CA1037816A - Liquid hydroxyalkyl iminodicarboxylate detergents - Google Patents
Liquid hydroxyalkyl iminodicarboxylate detergentsInfo
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- CA1037816A CA1037816A CA212,255A CA212255A CA1037816A CA 1037816 A CA1037816 A CA 1037816A CA 212255 A CA212255 A CA 212255A CA 1037816 A CA1037816 A CA 1037816A
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Abstract
A B S T R A C T
Non-phosphate liquid detergent compositions, include a mixture, in certain proportions, of an anionic and/or nonionic synthetic water soluble organic detergent and a hydroxyalkyl iminodicarboxylate builder salt in an aqueous solvent mixture at an alkaline pH. Preferred compositions contain an aqueous mixture of anionic and nonionic detergents, a hydrotrope, such as sodium xylene sulfonate, and disodium 2-hydroxyethyl iminodiacetate as a builder salt, and are made alkaline by an alkaline material such as sodium hydroxide. The liquids have detersive properties comparable or equivalent to those of phosphate detergents.
Non-phosphate liquid detergent compositions, include a mixture, in certain proportions, of an anionic and/or nonionic synthetic water soluble organic detergent and a hydroxyalkyl iminodicarboxylate builder salt in an aqueous solvent mixture at an alkaline pH. Preferred compositions contain an aqueous mixture of anionic and nonionic detergents, a hydrotrope, such as sodium xylene sulfonate, and disodium 2-hydroxyethyl iminodiacetate as a builder salt, and are made alkaline by an alkaline material such as sodium hydroxide. The liquids have detersive properties comparable or equivalent to those of phosphate detergents.
Description
~037~
This invention relates to liquid detergent compositions and more particularly, to detergent compositions devoid of phosphate builders. It is especially concerned with detergent compositions which are built with hydroxy-alkyl iminodicarboxylate salts and which have detersive actions comparable or equivalent to those of phosphate-built detergents.
Synthetic organic detergent compositions based on anionic and non-ionic organic detergents or surface active agents usually include a builder salt to improve detergency. Various phosphates, boron compounds, carbonates and silicates have been found to possess building properties and of these the phosphates, especially pentasodium tripolyphosphate, tetrasodium pyrophosphate and analogous polyphosphoric acid salts, were acknowledged to be far superior.
However due to opinions that phosphates in detergents contribute to eutrophi-cation of inland waters, causing excessive algae growth, and because of govern-ment regulations, efforts have been made to produce non-phosphate detergents including builders other than polyphosphate or pyrophosphate salts. One such substitute, trisodium nitrilotriacetate (NTA) is not being used in the United States because of an indication in some test results that it would, under certain circumstances, be carcinogenic.
When iminodicarboxylate salts are tested as builders for detergent compositions containing organic anionic and/or nonionic detergents, there were discoyered formulations with detersive actions approaching those of phosphate-built detergcnts. Several such formulations, equivalent in deter-sive actions to phosphate-built detergents, are disclosed in the coassigned applications of Francis R. Cala, filed concurrently with the present Canadian application, entitled "Particulate Hydroxyalkyl Iminodicarboxylate Detergent Compositions", "Particulate Silicate-Hydroxyalkyl Iminodiacetate Built Deter- ;;~
gent Compositions of Improved Properties", and "Manufacture of Improved Aqueous Alkali Metal Silicate-Alkali Metal Hydroxyalkyl Iminodiacetate Compositions", and bearing serial numbers 212,301; 212,349 and 212256, respectively. These applications, however, relate to solid detergent formulations and do not ~ -describe or teach stable liquid detergent compositions built with hydroxy-y '`. ~
- 1 - ` : : ` ' alkyl iminodicarboxylate salts.
In accordance with the present invention a built liquid detergent comparable or equivalent in detersive action to phosphate-built detergent comprises about 5 to 50% by weight of a water soluble synthetic organic deter-gent selected from the group consisting of anionic detergent salts, nonionic detergents, and mixtures thereof, about 2.5% to 20% by weight of a hydroxy-alkyl i~inodicarboxylate builder salt and about 30 to 90% by weight of an aqueous solvent medium at an alkaline pH. Preferably, the liquid detergent compositions of the invention have a pH above about 8.
In particular preferred embodiments of the invention the liquid detergent composition can contain about 3 to 10%, especially about 4.0 to -8,0% by weight, of an alkali metal silicate as an additional builder, about 4 to 20%, especially 5 to 15%, of a foam stabilizing agent and about 0.1 to 20%, especially 5 to 15% of a saturated lower aliphatic alcohol, as an addi-tional solvent. The liquid detergent compositions of the invention more pref- `
erably contain about 10 to 25% of the synthetic organic water soluble deter-gent, about 5 to 18% of the hydroxyalkyl iminodicarboxylate and about 50 to `-75%, especially about 60 to ?0% of aqueous solvent medium.
m e liquid detergents of the invention also preferably include about ;~
3 to 15%, especially about 5 to 8.0%, of an organic hydrotrope, w ually of the type known for this purpose in commercial liquid detergent formulations.
They may contain about 0.1 to 15% of an alkaline agent, such a~ a water solu-ble organic or inorganic base, which may be partly consumed upon admLxing to adjw t the liquid detergent~s pH. A preferred range is 0.1 to 1,5%.
In accordance with a preferred embodiment of the invention the water soluble synthetic organic detergent constituent is a mixture of nonionic and anionic detergents in a weight ratio of about 5:1 to 1:5, more preferably about 3:1 to 1:5 and especially of about 1:4.
In accordance with conventional detergent formulation the composi-tion of the invention can contain minor adjuvants, such as perfumes, optical
This invention relates to liquid detergent compositions and more particularly, to detergent compositions devoid of phosphate builders. It is especially concerned with detergent compositions which are built with hydroxy-alkyl iminodicarboxylate salts and which have detersive actions comparable or equivalent to those of phosphate-built detergents.
Synthetic organic detergent compositions based on anionic and non-ionic organic detergents or surface active agents usually include a builder salt to improve detergency. Various phosphates, boron compounds, carbonates and silicates have been found to possess building properties and of these the phosphates, especially pentasodium tripolyphosphate, tetrasodium pyrophosphate and analogous polyphosphoric acid salts, were acknowledged to be far superior.
However due to opinions that phosphates in detergents contribute to eutrophi-cation of inland waters, causing excessive algae growth, and because of govern-ment regulations, efforts have been made to produce non-phosphate detergents including builders other than polyphosphate or pyrophosphate salts. One such substitute, trisodium nitrilotriacetate (NTA) is not being used in the United States because of an indication in some test results that it would, under certain circumstances, be carcinogenic.
When iminodicarboxylate salts are tested as builders for detergent compositions containing organic anionic and/or nonionic detergents, there were discoyered formulations with detersive actions approaching those of phosphate-built detergcnts. Several such formulations, equivalent in deter-sive actions to phosphate-built detergents, are disclosed in the coassigned applications of Francis R. Cala, filed concurrently with the present Canadian application, entitled "Particulate Hydroxyalkyl Iminodicarboxylate Detergent Compositions", "Particulate Silicate-Hydroxyalkyl Iminodiacetate Built Deter- ;;~
gent Compositions of Improved Properties", and "Manufacture of Improved Aqueous Alkali Metal Silicate-Alkali Metal Hydroxyalkyl Iminodiacetate Compositions", and bearing serial numbers 212,301; 212,349 and 212256, respectively. These applications, however, relate to solid detergent formulations and do not ~ -describe or teach stable liquid detergent compositions built with hydroxy-y '`. ~
- 1 - ` : : ` ' alkyl iminodicarboxylate salts.
In accordance with the present invention a built liquid detergent comparable or equivalent in detersive action to phosphate-built detergent comprises about 5 to 50% by weight of a water soluble synthetic organic deter-gent selected from the group consisting of anionic detergent salts, nonionic detergents, and mixtures thereof, about 2.5% to 20% by weight of a hydroxy-alkyl i~inodicarboxylate builder salt and about 30 to 90% by weight of an aqueous solvent medium at an alkaline pH. Preferably, the liquid detergent compositions of the invention have a pH above about 8.
In particular preferred embodiments of the invention the liquid detergent composition can contain about 3 to 10%, especially about 4.0 to -8,0% by weight, of an alkali metal silicate as an additional builder, about 4 to 20%, especially 5 to 15%, of a foam stabilizing agent and about 0.1 to 20%, especially 5 to 15% of a saturated lower aliphatic alcohol, as an addi-tional solvent. The liquid detergent compositions of the invention more pref- `
erably contain about 10 to 25% of the synthetic organic water soluble deter-gent, about 5 to 18% of the hydroxyalkyl iminodicarboxylate and about 50 to `-75%, especially about 60 to ?0% of aqueous solvent medium.
m e liquid detergents of the invention also preferably include about ;~
3 to 15%, especially about 5 to 8.0%, of an organic hydrotrope, w ually of the type known for this purpose in commercial liquid detergent formulations.
They may contain about 0.1 to 15% of an alkaline agent, such a~ a water solu-ble organic or inorganic base, which may be partly consumed upon admLxing to adjw t the liquid detergent~s pH. A preferred range is 0.1 to 1,5%.
In accordance with a preferred embodiment of the invention the water soluble synthetic organic detergent constituent is a mixture of nonionic and anionic detergents in a weight ratio of about 5:1 to 1:5, more preferably about 3:1 to 1:5 and especially of about 1:4.
