US3720621A - Aquenous detergent compositions - Google Patents

Aquenous detergent compositions Download PDF

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US3720621A
US3720621A US00046472A US3720621DA US3720621A US 3720621 A US3720621 A US 3720621A US 00046472 A US00046472 A US 00046472A US 3720621D A US3720621D A US 3720621DA US 3720621 A US3720621 A US 3720621A
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potassium
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carbon atoms
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A Smeets
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Citrique Belge NV SA
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Citrex SA
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    • 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
    • C11D3/046—Salts
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof

Definitions

  • the present invention relates to aqueous detergent compositions which, although containing proportions of sodium tripolyphosphate greater than the saturation concentration of the said salt in water, are nevertheless in the form of substantially homogeneous solutions.
  • Such compositions may be used particularly for the cleansing of articles having non-porous surface and for the washing of textile materials.
  • TPP Sodium tripolyphosphate
  • TPP has a relatively low solubility in water, the saturation concentration in water at room temperature being about 164 g/liter, corresponding to about 14 percent by weight.
  • Such low solubility is not a disadvantage for solid detergent compositions, which may for example be in the form of powder, granules, flakes or the like.
  • Such low solubility represents a practically insolvable problem in the formulation of homogeneous liquid detergent compositions, due to the fact that these normally require a TPP content of about 18 to 40 percent by weight as this is the level of concentration in most commercial solid detergent compositions.
  • the proportion of TPP capable of being introduced into liquid detergent compositions is substantially lower than the theoretical 14 percent by weight (which 9 the saturation concentration of TPP) due to the presence particularly of surface-active agents.
  • TPP surface-active agents and TPP have a mutual effect on their respective solubilities, the higher the concentration of surface-active agent in liquid compositions the less the solubilitity of TPP, and vice versa.
  • Another problem, also affecting the solubility of TPP is its resistance to hydrolysis. It is known that in the presence of water, the hydrolysis tends to form an equilibrium according to the equation TPP 7- sodium pyrophosphate +sodium orthophosphate.
  • liquid detergent compositions instead of solid detergent compositions.
  • superiority of such liquid compositions includes the following:
  • liquid compositions are more easily delivered in measured doses than solid compositions in automatic washing machines (no blockage or residue or formation of dust);
  • liquid aqueous detergent compositions containing proportions of sodium tripolyphosphate considerably higher than the limit of solubility thereof in water, under normal conditions, in other, words in a concentration greater than 14 percent by weight and up to 35 percent by weight, by the presence in the compositions with sodium tripolyphosphate of a suitable proportion of an inorganic or organic potassium and/or ammonium salt together subsequently with desired surface-active agents, solubilizing agents, organic sequestering agents, and other adjuvants conventionally used in solid and/or liquid detergent compositions, per-compounds, the rest being water.
  • the object of the present invention provides homogeneous liquid detergent compositions comprising the following composition:
  • coloring agents i. from 0 to 5 percent by weight in total of coloring agents, scents, bodying agents, optical whiteners, anticorrosion agents and anti-staining agents,
  • the sodium tripolyphosphate, NaP,O, used in the aqueous detergent compositions according to the invention may be used in any of its crystallographic forms and in any state of hydration, from the anhydrous fonn Na ho to the hexahydrate compound Na,P,PO
  • compositions according to about 28 percent by weight, depending on the intended use of the composition and depending on the concentration of other ingredients present therein.
  • the potassium and/or ammonium salt used to enhance the solubility of the TPP in the aqueous detergent compositions according to the invention may be a salt of an inorganic acid for example a sulphate, chloride, nitrate, carbonate, bicarbonate, borate, orthophosphate, metaphosphate, pyrophosphate and the like, or may be a salt of an organic acid, for example a maleate, adipate, aconitate, citrate, tartrate, ethylenediamine-tetracetate, nitrilotriacetate, diethylene-triamine-pentacetate, succinate or the like.
  • an inorganic acid for example a sulphate, chloride, nitrate, carbonate, bicarbonate, borate, orthophosphate, metaphosphate, pyrophosphate and the like
  • organic acid for example a maleate, adipate, aconitate, citrate, tartrate, ethylenediamine-tetracetate, nitrilo
  • inorganic and organic sodium salts diminish the solubility of TPP in water
  • inorganic or organic potassium and/or ammonium salts used according to the invention enhance the solubility as hereinafter described.
  • the nature of the inorganic or organic anion of the potassium and/or ammonium salt incorporated in the compositions influences the solubility of TPP to a considerable extent.
  • potassium sulphate is more effective than potassium chloride, and the carbonate more effective than the bicarbonate.
