CA1087479A - Cleaning compositions - Google Patents
Cleaning compositionsInfo
- Publication number
- CA1087479A CA1087479A CA245,458A CA245458A CA1087479A CA 1087479 A CA1087479 A CA 1087479A CA 245458 A CA245458 A CA 245458A CA 1087479 A CA1087479 A CA 1087479A
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- Canada
- Prior art keywords
- composition
- weight
- polyphosphoric acid
- solution
- aqueous
- 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
C L E A N I N G C O M P O S I T T O N S
A B S T R A C T
Mixtures of alkali metal polyphosphate salts obtained by the neutralisation of a polyphosphoric acid solution which comprises from 80 to 81% by weight of phosphorus pentoxide, have been found to be especially valuable builders for liquid detergents of moderate alkalinity.
They combine good sequestering power with relatively high stability on prolonged storage. The cleaning composition will have a pH in the range 8 to 12.
A B S T R A C T
Mixtures of alkali metal polyphosphate salts obtained by the neutralisation of a polyphosphoric acid solution which comprises from 80 to 81% by weight of phosphorus pentoxide, have been found to be especially valuable builders for liquid detergents of moderate alkalinity.
They combine good sequestering power with relatively high stability on prolonged storage. The cleaning composition will have a pH in the range 8 to 12.
Description
4~!~
This invention relates to liquid cleaning compositions comprising a polyphosphate builder. In particular the invention relates to a class of polyphosphate builder salts which find particular application in cleaning compositions designed for specific cleaning tasks which have a moderate-ly alkaline pH.
The salts of the condensed phosphoric acids are well known and widely accepted in the detergent industry as ingredients of synthetic detergent compositions. They are valued ~ecause they exhibit, albeit to varying degrees, four important properties which are desirable facets of a liquid detergent. Firstly they are capable of sequestering heavy metal ions, such as calcium or magnesium ions which are found in hard water areas; secondly they act as dispersants for sOlia particles in aqueous environments thus preventing these particles from settling out during the cleaning operation; thirdly, they act as a buffer in liquid compositions thus stabilizing the pH of such compo-sitions and ourthly they interact synergistically with other detergent ingreaients e.g. synthetic detergents so as to to enhance~ their performance.
.The formulator of a detergent will select a particular polyphosphate builder according to the re~uired property of his finished compo$ition although this choice will almost inevitably involve some sacri~ice in respect of one or other of the desira~le properties outlined above.
In the case of liquid detergent formulations the problem is aggravated by -the requirement that all the ingredients of the composition should be compatible, In practice it . .
3~ is desirable that this compatibility be maximized so that : -a satisfactory-cleaning performance is given ~y th~ minimum ~ . .
~ 2 ~
l~D~74~7g volume of detergent. Furthermore the composition must be stabl~ even on prolonged storage and the ingredients must not separate out as a result of such storage even at low temperatures. Thus in ordex to fulfill this latter require-ment the composition will have a chill point well below room temperature and a short reli~uifaction time after storage at low temperatures.
A number of attempts have been made to mitigate these problems which have, in general, involved selecting a particular builder or a particular synthetic surface active a~ent or the incorporation of a suitable homogenizer which will maximize the compati~ility of the essential ingredients of the composition. In many ways the most via~le of these alternatives is a variation in t~le nature of the builder employed since the nature of the surface active agent may well be governed by the required detergency characteristics of the composition and the incorporation of homogenizers is not the ideal solution since it involves the additional expense of incorPorating organic chemicals into the composition without o~taining any significant improVement in t~e overall cleaning performance of the composition.
The ~ost commonly used polyphosphate builder for solid deter~ents is sodium tripolyphosphate, but this compound i5 ;nsuf~iciently compati~le with other detergent ingredients, due to its relatively low solubility in water, to make it use~ul as a ~uilder in liquid detergent compo-sitions. For the latter purpos~ potassium pyrophosphate and tripolyphosphate are most commonly employed~ Poly-phosphates containing more than three phosphorus atoms per molecule can onl~ be manufactured on a commercial scale in : , ~ ~ 3 ~
. --the form of mixtures of condensed polyphosphate species having an average length of greater than 3. There have been proposals (see for example s.P~ 919,249 and West German Application 2,359,767) to use condensed phosphates having an average chain length of greater than three as builders for liquid detergents. These have included salts obtained by neutralizing a phosphoric acid solution con-taining from 80 to 88% by weight of phosphorus pentoxide ~P2O51. These builders comprise mixtures of various individual polyphosphates as outlined above in which the proportion of longer chain polyphosphate species will in-crease with the P2O5 content of the acid from which they are derived. To achieve high sequestering power it has been considered desirable to incorporate in the detergent solution the maximum amount of phosphorus pentoxide in a form having the maximum degree of polymerization. This points to the use o~ an acid starting solution containing -the maximum proportion of P2O5, which in practice is 86~, since greater proportions lead to acids of too high a viscosity to be manageable. EIowever, if such highly polymerized acids are used, the polyphosphates in the detergent solution show an unsatisfactory degree of insta-bility, the more highly condensed species tend to hydrolyze to form salts of lower chain length. This has the result -of reducing the sequestering power of the detergent and decreasing the p~I, as well as the disadvantage of a compo- -sition which varies during storage. We have found surprisingly that when formulating a particular type of liquid cleanin~ composition an optimum combination of stability and long-term sequestering power is obtained if the polyphosphate mixture is derived from an acid containing 8a to 81% of P2O5.