In accordance with conventional detergent formulation the composi-tion of the invention can contain minor adjuvants, such as perfumes, optical
-2-brighteners, colorants and the like, which may be present in amounts up to 10% by weight but are preferably limited to a total concentration no greater than about 5% by weight of the liquid detergent product, The detergent composition of this invention includes as a primary detersive constituent a water soluble synthetic organic detergent selected from the group consisting of anionic detergent salts, nonionic detergents and mixtures thereof. Preferably the anionic detergent constituents of the in-vention are selected from organic sulfate and sulfonate salts, many of which are described in McCutcheon~s Deter~ents and Enulsifiers 1969 Annual, wherein such compounds are listed by chemical formulas and trade names. Additional suitable sulfonate and sulfate compounds are also described in the test Surface Active A~ents and Deter~ents, Vol. II, by Schwartz, Perry and Berch (Interscience Publishers, 1958). In short, such materials include hydro- -philic and lipophilic groups, the lipophilic portions whereof normally con- ; -tain a higher hydrocarbyl chain, usually of 10 to 20 carbon atoms and the hydrophilic portions of which include a salt-fonming cation, preferably of an ~ ~ ~
aIkali metal salt. Most of such acceptable detergents are sulfates or sul- ~ ~ -fonates but corresponding phosphates, phosphonates and other suitable deter-gent salts are also useful. Included among the anionic detergents, for exam-ple, are the linear higher alkyl aryl sulfonates, for example, alkyl benzene sulfonates of 10 to 20 carbons in the alkyl substituents; the higher branched ~ -alkyl aryl sulfonates (although these are not usually sufficiently biodegrad- -able to be ecologically desirable for dern detergent formulations); the higher fatty alkyl sulfates; the higher fatty acid monoglyceride sulfates;
the higher olefin sulfonate~, for example, alpha-olefin sulfonates of 10 to 20 carbon atomg; the higher alkyl sulfonateg; the sulfated aryloxy poly-lower ~ ~
alkoxy lower alkanols, for example, sulfated phenoxy polyethoxyethanol; the ~ - ;
sulfated derivatives of higher alkyl poly-lower alkoxy alkanols, such as are obtained by condensing a C10-C18 alCohol with a C2-C4 alkylene oxide, suCh as ethylene oxide, propylene oxide, butylene oxide; paraffin sulfonates; and the
aIkali metal salt. Most of such acceptable detergents are sulfates or sul- ~ ~ -fonates but corresponding phosphates, phosphonates and other suitable deter-gent salts are also useful. Included among the anionic detergents, for exam-ple, are the linear higher alkyl aryl sulfonates, for example, alkyl benzene sulfonates of 10 to 20 carbons in the alkyl substituents; the higher branched ~ -alkyl aryl sulfonates (although these are not usually sufficiently biodegrad- -able to be ecologically desirable for dern detergent formulations); the higher fatty alkyl sulfates; the higher fatty acid monoglyceride sulfates;
the higher olefin sulfonate~, for example, alpha-olefin sulfonates of 10 to 20 carbon atomg; the higher alkyl sulfonateg; the sulfated aryloxy poly-lower ~ ~
alkoxy lower alkanols, for example, sulfated phenoxy polyethoxyethanol; the ~ - ;
sulfated derivatives of higher alkyl poly-lower alkoxy alkanols, such as are obtained by condensing a C10-C18 alCohol with a C2-C4 alkylene oxide, suCh as ethylene oxide, propylene oxide, butylene oxide; paraffin sulfonates; and the
-3--, . . . ~ . :
~0378~6 corresponding phosphates and phosphonates. The hydrocarbyls, alkyls and higher fatty acid groups of such compounds will preferably be of 12 to 18 carbon atoms and the salt-forming ions thereof will preferably be alkali metal cations, e.g., sodium, potassium, although salt-forming cations derived from lower aIkylamines and lower alkanolamines can be used also, e.g., cations ~ -from alkylamines and alkanolamines of 1 to 4 carbon atoms, for example, di-n- -propylamine, triethylamine, methylamine, isopropanolamine, t-butylamine, di-isopropanolamine, ethanolamine, diethanol~mine and triethanolamine.
Specific exemplifications of such compounds include sodium linear tridecyl benzene sulfonate; mixed sodium and potassium dodecyl benzene sul-fonates; triethanolamine lauryl sulfate; sodium coconut oil fatty acids mono-glyceride sulfate; potassium tallow sulfate; potassium myristyl triethoxy sul-fate; n-decyl diethoxy sulfate, diethanolamine salt; potassium lauryl diethoxy sulfate; ammonium palmityl tetraethoxy sulfate, godium salt; mixed C14-C15 aIkyl; mixed tri- and tetraethaxy sulfate; stearyl pentaethoxy sulfate, tri-methylaDine salt; and mixed ClO_Cl~ primary alkyl triethoxy sulfate. Other ~-anioniC detergents may be made by sulfating or sulfonating the nonionic deter-gents of the class to be described subsequently. Preferably the higher alkyl substituents of the foregoing '~nixed" higher aIkyl polyalkoxy alkanol sulfates and aIkyl benzene sulfonates are linear, i.e., contain no more than 10 mole percent of branched chain isomers, so as to provide a detergent composition of especially good biodegradability and detersive action. Preferred anionic detergents of the invention are higher alpha-olefin sulfonates, linear higher alkyl benzene sulfonates and higher linear alkyl poly-lower alkoxy alkanol sulfates wherein alkoxy gro~ps are derived fram ethylene glycol or ethylene axide, i.e., the salt is a linear higher aIkyl polyethoxy ethanol sulfate.
Among the more preferred anionic detergents are the higher linear aIkyl poly-ethoxy ethanol sulfates corresponding to the structural formula RlO(C2H40)3S03M
wherein Rl is the residue of a linear primary alcohol of 12 to 15 carbon atoms .
- - : : -~ : ,. . .
10;~78~6 ::
and M is a salt-forning cation. Preferably M is sodium or potassium but other solubilizing metal ions or organic radicals may also be used. m e especially preferred anionic salt detergent of the above structural fornula is exempli-fied in Neodol(trademark) 25-3S, a mixture of the sulfated derivatives of triethoxylated linear primary C12, C13, C14 and C15 alcohols~ which is manu-factured by Shell Chemical Company. -m e nonionic synthetic organic detergents which can be employed as ~ -constituents of the present liquid detergent composition include higher alkyl ~ ~ ~
polyalkoxy alkanols, i.e., the condensation products of C10-C20, alCohols ~ -with lower (C2-C4) alkylene oxides, e.g., ethylene oxide or propylene oxide, and/or lower alkylene glyCols, e.g., ethylene glycol, butylene glycol, as exemplified by Neodol(trademark) 45-11 (manufactured by Shell Chemical Co.), PlurafaC(trademark) B-26 (manufactured by Wyandotte Chemicals Corporation) ~-~
and Alfonic(trademark) 1618-65 (manufactured by Continental Oil Co.) In general the molar ratio of alkylene oxide or glyCol residue to higher alkanol residue in theæe condensates is about 6 to 20, especially about 8 to 13, and the condensates are liquid or semi-solid at room temperature in those ranges. ~ -Also useful are the block copolymers of propylene glycol propylene ;
oxide ethylene oxide such as the Pluronics(trademark), e.g., Pluronic(trade-mard) L-44 and Pluronic(trademark) F-68 (manufactured by Wyandotte Chemicals Corporation) and the middle alkyl phenyl polyethoxy ethanols such as those sold as Igepals(trademark) (GAF Corporation).
Preferred nonionic detergents employed in the inventi are higher alkyl polyalkoxy alkanols which are derived from linear higher aliphatic alcohols. Preferably also, Ithe alkoxy group of the higher alkyl polyalkoxy alkanol is ethoxy, i.e., the nonionic detergent is a higher alkyl polyethoxy etbanol. An especially good result is obtained employing a linear higher alkyl polyethoxy ethanol corresponding to the structural formula RO(C2H40) 30 wherein R is a linear alkyl group of 12 to 15 or 18 carbon atoms and n is an _5_ , .. ~;
. .
integer from 9 to 13. However, the lower alkylene oxide or glycol condensa-tion product nonionics of molecular weights from 200 to 5,000, with lower alkylene oxide chains of 5 to 50 units and alkylene oxide contents of 20 to 75% are useful components of the liquid detergents.
The iminodicarboxylate builder salts of this invention are water soluble hydroxyalkyl iminodicarboxylates wherein the carboxylates, i.e., the alkanoate residues, are of 2 to 4 carbon atoms, preferably of 2 to 3 carbon atoms and most preferably are of 2 carbon atoms, i.e., are acetate residues.
In these compounds the alkanoate residue is attached to an imino nitrogen atom at the carbon atom which is alpha to the carboxylate group.
The hydroxyalkyl group of the hydroxyalkyl iminodicarboxylate salts ~ ~ -is hydroxy-lower alkyl wherein the aIkyl is of 2 to 4 carbon atoms, and although the hydroxy groups need not be tenminal for best effects this posi-tioning is favored. Preferably, the hydroxy-lower alkyl group is hydroxyethyl.
The hydroxyalkyl iminodicarboxylates are found to be excellent builders for liquid synthetic organic detergents and have desirable sequester-ing effects against water hardness ions, such as calcium and magnesium which might otherwise interfere with the washing action of the detergent. The hydroxyaIkyl iminodicarboxylates employed are preferably dialkali metal salts, for example, the dipotas~ium and disodium salts. If desired, however, water soluble hydroxyalkyl iminodicarboxylate salts of other cations can be employed.
For example am~onium, the no-, di- and tri-alkyl ammonium and the mono-, di- `--and tri-alkanol ammonium wherein the alkyl and the aIkanol groups are lower, -~
i.e., of 1 to 4 carbon atoms, preferably of 1 to 3 carbon atoms and most pref-erably of 2 carbon atoms, a~e also useful. Examples of such materials include di-triethano~amine 2-hydroxypropyl iminodi-alpha-propionate; di-tributylamine
~0378~6 corresponding phosphates and phosphonates. The hydrocarbyls, alkyls and higher fatty acid groups of such compounds will preferably be of 12 to 18 carbon atoms and the salt-forming ions thereof will preferably be alkali metal cations, e.g., sodium, potassium, although salt-forming cations derived from lower aIkylamines and lower alkanolamines can be used also, e.g., cations ~ -from alkylamines and alkanolamines of 1 to 4 carbon atoms, for example, di-n- -propylamine, triethylamine, methylamine, isopropanolamine, t-butylamine, di-isopropanolamine, ethanolamine, diethanol~mine and triethanolamine.
Specific exemplifications of such compounds include sodium linear tridecyl benzene sulfonate; mixed sodium and potassium dodecyl benzene sul-fonates; triethanolamine lauryl sulfate; sodium coconut oil fatty acids mono-glyceride sulfate; potassium tallow sulfate; potassium myristyl triethoxy sul-fate; n-decyl diethoxy sulfate, diethanolamine salt; potassium lauryl diethoxy sulfate; ammonium palmityl tetraethoxy sulfate, godium salt; mixed C14-C15 aIkyl; mixed tri- and tetraethaxy sulfate; stearyl pentaethoxy sulfate, tri-methylaDine salt; and mixed ClO_Cl~ primary alkyl triethoxy sulfate. Other ~-anioniC detergents may be made by sulfating or sulfonating the nonionic deter-gents of the class to be described subsequently. Preferably the higher alkyl substituents of the foregoing '~nixed" higher aIkyl polyalkoxy alkanol sulfates and aIkyl benzene sulfonates are linear, i.e., contain no more than 10 mole percent of branched chain isomers, so as to provide a detergent composition of especially good biodegradability and detersive action. Preferred anionic detergents of the invention are higher alpha-olefin sulfonates, linear higher alkyl benzene sulfonates and higher linear alkyl poly-lower alkoxy alkanol sulfates wherein alkoxy gro~ps are derived fram ethylene glycol or ethylene axide, i.e., the salt is a linear higher aIkyl polyethoxy ethanol sulfate.