  • the potassium and/or ammonium salt may be present in a proportion of down to 0.1 percent by weight or up to 50 percent by weight, based on the total aqueous detergent composition.
  • no more of the potassium salt should be used than is necessary, a portion of from 1 to 10 percent by weight based on the total composition, is preferred.
  • Potassium pyrophosphate is the preferred potassium salt. It is effective not only as a sequestering agent i which enhances the solubility of TPP in water, but the applicants have discovered that it effectively stabilizes the tripolyphosphate agent hydrolysis in aqueous solution into sodium pyrophosphate and sodium orthophosphate (as shown in the experiments hereinafter described). It is therefore particularly interesting to introduce potassium pyrophosphate in the aqueous detergent compositions of the present invention. The content should not therefore be too great so as to undergo a double-decomposition reaction with TPP to form sodium pyrophosphate, which as is well known, has a very low solubility in water and therefore tends to separate out as a precipitate. The applicants investigations have shown that the optimum proportion of potassium pyrophosphate incorporated in the liquid detergent compositions according to the invention is between 5 and 25 percent based on the TPP present in the said compositions.
  • the salts of sulphonated esters of a polycarboxylic acid which may be used as surface-active agent according to the present invention have properties superior to anionic and non-ionic surface-active agents for the production of liquid detergent compositions due to the face that (1 they are equally effective at lesser concentrations, (2) they are more soluble in water, (3) they Examples of such salts of sulphonated esters of polycarboxylic acids are the potassium salts of sulphonated derivatives of one or more alpha-beta unsaturated dior tri-carboxylic acids esterified with the hydroxyl group of one or more non-ionic surface-active agents described in the Applicants British Pat. Specification No.
  • sodium salts or organic amine salts for example triethanolamine salts.
  • the starting acid is an unsaturated polycarboxylic acid obtained by the pyrolysis of calcium citrate according to the procedure described in the Applicants British Pat. Specification No. 31014/67.
  • Compound No. 1 (termed ASP 1) is obtained by reacting the pyrolysis product of calcium citrate with a sulphur-containing anhydride to fix an SO H group across the double bond to obtain after acidification a sulphonated polycarboxylic acid.
  • a quarter of the COOH groups of the said acid is esterified with a nonionic surface-active agent obtained by ethoxylating a C -C linear alcohol with 6 moles of ethylene oxide (13.0.).
  • the remaining three-fourths of the COOH groups and the S0, group are then neutralized with potassium hydroxide (see British Pat. Specification Nos. 59220/68 and 31014/67).
  • ASP 2 Compound No. 2 (ASP 2) is the same as ASP 1, except that the non-ionic agent is a C -C alcohol ethoxylated with 3 moles of 13.0.
  • ASP 3 Compound No. 3 is the same as ASP 1, except that the non-ionic agent is nonylphenol ethoxylated with 6 moles of 15.0.
  • ASP 4 Compound No. '4 (ASP 4) is the same as ASP 1, except that the non-ionic agent is a secondary C -C lethoxylated with 7 moles of 15.0.
  • Compound No. 5 (ASP 5) is similar to ASP 4, but it was neutralized with sodium hydroxide.
  • Compound No. 6 (ASP 6) is similar to ASP 1, but the non-ionic agent is a C -C alcohol ethoxylated with 9 moles of 15.0.
  • Compound No. 7 is the sulphonated product of aconitique acid, in other words sulphotricarballylic acid, a carboxyl group of which is esterified with a non-ionic agent obtained by ethoxylating nonylphenol with 8.5 moles of 13.0. and then neutralizing two of the remaining COOl-l groups and the 80,11 group with potassium hydroxide (see British Pat. Specification No. 47677/67).
  • ASP 8 is the sulphonated product of maleic acid, that is to say sulphosuccinic acid, a carboxyl group of which was esterified with a non-ionic agent obtained by ethoxylating a C,,-C linear alcohol with 6 moles of 15.0. and neutralizing the remaining carboxyl group and the S0 11 group with potassium hydroxide (see British Pat. Specification 47677/67).
  • the sulphopolycarboxylic acids represented by compounds 1 to 8 hereinbefore described, are able to be used in the liquid detergent compositions according to the invention in a proportion of from 0 to 35 percent by weight based on the total composition, preferably from 1 to 20 percent by weight.
  • Anionic surface-active agents for use in the liquid detergent compositions according to the invention are particularly selected from the group of soaps, sulphonates and organic synthetic sulphates.
