EP0253676A2 - Amine-acid thickening compositions - Google Patents
Amine-acid thickening compositions Download PDFInfo
- Publication number
- EP0253676A2 EP0253676A2 EP19870306355 EP87306355A EP0253676A2 EP 0253676 A2 EP0253676 A2 EP 0253676A2 EP 19870306355 EP19870306355 EP 19870306355 EP 87306355 A EP87306355 A EP 87306355A EP 0253676 A2 EP0253676 A2 EP 0253676A2
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- European Patent Office
- Prior art keywords
- composition
- acid
- thickening agent
- substituted
- unsubstituted alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/75—Amino oxides
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/40—Monoamines or polyamines; Salts thereof
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/58—Heterocyclic compounds
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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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
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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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
Definitions
- the present invention relates to aqueous compositions of acids or acidic salts and more particularly to novel compositions of these acids or acidic salts which include a thickening agent.
- acidic salts refer to those compounds which in an aqueous solution liberate protons.
- compositions for cleaning include toilet bowl cleaners, metal cleaners and brighteners, rust stain removers, denture cleansers, metal descalers, general hard surface cleaners and disinfectants.
- compositions have sufficient viscosity so as to allow the composition to be effectively applied to surfaces, for example, by brushing, or to allow the composition to remain in contact with the surface for a sufficient time to act.
- the latter function has particular relevance to the cleaning of angular surfaces such as those found in toilet bowls where prolonged contact between the composition and the bowl is required for effective cleaning.
- compositions known in the art that have the requisite viscosity characteristics. Most of such compositions achieve their viscosity through the use of one or more of the following thickening agents:-
- the cellulose derivatives and gums tend to hydrolyse on storage which results in a reduction in viscosity of the composition. They are also generally difficult to dissolve, in some cases intensive mixing being required in order to bring them into solution.
- Acrylic acid polymers are generally only useful in solutions which have a pH near neutral and above. They also tend to hydrolyse on storage and to achieve viscosity, need to be neutralized with a fairly strong alkali.
- Nonionic surfactants have the disadvantage that usually high levels of about 5-10 0 /o are required to achieve satisfactory viscosity, thus making them expensive to use.
- poly(ethyleneoxide) water soluble resins also require generally high levels to achieve desirable composition viscosity and additionally, in some acid solutions show significant instability.
- Sodium silicates are able to produce aqueous acid or acidic salt gel compositions.
- the viscosity generally develops over a long period of time, for example, as much as twelve hours. In commercial manufacturing processes, this is often inconvenient. It is also to be noted that on storage, such gels tend to break down into small pieces which in many instances is undesirable.
- compositions disclosed in the art which relate to an aqueous acid and/or acidic salt compositions include:-
- the present inventor has recognized the difficulties of the prior art thickening agents for such aqueous acid or acidic salt compositions. Accordingly, the present invention seeks to provide alternative compositions to those of the prior art.
- the present invention consists in a thickened aqueous composition
- a thickening agent which is at least one of the compounds selected from the group consisting of compounds of the formula: in which R, R 3 is a substituted or unsubstituted alkyl, aryl, alkaryl, aralkyl or alkenyl group, R 1 is hydrogen, a substituted or unsubstituted alkyl, aryl, alkaryl, aralkyl or alkenyl group, R 2 is hydrogen, a substituted or unsubstituted alkyl, aryl, alkaryl, aralkyl or alkenyl group, R 4 is a substituted or unsubstituted alkyl, aryl, alkaryl, aralkyl or alkenyl group, Rs is a substituted or unsubstituted alkyl, aryl, alkaryl, aralkyl or alkenyl group, Rs is a substituted or unsubstituted al
- the present invention consists in a method of forming a thickened aqueous solution, comprising dissolving in water (a) at least one compound selected from the group consisting of acids and acidic salts (b) a thickening agent which is at least one of the compounds selected from the group consisting of compounds of the formula: in which R, Rs is a substituted or an unsubstituted alkyl, aryl, alkaryl, aralkyl or alkenyl group, R 1 is hydrogen, a substituted or unsubstituted alkyl, aryl, alkaryl, aralkyl or alkenyl group, R 2 is hydrogen, a substituted or unsubstituted alkyl, aryl, alkaryl, aralkyl or alkenyl group, R 4 is a substituted or unsubstituted alkyl, aryl, alkaryl, aralkyl or alkenyl group, R 5 is a substituted or unsubstituted alky
- substantially water soluble means that a thickening agent and an acid or acidic salt selected in accordance with the invention, will together either be soluble in water at 25° C or at most will form a hazy soluble that does not separate into two phases during normal storage.