Among the more preferred anionic detergents are the higher linear aIkyl poly-ethoxy ethanol sulfates corresponding to the structural formula RlO(C2H40)3S03M
wherein Rl is the residue of a linear primary alcohol of 12 to 15 carbon atoms .
- - : : -~ : ,. . .
10;~78~6 ::
and M is a salt-forning cation. Preferably M is sodium or potassium but other solubilizing metal ions or organic radicals may also be used. m e especially preferred anionic salt detergent of the above structural fornula is exempli-fied in Neodol(trademark) 25-3S, a mixture of the sulfated derivatives of triethoxylated linear primary C12, C13, C14 and C15 alcohols~ which is manu-factured by Shell Chemical Company. -m e nonionic synthetic organic detergents which can be employed as ~ -constituents of the present liquid detergent composition include higher alkyl ~ ~ ~
polyalkoxy alkanols, i.e., the condensation products of C10-C20, alCohols ~ -with lower (C2-C4) alkylene oxides, e.g., ethylene oxide or propylene oxide, and/or lower alkylene glyCols, e.g., ethylene glycol, butylene glycol, as exemplified by Neodol(trademark) 45-11 (manufactured by Shell Chemical Co.), PlurafaC(trademark) B-26 (manufactured by Wyandotte Chemicals Corporation) ~-~
and Alfonic(trademark) 1618-65 (manufactured by Continental Oil Co.) In general the molar ratio of alkylene oxide or glyCol residue to higher alkanol residue in theæe condensates is about 6 to 20, especially about 8 to 13, and the condensates are liquid or semi-solid at room temperature in those ranges. ~ -Also useful are the block copolymers of propylene glycol propylene ;
oxide ethylene oxide such as the Pluronics(trademark), e.g., Pluronic(trade-mard) L-44 and Pluronic(trademark) F-68 (manufactured by Wyandotte Chemicals Corporation) and the middle alkyl phenyl polyethoxy ethanols such as those sold as Igepals(trademark) (GAF Corporation).
Preferred nonionic detergents employed in the inventi are higher alkyl polyalkoxy alkanols which are derived from linear higher aliphatic alcohols. Preferably also, Ithe alkoxy group of the higher alkyl polyalkoxy alkanol is ethoxy, i.e., the nonionic detergent is a higher alkyl polyethoxy etbanol. An especially good result is obtained employing a linear higher alkyl polyethoxy ethanol corresponding to the structural formula RO(C2H40) 30 wherein R is a linear alkyl group of 12 to 15 or 18 carbon atoms and n is an _5_ , .. ~;
. .
integer from 9 to 13. However, the lower alkylene oxide or glycol condensa-tion product nonionics of molecular weights from 200 to 5,000, with lower alkylene oxide chains of 5 to 50 units and alkylene oxide contents of 20 to 75% are useful components of the liquid detergents.
The iminodicarboxylate builder salts of this invention are water soluble hydroxyalkyl iminodicarboxylates wherein the carboxylates, i.e., the alkanoate residues, are of 2 to 4 carbon atoms, preferably of 2 to 3 carbon atoms and most preferably are of 2 carbon atoms, i.e., are acetate residues.
In these compounds the alkanoate residue is attached to an imino nitrogen atom at the carbon atom which is alpha to the carboxylate group.
The hydroxyalkyl group of the hydroxyalkyl iminodicarboxylate salts ~ ~ -is hydroxy-lower alkyl wherein the aIkyl is of 2 to 4 carbon atoms, and although the hydroxy groups need not be tenminal for best effects this posi-tioning is favored. Preferably, the hydroxy-lower alkyl group is hydroxyethyl.
The hydroxyalkyl iminodicarboxylates are found to be excellent builders for liquid synthetic organic detergents and have desirable sequester-ing effects against water hardness ions, such as calcium and magnesium which might otherwise interfere with the washing action of the detergent. The hydroxyaIkyl iminodicarboxylates employed are preferably dialkali metal salts, for example, the dipotas~ium and disodium salts. If desired, however, water soluble hydroxyalkyl iminodicarboxylate salts of other cations can be employed.
For example am~onium, the no-, di- and tri-alkyl ammonium and the mono-, di- `--and tri-alkanol ammonium wherein the alkyl and the aIkanol groups are lower, -~
i.e., of 1 to 4 carbon atoms, preferably of 1 to 3 carbon atoms and most pref-erably of 2 carbon atoms, a~e also useful. Examples of such materials include di-triethano~amine 2-hydroxypropyl iminodi-alpha-propionate; di-tributylamine
4-bydroxybutyl iminodiacetate; di-monoisopropanolamine hydroxyethyl iminodi-acetate and di-trimethylamine hydroxyethyl iminodiacetate.
The present builder salts, hydroxyalkyl iminodicarboxylate salts, such as disodium 2-hydroxyethyl iminodiacetate, are usually available commer-`:
-6- ~ ~ .
.. ~ . ~ - ' ' ' ,. ~ .
cially as 50 to 53 weight percent aqueous solution9 of 9uch elevated pH, i.e., 12 to 13.7, as to produce aIkaline liquid detergent compositions, i.eO, deter-gent c~mpositions having a pH above 7 and generally in excess of 8, when the builder salt is admixed with the other components of the present invention.
However, to insure obtaining an alkaline detergent composition, it is advan-tageous to incorporate from about 0.4 to 15%, preferably about 0.4 to 1.5%
of water soluble base into the present composition. The base is preferably water soluble inorganic base such as an alkali metal hydroxide or carbonate, ~ -e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, potassium 10 carbonate, or an organic no-, di- or tri-lower alkyl or lower alkanol amine., ., ~ , .... .... ... .
of the type exemplified above. Especially preferred as alkaline agents are sodium hydroxide, potassium hydroxide and triethanolamine. Sodium hydroxide is rated best for these alkalizing steps.
The organic hydrotrope which is preferably incorporated in the liquid detergent composition not only aids in maintaining a high concentra-tion of the 2-hydroxyalkyl iminodicarboxylate builder salt in solution and but also acts to solubilize any anionic detergent constituent so ag to facil-itate obtainment of a concentrated detergent liquid. The hydrotrope also helps to prevent settling out of the silicate constituent either ag an insolu-20 ble precipitate or as a separate liquid phase. Additionally the hydrotrope assists in maintaining in solution various adjuvant materials of comparatively low solubilities, e.g., optical brighteners.
The organic hydrotropes utilized in the invention are preferably salts of aryl sulfonic acids, especially benzene sulfonic acids, wherein tbe benzene nucleug may be unsu~stituted or substituted with lower aIkyl group(s), i.e., Cl to C4 alkyl group(s), preferably methyl, ethyl or isopropyl groups. ~~
Up to 3 such substituents may be p m ent on the benzene nucleus but none, one or two are preferred. The salt-fonming cation of the hydrotrope is prefer- x ~ :
ably aIkali netal, such as sodium or potassium. However, any of the water 30 soluble cations exemplified above in connection with descriptions of the an- --. : .
_7_ ~037816 ionic detergent and builder salts, such as ammonium, mono-, di- and tri-lower alkyl- and -lower alkanolammonium can be used in place of the alkali metal cations, Typical illustrative examples of suitable hydrotropes include sodium benzene sulfonate, potassium toluene sulfonate, ammonium xylene sulfonate and monoisopropanolammonium cumene sulfonate. The xylene sulfonate salts, especially the alkali metal salts thereof, e.g., the potassium salt, provide especially good results. ~-The solvent medium for the present liquid detergent composition is an aqueous one and may be water alone or may be substantially water with additional solvents added to solubilize particular ingredients. Because of ; -the availability of water and its minimum cost, it is preferred to use it as the sole solvent present. Yet, amounts of other solvents, usually in propor-tions from about 0.1 to 20%, preferably about S to 15% of the liquid detergent composition, may be present. Generally, such a supplemental solvent is a . . .
lower aliphatic alcohol (including both monohydric and polyhydric alcohols, ~ -such as diols and triols, as well as ether alcohols and polyols) e.g., methan-ol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, propylene ~lycol, glycerol, diethylene glycol and the like. Preferably the alcoholic sol~ent is ethanol.
The water utilized in preparing the present liquid detergent may be deionized but in general tap water can be used. This is so because any low or medium degree of hardness in the water will generally be overcome by the strong sequestering action of the hydroxyalkyl iminodicarboxylate builder salt. Very hard waters, however, are desirably avoided in practice and de-ionized waters of low or me~ium hardness are employed instead.
The aIkali metal silicate, which is an optional but preferred com, ponent of the present liquid detergent camposition, functions as a supplemen-tal builder, increasing the desirable effects of the hydroxyalkyl iminodi-carboxylate builder salt on the synthetic organic detergent. The silicate is an alkaline material which also acts as an anticorrosion or protective addi-,:
. . .
tive. The silicate constituent is particularly helpful in removine particu-late soil from the laundry and in preventing harm to ceramic, porcelain, vit-reous, aluminum and steel parts of washing machines, similar equipment and laundered items.
Although various alkali metal silicates, such as sodium and potas-sium silicates, may be used, those which are most effective and which are also readily available are those wherein the molar ratio of aIkali metal oxide to silica, e.g., Na20:SiO2; K20:SiO2, are within the range of about 1:1.5 to 1:2,5. Particularly useful are sodium silicates wherein the sodium oxide to silica ratio is about 1:1.6 to 1:2.4. Of these the more alkaline 1:1.6 ratio silicate is advantageous because of its greater alkalizing, neutralizing and solubilizing abilities. It will often be highly desirable to adjust the final Na20:SiO2 ratio, for example, to about 1:2.0 which is very effective and convenient, by utilizing a mixture of about equal proportions of the readily available sodium silicates having Na20:SiO2 ratios of 1:1.6 and 1:2.35.
According to another embodiment of the invention the liquid deter-gent conposition may also contain a conventional foam stabilizine agent. Gen-erally, such a foam stabilizer is a lower hydroxyalkyl or alkyl higher ali-phatic (preferably aIkyl or poly-lower alkoxy) amine oxide, e.g., those manu-factured under the trademark Aromax by Armour Industrial Chemical Co., andtypically represented by Aromox(trademark) T/12, a bis(2-hydroxyethyl) tallow amine oxide. m e di-lower alkyl higher alkyl amine oxides such as dimethyl ~ ;
lauryl amine axide and diethyl stearyl amine oxide are also very useful.
Lower alkanolamides may also be employed.