  • the sulphonates and organic synthetic sulphates are preferably selected from the following groups:
  • Sulphonates of olefines containing eight to 25 carbon atoms for example sodium or potassium dodecyl sulphonate,
  • Alkylbenzene sulphonates the alkyl groups of which contain from to 16 carbon atoms and which may be straight-chain or branched, for example potassium salts of decyl-, undecyl-, dodecyltridecyltetradecyl-, pentadecylor hexadecyl sulphonic acids,
  • anionic surface-active agent of the types hereinbefore described is used in the liquid detergent compositions according to the invention in proportions of from 0 to 20 percent by weight based on the total composition, preferably from 1 to percent by weight.
  • non-ionic surface-active agent which may be used in the liquid detergent compositions of the present invention is preferably selected from the following groups:
  • Alkanolamides and ethoxylated alkylamides for example the diethanolamide of ethoxylated coconut fatty acids,
  • Copolymers derived from different alkylene oxides known commercially under the Trade Mark PLURONIC
  • polymers such as polyethylene glycol and propylene glycol
  • esters of polyhydroxy compounds for example sucrose stearate, lauryl sucrose and the like,
  • Tertiary amine oxides and tertiary phosphine oxides for example dimethyldodecylamine oxide, N- dodecylmorpholine oxide, dodecyldimethylphosphine oxide and the like.
  • non-ionic surface-active agent hereinbefore described is incorporated in compositions according to the invention in proportions of from 0 to 15 percent by weight based on the total composition, preferably from 1 to 10 percent by weight.
  • the anionic surfaceactive agents quoted as (d), as do the non-ionic surface-active agents quoted as (e), provide a substantially lower resistance to salting out the surface-active agents of the sulpho-polycarboxylic acid ester type quoted under (c). This is because they are used in the minimum quantities to provide the detergent properties required without salting out in the aqueous liquid detergent compositions of the invention. If it is desired to use considerably greater proportions, in other words close to the upper limit of the concentration hereinbefore specified, it is then necessary to employ a solubilizing agent or a mixture of a solubilizing agent with a sulphopolycarboxylic acid of the type quoted under (c).
  • the solubilizing agent is an organic compound which enhances the water-solubility of a sparingly-soluble substance.
  • Known examples of such agents are xylene sulphonic acids, p-toluene sulphonic acids, pcumene sulphonic acids and the like, preferably used in the form of their potassium salts.
  • the solubilizing agent may be replaced partially by a potassium salt of an ester of a sulpho-carboxylic acid described under (c). Such partial replacement is advantageous because the ester of the sulpho-polycarboxylic acid has excellent detergent properties, such properties being absent from the solubilizing agent therein which therefore constitutes an inactive component in the aqueous liquid detergent compositions of the invention.
  • the solubilizing agent is used in proportions of from 0 to 20 percent by weight of the total aqueous liquid detergent composition, preferably in proportions of from 1 to 12 percent by weight.
  • the organic sequestering agent used according to the invention is an aminopolycarboxylic acid such as ethylene-diamine-tetracetic acid (EDTA), nitrilotriacetic acid (NTA), diethylene-triamine-pentacetic acid acid (DTPA) or a hydroxylpolycarboxylic acid, or the like, preferably used in the form of the potassium salt.
  • the sequestering agent may be in the form of watersoluble complexes with heavy ions responsible for water hardness (calcium, magnesium and the like).
  • the compositions of the invention may contain from 0 to 20 percent by weight based on the total composition, preferably from 0.5 to 10 percent by weight.
  • the per-compound subsequently incorporated in the compositions of the invention is a water-soluble per-compound, for example hydrogen peroxide, perborate, percarbonate or a persulphate, preferably the potassium compound there e quantity of percompound added is from 0 to 20 percent by weight based on the total aqueous liquid detergent composition, preferably from 1 to 5 percent by weight.
  • compositions according to the invention may contain adjuvants conventionally used in liquid and/or solid detergent compositions.
  • adjuvants are for exaMple coloring agents, scents, thickening agents such as carboxymethyl cellulose, polyvinylpyrollidone, polyvinyl alcohol or the like, optical whiteners, anticorrosion agents, anti-staining agents or the like.
  • the total proportion of such adjuvants is from 0 to 5 percent by weight based on the total liquid detergent composition, preferably from 1 to 4 percent by weight.
  • compositions of the invention contain water in at least the proportion necessary to. obtain a liquid detergent com position.
  • liquid detergent compositions according to the invention may be obtained containing many different constituents as hereinbefore described.
  • the common factor is that they must contain a proportion of TPP more than 164 g/liter (i.e., 14 percent by weight), which to the knowledge of the applicants has not previously been in liquid detergent compositions, and that they must contain a potassium or ammonium salt of an inorganic or organic acid in a proportion sufficient to ensure the solubility in water of the TF1.
  • the other constituents of the compositions of the invention are optional and are selected in a proportion according to the end use of the compositions.
