en) |
| DE (1) | DE2447500A1 (en) |
| ES (1) | ES430696A1 (en) |
| FR (1) | FR2246535B1 (en) |
| GB (1) | GB1489867A (en) |
| IT (1) | IT1020939B (en) |
| NL (1) | NL7413111A (en) |
| SE (1) | SE7412479L (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1170949A (en) * | 1980-02-05 | 1984-07-17 | John B. Welch | Liquid detergent composition |
| US6911422B1 (en) | 1999-07-01 | 2005-06-28 | The Procter & Gamble Company | Transparent or translucent, liquid or gel type automatic dishwashing detergent product |
| MXPA02000264A (en) * | 1999-07-01 | 2002-06-21 | Procter & Gamble | Transparent or translucent, liquid or gel type automatic dishwashing detergent product. |
| WO2001004249A1 (en) * | 1999-07-12 | 2001-01-18 | The Procter & Gamble Company | Nitrogen/phosphate copolymers and compositions containing the same |
| US10626350B2 (en) | 2015-12-08 | 2020-04-21 | Ecolab Usa Inc. | Pressed manual dish detergent |
-
1973
- 1973-10-05 GB GB46657/73A patent/GB1489867A/en not_active Expired
-
1974
- 1974-10-01 CA CA210,447A patent/CA1050381A/en not_active Expired
- 1974-10-03 AU AU73964/74A patent/AU507654B2/en not_active Expired
- 1974-10-03 SE SE7412479A patent/SE7412479L/xx unknown
- 1974-10-04 IT IT69972/74A patent/IT1020939B/en active
- 1974-10-04 ES ES430696A patent/ES430696A1/en not_active Expired
- 1974-10-04 BE BE149213A patent/BE820707A/en unknown
- 1974-10-04 FR FR7433535A patent/FR2246535B1/fr not_active Expired
- 1974-10-04 NL NL7413111A patent/NL7413111A/en not_active Application Discontinuation
- 1974-10-04 DE DE19742447500 patent/DE2447500A1/en not_active Withdrawn
- 1974-10-05 JP JP49115112A patent/JPS5078606A/ja active Pending
- 1974-10-07 BR BR8281/74A patent/BR7408281D0/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BE820707A (en) | 1975-02-03 |
| JPS5078606A (en) | 1975-06-26 |
| ES430696A1 (en) | 1977-04-16 |
| GB1489867A (en) | 1977-10-26 |
| NL7413111A (en) | 1975-04-08 |
| BR7408281D0 (en) | 1975-07-22 |
| DE2447500A1 (en) | 1975-04-24 |
| AU7396474A (en) | 1976-04-08 |
| FR2246535A1 (en) | 1975-05-02 |
| FR2246535B1 (en) | 1976-10-22 |
| AU507654B2 (en) | 1980-02-21 |
| IT1020939B (en) | 1977-12-30 |
| SE7412479L (en) | 1975-04-07 |
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