Various other optlional minor conventional adjuvants may be present in the liquid detergent ccmposition to give it additional desired properties, either of functional or aesthetic Datures. Of these minor adjuvants, perhaps the mogt important functi~nally are the optical brighteners, which include a variety of structural types, selectively substantive to different textiles and fabrics. Cotton brighteners include, for example, the reaction product .. .
_g_ :
: ... . . . . . . ..
of cyanuric chloride and disodium diaminostilbene disulfonate. Brighteners for polyamides are generally either aminocoumarin or diphenyl pyrazoline derivatives. Polyester brighteners, which are also useful on polyamide fabrics, include naphthotriazolyl stilbene derivatives. Additionally, bright-eners having stability to bleach are important and such compounds are usually benzidine sulfone disulfonic acid derivatives, naphthotrizolyl stilbene sul-fonic acids and benzimidazoyl derivatives. The brighteners are normally charged as their water soluble salts, usually as their alkali metal salts or equivalent lower alkanola~ine salts. Typical proprietary optical brighteners include those sold under the trademarks Calcofluor White ALF (manufactured by American Cyanamid); ALF-N (AmeriCan Cyanamid); SOF-A2001 (CIBA); Uvitex 3257 (CIBA); CWD (Hilton Davis); Phorwite RKH (Verona), Phorwite BHC (Verona);
CSL powder, acid (AmeriCan Cyanamid); CSL, liquid, monoethanolamine salt, -;
(AmeriCan Cyanamid); FB 766 (Verona); BlanCophor PD (GAF); UNPA (Geigy);
Tinopal RBS (Geigy); and Tinopal RBS 200 (Geigy). Other typical optical brighteners are illustrated and discussed by P.S. Stensby in the article ODtical Bri~hteners and Their Evaluation, a reprint of articles published in Soap and Chemical Specialties in April, May, July, August and Sept~mber, 1967.
Normally, the optical brightener concentration is about 0.1 to 2%, especially .~., : .
about 0.2 to 1%.
In addition to optical brighteners other optional minor adjuvants include colorants, generally water soluble dyestuffs and/or water-dispersible organic pigments; foam regulating or inhibiting agents, e.g., water soluble saturated higher fatty acid soaps, normally incorporated at a concentration of 0.5 to 5%, especially 1 ~o 2%; foam destroyers, such as silicones; enzymes, e.g., proteases, amylases; anti-redeposition or soil suspending agents, e.g., polyvinyl alcohol, sodium carboxynethyl cellulosej hydroxynethyl cellulose;
bactericides, e.g., tetrachlorosalicylanilide, hexachlorophene, trichloro-carbanilide; fabric softeners, e.g., ethoxylated lanolin, higher fatty acid soaps, thickeners, e.g., starches, gums, alginates, cellulose derivatives;
- .. ~ ., .
. . r 10378~6 :
pearlescing agents; opacifying agents, e.g., behenic acid, polystyrene sus-pensions, castor wax; buffering agents, e.g., aIkali metal borates, acetates, bisulfates; supplementary inorganic builder salts, e.g., borax; and perfumes.
The liquid phosphate-free detergents of the invention can be made by comparatively simple manufacturing procedures. In a typical method the water soluble synthetic organic detergent is blended with water which may contain in solution any hydrotrope charged. To the mixture is charged any dyestuff to be added, preferably in the foam of an aqueous solution or emul-sion. The iminodicarboxylate salt is then added, also conveniently in aqueous solution. On completion of the addition of the builder salt, any remaining water for the formulation is added and the mass is thoroughly stirred. The resultant product may be filtered through a suitable filter medium such as glass wool, paper or cloth, preferably using a mechanical filter, to obtain the detergent as a clear liquid, Of course pearlescing agents, suspensions and emulsifiers may then be added if a cloudy or opaque product is wanted.
When optical brighteners or other adjuvants are to be incorporated, aqueous solutions thereof may be added before the addition of the remaining water.
If desirable, some of the water may be utilized to suspend such materials or --dissolve them before addition.
If an alkali metal silicate is to be incorporated in the liguid detergent composition, so as to prevent unsightly silica precipitates the hydroxyalkyl i~inodicarboxylate-containing agueous solution is desirably admixed at a pH above 12, preferably at 12.5 to 13.5, with the aqueous alkali metal silicate, preferably at a moderately elevated temperature, e.g., about 55 to 80 C. ~11 or a portilon of the alkaline additive may be utilized to adjust the pH of the builder salt solution to above 12, before the mixing ~ith silicate. Preparation of precipitate-free iminodicarboxylate salt-aIkali metal silicate agueous golutions may be carried out in accord with the tech-nigue described in the aforementioned coagsigned application of Francis R.
Cala entitled (ManufaCture of Improved Aqueous Alkali Metal Hydroxyalkyl --11-- ' ' ' '-,. . .
;, , ., ~
Iminodiacetate Compositions", which is incorporated herein by reference, Other than the above described moderate heating used in preparing precipitate free-mixtures of the organic builders and aIkali metal silicate solutions, preparation of the present liquid detergent compositions can be effected at room temperature. If desired however, the mixing of the other constituents can be carried out at other suitable temperatures, usually with-in a range of 10 to 90C., preferably 20 to 60C.
The pH of the resultant liquid detergent produCt is preferably above about 8 and is rarely above 12, preferably being from 9 to 11, most preferably 9.5 to 10.5.
The product is a clear sparkling liquid (in the absence of any intentional addition of opacifying agents) which maintains its homogeneity a~
a ~ingle phase system on long term storage. When utilized to launder cloth-ing in conventional manner, in an automatic washing machine, it provides com- p parable to equivalent soil and dirt removal when compared to a tripolyphos- -phate-built liquid detergent.
The amount of the present liquid detergent which is used in the wash water will, of course, vary samewhat, depending on the type of washing eguipment used. In general however, only a relatively small amount of the liquid detergent, amounting to about 1/4 to 1/2 cup, is needed for a fuIl tub of wash (4 to 15 lbs,), using either a top loading (vertical axis, agita-tor type) or front loading (horizontal tumbling drum type) washing machine, in which the water volume is from 5 to 20 gallons, usually from 15 to 18 gallons. Normally, only about 1/8 to 1/4 cup of the present liquid detergent product is employed for thelfront loading machines.
The liguid detergent composition of this invention is highly effec-tive in washing clothes, even in very hard waters (over 150 p.p.m. hardness, as CaC03, but preferably a moderately soft water is used, with a hardness less than lSO p.p.m., preferably of 25 to 100 p.p.m. While the washing temperature employed with the present produCt can range from 10 to 90C., preferably it .
is from about 20 to 70C. The washing is followed by rinsing and spinning or other draining or wringing cycles or operations which are preferably auto-matic. Of course, the present liquid detergent may also be used for manual washing of laundry. In such instances it may be used full strength on certain stains or heavy soils or the laundry may be soaked in a higher concentration solution of the detergent prior to normal machine washing. The washing opera-tions will generally take from three minutes to one hour, depending on the fabrics being washed and the degrees of soiling of the clothing. After com-pletion of the washing and the spinning, draining or wringing operations it -is preferred to dry the laundry in an automatic dryer soon thereafter but -... . . . .. .
line drying may also be employed. A fabric softener rinse may be interposed between washing and drying or at other suitable stage in the laundering or drying processes.
The present product dissolves very easily in the wash water, whether ~`
that water is warm or cold, and very effectively cleans clothing and other items of laundry. It may be used in either top or front loading washing ~ -machines and may be desirably adjusted to foam to the correct extent. It is an attractive clear, stable liquid which maintains its activity and homogen-eity over a long shelf life. It is convenient to store, non-dusting and non-caking of course, and very easy to measure out. In tests in which it is com-pared to conventional commercial laundry detergents, it is rated very favor-ably. This is an especially significant accomplishment when it is considered that the composition is free of phosphate and nitrilotriacetate builders and -hence requires no special treatment before disposal into ordinary drains and sewers. It is often prefer~ed for convenience of use and excellent detergency i9 observed. Yet, even if the results of washing with this product were not `~
as epod as those obtained with commercial products loaded with polyphosphates, the importance of the development of this nanti-pollution" detergent would be a significant enough advantage to warrant its replacing phosphate builders in comparable detergent formulations. m erefore, when detergency resulting : i. - -, . .; . ::- . ;- ; . . -1~137~16 from the use of the present product is of the same order ag that obtained with phosphate-built detergents, the present product will be favored.
The following examples illustrate the invention but do not limit it.
Parts, perce~tages and proportions are by weight and temperatures are in C., unless otherwise noted.
E~AMPLE 1 Parts R~O(C2H O) SO Na (Neodol 25-3S*, a trademark charged as a 12,0 4 3 3 60% aqueous solution containing 14% ~
ethanol, 1% unsulfated alcohol, with ~-Rl = mixed 12, 13, 14 15 carbon atoms linear primary alkyls3 Polyethylene glycol ether of higher linear alcohol 3.0 (Tergitol 15-S-9**, a trademark) Sodium xylene sulfonate (charged as 60% aqueous solution) 6.0 NaOH
Disodium 2-hydroxyethyl iminodiacetate (charged as 51.5% 15.0 aqueous solution having a pH of 13.6) Optical brightener (benzidine sulfone derivative type) 0.15 Organic dye (Polar Brilliant Blue, charged as a 1% aqueous 0.005 sol~tion) Perfume 0.5 Water 62.9 * Manufactured by Shell Chemical Corporation.
*~ Manufactured by Union Carbide Corporation.
The anionic detergent is admixed at room temperature with a solution containing the hydrotrope dissolved at 60% concentration in a portion of the water, To the resultant mixture is charged aqueous solution of dye. Then, the hydroxyalkyl iminodicarboxylate salt solution is added, followed by addi-tion of the sodium hydroxide (preferably first dissolved in some of the water)and the optical brightener. After addition of the remaining water the mixture is thoroughly stirred and filtered through a glasg wool filter pad to obtain a clear, sparkling single phase detergent liquid.
. . .... . .~-:
.
The detergent product is comparable in detergency with a high phos-phate content liquid detergent containing about 5 to 25% of pentasodium tri- ~.
polyphosphate. Utilizing standard concentrations for liquid detergents in automatic washing machines, 1/4 to l/2 cup per wash load), the product is of acceptable to superior washing ability in hot and cold water, in hard and soft water and when tested against varying types of soils from clay soils to j ~ :
phospholipid or sebum soils, as compared to a commercially available liquid ~ -phosphate-containing detergent.