  • compositions according to the invention a method may be used as hereinafter described which is given by way of example only and which is not intended to be limiting:
  • the solubilizing agent and then the optical whitener is added, and agitation is continued until a homogeneous solution is obtained.
  • the potassium salts and then water up to about 85 percent of the final quantity is added, and the TPP is then added with vigorous agitation, and when it is dissolved the solution is filtered.
  • the per-compound is then added, and to adjust the pH to between about 7 and 9, either sulphuric acid or potassium hydroxide is added, and the water made up to the full quantity.
  • liquid compositions of the invention may be put, there may be mentioned water-softening, the cleansing of articles having a non-porous surface, for example glass, porcelain, enamel, wood, metal, layers coated with plastics materials for example in vehicle building, and the like, and similarly the washing of textile materials of all kinds, i.e. natural or synthetic textiles, whether for light duty washing or heavy duty washing.
  • EXAMPLE 1 Effect of Potassium Salts on the solubility in water of TPP Solutions were prepared containing increasing quantities of solubilizing salt (potassium or ammonium salt). To 100 mls. of each of the solutions were added, with vigorous agitation, sodium tripolyphosphate in a quantity such that a proportion thereof remained undissolved. The suspension thus obtained was agitated during a period of 1 hour with a magnetic agitator, and
  • the sodium tripolyphosphate was used in the form of the hexahydrate, because the anhydrous form produces a supersaturated solution which subsequently crystallizes out.
  • the contents are expressed in grams per liter.
  • the T1? is expressed as g/liters as the anhydride equivalent.
  • aqueous solutions were prepared containing respectively I percent, 5 percent and I percent by weight of active material.
  • a solution was prepared containing 900 g/liter of potassium citrate monohydrate and used for titrating the three solutions of active material. The quantity of citrate was noted which was required to be added to each of these solutions to produce phase separation.
  • the table shows that the salts of esters of sulphopolycarboxylic acids of group (0), preferably used as surface-active agents, have a resistance to salting out by electrolytes clearly superior to anionic and non-ionic surface-active agents of groups (d) and (e).
  • liquid detergent composition which contains a potassium salt of an ester of a sulphopolycarboxylic acid (ASP 1), the commercially-available non-ionic surface-active agent TERGITOL 1583 which is the condensation product of a C C secondary alcohol with 3 moles of 12.0., TPP, potassium pyrophosphate and potassium xylenesulphate (P.X.S.), the latter being the solubilizing agent.
  • ASP 1 sulphopolycarboxylic acid
  • TERGITOL 1583 which is the condensation product of a C C secondary alcohol with 3 moles of 12.0., TPP, potassium pyrophosphate and potassium xylenesulphate (P.X.S.), the latter being the solubilizing agent.
  • Tests 1 to 3 were effected with compositions according to the invention, all of which contained:
  • composition for test No. 1 contained 20 g/l of nonylphenol ethoxylated with 6 BO, 50 g/l of boric acid and 12.5 g/l of KOH;
  • composition for test No. 2 contained 20 g/l of nonylphenol ethoxylated with 6 15.0. and 50 g/l of potassiumcitrate;
  • composition for test No. 3 contained 20 g/l of C -C alcohol ethoxylated with 6 E0. and 50 g. of KHCO Tests No.4 and No.5 were carried out with commercial heavy duty powders, namely ALL (No. 4) and PRODlXAN" (No. 5), respectively, used in a proportion of5 g/liter.
  • EXAMPLE 3 Demonstration of the greater concentration of TPP in liquid detergent compositions
  • the test carried out in this Example is the same as that of Example 7, using similar swatches TF and U.S.T. and in the comparison of the use of washing powders ALL" and PROD1XAN.”
  • the water used had a hardness of in French units.
  • Tests No. 1 to 5 were carried out with liquid compositions according to the invention containing increasing proportions of TPP, namely: 0, 50, 100, 150 and 200 (g/liter), the compositions containing also the following:
  • EXAMPLE 7 100 g/l of ASP 2 Liquid detergent compositions for heavy duty at high temperature The efficiency of the heavy duty compositions was tested in a Launder-O-Meter at a temperature of 85C,
  • Standard artificially soiled swatches were supplied by TEST 65 FABRICS lnc. STANDARD (referred to as TF) and by US TESTING CY STANDARD (referred to as U.S.T). lnthe said test the percentage ofsoil removed from the swatches was measu'red.
  • the Table clearly shows the effectiveness of the compositions with increasing TPP content.
  • Composi- Composi- EXAMPLE 10 Liquid detergent compositions for light duty The tests were carried out in a Tergometer for 10 minutes at a temperature of 40C, using 5 mls. of detergent composition per liter of water having a hardness of 17 French units.