.
. ' .
. ..... . . . . . , . ~ .
";''''` -. .,~''',.'':'.',',,'', ' '-,''''''''''','`,','", . ' ;,' ' ' ' ~q~ L7~
The compositions in question are those of moderate al~alinity characterized in that they have a pH in the range 8 to 12 which ~ind particular application as hard sur~ace cleaners.
The invention provides a liquid cleaning composition having a pH in the range 8 to 12 which comprises one or more sur~ace active agents together with an aqueous builder solution of alkali metal salts of a plurality of polyphos-phoric acids which ~uilder solution has been obtained by reacting an aqueous polyphosphoric acid solution containing from 80 to 81~ by weight o~ phosphorus pentoxide with a basic derivative of an alkali metal in such a manner that no substantial hydrolysis of the polyphosphoric acid species present in the said polyphosphoric acid solution takes place. PreEerably the composition will have a p~
in the range 10 to 11.
The composition of the mixture of polyphosphoric acid species contained in a concentrated solution of -phosphorus pentoxide in water is governed by that concen-tration as is described for example in the Canadian Journal of Chemistry volume 34 (l956l pacJe 7~0. The analyses of the aqueous polyphosphoric acid solutions reported here ~ -make it clear that the composition of these mixtures o~
polyphosphoric acids is radically altered by apparently small changes in the phosphorus pentoxide content of the solution. The applicants have selected a particularly useful range of polyphosphate builders which are obtained by the neutralization of a selected group of polyphosphoric ~ acid solutions; the neutralization of the polyphosphoric acid bein~ carried out in such a manner as to substantially avoid any hydrol~sis of the polyphosphate species present.
: , -'" - .
~ 5 ~
,: :
., 7~ :
It is characteristic of the polyphosphate salt mixtures used in the present inven-tion that the spectrum of poly-phosphate anions presen-t substantially corresponds to the spectrum of polyphosphoric acid species present in the aqueous solution of phosphorus pentoxide from which the salts are derived.
When employed as builders in liquid detergent formu-lations of moderate alkalinity the polyphosphate builder mixtures of the invention have ~een found to exhibit a com-bination of properties which renders them well suited for use in this area. They combine the detergent building action expected from such condensed phosphate species with moderately high sequestering powers, and the alkaline compositions into which they are incorporated are sufficiently stable to ~e stored ~or lengthy periods without undergoing any substantial change.
The polyphosphate ~uilder salts of the invention are obtained from aqueous solutions of phosphorus pentoxide in water which comprises from 80 to 81~ by weight of phos-phorus pentoxide. Such solutions may be made by conventional means such as concentration of orthophosphoric acid solutions, dilution of polyphosphoric acid solutions havin~ greater than the desired content of phosphorus pentoxide or ~y dissolution of phosphorus pentoxide in water or in orthophosphoric acid. The polyphosphoric acid species present in any such solution should be allowed to at~ain a state of dynamic equilibrium before neutraliza- -tion takes place. This equîlibrium ~g readily set up if the polyphosphoric acid solution is allowed to stand at room temperature for ~ $hort period as would normally happen in the course of a conventional manufacturing oper-. .. ' .,:,, ,' ' '.
~ 6 ~ ~
. - ~ ' .
~7~
ation. Aqueous polyphosphoric acid solutions derived from the dissolution of phosphorus pentoxide in orthophosphoric acid are preferred for present use. While the presence of other materials in the polyphosphoric acid solutions is not excluded it is desirable that these solutions be substantially unadulterated and for this reason polyphos-phoric acid solutions which have been derived by any of the above mentioned processes from phosphorlls pentoxide obtained by the burning of electro~thermally produced phosphorus are preferred. Polyphosphoric acid solutions derived by the dissolution of phosphorus pentoxide in so-called "wet process" phosphoric acid obtained by the acidulation of phosphate rock are less prefexred.
The builder solutions may be obtained by reaction of the polyphosphoric acid solutions with a basic derivative of an alkali metal according to the methods described in . . ~
our published West German Patent Application 2,359,767.
Thus the neutralization o~ the polyphosphoric acid will be carried out in a reaction med:ium having a pH in the ; 20 range 6 to 12, the temperature of which is below 70C.
Preferably 10 to 11.5. The temperature will conveniently be maintained in the range 15 to 70C, more preferably 15 to 40C.
In a preferred procedure the neutralization reaction is carried out by running the aqueous polyphosphoric acid and an~aqueous solution of an appropriate base simultaneous--ly into a stirred cooled heel of a preferred mixed poly-` phosphate salt solution. The reaction vessel will be ~itted with suitable cooling means in order that the temperature of the reaction medium is maintained within -~
the specified range. The pE of the reaction medium is ' -'' ~ 7 ~ ~
10~374L79 monitored by a suita~le meter and appropriate adjustments to the rate of addition of one or more of the reactants are made in order to maintain the pH within the specified range.
The quantity of water introduced into the builder ~olution at the reaction stage, whether as heel or as a solvent for the basic derivative is governed solely by the desired concentration of the final builder solution.
This latter concentration will normally be in the range 4 to 25% by weight, more usually 15 to 23% by weight, expressed as the percentage weight of phosphorus pentoxide or the total weight of the solution.