- compositions of the present invention may be readily distinguished over those disclosed in the aforementioned patent application GB2071688 (Jeyes Limited) in that the compositions claimed therein are directed towards substantially acid insoluble amines or amine oxides, which require a substantially acid soluble cationic or nonionic surfactant to achieve thickening.
- the present invention is limited to either amines or amine oxides which together with the selected acid or acidic salt are substantially water soluble, without a cationic or nonionic surfactant being required in the case of the amines to achieve solution and thickening, and in the case of the amine oxides, without the use of a cationic, nonionic or anionic surfactant, particulary an alkyl sulphate to achieve solution and thickening. It is also to be noted that in GB2071688 it is stated that neither of the amine, amine oxide, cationic surfactant or nonionic surfactant alone with an aqueous solution of an inorganic acid or acid salt will cause thickening.
- Bolsing in the simplest embodiment of his invention disperses the selected amine in water, heats the dispersion to between 40°C and 100°C and then adds to it at least a neutralising amount of phosphoric acid, preheated to between 40°C and 120°C. Stirring is continued until the temperature falls to between 5°C and 25° C and the resultant composition is a paste consisting of the reaction products between phosphoric acid and selected amine.
- Bolsing also discloses that other acids such as sulphuric, hydrochloric, tartaric, oxalic, hydrofluoric and nitric may be used as an additive to a base paste of his invention. He further discloses that other amines may also be used as additives.
- the present invention may be distinguished over Bolsing when it is considered that the amines of the Bolsing invention must be derivatives of substituted or unsubstituted hydrocarbons having 8-24 carbon atoms, the selected amine must be reacted by heating with phosphoric acid to achieve viscosity and there is no hint or suggestion that acids other than phosphoric acid are operative. Additionally, with respect to acidic salts, it is noted that Bolsing refers to ammonium chloride as an auxilliary.
- the present invention teaches that thickening can be achieved with a range of acids and acidic salts, no heating is required to obtain thickening and the present inventor believes that amines additional to those of Bolsing are operative.
- either of the groups R or R s contains at least six carbon atoms. More preferably, either of the groups R or R 3 contains from 8 to 24 carbon atoms. Most preferably either of the groups R or R 3 contains from 8 to 24 carbon atoms in an unsubstituted alkyl or alkenyl group.
- the groups R 1 and R 2 are independently a hydrogen atom or a lower unsubstituted alkyl group, where lower refers to groups containing 1 to 4 carbon atoms or a substituted alkyl group. More preferably the groups R i and R 2 are independently a hydrogen atom or a lower unsubstituted alkyl group. Most preferably, the groups R 1 and R 2 are independently a hydrogen atom or a methyl group.
- the groups R 4 and Rs are independently a lower unsubstituted alkyl group, where lower refers to groups containing 1 to 4 carbon atoms or a substituted alkyl group. More preferably, the groups R 4 and Rs are independently a lower substituted or unsubstituted alkyl group. Most preferably the groups R 4 and Rs are independently a methyl, or hydroxyethyl, or hydroxy propyl group.
- Preferred thickening agents of the present invention that are primary amines include Farmin O (Farmin is a registered trade mark of Kao Soap Co.) or Genamin OL-100D (Genamin is a registered trade mark of Hoechst), both of which are mainly oleylamine and Farmin T or Genamin TA100D, both of which are tallow fatty amine distilled.
- These thickening agents are able to thicken organic acids including formic, acetic, DL lactic, adipic, glycollic, malonic, succinic, pentetic, ascorbic, chloroacetic, citric and propionic acids.
- a strong ionic salt such as sodium chloride is required to achieve adequate composition viscosity in the preferred concentration range of thickening agent.
- a strong ionic salt such as sodium chloride
- increasing the concentration of thickening agent will increase viscosity in many cases.
- the addition of extra thickening agent may increase the pH and thereby decrease the efficiency of a composition.
- Preferred thickening agents of the present invention that are tertiary amines include Genamin S0302D (dimethyl soya bean oil fatty amine distilled) and Genamin TA302D (dimethyl tallow fatty amine distilled). These amines are able to thicken organic acids including citric acid, L tartaric acid, formic acid, DL malic acid, acetic acid, DL lactic acid, adipic acid, maleic acid, ethylenediaminetetraacetic acid, glycollic, malonic, succinic and propionic acid and inorganic acids including sulfamic acid, phosphoric acid, boric, hydrofluoric and sulphuric acid. Generally, for reasons outlined above, these amines require the addition of a strong ionic salt, such as sodium chloride in order to achieve adequate composition viscosity in the preferred concentration range of thickening agent.
- a strong ionic salt such as sodium chloride
- Preferred thickening agents of the present invention that are tertiary amines able to thicken acidic salts include Genamin TA302D and Genamin S0302D.