  • compositions according to the invention were used, each containing:
  • compositions according to the invention are shown despite the fact that the commercial compositions (Test No. 5 and 6) contained greater portions of surface-active material (more than 25 percent).
  • the compositions according to the invention are as well suited for hand washing as for machine washing.
  • a homogeneous aqueous solution consisting essentially of water and (a) from 14 to 35 percent by weight of sodium tripolyphosphate and (b) from 0.1 to 50 percent by weight of at least one salt selected from the group consisting of potassium and ammonium sulfate, chloride, nitrate, carbonate bicarbonate, orthoborate, metaborate, tetraborate perborate, orthophosphate, metaphosphate, pyrophosphate,
  • a homogeneous liquid detergent composition in the form of an aqueous solution consisting essentially of water and a. from 14 to 35 percent by weight of sodium tripolyphosphate,
  • tetraborate perborate, orthophosphate, metaphosphate, pyrophosphate, maleate, adipate, aconitate, citrate, tartrate, succinate,
  • sulfopolycarboxylic acid ester with at least one hydroxy-containing non-ionic surface-active agent selected from the group consisting of aliphatic alcohols containing from eight to 22 carbon atoms ethoxylated with from 1 to 50 moles of ethylene oxide per mole of alcohol, and alkylphenols containing six to 12 carbon atoms in the alkyl chain and ethoxylated with from 3 to 25 moles of ethylene oxide per mole of alkylphenol, said sulfopolycarboxylic acid being selected from the group consisting of sulfosuccinic acid, sulfotricarballylic acid and the sulfopolycarboxylic acid obtained by sulfonating and acidifying the pyrolysis product of calcium citrate.
  • At least one anionic surface-active agent selected from the group consisting of fatty acid soaps containing from 10 to 22 carbon atoms, alkyl sulfonates containing from 8 to 25 carbon .atoms, alkylbenzene sulfonates containing from 10 to l6 carbon atoms in the alkyl group, alkyl sulfates containing from eight to 18 carbon atoms, alkyl polyoxyethylene ether sulfates and alkylaryl polyoxyethylene ether sulfates, the alkyl group of which contains eight to 18 carbon atoms and the polyoxyethylene group of which contains from 1 to 4 ethylene oxide units,
  • At least one nonionic surface-active agent selected from the group consisting of alkylphenols containing from six to 12 carbon atoms in the alkyl chain and ethoxylated with from 3 to 25 moles of ethylene oxide per mole of alkylphenol, aliphatic alcohols containing from eight to 22 carbon atoms ethoxylated with from 1 to 50 moles of ethylene oxide per mole of alcohol, fatty acid ethanolamides and ethoxylated fatty acid ethanolamides, and
  • At least one solubilizing agent selected from the group consisting of potassium xylene sulfonate, potassium toluene sulfonate and potassium cumene sulfonate, at least one of compounds (c), (d) and (e) being present.
  • composition according to claim 2 wherein the salt (b) potassium pyrophosphate is in a proportion of from 5 to 25 percent by weight based on the amount of sodium tripolyphosphate.
  • composition according to claim 2 wherein the salt (0) is a potassium salt.
  • composition according to claim 2 wherein the anionic surface-active agent (d) is a potassium salt.
  • composition according to claim 2 wherein at least one of compounds ((1) and (e) is present, compound (d) in a proportion of from 1 to 15 percent by weight and compound (e) in a proportion of from 1 to percent by weight of the total composition, and solubilizing agent (f) is present in a proportion of from 1 to 12 percent by weight of the total composition.
  • salt (c) is present in a proportion of from 1 to 20 percent by weight of the total composition and at least one of compounds (d) and (e) is present, compound (d) in a proportion of from 1 to 15 percent by weight and compound (e) in a proportion of from 1 to 10 percent by weight of the total composition, and solubilizing agent (f) is present in a proportion of from 1 to l2 percent by weight of the total composition.
  • a homogeneous liquid detergent composition in the form of an aqueous solution consisting essentially of water and a. from 18 to 28 percent by weight of sodium tripolyphosphate,
  • At least one salt selected from the group consisting of potassium and ammonium sulfate, chloride, nitrate, carbonate, bicarbonate, orthoborate, metaborate, tetraborate, perborate, orthophosphate, metaphosphate, pyrophosphate, maleate, adipate, aconitate, citrate, tartrate, succinate, ethylenediaminetetraacetate, nitrilotriacetate and diethylenetriaminepentaacetate, and
  • composition according to claim 9 wherein the salt (b) potassium pyrophosphate is in a proportion of from 5 to 25 percent by weight based on the amount of sodium tripolyphosphate.