The relative proportions o the reactants in the neutralîzation reaction will normally be in the range 1.5:1 to 2.5:1, preferably 1.8:1 to 2.2:1 expressed on a basis o~ cations to phosphorus atoms. Preferably sufficient base is used to completely neutralize the acid. The final pH of the polyphosphate product will preferably be in the ran~e lQ to 11.5, more prefera~ly 10 to ll. The polyphos-phate huilder salts may be the s~lts of any alkali metal but on grounds ~f economy will normally ~e the sodium or potassi~n salts or mIxtures o~ the two. Preferably at ' least 50% of the cations ~ill ~e potassium while the most I preferred polyphosphate salts ~or present use are the potassium salts.
The liquid cleaning compositions of the invention are homogenous ~i~uids which may ~e in the form of aqueous solutions or emulsions or suspensions o~ the various :
ingredients. The proportion o~ surface active agent in these composit;ons may vary within wide limits depending upon the required detergency characteristics of the compo ,, :
. :' . , ', sition and the nature of the surface active agent or agents employed. In general in the particular compositions of the invention the surface active agent(s) will constitute between 0.5 and 20% by weight of the composition, preferably between 2 and 10% by weight.
The compositions of the invention find wide applica-tion in the cleaning of hard surfaces such as linoleum, ceramic tiles, paintwork, enamelled or laminated surfaces and stainless steel. They have good foaming power and freely suspended particulate soil and emulsify grease, thus giving adequate cleaning performance without necessarily requiring the incorporation of an a~rasive solid material~
The surface active agents employed in the novel compositions include non~ionic, cationic, anionic and amphoteric surface active agents generally such as these mentioned in volume l9, pages 507-~66 of the encyclopaedia ¦ of Chemical Technology, Second Edition by Kirk-Othmer published by Interscience, 1~69, the relevant disclosure of which is hereby incorporated by reference herein.
Particular surface active agents which may ~ind us~
in the novel compositions include; alkyl aryl sulphonates such as sodium, potassium, ammonium or other water-soluble salts of sulphonic acids of alkyl substituted benzenes such as decyl toluene, dodecyl~xylene, oxtylbenzene, nonylbenzene, decylbenzene, tridecylbenzene, tetradecyl-benzene, pentadecylbenzene, dodecylbenzene and hexadecyl-benzene.
Olefin sulphonates such as water-soluble alkali metal and alkaline earth metal salts of mono or di-olefin sulphonic acids comprising from 8 to 24 carbon groups;
Alkali metal or ammonium alkyl sulphates in which . ~ .
' ~ ~
. ': , , !
~ 7~7~
the alkyl groups have from 10 -to 18 carbon atoms and poly-oxyethylenated and polyoxypropylenated derivatives thereof.
Alkali metals or ammonium salts of alkane sulphonates.
Alkali metal or ammonium salts of sulphosuccinated materials of the average formula:
O ,.
CH2 - C (OCH2 CH)n OR2 wherein n is from 0 to 25; R is hydrogen or a methyl group and R2 an alkyl group having from 8 to 25 carbon atoms.
Fatty acid soaps.
Amine oxides such as those described in B.P. 943,353 having the formula RlR2R3NO wherein Rl is an alkyl radical having from 9 to 25, preferably 10 to 16 carbon atoms and R2 and R3 are methyl or ethyl groups.
Betaines of the general formula:
R N - R
wherein R2 and R3 are alkyl or alkenyl groups containing 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.
Polyoxyethylene compounds of the general formula RO~CHCHRlO)XH where R is an alkyl, aryl, alkaryl, alicyclic, ~-acyl, amino or alkylamino group;~R is hydrogen or an alkyl -group having ~rom 1 to 4 carbon atoms and x is from 3 to 100 usually from 6 to 50. Such compounds include fatty alcohol polyethoxylates, fatty acid polyethoxylates, polyethylene glycol ethers, mixed polyethylene and polypropylene glycol . ~ ~ ~
- lQ ~ ~
, , ~
~7~t79 ethers, amine and diamine polye~hoxylates, and fatty alkylolamide ethoxylates.
Fatty alcohol phosphates and polyethoxylated and polypropyloxylated derivatives thereof.
In general the use of anionic or non-ionic surface active materials is preferred. Particular types of sur~ace active agent which find application in ~he compositions of our invention include alkyl aryl sulphonates, fatty alcohol sulphates and ethoxylated derivatives thereof, fatty acid soaps, alkyl phenol ethoxylates, fatty alcohol ethoxylates and fatty acid alkanolamides and ethoxylated derivatives thereof.
The polyphosphate builder salts o~ the invention will also be employed in a sufficient proportion to give a composition having satisfactory cleaning properties. In I general, the compositions of the invention will comprise ¦ from S to 30% of an aqueous solution of the polyphosphate builder salts containing from 15 to 25% by weight of phosphorus pentoxide, preferably 18 to 22%. This proportion will vary with the concentration of builder salt used to formulate the composition~.