Parts ~O(C2H4o)3so3Na (as in Example 1) 12.0 Polyethylene glycol ether of higher linear alcohol (as in 3.0 Example 1) Sodium xylene sulfonate (as in Example l) 6.0 Disodium 2-hydroxyethyl iminodiacetate (as in Example 1) 15.0 ~ -Optical Brightener (as in Example l) 0.15 -~
Organic dye (as in Example l) 0.005 Perfume 0-5 ~ :
Sodium silicate (mole ratio of Na20:SiO2 is 1:2~4, charged 5.0 ~ :
as 40~ aqueous solutlon) ~. .
. . . .
Water 57-9 The procedure of Example 1 is followed substantially as described except that after addition of the dye solution the sodium hydroxide is added to the builder salt-containing solution which i9 then charged to the silicate golution which has been previously heated to about 70. The mixture is cooled !~
to room temperature and the remaining constituents are added as in Example l.
The product is a clear liquid detergent equal or superior in detergency to the product of Example 1.
In the following Examples 3 and 4 the procedure of Example 1 is repeated with the variations noted to produce liquid detergent compositions which have detersive effectg substantially equivalent to those of the product -15- :~
of Example 1.
EXA~PLE 3 Parts ~ (C2H40)3S03Na (as in Example 1) 7 5 Polyethylene glycol ether of higher linear alcohol (as in 3.0 Example 1) -Sodium xylene sulfonate (as in Example 1) 6.0 NaOH 0.5 Disodium 2-hydroxyethylene iminodiacetate (as in Example 1) 15.0 Optical brightener (as in Example 1) 0.15 Organic dye (as in Example 1) 0.005 Perfume 0.2 Water 68,4 In the above example the concentrations of the anionic and nonionic detergents are varied from those used in Example 1.
Parts Polyethylene glycol ether of higher linear alcohol (as in 7.5 Example 1) Bis(2-hydroxyethyl) tAllow amine oxide (foam stabilizer 15.0 Aromox T/12, charged as 50% aqueous solution~*
Diaodium 2-hydroxyethyl iminodiacetate (as in Example 1) 1?.0 Optical brighteners Phorwite BHC*~ ~ 0.15 Uvitex 325?**~ 0.15 ~OH (as 45% solution) 1.0 Ethyl alcohol (standard denaltured No. 40) 0.10 Organic dye (as in Example 1) 0.005 Perfume 0.15 Water 58.9 * Trademark for product manufactured by Armour Chemical Corp.
** Trademark for product manufactured by Verona Dye9tuff Conc.
*** Trademark for product manufactured by CIBA Corp.
The procedure of Example 1 is followed except that the anionic detergent is replaced with an aqueoug foam stabilizer, the aqueous solvent containS a small additional proportion of ethyl alcohol, the alkaline additive is different, the concentration of nonionic detergent is changed and a dif-ferent optical brightener system is used.
In next Exanples 5 and 6 the formulation and procedure of Example 2 are changed but the liquid detergent compositions made are of substantially equivalent detersive effects, compared to the product of Example 2.
Parts Sodium higher alpha-olefin sulfonate (charged as a 35% 12.0 aqueous solution; Bioterg AS-35-CL*, a ~ ~-trademark) Sodium silicate (Na20:SiO2 molar ratio 1:2.0, charged as 4.8 43% aqueous solution) Disodium 2-hydroxyethyl iminodiacetate (as in Example 1) 18.0 ~`
Sodium xylene sulfonate (as in Example 1) 7.5 Water 57-7 -* M~nufactured by Stepan Chemical Co.
The procedure of Example 2 is followed except that a different an- ` ;
ionic detergent salt is charged, the nonionic detergent, alkaline additive, perfume and optical brightener are omitted, different concentrations of the hydrotrope and builder salt are used and a different concentration and type of sodium silicate are employed.
I Parts Potasgium dodecyl benzene sulfonate (charged as 58% 10,8 aqueous solution) Sodium silicate (as in Example 5) 5.4 Disodium 2-hydroxyethyl iminodiacetate (as in Example 1) 18.0 Sodium xylene sulfonate (as in Example 1) 7.2 Water 58.6 -17- ~ -.
- , . ~ .
The procedure of Example 2 is repeated substantially as described except that a different anionic detergent salt is charged, the nonionic deter-gent, perfume, optical brightener, alkaline additive are omitted, a different type of sodium silicate is used and concentrations of the constituents are different.
Roth the products of Examples 5 and 6 are good liquid detergents, effective in cleaning severe soils and stains from clothing and items to be laundered, when applied at 100% concentrations and when pre-soaked, and effective in usual heavy duty laundering operations at normal 1/8 to 1/2 cup per wash-load concentrations in automatic washing machines, using hot or cold water of a hardness of 0 to 200 p.p.m. as CaC03. Clothes washed are Clean and bright and are not structurally adversely affected by the liguid detergent components.
EXAMPLE 7 ~;
The products of Examples 1-6 are made with changes effected in the formulations whereby, selectively and combining changes, the anionic detergent contents are changed to 5, lO and 15%, the nonionic detergent contents are changed to 2, 5 and 9%, the hydrotrope contents are changed to 3, 5 and 7%, the alkali~er contents are changed to 0.2 and 1% (and 5% when sodium carbon-ate is employed), the iminodicarboxylate contents are changed to 3, lO and18%, the silicate cQntents, if silicate is present, are changed to 4, 7 and 9%, the adjuvant contents are maintained in the 0-10% and 0-5% ranges and the proportions of water present are adjusted accordingly. In such products the anionic detergent is of the formula R2( C2H40 )4S03Na or the corresponding potassium salt, wherein R2 is tridecyl, sodium linear tetradecyl benzene sulfonate, triethanolamine lauryl sulfate and potassium higher (C10 18 mixture) alpha-olefin sulfonate; the nonionic detergent is a higher linear alcohol polyethoxy othanol wherein the alcohol is a mixed alcohol of lO to 18 carbon atoms, and respectively, 3, 7, 9 and 12 lecules '" - ' ' ' -18- ' ~ ;
~03781~
of ethylene oxide are present per mol of higher linear alcohol; the hydro-trope is potassium cumene sulfonate, potassium benzene sulfonate and sodium toluene sulfonate; potassium hydroxide, potassium carbonate and sodium carb-onate are the alkalizing agents; the organic builder is dipotassium-2-hydroxy-ethyl ;~;nodiacetate, disodium 2-hydroxyethyl iminodipropionate, dipotassium 3-hydroxy-n-propyl iminodiaceta~e and dipotassium 3-hydroxy-n-propyl iminodi-propionate; and the silicate is of Na20:SiO2 and K20:SiO2 ratios of 1:1.8, 1:2.1 and 1:2.35. Other builders are utilized to replace all or part of the sodium silicate in the formula of Example 2 and the proportions thereof are varied from 3 to 10% of the product, with good results being obtainable.
Such supplemental builders include permissible proportions of pentasodium tripolyphosphate, pentapotassium tripolyphosphate, tetrasodium pyrophosphate and tetrapotassium pyrophosphate, borax, sodium and potassium gluconates, - ;
sodium and potassium citrates, sodium and potassium bicarbonates and sodium and potassium sequicarbonates. Similarly, small proportions of filler salts such as sodium and potassium chlorides and sodium and potassium sulfates are also present but usually these are held to no more than 3% each, e.g., 1%.
The products described are made by the method given in Example 1.
Clear, stable liquid detergents result which are readily pourable and measur-able and are easy to employ in both hand and automatic laundry washing opera-tions. They are effective as pre-laundering treatments to clean "ground-in"
soils from shirt collars and cuffs and for the removal of greasy spots on laundry, when applied full strength or at high concentrations in water. In modifications of the formula, to promote solubilizations of various components and to help maintain storagç stability, especially during freezing weather, additional proportions of alcohol are utilized, 5 and 10%, and the alcohol is sometin~s changed to isopropanol or mixtures of ethanol and isopropanol. When used in 1/8-1/4 cup charges to front loading automatic washing machines or at approximately twice such charges to top loading machines of the oscillating agitator type the liguid detergents are found to wash and brighten clothing .. . .
. . . . : , . :
. . . ~ , . ,: - : - . :
satisfactorily. This is also the case when the various dyes and brighteners in the fonmulag are replaced by others known in the art.
In further changes of the formulas the alkalinities thereof are adjusted so that the pH is 9 and 11, instead of the normal 10. The products are also satisfactory but it will normally be attempted to keep the pH at about 10 to have best combination of washing power and mildness to the mater-ials washed.
The combination of clarity of formulation, stability on storage and good washing properties of the described fonmulations is attributable in large part to the particular organic builder saltg which are found to produce exceptionally satisfactory non-phosphate heavy duty detergents in the liquid medium. It is considered unexpected that the desired combination of proper-tieg should be so well obtained and while the effects appear in large part to be due to the sequestering and building actions of the iminodiaIkanoates, they also depend on the compatibilities of such compounds with the other com-ponents of the compositions. They are also compatible with the same composi-tions to which 0.3, 0.5 and 0.8% of sodium carboxymethyl cellulose or other anti-redeposition agent, e.g., polyvinyl alcohol, hydroxypropyl methyl cellu-lose, have been added but the proportion of such agent present should be con-trolled for best stability of the product on storage and clarity.
The invention has been described with respect to specific examplesand ill w trations thereof but is not to be lim;ted to these because it is evident that one of skill in the art, with the present specification before him~ will be able to utilize equivalents and substitutes, while still being wit_in the concept and scope of the invention.
.~' ', ~ . ' . ' ' . ,~ . ' , . ,': '
The present builder salts, hydroxyalkyl iminodicarboxylate salts, such as disodium 2-hydroxyethyl iminodiacetate, are usually available commer-`:
-6- ~ ~ .
.. ~ . ~ - ' ' ' ,. ~ .
cially as 50 to 53 weight percent aqueous solution9 of 9uch elevated pH, i.e., 12 to 13.7, as to produce aIkaline liquid detergent compositions, i.eO, deter-gent c~mpositions having a pH above 7 and generally in excess of 8, when the builder salt is admixed with the other components of the present invention.
However, to insure obtaining an alkaline detergent composition, it is advan-tageous to incorporate from about 0.4 to 15%, preferably about 0.4 to 1.5%
of water soluble base into the present composition. The base is preferably water soluble inorganic base such as an alkali metal hydroxide or carbonate, ~ -e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, potassium 10 carbonate, or an organic no-, di- or tri-lower alkyl or lower alkanol amine., ., ~ , .... .... ... .
of the type exemplified above. Especially preferred as alkaline agents are sodium hydroxide, potassium hydroxide and triethanolamine. Sodium hydroxide is rated best for these alkalizing steps.