  • a homogeneous liquid detergent composition in the form of an aqueous solution consisting essentially of water and a. from 18 to 28 percent by weight of sodium tripolyphosphate,
  • At least one salt selected from the group consisting of potassium and ammonium sulfate, chloride, nitrate, carbonate, bicarbonate, orthoborate, metaborate, tetraborate, perborate, orthophosphate, metaphosphate, pyrophosphate, maleate, adipate, aconitate, citrate, tartrate, succinate, ethylenediaminetetraacetate, nitrilotriacetate and diethylenetriaminepentaacetate,
  • at least one salt selected from the group consisting of potassium and ammonium sulfate, chloride, nitrate, carbonate, bicarbonate, orthoborate, metaborate, tetraborate, perborate, orthophosphate, metaphosphate, pyrophosphate, maleate, adipate, aconitate, citrate, tartrate, succinate, ethylenediaminetetraacetate, nitrilotriacetate and diethylenetriaminepentaacetate,
  • sulfopolycarboxylic acid ester with at least one hydroxy-containing non-ionic surface-active agent selected from the group consisting of aliphatic alcohols containing from eight to 22 carbon atoms ethoxylated with from 1 to 50 moles of ethylene oxide per mole of alcohol, and alkylphenols containing six to 12 carbon atoms in the alkyl chain and ethoxylated with from 3 'to 25 moles of ethylene oxide per mole of alkylphenol, said sulfopolycarboxylic acid being selected from the group consisting of sulfosuccinic acid, sulfotricarballylic acid and the sulfopolycarboxylic acid obtained by sulfonating and acidifying the pyrolysis product of calcium citrate, and
  • At least one anionic surface-active agent selected from the group consisting of fatty acid soaps containing from 10 to 22 carbon atoms, alkyl sulfonates containing from eight to 25 carbon atoms, alkylbenzene sulfonates containing from 10 to 16 carbon atoms in the alkyl group, alkyl sulfates containing from eight to 18 carbon atoms, alkyl polyoxyethylene ether sulfates and alkylaryl polyoxyethylene ether sulfates, the alkyl group of which contains eight to l8 carbon atoms and the polyoxyethylene group of which contains from 1 to 4 ethylene oxide unites, and/or e.
  • anionic surface-active agent selected from the group consisting of fatty acid soaps containing from 10 to 22 carbon atoms, alkyl sulfonates containing from eight to 25 carbon atoms, alkylbenzene sulfonates containing from 10 to 16 carbon atoms in the alkyl group, alkyl
  • nonionic surface-active agent selected from the group consisting of alkylphenols containing from six to 12 carbon atoms in the alkyl chain and ethoxylated with from 3 to 25 moles of ethylene oxide per mole of alkylphenol, aliphatic alcohols containing from eight to 22 carbon atoms ethoxylated with from 1 to 50 moles of ethylene oxide per mole of alcohol, fatty acid ethanolamides and ethoxylated fatty LII acid ethanolamides, and

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US00046472A 1969-06-17 1970-06-15 Aquenous detergent compositions Expired - Lifetime US3720621A (en)

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JP (1) JPS526708B1 (en, 2012)
BE (1) BE752030A (en, 2012)
DE (1) DE2029598A1 (en, 2012)
FR (1) FR2052646A5 (en, 2012)
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Cited By (25)

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US3925224A (en) * 1973-04-17 1975-12-09 Church & Dwight Co Inc Detergent additive composition
US3931033A (en) * 1973-12-14 1976-01-06 Henkel & Cie G.M.B.H. Liquid foam-regulated nonionic detergent compositions
JPS5277111A (en) * 1975-12-23 1977-06-29 Kao Corp Detergent composition for bath room
US4316812A (en) * 1977-06-09 1982-02-23 Imperial Chemical Industries Limited Detergent composition
US4340509A (en) * 1978-03-24 1982-07-20 Michael A. Canale Composition, concentrate and fountain solution for lithographic printing operations
US4374036A (en) * 1980-04-16 1983-02-15 Michael A. Canale Composition and concentrate useful for making a fountain solution for lithographic printing operations
US4537708A (en) * 1983-08-30 1985-08-27 Fmc Corporation Homogeneous laundry detergent slurries containing nonionic surface-active agents
US4597889A (en) * 1984-08-30 1986-07-01 Fmc Corporation Homogeneous laundry detergent slurries containing polymeric acrylic stabilizers