In certain compos~tions a larger quantity of poly-phosphate may be incorporated if desired. Thus they may comprise from 2.Q to 15% (expressed as weight of phosphorus pentoxide on the weight o~ solution~ of the polyphosphate while more usually they will comprise from 3.0 to 10%
b~ weI~ht of the polyphosphate. ;~
Although the compositions of this inv~ntion derive their alkalinity wholly or mainly from the polyphosphate salts, it may be desirable in certain cases to add alkali to bring the pH up to 12. It is not desired to include in . . , 1~379L79 the invention composi-tions having a pH greater than 12 since the polyphosphate builder would hydrolyze, thus reducing the stability of the product. Howe~er, with khis limitation additional alkaline materials such as sodium hydroxide or sodium metasilicate may be incorporated.
The novel compositions may also comprise known adjuvants ~or liquid cleaning compositions such as anti-soil redeposition agents e.g., carboxymethyl cellulose, or polyvinylpyrrolidone; optical ~rightening agents; perfumes;
dyes; bacteristats and ~acteriocides; opacifying agents;
colorants; sudsing agents e.g~ ethanolamides such as coconut ethanolamide and fatty alcohols such as lauryl alcohol; phase sta~ilizers such as lower aliphatic : alcohols and homogenizin~ ~gents. Chlcrine releasing agentssuch as sodium hypochlorite and chlorinated isocyanurates, a~rasive aaents suc~ as calcite etc.
EXAMPLE 1 - Preparation o~ potassium polyp~osphate mixture.
A heel comprising lQ0 parts ~y weight of water and 30 parts o~ a pre~ormed heel o~ potassium polyphosphate mixture o~tained from a prior identical preparation were placed in a stainless steel pot. T~e pot was fitted with means for cooling the contents and for externally recirculating a por~ion thareof so as to aid the cooling and facilitate the monitoring of the contents of the vessel. 267 parts of an aqueous polyphosphoric acid solution comprising 80.5% by weight of phosphorus pentoxide at a temperature of 60C
were ~ed into the ves$el under gravity and simultaneously 633 parts by weight of a 49~ w/w solution of potassium hydroxide was pumped through an inlet in the opposite wall of the vessel. The reaction mixture was cooled so that its temperature remainder lower than 40C and the rate at which ,.
~ ~ 12 ~
7~
the two rea~tants were introduced into the vessel was governed by suitable valves controlled by electrical means connected to a pH meter. The product was a clear colour-less liquid having a pH of 11, a spec.ific gravity of 1.52 at 25C comprising 21.5% by weight of P2O5 and 26% by weight of K2O.
EXAr~LE 2 The product of Example 1 was incorporated into two formulations which were useful as hard surface cleaners.
(a) Emulsion (opaque~ formulation:
(all percentages as parts by weightl Potassium polyphosphate (as prepared in (1~) 15.0%
Coconut fatty acid d~ethanolamide5.0%
Sodium dodecyl benzene sulphonate4.5%
Water to 100.0%
.b~ Clear homogeneous formulation: .
Potassium polyphosphate 25.0%
Sodium toluene sulphonate 5.0%
Iso propyl alcohol 5.0%
Lauryl alcohol ~ mole et~oxylate4.0%
Water to 100.0%
Each o these products were stable on standing at room temperature.
' ~
'.
. ~, .
j ~ 12a ~
-~ ~
This invention relates to liquid cleaning compositions comprising a polyphosphate builder. In particular the invention relates to a class of polyphosphate builder salts which find particular application in cleaning compositions designed for specific cleaning tasks which have a moderate-ly alkaline pH.
The salts of the condensed phosphoric acids are well known and widely accepted in the detergent industry as ingredients of synthetic detergent compositions. They are valued ~ecause they exhibit, albeit to varying degrees, four important properties which are desirable facets of a liquid detergent. Firstly they are capable of sequestering heavy metal ions, such as calcium or magnesium ions which are found in hard water areas; secondly they act as dispersants for sOlia particles in aqueous environments thus preventing these particles from settling out during the cleaning operation; thirdly, they act as a buffer in liquid compositions thus stabilizing the pH of such compo-sitions and ourthly they interact synergistically with other detergent ingreaients e.g. synthetic detergents so as to to enhance~ their performance.
.The formulator of a detergent will select a particular polyphosphate builder according to the re~uired property of his finished compo$ition although this choice will almost inevitably involve some sacri~ice in respect of one or other of the desira~le properties outlined above.
In the case of liquid detergent formulations the problem is aggravated by -the requirement that all the ingredients of the composition should be compatible, In practice it . .
3~ is desirable that this compatibility be maximized so that : -a satisfactory-cleaning performance is given ~y th~ minimum ~ . .
~ 2 ~
l~D~74~7g volume of detergent. Furthermore the composition must be stabl~ even on prolonged storage and the ingredients must not separate out as a result of such storage even at low temperatures. Thus in ordex to fulfill this latter require-ment the composition will have a chill point well below room temperature and a short reli~uifaction time after storage at low temperatures.
A number of attempts have been made to mitigate these problems which have, in general, involved selecting a particular builder or a particular synthetic surface active a~ent or the incorporation of a suitable homogenizer which will maximize the compati~ility of the essential ingredients of the composition. In many ways the most via~le of these alternatives is a variation in t~le nature of the builder employed since the nature of the surface active agent may well be governed by the required detergency characteristics of the composition and the incorporation of homogenizers is not the ideal solution since it involves the additional expense of incorPorating organic chemicals into the composition without o~taining any significant improVement in t~e overall cleaning performance of the composition.