The organic hydrotrope which is preferably incorporated in the liquid detergent composition not only aids in maintaining a high concentra-tion of the 2-hydroxyalkyl iminodicarboxylate builder salt in solution and but also acts to solubilize any anionic detergent constituent so ag to facil-itate obtainment of a concentrated detergent liquid. The hydrotrope also helps to prevent settling out of the silicate constituent either ag an insolu-20 ble precipitate or as a separate liquid phase. Additionally the hydrotrope assists in maintaining in solution various adjuvant materials of comparatively low solubilities, e.g., optical brighteners.
The organic hydrotropes utilized in the invention are preferably salts of aryl sulfonic acids, especially benzene sulfonic acids, wherein tbe benzene nucleug may be unsu~stituted or substituted with lower aIkyl group(s), i.e., Cl to C4 alkyl group(s), preferably methyl, ethyl or isopropyl groups. ~~
Up to 3 such substituents may be p m ent on the benzene nucleus but none, one or two are preferred. The salt-fonming cation of the hydrotrope is prefer- x ~ :
ably aIkali netal, such as sodium or potassium. However, any of the water 30 soluble cations exemplified above in connection with descriptions of the an- --. : .
_7_ ~037816 ionic detergent and builder salts, such as ammonium, mono-, di- and tri-lower alkyl- and -lower alkanolammonium can be used in place of the alkali metal cations, Typical illustrative examples of suitable hydrotropes include sodium benzene sulfonate, potassium toluene sulfonate, ammonium xylene sulfonate and monoisopropanolammonium cumene sulfonate. The xylene sulfonate salts, especially the alkali metal salts thereof, e.g., the potassium salt, provide especially good results. ~-The solvent medium for the present liquid detergent composition is an aqueous one and may be water alone or may be substantially water with additional solvents added to solubilize particular ingredients. Because of ; -the availability of water and its minimum cost, it is preferred to use it as the sole solvent present. Yet, amounts of other solvents, usually in propor-tions from about 0.1 to 20%, preferably about S to 15% of the liquid detergent composition, may be present. Generally, such a supplemental solvent is a . . .
lower aliphatic alcohol (including both monohydric and polyhydric alcohols, ~ -such as diols and triols, as well as ether alcohols and polyols) e.g., methan-ol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, propylene ~lycol, glycerol, diethylene glycol and the like. Preferably the alcoholic sol~ent is ethanol.
The water utilized in preparing the present liquid detergent may be deionized but in general tap water can be used. This is so because any low or medium degree of hardness in the water will generally be overcome by the strong sequestering action of the hydroxyalkyl iminodicarboxylate builder salt. Very hard waters, however, are desirably avoided in practice and de-ionized waters of low or me~ium hardness are employed instead.
The aIkali metal silicate, which is an optional but preferred com, ponent of the present liquid detergent camposition, functions as a supplemen-tal builder, increasing the desirable effects of the hydroxyalkyl iminodi-carboxylate builder salt on the synthetic organic detergent. The silicate is an alkaline material which also acts as an anticorrosion or protective addi-,:
. . .
tive. The silicate constituent is particularly helpful in removine particu-late soil from the laundry and in preventing harm to ceramic, porcelain, vit-reous, aluminum and steel parts of washing machines, similar equipment and laundered items.
Although various alkali metal silicates, such as sodium and potas-sium silicates, may be used, those which are most effective and which are also readily available are those wherein the molar ratio of aIkali metal oxide to silica, e.g., Na20:SiO2; K20:SiO2, are within the range of about 1:1.5 to 1:2,5. Particularly useful are sodium silicates wherein the sodium oxide to silica ratio is about 1:1.6 to 1:2.4. Of these the more alkaline 1:1.6 ratio silicate is advantageous because of its greater alkalizing, neutralizing and solubilizing abilities. It will often be highly desirable to adjust the final Na20:SiO2 ratio, for example, to about 1:2.0 which is very effective and convenient, by utilizing a mixture of about equal proportions of the readily available sodium silicates having Na20:SiO2 ratios of 1:1.6 and 1:2.35.
According to another embodiment of the invention the liquid deter-gent conposition may also contain a conventional foam stabilizine agent. Gen-erally, such a foam stabilizer is a lower hydroxyalkyl or alkyl higher ali-phatic (preferably aIkyl or poly-lower alkoxy) amine oxide, e.g., those manu-factured under the trademark Aromax by Armour Industrial Chemical Co., andtypically represented by Aromox(trademark) T/12, a bis(2-hydroxyethyl) tallow amine oxide. m e di-lower alkyl higher alkyl amine oxides such as dimethyl ~ ;
lauryl amine axide and diethyl stearyl amine oxide are also very useful.
Lower alkanolamides may also be employed.
Various other optlional minor conventional adjuvants may be present in the liquid detergent ccmposition to give it additional desired properties, either of functional or aesthetic Datures. Of these minor adjuvants, perhaps the mogt important functi~nally are the optical brighteners, which include a variety of structural types, selectively substantive to different textiles and fabrics. Cotton brighteners include, for example, the reaction product .. .
_g_ :
: ... . . . . . . ..
of cyanuric chloride and disodium diaminostilbene disulfonate. Brighteners for polyamides are generally either aminocoumarin or diphenyl pyrazoline derivatives. Polyester brighteners, which are also useful on polyamide fabrics, include naphthotriazolyl stilbene derivatives. Additionally, bright-eners having stability to bleach are important and such compounds are usually benzidine sulfone disulfonic acid derivatives, naphthotrizolyl stilbene sul-fonic acids and benzimidazoyl derivatives. The brighteners are normally charged as their water soluble salts, usually as their alkali metal salts or equivalent lower alkanola~ine salts. Typical proprietary optical brighteners include those sold under the trademarks Calcofluor White ALF (manufactured by American Cyanamid); ALF-N (AmeriCan Cyanamid); SOF-A2001 (CIBA); Uvitex 3257 (CIBA); CWD (Hilton Davis); Phorwite RKH (Verona), Phorwite BHC (Verona);
CSL powder, acid (AmeriCan Cyanamid); CSL, liquid, monoethanolamine salt, -;
(AmeriCan Cyanamid); FB 766 (Verona); BlanCophor PD (GAF); UNPA (Geigy);
Tinopal RBS (Geigy); and Tinopal RBS 200 (Geigy). Other typical optical brighteners are illustrated and discussed by P.S. Stensby in the article ODtical Bri~hteners and Their Evaluation, a reprint of articles published in Soap and Chemical Specialties in April, May, July, August and Sept~mber, 1967.
Normally, the optical brightener concentration is about 0.1 to 2%, especially .~., : .
about 0.2 to 1%.
In addition to optical brighteners other optional minor adjuvants include colorants, generally water soluble dyestuffs and/or water-dispersible organic pigments; foam regulating or inhibiting agents, e.g., water soluble saturated higher fatty acid soaps, normally incorporated at a concentration of 0.5 to 5%, especially 1 ~o 2%; foam destroyers, such as silicones; enzymes, e.g., proteases, amylases; anti-redeposition or soil suspending agents, e.g., polyvinyl alcohol, sodium carboxynethyl cellulosej hydroxynethyl cellulose;
bactericides, e.g., tetrachlorosalicylanilide, hexachlorophene, trichloro-carbanilide; fabric softeners, e.g., ethoxylated lanolin, higher fatty acid soaps, thickeners, e.g., starches, gums, alginates, cellulose derivatives;
- .. ~ ., .
. . r 10378~6 :
pearlescing agents; opacifying agents, e.g., behenic acid, polystyrene sus-pensions, castor wax; buffering agents, e.g., aIkali metal borates, acetates, bisulfates; supplementary inorganic builder salts, e.g., borax; and perfumes.
The liquid phosphate-free detergents of the invention can be made by comparatively simple manufacturing procedures. In a typical method the water soluble synthetic organic detergent is blended with water which may contain in solution any hydrotrope charged. To the mixture is charged any dyestuff to be added, preferably in the foam of an aqueous solution or emul-sion. The iminodicarboxylate salt is then added, also conveniently in aqueous solution. On completion of the addition of the builder salt, any remaining water for the formulation is added and the mass is thoroughly stirred. The resultant product may be filtered through a suitable filter medium such as glass wool, paper or cloth, preferably using a mechanical filter, to obtain the detergent as a clear liquid, Of course pearlescing agents, suspensions and emulsifiers may then be added if a cloudy or opaque product is wanted.
When optical brighteners or other adjuvants are to be incorporated, aqueous solutions thereof may be added before the addition of the remaining water.
If desirable, some of the water may be utilized to suspend such materials or --dissolve them before addition.
If an alkali metal silicate is to be incorporated in the liguid detergent composition, so as to prevent unsightly silica precipitates the hydroxyalkyl i~inodicarboxylate-containing agueous solution is desirably admixed at a pH above 12, preferably at 12.5 to 13.5, with the aqueous alkali metal silicate, preferably at a moderately elevated temperature, e.g., about 55 to 80 C. ~11 or a portilon of the alkaline additive may be utilized to adjust the pH of the builder salt solution to above 12, before the mixing ~ith silicate. Preparation of precipitate-free iminodicarboxylate salt-aIkali metal silicate agueous golutions may be carried out in accord with the tech-nigue described in the aforementioned coagsigned application of Francis R.
Cala entitled (ManufaCture of Improved Aqueous Alkali Metal Hydroxyalkyl --11-- ' ' ' '-,. . .
;, , ., ~
Iminodiacetate Compositions", which is incorporated herein by reference, Other than the above described moderate heating used in preparing precipitate free-mixtures of the organic builders and aIkali metal silicate solutions, preparation of the present liquid detergent compositions can be effected at room temperature. If desired however, the mixing of the other constituents can be carried out at other suitable temperatures, usually with-in a range of 10 to 90C., preferably 20 to 60C.
The pH of the resultant liquid detergent produCt is preferably above about 8 and is rarely above 12, preferably being from 9 to 11, most preferably 9.5 to 10.5.
The product is a clear sparkling liquid (in the absence of any intentional addition of opacifying agents) which maintains its homogeneity a~
a ~ingle phase system on long term storage. When utilized to launder cloth-ing in conventional manner, in an automatic washing machine, it provides com- p parable to equivalent soil and dirt removal when compared to a tripolyphos- -phate-built liquid detergent.
The amount of the present liquid detergent which is used in the wash water will, of course, vary samewhat, depending on the type of washing eguipment used. In general however, only a relatively small amount of the liquid detergent, amounting to about 1/4 to 1/2 cup, is needed for a fuIl tub of wash (4 to 15 lbs,), using either a top loading (vertical axis, agita-tor type) or front loading (horizontal tumbling drum type) washing machine, in which the water volume is from 5 to 20 gallons, usually from 15 to 18 gallons. Normally, only about 1/8 to 1/4 cup of the present liquid detergent product is employed for thelfront loading machines.