US4836948A (en) * 1987-12-30 1989-06-06 Lever Brothers Company Viscoelastic gel detergent compositions
US5047167A (en) * 1987-12-30 1991-09-10 Lever Brothers Company, Division Of Conopco, Inc. Clear viscoelastic detergent gel compositions containing alkyl polyglycosides
US5160448A (en) * 1987-12-30 1992-11-03 Lever Brothers Company, Division Of Conopco, Inc. Gel detergent compositions containing a clay and a cross-linked polycarboxylic polymer
US5213706A (en) * 1991-11-08 1993-05-25 Lever Brothers Company, Division Of Conopco, Inc. Homogeneous detergent gel compositions for use in automatic dishwashers
US5252242A (en) * 1989-05-18 1993-10-12 Colgate-Palmolive Co. Linear visoelastic aqueous liquid detergent composition, especially for automatic dishwashers, of improved high temperature stability
US5362413A (en) * 1984-03-23 1994-11-08 The Clorox Company Low-temperature-effective detergent compositions and delivery systems therefor
USH1467H (en) * 1993-11-16 1995-08-01 Shell Oil Company Detergent formulations containing a surface active composition containing a nonionic surfactant component and a secondary alkyl sulfate anionic surfactant component
USH1478H (en) * 1993-09-30 1995-09-05 Shell Oil Company Secondary alkyl sulfate-containing liquid laundry detergent compositions
WO2002016541A1 (en) * 2000-08-25 2002-02-28 Reckitt Benckiser N.V. Water-soluble packages containing liquid compositions
WO2003010270A1 (en) * 2001-07-20 2003-02-06 Huntsman International Llc Phosphate suspensions
US20040162226A1 (en) * 2001-07-07 2004-08-19 Matthias Sunder Nonaqueous 3 in 1 dishwasher products
US20040167048A1 (en) * 2001-07-07 2004-08-26 Matthias Sunder Aqueous 3 in 1 dishwasher products
US20050075258A1 (en) * 2001-08-17 2005-04-07 Arnd Kessler Dishwasher detergent with improved protection against glass corrosion
US20080045441A1 (en) * 2004-09-17 2008-02-21 Henkel Kgaa Cleaning Agent Components
US20110092074A1 (en) * 2007-12-06 2011-04-21 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Texturing and cleaning agent for the surface treatment of wafers and use thereof
US9127235B2 (en) 2013-10-09 2015-09-08 Ecolab Usa Inc. Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control
US9487738B2 (en) 2013-10-09 2016-11-08 Ecolab Usa Inc. Solidification matrix comprising a carboxylic acid terpolymer

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DE2230452A1 (de) * 1972-06-22 1974-01-17 Benckiser Gmbh Joh A Grundstoffansatz fuer wasch- und reinigungsmittel
DE3035805A1 (de) * 1980-09-23 1982-05-06 Hoechst Ag, 6000 Frankfurt Verfahren zur herstellung von granulaten kondensierter phosphate
GB8813978D0 (en) * 1988-06-13 1988-07-20 Unilever Plc Liquid detergents
GB8821763D0 (en) * 1988-09-16 1988-10-19 Unilever Plc Liquid detergents
MX170188B (es) * 1989-02-10 1993-08-10 Ciba Geigy Agentes de lavado para el lavado posterior de materiales textiles en el estampado y teñido con colores reactivos
US5633223A (en) 1995-08-30 1997-05-27 Lever Brothers Company, Division Of Conopco, Inc. Heavy duty liquid compositions comprising structuring solids of defined dimension and morphology
GB2401371A (en) 2003-03-11 2004-11-10 Reckitt Benckiser Nv Water-soluble package containing phthalimidoperhexanoic acid detergent
US8021610B2 (en) 2006-09-07 2011-09-20 Biolargo Life Technologies, Inc. Systems providing antimicrobial activity to an environment
US9414601B2 (en) 2006-09-07 2016-08-16 Biolargo Life Technologies, Incorporated Material having antimicrobial activity when wet

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GB943271A (en) * 1960-10-18 1963-12-04 Unilever Ltd Liquid detergent compositions
US3591508A (en) * 1967-12-07 1971-07-06 Monsanto Co Process for making heavy duty liquid detergent compositions

Cited By (34)

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US3925224A (en) * 1973-04-17 1975-12-09 Church & Dwight Co Inc Detergent additive composition
US3931033A (en) * 1973-12-14 1976-01-06 Henkel & Cie G.M.B.H. Liquid foam-regulated nonionic detergent compositions
JPS5277111A (en) * 1975-12-23 1977-06-29 Kao Corp Detergent composition for bath room
US4316812A (en) * 1977-06-09 1982-02-23 Imperial Chemical Industries Limited Detergent composition
US4340509A (en) * 1978-03-24 1982-07-20 Michael A. Canale Composition, concentrate and fountain solution for lithographic printing operations