The ~ost commonly used polyphosphate builder for solid deter~ents is sodium tripolyphosphate, but this compound i5 ;nsuf~iciently compati~le with other detergent ingredients, due to its relatively low solubility in water, to make it use~ul as a ~uilder in liquid detergent compo-sitions. For the latter purpos~ potassium pyrophosphate and tripolyphosphate are most commonly employed~ Poly-phosphates containing more than three phosphorus atoms per molecule can onl~ be manufactured on a commercial scale in : , ~ ~ 3 ~
. --the form of mixtures of condensed polyphosphate species having an average length of greater than 3. There have been proposals (see for example s.P~ 919,249 and West German Application 2,359,767) to use condensed phosphates having an average chain length of greater than three as builders for liquid detergents. These have included salts obtained by neutralizing a phosphoric acid solution con-taining from 80 to 88% by weight of phosphorus pentoxide ~P2O51. These builders comprise mixtures of various individual polyphosphates as outlined above in which the proportion of longer chain polyphosphate species will in-crease with the P2O5 content of the acid from which they are derived. To achieve high sequestering power it has been considered desirable to incorporate in the detergent solution the maximum amount of phosphorus pentoxide in a form having the maximum degree of polymerization. This points to the use o~ an acid starting solution containing -the maximum proportion of P2O5, which in practice is 86~, since greater proportions lead to acids of too high a viscosity to be manageable. EIowever, if such highly polymerized acids are used, the polyphosphates in the detergent solution show an unsatisfactory degree of insta-bility, the more highly condensed species tend to hydrolyze to form salts of lower chain length. This has the result -of reducing the sequestering power of the detergent and decreasing the p~I, as well as the disadvantage of a compo- -sition which varies during storage. We have found surprisingly that when formulating a particular type of liquid cleanin~ composition an optimum combination of stability and long-term sequestering power is obtained if the polyphosphate mixture is derived from an acid containing 8a to 81% of P2O5.
.
. ' .
. ..... . . . . . , . ~ .
";''''` -. .,~''',.'':'.',',,'', ' '-,''''''''''','`,','", . ' ;,' ' ' ' ~q~ L7~
The compositions in question are those of moderate al~alinity characterized in that they have a pH in the range 8 to 12 which ~ind particular application as hard sur~ace cleaners.
The invention provides a liquid cleaning composition having a pH in the range 8 to 12 which comprises one or more sur~ace active agents together with an aqueous builder solution of alkali metal salts of a plurality of polyphos-phoric acids which ~uilder solution has been obtained by reacting an aqueous polyphosphoric acid solution containing from 80 to 81~ by weight o~ phosphorus pentoxide with a basic derivative of an alkali metal in such a manner that no substantial hydrolysis of the polyphosphoric acid species present in the said polyphosphoric acid solution takes place. PreEerably the composition will have a p~
in the range 10 to 11.
The composition of the mixture of polyphosphoric acid species contained in a concentrated solution of -phosphorus pentoxide in water is governed by that concen-tration as is described for example in the Canadian Journal of Chemistry volume 34 (l956l pacJe 7~0. The analyses of the aqueous polyphosphoric acid solutions reported here ~ -make it clear that the composition of these mixtures o~
polyphosphoric acids is radically altered by apparently small changes in the phosphorus pentoxide content of the solution. The applicants have selected a particularly useful range of polyphosphate builders which are obtained by the neutralization of a selected group of polyphosphoric ~ acid solutions; the neutralization of the polyphosphoric acid bein~ carried out in such a manner as to substantially avoid any hydrol~sis of the polyphosphate species present.
: , -'" - .
~ 5 ~
,: :
., 7~ :
It is characteristic of the polyphosphate salt mixtures used in the present inven-tion that the spectrum of poly-phosphate anions presen-t substantially corresponds to the spectrum of polyphosphoric acid species present in the aqueous solution of phosphorus pentoxide from which the salts are derived.
When employed as builders in liquid detergent formu-lations of moderate alkalinity the polyphosphate builder mixtures of the invention have ~een found to exhibit a com-bination of properties which renders them well suited for use in this area. They combine the detergent building action expected from such condensed phosphate species with moderately high sequestering powers, and the alkaline compositions into which they are incorporated are sufficiently stable to ~e stored ~or lengthy periods without undergoing any substantial change.
The polyphosphate ~uilder salts of the invention are obtained from aqueous solutions of phosphorus pentoxide in water which comprises from 80 to 81~ by weight of phos-phorus pentoxide. Such solutions may be made by conventional means such as concentration of orthophosphoric acid solutions, dilution of polyphosphoric acid solutions havin~ greater than the desired content of phosphorus pentoxide or ~y dissolution of phosphorus pentoxide in water or in orthophosphoric acid. The polyphosphoric acid species present in any such solution should be allowed to at~ain a state of dynamic equilibrium before neutraliza- -tion takes place. This equîlibrium ~g readily set up if the polyphosphoric acid solution is allowed to stand at room temperature for ~ $hort period as would normally happen in the course of a conventional manufacturing oper-. .. ' .,:,, ,' ' '.
~ 6 ~ ~
. - ~ ' .
~7~
ation. Aqueous polyphosphoric acid solutions derived from the dissolution of phosphorus pentoxide in orthophosphoric acid are preferred for present use. While the presence of other materials in the polyphosphoric acid solutions is not excluded it is desirable that these solutions be substantially unadulterated and for this reason polyphos-phoric acid solutions which have been derived by any of the above mentioned processes from phosphorlls pentoxide obtained by the burning of electro~thermally produced phosphorus are preferred. Polyphosphoric acid solutions derived by the dissolution of phosphorus pentoxide in so-called "wet process" phosphoric acid obtained by the acidulation of phosphate rock are less prefexred.