The liguid detergent composition of this invention is highly effec-tive in washing clothes, even in very hard waters (over 150 p.p.m. hardness, as CaC03, but preferably a moderately soft water is used, with a hardness less than lSO p.p.m., preferably of 25 to 100 p.p.m. While the washing temperature employed with the present produCt can range from 10 to 90C., preferably it .
is from about 20 to 70C. The washing is followed by rinsing and spinning or other draining or wringing cycles or operations which are preferably auto-matic. Of course, the present liquid detergent may also be used for manual washing of laundry. In such instances it may be used full strength on certain stains or heavy soils or the laundry may be soaked in a higher concentration solution of the detergent prior to normal machine washing. The washing opera-tions will generally take from three minutes to one hour, depending on the fabrics being washed and the degrees of soiling of the clothing. After com-pletion of the washing and the spinning, draining or wringing operations it -is preferred to dry the laundry in an automatic dryer soon thereafter but -... . . . .. .
line drying may also be employed. A fabric softener rinse may be interposed between washing and drying or at other suitable stage in the laundering or drying processes.
The present product dissolves very easily in the wash water, whether ~`
that water is warm or cold, and very effectively cleans clothing and other items of laundry. It may be used in either top or front loading washing ~ -machines and may be desirably adjusted to foam to the correct extent. It is an attractive clear, stable liquid which maintains its activity and homogen-eity over a long shelf life. It is convenient to store, non-dusting and non-caking of course, and very easy to measure out. In tests in which it is com-pared to conventional commercial laundry detergents, it is rated very favor-ably. This is an especially significant accomplishment when it is considered that the composition is free of phosphate and nitrilotriacetate builders and -hence requires no special treatment before disposal into ordinary drains and sewers. It is often prefer~ed for convenience of use and excellent detergency i9 observed. Yet, even if the results of washing with this product were not `~
as epod as those obtained with commercial products loaded with polyphosphates, the importance of the development of this nanti-pollution" detergent would be a significant enough advantage to warrant its replacing phosphate builders in comparable detergent formulations. m erefore, when detergency resulting : i. - -, . .; . ::- . ;- ; . . -1~137~16 from the use of the present product is of the same order ag that obtained with phosphate-built detergents, the present product will be favored.
The following examples illustrate the invention but do not limit it.
Parts, perce~tages and proportions are by weight and temperatures are in C., unless otherwise noted.
E~AMPLE 1 Parts R~O(C2H O) SO Na (Neodol 25-3S*, a trademark charged as a 12,0 4 3 3 60% aqueous solution containing 14% ~
ethanol, 1% unsulfated alcohol, with ~-Rl = mixed 12, 13, 14 15 carbon atoms linear primary alkyls3 Polyethylene glycol ether of higher linear alcohol 3.0 (Tergitol 15-S-9**, a trademark) Sodium xylene sulfonate (charged as 60% aqueous solution) 6.0 NaOH
Disodium 2-hydroxyethyl iminodiacetate (charged as 51.5% 15.0 aqueous solution having a pH of 13.6) Optical brightener (benzidine sulfone derivative type) 0.15 Organic dye (Polar Brilliant Blue, charged as a 1% aqueous 0.005 sol~tion) Perfume 0.5 Water 62.9 * Manufactured by Shell Chemical Corporation.
*~ Manufactured by Union Carbide Corporation.
The anionic detergent is admixed at room temperature with a solution containing the hydrotrope dissolved at 60% concentration in a portion of the water, To the resultant mixture is charged aqueous solution of dye. Then, the hydroxyalkyl iminodicarboxylate salt solution is added, followed by addi-tion of the sodium hydroxide (preferably first dissolved in some of the water)and the optical brightener. After addition of the remaining water the mixture is thoroughly stirred and filtered through a glasg wool filter pad to obtain a clear, sparkling single phase detergent liquid.
. . .... . .~-:
.
The detergent product is comparable in detergency with a high phos-phate content liquid detergent containing about 5 to 25% of pentasodium tri- ~.
polyphosphate. Utilizing standard concentrations for liquid detergents in automatic washing machines, 1/4 to l/2 cup per wash load), the product is of acceptable to superior washing ability in hot and cold water, in hard and soft water and when tested against varying types of soils from clay soils to j ~ :
phospholipid or sebum soils, as compared to a commercially available liquid ~ -phosphate-containing detergent.
Parts ~O(C2H4o)3so3Na (as in Example 1) 12.0 Polyethylene glycol ether of higher linear alcohol (as in 3.0 Example 1) Sodium xylene sulfonate (as in Example l) 6.0 Disodium 2-hydroxyethyl iminodiacetate (as in Example 1) 15.0 ~ -Optical Brightener (as in Example l) 0.15 -~
Organic dye (as in Example l) 0.005 Perfume 0-5 ~ :
Sodium silicate (mole ratio of Na20:SiO2 is 1:2~4, charged 5.0 ~ :
as 40~ aqueous solutlon) ~. .
. . . .
Water 57-9 The procedure of Example 1 is followed substantially as described except that after addition of the dye solution the sodium hydroxide is added to the builder salt-containing solution which i9 then charged to the silicate golution which has been previously heated to about 70. The mixture is cooled !~
to room temperature and the remaining constituents are added as in Example l.
The product is a clear liquid detergent equal or superior in detergency to the product of Example 1.
In the following Examples 3 and 4 the procedure of Example 1 is repeated with the variations noted to produce liquid detergent compositions which have detersive effectg substantially equivalent to those of the product -15- :~
of Example 1.
EXA~PLE 3 Parts ~ (C2H40)3S03Na (as in Example 1) 7 5 Polyethylene glycol ether of higher linear alcohol (as in 3.0 Example 1) -Sodium xylene sulfonate (as in Example 1) 6.0 NaOH 0.5 Disodium 2-hydroxyethylene iminodiacetate (as in Example 1) 15.0 Optical brightener (as in Example 1) 0.15 Organic dye (as in Example 1) 0.005 Perfume 0.2 Water 68,4 In the above example the concentrations of the anionic and nonionic detergents are varied from those used in Example 1.
Parts Polyethylene glycol ether of higher linear alcohol (as in 7.5 Example 1) Bis(2-hydroxyethyl) tAllow amine oxide (foam stabilizer 15.0 Aromox T/12, charged as 50% aqueous solution~*
Diaodium 2-hydroxyethyl iminodiacetate (as in Example 1) 1?.0 Optical brighteners Phorwite BHC*~ ~ 0.15 Uvitex 325?**~ 0.15 ~OH (as 45% solution) 1.0 Ethyl alcohol (standard denaltured No. 40) 0.10 Organic dye (as in Example 1) 0.005 Perfume 0.15 Water 58.9 * Trademark for product manufactured by Armour Chemical Corp.
** Trademark for product manufactured by Verona Dye9tuff Conc.
*** Trademark for product manufactured by CIBA Corp.
The procedure of Example 1 is followed except that the anionic detergent is replaced with an aqueoug foam stabilizer, the aqueous solvent containS a small additional proportion of ethyl alcohol, the alkaline additive is different, the concentration of nonionic detergent is changed and a dif-ferent optical brightener system is used.
In next Exanples 5 and 6 the formulation and procedure of Example 2 are changed but the liquid detergent compositions made are of substantially equivalent detersive effects, compared to the product of Example 2.
Parts Sodium higher alpha-olefin sulfonate (charged as a 35% 12.0 aqueous solution; Bioterg AS-35-CL*, a ~ ~-trademark) Sodium silicate (Na20:SiO2 molar ratio 1:2.0, charged as 4.8 43% aqueous solution) Disodium 2-hydroxyethyl iminodiacetate (as in Example 1) 18.0 ~`
Sodium xylene sulfonate (as in Example 1) 7.5 Water 57-7 -* M~nufactured by Stepan Chemical Co.
The procedure of Example 2 is followed except that a different an- ` ;
ionic detergent salt is charged, the nonionic detergent, alkaline additive, perfume and optical brightener are omitted, different concentrations of the hydrotrope and builder salt are used and a different concentration and type of sodium silicate are employed.
I Parts Potasgium dodecyl benzene sulfonate (charged as 58% 10,8 aqueous solution) Sodium silicate (as in Example 5) 5.4 Disodium 2-hydroxyethyl iminodiacetate (as in Example 1) 18.0 Sodium xylene sulfonate (as in Example 1) 7.2 Water 58.6 -17- ~ -.
- , . ~ .
The procedure of Example 2 is repeated substantially as described except that a different anionic detergent salt is charged, the nonionic deter-gent, perfume, optical brightener, alkaline additive are omitted, a different type of sodium silicate is used and concentrations of the constituents are different.
Roth the products of Examples 5 and 6 are good liquid detergents, effective in cleaning severe soils and stains from clothing and items to be laundered, when applied at 100% concentrations and when pre-soaked, and effective in usual heavy duty laundering operations at normal 1/8 to 1/2 cup per wash-load concentrations in automatic washing machines, using hot or cold water of a hardness of 0 to 200 p.p.m. as CaC03. Clothes washed are Clean and bright and are not structurally adversely affected by the liguid detergent components.
EXAMPLE 7 ~;
The products of Examples 1-6 are made with changes effected in the formulations whereby, selectively and combining changes, the anionic detergent contents are changed to 5, lO and 15%, the nonionic detergent contents are changed to 2, 5 and 9%, the hydrotrope contents are changed to 3, 5 and 7%, the alkali~er contents are changed to 0.2 and 1% (and 5% when sodium carbon-ate is employed), the iminodicarboxylate contents are changed to 3, lO and18%, the silicate cQntents, if silicate is present, are changed to 4, 7 and 9%, the adjuvant contents are maintained in the 0-10% and 0-5% ranges and the proportions of water present are adjusted accordingly. In such products the anionic detergent is of the formula R2( C2H40 )4S03Na or the corresponding potassium salt, wherein R2 is tridecyl, sodium linear tetradecyl benzene sulfonate, triethanolamine lauryl sulfate and potassium higher (C10 18 mixture) alpha-olefin sulfonate; the nonionic detergent is a higher linear alcohol polyethoxy othanol wherein the alcohol is a mixed alcohol of lO to 18 carbon atoms, and respectively, 3, 7, 9 and 12 lecules '" - ' ' ' -18- ' ~ ;
~03781~
of ethylene oxide are present per mol of higher linear alcohol; the hydro-trope is potassium cumene sulfonate, potassium benzene sulfonate and sodium toluene sulfonate; potassium hydroxide, potassium carbonate and sodium carb-onate are the alkalizing agents; the organic builder is dipotassium-2-hydroxy-ethyl ;~;nodiacetate, disodium 2-hydroxyethyl iminodipropionate, dipotassium 3-hydroxy-n-propyl iminodiaceta~e and dipotassium 3-hydroxy-n-propyl iminodi-propionate; and the silicate is of Na20:SiO2 and K20:SiO2 ratios of 1:1.8, 1:2.1 and 1:2.35. Other builders are utilized to replace all or part of the sodium silicate in the formula of Example 2 and the proportions thereof are varied from 3 to 10% of the product, with good results being obtainable.