US4374036A (en) * 1980-04-16 1983-02-15 Michael A. Canale Composition and concentrate useful for making a fountain solution for lithographic printing operations
US4537708A (en) * 1983-08-30 1985-08-27 Fmc Corporation Homogeneous laundry detergent slurries containing nonionic surface-active agents
US5362413A (en) * 1984-03-23 1994-11-08 The Clorox Company Low-temperature-effective detergent compositions and delivery systems therefor
US4597889A (en) * 1984-08-30 1986-07-01 Fmc Corporation Homogeneous laundry detergent slurries containing polymeric acrylic stabilizers
US4836948A (en) * 1987-12-30 1989-06-06 Lever Brothers Company Viscoelastic gel detergent compositions
US5160448A (en) * 1987-12-30 1992-11-03 Lever Brothers Company, Division Of Conopco, Inc. Gel detergent compositions containing a clay and a cross-linked polycarboxylic polymer
US5047167A (en) * 1987-12-30 1991-09-10 Lever Brothers Company, Division Of Conopco, Inc. Clear viscoelastic detergent gel compositions containing alkyl polyglycosides
US5252242A (en) * 1989-05-18 1993-10-12 Colgate-Palmolive Co. Linear visoelastic aqueous liquid detergent composition, especially for automatic dishwashers, of improved high temperature stability
US5213706A (en) * 1991-11-08 1993-05-25 Lever Brothers Company, Division Of Conopco, Inc. Homogeneous detergent gel compositions for use in automatic dishwashers
USH1478H (en) * 1993-09-30 1995-09-05 Shell Oil Company Secondary alkyl sulfate-containing liquid laundry detergent compositions
USH1467H (en) * 1993-11-16 1995-08-01 Shell Oil Company Detergent formulations containing a surface active composition containing a nonionic surfactant component and a secondary alkyl sulfate anionic surfactant component
WO2002016541A1 (en) * 2000-08-25 2002-02-28 Reckitt Benckiser N.V. Water-soluble packages containing liquid compositions
US20050026806A1 (en) * 2000-08-25 2005-02-03 Roger Kaiser Water soluble packages containing liquid compsitions
US20050222005A2 (en) * 2000-08-25 2005-10-06 Reckitt Benckiser N.V. and Reckitt Benckiser (UK) Limited Water Soluble Packages Containing Liquid Compositions
US7271141B2 (en) 2000-08-25 2007-09-18 Reckitt Benckiser N.V. & Reckitt Benckiser (Uk) Limited Water soluble packages containing liquid compositions
US7192911B2 (en) 2001-07-07 2007-03-20 Henkel Kgaa Nonaqueous 3 in 1 dishwasher products
US20040162226A1 (en) * 2001-07-07 2004-08-19 Matthias Sunder Nonaqueous 3 in 1 dishwasher products
US20040167048A1 (en) * 2001-07-07 2004-08-26 Matthias Sunder Aqueous 3 in 1 dishwasher products
US7041628B2 (en) 2001-07-07 2006-05-09 Henkel Kommanditgesellschaft Auf Aktien Aqueous 3 in 1 dishwasher products
WO2003010270A1 (en) * 2001-07-20 2003-02-06 Huntsman International Llc Phosphate suspensions
US20050075258A1 (en) * 2001-08-17 2005-04-07 Arnd Kessler Dishwasher detergent with improved protection against glass corrosion
US7153816B2 (en) 2001-08-17 2006-12-26 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Dishwasher detergent with improved protection against glass corrosion
US20080045441A1 (en) * 2004-09-17 2008-02-21 Henkel Kgaa Cleaning Agent Components
US20110092074A1 (en) * 2007-12-06 2011-04-21 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Texturing and cleaning agent for the surface treatment of wafers and use thereof
US8900472B2 (en) * 2007-12-06 2014-12-02 Fraunhofer-Gesellschaft zur Föerderung der Angewandten Forschung E.V. Texturing and cleaning agent for the surface treatment of wafers and use thereof
US9127235B2 (en) 2013-10-09 2015-09-08 Ecolab Usa Inc. Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control
US9487738B2 (en) 2013-10-09 2016-11-08 Ecolab Usa Inc. Solidification matrix comprising a carboxylic acid terpolymer
US9840683B2 (en) 2013-10-09 2017-12-12 Basf Se Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control
US10364409B2 (en) 2013-10-09 2019-07-30 Ecolab Usa Inc. Solidification matrix comprising a carboxylic acid terpolymer

Also Published As

Publication number Publication date
DE2029598A1 (en, 2012) 1970-12-23
JPS526708B1 (en, 2012) 1977-02-24
GB1302543A (en, 2012) 1973-01-10
NL7008605A (en, 2012) 1970-12-21
FR2052646A5 (en, 2012) 1971-04-09
BE752030A (nl) 1970-12-16

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