The builder solutions may be obtained by reaction of the polyphosphoric acid solutions with a basic derivative of an alkali metal according to the methods described in . . ~
our published West German Patent Application 2,359,767.
Thus the neutralization o~ the polyphosphoric acid will be carried out in a reaction med:ium having a pH in the ; 20 range 6 to 12, the temperature of which is below 70C.
Preferably 10 to 11.5. The temperature will conveniently be maintained in the range 15 to 70C, more preferably 15 to 40C.
In a preferred procedure the neutralization reaction is carried out by running the aqueous polyphosphoric acid and an~aqueous solution of an appropriate base simultaneous--ly into a stirred cooled heel of a preferred mixed poly-` phosphate salt solution. The reaction vessel will be ~itted with suitable cooling means in order that the temperature of the reaction medium is maintained within -~
the specified range. The pE of the reaction medium is ' -'' ~ 7 ~ ~
10~374L79 monitored by a suita~le meter and appropriate adjustments to the rate of addition of one or more of the reactants are made in order to maintain the pH within the specified range.
The quantity of water introduced into the builder ~olution at the reaction stage, whether as heel or as a solvent for the basic derivative is governed solely by the desired concentration of the final builder solution.
This latter concentration will normally be in the range 4 to 25% by weight, more usually 15 to 23% by weight, expressed as the percentage weight of phosphorus pentoxide or the total weight of the solution.
The relative proportions o the reactants in the neutralîzation reaction will normally be in the range 1.5:1 to 2.5:1, preferably 1.8:1 to 2.2:1 expressed on a basis o~ cations to phosphorus atoms. Preferably sufficient base is used to completely neutralize the acid. The final pH of the polyphosphate product will preferably be in the ran~e lQ to 11.5, more prefera~ly 10 to ll. The polyphos-phate huilder salts may be the s~lts of any alkali metal but on grounds ~f economy will normally ~e the sodium or potassi~n salts or mIxtures o~ the two. Preferably at ' least 50% of the cations ~ill ~e potassium while the most I preferred polyphosphate salts ~or present use are the potassium salts.
The liquid cleaning compositions of the invention are homogenous ~i~uids which may ~e in the form of aqueous solutions or emulsions or suspensions o~ the various :
ingredients. The proportion o~ surface active agent in these composit;ons may vary within wide limits depending upon the required detergency characteristics of the compo ,, :
. :' . , ', sition and the nature of the surface active agent or agents employed. In general in the particular compositions of the invention the surface active agent(s) will constitute between 0.5 and 20% by weight of the composition, preferably between 2 and 10% by weight.
The compositions of the invention find wide applica-tion in the cleaning of hard surfaces such as linoleum, ceramic tiles, paintwork, enamelled or laminated surfaces and stainless steel. They have good foaming power and freely suspended particulate soil and emulsify grease, thus giving adequate cleaning performance without necessarily requiring the incorporation of an a~rasive solid material~
The surface active agents employed in the novel compositions include non~ionic, cationic, anionic and amphoteric surface active agents generally such as these mentioned in volume l9, pages 507-~66 of the encyclopaedia ¦ of Chemical Technology, Second Edition by Kirk-Othmer published by Interscience, 1~69, the relevant disclosure of which is hereby incorporated by reference herein.
Particular surface active agents which may ~ind us~
in the novel compositions include; alkyl aryl sulphonates such as sodium, potassium, ammonium or other water-soluble salts of sulphonic acids of alkyl substituted benzenes such as decyl toluene, dodecyl~xylene, oxtylbenzene, nonylbenzene, decylbenzene, tridecylbenzene, tetradecyl-benzene, pentadecylbenzene, dodecylbenzene and hexadecyl-benzene.
Olefin sulphonates such as water-soluble alkali metal and alkaline earth metal salts of mono or di-olefin sulphonic acids comprising from 8 to 24 carbon groups;
Alkali metal or ammonium alkyl sulphates in which . ~ .
' ~ ~
. ': , , !
~ 7~7~
the alkyl groups have from 10 -to 18 carbon atoms and poly-oxyethylenated and polyoxypropylenated derivatives thereof.
Alkali metals or ammonium salts of alkane sulphonates.
Alkali metal or ammonium salts of sulphosuccinated materials of the average formula:
O ,.
CH2 - C (OCH2 CH)n OR2 wherein n is from 0 to 25; R is hydrogen or a methyl group and R2 an alkyl group having from 8 to 25 carbon atoms.
Fatty acid soaps.
Amine oxides such as those described in B.P. 943,353 having the formula RlR2R3NO wherein Rl is an alkyl radical having from 9 to 25, preferably 10 to 16 carbon atoms and R2 and R3 are methyl or ethyl groups.
Betaines of the general formula:
R N - R
wherein R2 and R3 are alkyl or alkenyl groups containing 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.