Such supplemental builders include permissible proportions of pentasodium tripolyphosphate, pentapotassium tripolyphosphate, tetrasodium pyrophosphate and tetrapotassium pyrophosphate, borax, sodium and potassium gluconates, - ;
sodium and potassium citrates, sodium and potassium bicarbonates and sodium and potassium sequicarbonates. Similarly, small proportions of filler salts such as sodium and potassium chlorides and sodium and potassium sulfates are also present but usually these are held to no more than 3% each, e.g., 1%.
The products described are made by the method given in Example 1.
Clear, stable liquid detergents result which are readily pourable and measur-able and are easy to employ in both hand and automatic laundry washing opera-tions. They are effective as pre-laundering treatments to clean "ground-in"
soils from shirt collars and cuffs and for the removal of greasy spots on laundry, when applied full strength or at high concentrations in water. In modifications of the formula, to promote solubilizations of various components and to help maintain storagç stability, especially during freezing weather, additional proportions of alcohol are utilized, 5 and 10%, and the alcohol is sometin~s changed to isopropanol or mixtures of ethanol and isopropanol. When used in 1/8-1/4 cup charges to front loading automatic washing machines or at approximately twice such charges to top loading machines of the oscillating agitator type the liguid detergents are found to wash and brighten clothing .. . .
. . . . : , . :
. . . ~ , . ,: - : - . :
satisfactorily. This is also the case when the various dyes and brighteners in the fonmulag are replaced by others known in the art.
In further changes of the formulas the alkalinities thereof are adjusted so that the pH is 9 and 11, instead of the normal 10. The products are also satisfactory but it will normally be attempted to keep the pH at about 10 to have best combination of washing power and mildness to the mater-ials washed.
The combination of clarity of formulation, stability on storage and good washing properties of the described fonmulations is attributable in large part to the particular organic builder saltg which are found to produce exceptionally satisfactory non-phosphate heavy duty detergents in the liquid medium. It is considered unexpected that the desired combination of proper-tieg should be so well obtained and while the effects appear in large part to be due to the sequestering and building actions of the iminodiaIkanoates, they also depend on the compatibilities of such compounds with the other com-ponents of the compositions. They are also compatible with the same composi-tions to which 0.3, 0.5 and 0.8% of sodium carboxymethyl cellulose or other anti-redeposition agent, e.g., polyvinyl alcohol, hydroxypropyl methyl cellu-lose, have been added but the proportion of such agent present should be con-trolled for best stability of the product on storage and clarity.
The invention has been described with respect to specific examplesand ill w trations thereof but is not to be lim;ted to these because it is evident that one of skill in the art, with the present specification before him~ will be able to utilize equivalents and substitutes, while still being wit_in the concept and scope of the invention.
.~' ', ~ . ' . ' ' . ,~ . ' , . ,': '
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A liquid laundry detergent composition which comprises about 5 to 50% by weight of a water soluble synthetic organic detergent selected from the group consisting of anionic detergent salts, nonionic detergents, and mixtures thereof, about 2.5 to 20% by weight of a hydroxyalkyl iminodicarboxy-late builder salt wherein the carboxylate residues are of 2 to 4 carbon atoms and about 30 to 90% by weight of an aqueous solvent medium, said composition having an alkaline pH.
2. A detergent composition according to claim 1 wherein the anionic detergent is a sulfated or sulfonated compound, the nonionic detergent is a poly-lower alkylene oxide condensation product and the iminodicarboxylate is a hydroxy-lower alkyl iminocarboxylate, which contains about 3 to 10% by weight of a water soluble alkali metal silicate or mixture of silicates wherein the molar ratio of metal oxide to silica is in the range of about 1:1.5 to 1:2.5 and about 0.1 to 20% by weight of a saturated lower aliphatic alcohol, and the pH of which is greater than about 8Ø
3. A detergent composition according to claim 2 wherein the anionic detergent is a higher fatty alcohol ethoxylate sulfate, higher fatty alcohol sulfate, higher alkyl benzene sulfonate or higher olefin sulfonate, the imino-dicarboxylate is a hydroxy-lower alkyl iminodi-lower carboxylate, the molar ratio of alkali metal oxide to silica in the silicate is in the range of about 1:1.6 to 1:2.4, the lower aliphatic alcohol is ethyl alcohol or isopropanol ant a hydrotrope is present.
4. A detergent composition according to claim 3 wherein the anionic detergent is an alkali metal higher fatty alcohol ethoxylate sulfate, the alkali metal silicate is a sodium silicate which is present in a concentration of about 4 to 8% and has a molar ratio of sodium oxide to silica of about 1:2, the alcohol is ethyl alcohol and is present in a concentration of about 5 to 15%, a foam stabilizer, lower alkylated or lower hydroxyalkyl higher aliphatic amine oxide, is present in a foam stabilizing proportion and the hydrotrope is an alkali metal benzene sulfonate or lower alkyl or polyalkyl benzene sul-fonate present in a hydrotropic proportion.
5. A detergent composition according to claim 1 wherein the concentra-tion of water soluble synthetic organic detergent is about 10 to 25% by weight, the anionic detergent salt is a sulfate or sulfonate, the nonionic detergent is a higher alkyl poly-lower alkoxy lower alkanol, there is present about 3 to 15% by weight of an organic hydrotrope which is a salt of benzene sulfonic acid or of an alkyl benzene sufonic acid, the hydroxyalkyl iminodicarboxylate builder salt is a dialkali metal hydroxy-lower alkyl iminodiacetate or -iminodipropionate and is present in a concentration of 5 to 18%, there is present about 0.1 to 15% by weight of an alkaline agent selected from the group consisting of alkali metal hydroxides, carbonates, lower alkylamines and lower alkanolamines, and the concentration of aqueous solvent medium is from about 50 to 75%.
6. A detergent composition according to claim 5 wherein the detergent is a mixture of a nonionic detergent and an anionic detergent salt in a weight ratio of about 5:1 to 1:5, the anionic detergent salt is a higher alpha-olefin sulfonate salt, a higher alkyl aryl sulfonate salt and/or a higher alkyl poly-lower alkoxy lower alkanol sulfate, the lower alkoxy group of the nonionic detergent is ethoxy, the alkyl substituents of the alky aryl sulfonate salt, the alkyl poly-lower alkoxy lower alkanol sulfate salt and the alkyl poly-lower alkoxy lower alkanol being linear alkyl, the organic hydrotrope is present in a concentration of about 4.0 to 8% and is selected from water solu-ble salts of the groups consisting of benzene sulfonates, toluene sulfonates, xylene sulfonates and cumene sulfonates, the builder salt is an alkali metal 2-hydroxyethyl iminodiacetate or dipropionate and the concentration of the alkaline agent is about 0.1 to 1.5%.
7. A composition according to claim 6 wherein the nonionic detergent is of the formula RO(C2H4O)nH
wherein R is a linear alkyl group of 12 to 15 carbon atoms and n is an integer from 9 to 13, the anionic detergent corresponds to the structural formula R1O(C2H4O)3SO3M
wherein R1 is the residue of a linear primary alcohol of 12 to 15 carbon atoms and M is a salt-forming cation, the builder salt is disodium 2-hydroxyethyl iminodiacetate, and the alkaline agent is sodium hydroxide, potassium hydrox-ide or triethanolamine.
wherein R is a linear alkyl group of 12 to 15 carbon atoms and n is an integer from 9 to 13, the anionic detergent corresponds to the structural formula R1O(C2H4O)3SO3M
wherein R1 is the residue of a linear primary alcohol of 12 to 15 carbon atoms and M is a salt-forming cation, the builder salt is disodium 2-hydroxyethyl iminodiacetate, and the alkaline agent is sodium hydroxide, potassium hydrox-ide or triethanolamine.
8. A detergent composition according to claim 7 wherein the cation of the anionic detergent salt is an alkali metal, the hydrotrope is an alkali metal salt, the concentration of aqueous solvent medium is about 60 to 70%
by weight, and the composition contains up to about 10% by weight of an ad-juvant material selected from the group consisting of optical brighteners organic colorants which are water soluble dyes or water dispersible pigments, pearlescing agents, opacifiers, foam inhibitors or depressors, enzymes, anti-redeposition agents, inorganic builder salts, buffers, fabric softeners and perfumes and mixtures thereof.
by weight, and the composition contains up to about 10% by weight of an ad-juvant material selected from the group consisting of optical brighteners organic colorants which are water soluble dyes or water dispersible pigments, pearlescing agents, opacifiers, foam inhibitors or depressors, enzymes, anti-redeposition agents, inorganic builder salts, buffers, fabric softeners and perfumes and mixtures thereof.
9. A detergent composition according to claim 8 wherein the hydrotrope is sodium xylene sulfonate, the ratio of nonionic detergent to anionic deter-gent is in the range of 3:1 to 1:5 and the composition contains no more than about 5% by weight of adjuvant materials.
10. A detergent composition according to claim 9 wherein the concentra-tion of detergent is about 15% by weight, the ratio of nonionic detergent to anionic detergent is about 1:4, the concentration of sodium xylene sulfonate is about 6%, the alkaline agent is sodium hydroxide in a concentration of about 0.5%, the concentration of disodium 2-hydroxyethyl iminodiacetate is about 15% by weight, the aqueous solvent medium is water present in a concen-tration of about 60% and the composition contains minor proportions of optical brightener, organic dye and perfume and is at a pH in the range of 9.5 to 10.5.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US40990773A | 1973-10-26 | 1973-10-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1037816A true CA1037816A (en) | 1978-09-05 |
Family
ID=23622446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA212,255A Expired CA1037816A (en) | 1973-10-26 | 1974-10-25 | Liquid hydroxyalkyl iminodicarboxylate detergents |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1037816A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4704233A (en) * | 1986-11-10 | 1987-11-03 | The Procter & Gamble Company | Detergent compositions containing ethylenediamine-N,N'-disuccinic acid |
-
1974
- 1974-10-25 CA CA212,255A patent/CA1037816A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4704233A (en) * | 1986-11-10 | 1987-11-03 | The Procter & Gamble Company | Detergent compositions containing ethylenediamine-N,N'-disuccinic acid |
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