Polyoxyethylene compounds of the general formula RO~CHCHRlO)XH where R is an alkyl, aryl, alkaryl, alicyclic, ~-acyl, amino or alkylamino group;~R is hydrogen or an alkyl -group having ~rom 1 to 4 carbon atoms and x is from 3 to 100 usually from 6 to 50. Such compounds include fatty alcohol polyethoxylates, fatty acid polyethoxylates, polyethylene glycol ethers, mixed polyethylene and polypropylene glycol . ~ ~ ~
- lQ ~ ~
, , ~
~7~t79 ethers, amine and diamine polye~hoxylates, and fatty alkylolamide ethoxylates.
Fatty alcohol phosphates and polyethoxylated and polypropyloxylated derivatives thereof.
In general the use of anionic or non-ionic surface active materials is preferred. Particular types of sur~ace active agent which find application in ~he compositions of our invention include alkyl aryl sulphonates, fatty alcohol sulphates and ethoxylated derivatives thereof, fatty acid soaps, alkyl phenol ethoxylates, fatty alcohol ethoxylates and fatty acid alkanolamides and ethoxylated derivatives thereof.
The polyphosphate builder salts o~ the invention will also be employed in a sufficient proportion to give a composition having satisfactory cleaning properties. In I general, the compositions of the invention will comprise ¦ from S to 30% of an aqueous solution of the polyphosphate builder salts containing from 15 to 25% by weight of phosphorus pentoxide, preferably 18 to 22%. This proportion will vary with the concentration of builder salt used to formulate the composition~.
In certain compos~tions a larger quantity of poly-phosphate may be incorporated if desired. Thus they may comprise from 2.Q to 15% (expressed as weight of phosphorus pentoxide on the weight o~ solution~ of the polyphosphate while more usually they will comprise from 3.0 to 10%
b~ weI~ht of the polyphosphate. ;~
Although the compositions of this inv~ntion derive their alkalinity wholly or mainly from the polyphosphate salts, it may be desirable in certain cases to add alkali to bring the pH up to 12. It is not desired to include in . . , 1~379L79 the invention composi-tions having a pH greater than 12 since the polyphosphate builder would hydrolyze, thus reducing the stability of the product. Howe~er, with khis limitation additional alkaline materials such as sodium hydroxide or sodium metasilicate may be incorporated.
The novel compositions may also comprise known adjuvants ~or liquid cleaning compositions such as anti-soil redeposition agents e.g., carboxymethyl cellulose, or polyvinylpyrrolidone; optical ~rightening agents; perfumes;
dyes; bacteristats and ~acteriocides; opacifying agents;
colorants; sudsing agents e.g~ ethanolamides such as coconut ethanolamide and fatty alcohols such as lauryl alcohol; phase sta~ilizers such as lower aliphatic : alcohols and homogenizin~ ~gents. Chlcrine releasing agentssuch as sodium hypochlorite and chlorinated isocyanurates, a~rasive aaents suc~ as calcite etc.
EXAMPLE 1 - Preparation o~ potassium polyp~osphate mixture.
A heel comprising lQ0 parts ~y weight of water and 30 parts o~ a pre~ormed heel o~ potassium polyphosphate mixture o~tained from a prior identical preparation were placed in a stainless steel pot. T~e pot was fitted with means for cooling the contents and for externally recirculating a por~ion thareof so as to aid the cooling and facilitate the monitoring of the contents of the vessel. 267 parts of an aqueous polyphosphoric acid solution comprising 80.5% by weight of phosphorus pentoxide at a temperature of 60C
were ~ed into the ves$el under gravity and simultaneously 633 parts by weight of a 49~ w/w solution of potassium hydroxide was pumped through an inlet in the opposite wall of the vessel. The reaction mixture was cooled so that its temperature remainder lower than 40C and the rate at which ,.
~ ~ 12 ~
7~
the two rea~tants were introduced into the vessel was governed by suitable valves controlled by electrical means connected to a pH meter. The product was a clear colour-less liquid having a pH of 11, a spec.ific gravity of 1.52 at 25C comprising 21.5% by weight of P2O5 and 26% by weight of K2O.
EXAr~LE 2 The product of Example 1 was incorporated into two formulations which were useful as hard surface cleaners.
(a) Emulsion (opaque~ formulation:
(all percentages as parts by weightl Potassium polyphosphate (as prepared in (1~) 15.0%
Coconut fatty acid d~ethanolamide5.0%
Sodium dodecyl benzene sulphonate4.5%
Water to 100.0%
.b~ Clear homogeneous formulation: .
Potassium polyphosphate 25.0%
Sodium toluene sulphonate 5.0%
Iso propyl alcohol 5.0%
Lauryl alcohol ~ mole et~oxylate4.0%
Water to 100.0%
Each o these products were stable on standing at room temperature.
' ~
'.
. ~, .
j ~ 12a ~
-~ ~
Claims (8)
1. A liquid cleaning composition having a pH in the range of 8 to 12 consisting essentially of:
0.5 to 20% by weight of the composition of one or more surface active agents, and an aqueous builder solution of alkali metal salts of a plurality of polyphosphoric acid, said aqueous builder solution being obtained by reacting an aqueous polyphosphoric acid solution containing from 80 to 81% by weight of phosphorus pentoxide with a basic derivative of an alkali metal in such a manner that no substantial hydrolysis of the polyphosphoric acid species present in the polyphosphoric acid solution takes place, the aqueous builder solution containing from 2 to 15% by weight, expressed as the weight of phosphorus pent-oxide on the total weight of the solution, of the polyphosphate, the balance of the composition being water.
0.5 to 20% by weight of the composition of one or more surface active agents, and an aqueous builder solution of alkali metal salts of a plurality of polyphosphoric acid, said aqueous builder solution being obtained by reacting an aqueous polyphosphoric acid solution containing from 80 to 81% by weight of phosphorus pentoxide with a basic derivative of an alkali metal in such a manner that no substantial hydrolysis of the polyphosphoric acid species present in the polyphosphoric acid solution takes place, the aqueous builder solution containing from 2 to 15% by weight, expressed as the weight of phosphorus pent-oxide on the total weight of the solution, of the polyphosphate, the balance of the composition being water.
2. The composition of claim 1 wherein the reaction between the polyphosphoric acid and the basic derivative of an alkali metal is carried out at a pH in the range of 6 to 12 and at a temperature in the range 15 to 70°C.
3. The composition of claim 1 wherein the basic derivative of an alkali metal is a basic derivative of potassium or a mixture thereof comprising up to 50 mole percent of a basic derivative of sodium.
4. The composition of any one of claims 1 to 3 having a pH in the range 10 to 11.
5. The composition of claim 1 wherein the quantity of polyphosphate is from 3 to 10% by weight.
6. The composition of claim 1 or 5 wherein the poly-phosphate is added to the composition in the form of an aqueous solution thereof which comprises 15 to 25% by weight of phosphorus pentoxide.
7. The composition of claim 1 wherein the surface active agent is present in an amount of from 2.0 to 10% by weight.
8. The composition of claim 1 or 7 wherein the surface active agent is an alkyl-aryl sulphonate, a fatty alcohol sulphate or an alkoxylated derivative thereof, or an alkoxylated derivative of an alkyl substituted phenol, a fatty acid alkanolamide or a fatty alcohol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB5845/75 | 1975-02-11 | ||
| GB584575A GB1541561A (en) | 1975-02-11 | 1975-02-11 | Cleaning compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1087479A true CA1087479A (en) | 1980-10-14 |
Family
ID=9803710
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA245,458A Expired CA1087479A (en) | 1975-02-11 | 1976-02-10 | Cleaning compositions |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS51105309A (en) |
| AU (1) | AU507577B2 (en) |
| BE (1) | BE838446A (en) |
| CA (1) | CA1087479A (en) |
| DE (1) | DE2605341A1 (en) |
| FR (1) | FR2300796A1 (en) |
| GB (1) | GB1541561A (en) |
| IT (1) | IT1057164B (en) |
| NL (1) | NL7601385A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0462956A2 (en) * | 1990-06-18 | 1991-12-27 | FMC Corporation | Production of concentrated aqueous polyphosphate solutions |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63295700A (en) * | 1987-01-12 | 1988-12-02 | Kurita Water Ind Ltd | Detergent for air conditioner |
| SE504143C2 (en) * | 1995-03-21 | 1996-11-18 | Akzo Nobel Nv | Alkaline detergent containing nonionic surfactant and complexing agent and use of an amphoteric compound as a solubilizing agent |
| WO2000011514A1 (en) * | 1998-08-21 | 2000-03-02 | Senju Pharmaceutical Co., Ltd. | Compositions for contact lenses |
| DE102005048433A1 (en) * | 2005-10-07 | 2007-04-12 | Bk Giulini Gmbh | Stable builder solution, useful for preparing washing- and cleaning agents, comprises sodium polyphosphate builder with phosphorus pentoxide, stabilizing additive and water |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3361523A (en) * | 1963-03-19 | 1968-01-02 | Monsanto Co | Method for producing phosphates |
| GB1460710A (en) * | 1972-11-30 | 1977-01-06 | Albright & Wilson | Liquid cleaning compositions |
-
1975
- 1975-02-11 GB GB584575A patent/GB1541561A/en not_active Expired
-
1976
- 1976-02-10 AU AU10977/76A patent/AU507577B2/en not_active Expired
- 1976-02-10 CA CA245,458A patent/CA1087479A/en not_active Expired
- 1976-02-11 IT IT6730476A patent/IT1057164B/en active
- 1976-02-11 DE DE19762605341 patent/DE2605341A1/en not_active Withdrawn
- 1976-02-11 FR FR7603685A patent/FR2300796A1/en active Granted
- 1976-02-11 BE BE164228A patent/BE838446A/en unknown
- 1976-02-11 NL NL7601385A patent/NL7601385A/en not_active Application Discontinuation
- 1976-02-12 JP JP1330876A patent/JPS51105309A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0462956A2 (en) * | 1990-06-18 | 1991-12-27 | FMC Corporation | Production of concentrated aqueous polyphosphate solutions |
| EP0462956A3 (en) * | 1990-06-18 | 1992-09-30 | Fmc Corporation | Production of concentrated aqueous polyphosphate solutions |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2300796B1 (en) | 1979-08-24 |
| AU1097776A (en) | 1977-08-18 |
| BE838446A (en) | 1976-08-11 |
| NL7601385A (en) | 1976-08-13 |
| GB1541561A (en) | 1979-03-07 |
| AU507577B2 (en) | 1980-02-21 |
| FR2300796A1 (en) | 1976-09-10 |
| JPS51105309A (en) | 1976-09-17 |
| DE2605341A1 (en) | 1976-08-26 |
| IT1057164B (en) | 1982-03-10 |
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