- Genamin TA302D is able to thicken aqueous solutions of monosodium citrate, and potassium hydrogen tartrate with the addition of a strong ionic salt such as sodium chloride.
- Genamin S0302D is able to thicken aqueous solutions of aluminium sulphate, sodium hydrogen sulphate, sodium dihydrogen orthophosphate, disodium ethylenediaminetetraacetate and aluminium potassium sulphate with a small addition of a strong ionic salt such as sodium chloride required in some cases; the sodium chloride being required to achieve adequate composition viscosity as previously described.
- a strong ionic salt such as sodium chloride required in some cases; the sodium chloride being required to achieve adequate composition viscosity as previously described.
- Preferred thickening agents of the present invention that are primary amines able to thicken acidic salts include farmin O, genamin OL-100D, Farmin T and Genamin TA-100D. These amines are able to thicken aqueous solutions of aluminium acetate.
- the abovementioned preferred amines are in fact mixtures of a number of amines with one amine being predominant.
- the present inventor believes that the predominant amine may function to solubilize the minor amines in compositions of the present invention.
- Farmin O is predominantly oleylamine having an approximate alkyl content of 6% C 14 , 13% C 16 and 81% C 18
- Genamin S0302D has an approximate average chain length distribution of 2% C 14 , 15% C 16 and 83% C 18
- Genamin TA302D has an approximate average chain length distribution of 5% C 14 , 30% C16 and 65% Cis.
- Preferred thickening agents of the present invention that are amine oxides include Aromox T/12 (bis[2-hydroxyethyl]tallow amine oxide) and Ammonyx MCO (mixture of myristyl and cetyl dimethyl amine oxides).
- Aromox is a trade mark of Armour Hess and Ammonyx is a trade mark of Onyx Chemicals Co.
- Aromox T/12 is able to thicken citric, phosphoric and sulphuric acids.
- composition containing Ammonyx MCO was prepared to contain:
- the preferred amine oxides falling within the scope of this invention are mixtures of amine oxides.
- AromoxT/12 has an average chain length distribution of 1% C 12 , 3% C 14 , 27% C 16 , 24 0 / 0 C 18 , 1% C 14 (unsat), 40/0 C 16 (unsat) 39% C 18 (unsat), 1% C 18 (double unsat).
- the amine oxides of the invention may require a small addition of a strong ionic salt to achieve adequate composition viscosity, as previously described.
- amines or amine oxides of the invention may be generally derived from natural or synthetic sources of tallow, soya bean oil, oleic acid, palmitic acid, myristic acid, linoleic acid, linolenic acid, ricinoleic acid or hexadecanoic acid.
- the acids to which the present invention is directed include inorganic acids such as sulphuric hydrofluoric, boric, sulphamic and phosphoric acids and the organic acids
- inorganic acids such as sulphuric hydrofluoric, boric, sulphamic and phosphoric acids
- organic acids Formic, acetic, DL lactic, propionic, citric, DL malic, L tartaric, adipic, maleic and ethylenediaminetetraacetic acid, malonic, glycollic, succinic, ascorbic, pentetic and chloroacetic acids.
- the acidic salts to which the present invention is directed include the acid salts of inorganic or organic acids such as monosodium citrate, sodium hydrogen sulphate, sodium dihydrogen orthophosphate, disodium ethylenediaminetetraacetate, aluminium acetate and potassium hydrogen tartrate, aluminium sulphate and aluminium potassium sulphate.
- inorganic or organic acids such as monosodium citrate, sodium hydrogen sulphate, sodium dihydrogen orthophosphate, disodium ethylenediaminetetraacetate, aluminium acetate and potassium hydrogen tartrate, aluminium sulphate and aluminium potassium sulphate.
- the concentration of acid or acidic salt may be varied over a wide range depending on the end use of the composition. In some cases, particularly where a strong acid such as hydrofluoric acid is used and a near neutral product is required, the concentration of acid or acidic salt may be as low as 0.01% w/w.
- the concentration of acid or acidic salt may be in excess of 90%.
- the concentration of acid or acidic salt will lie in the range of from 0.1 to 30% w/w.
- the thickening agent will be present in a concentration in the composition of from 0.1 to 10% w/w.
- concentration in the composition will lie in the range of from 0.4 to 5.0% w/w.
- the concentration of the thickening agent may be varied appropriately. However, in some cases, it has been found that it is not possible to achieve sufficient composition viscosity for some applications. In such cases, the addition of a salt which has high ionic strength has been found to enhance the viscosity of these compositions. In most cases however, the concentration of thickening agent and high ionic strength salt will be optimized in order to produce a cost effective composition of the desired viscosity.
- the ionic salts will be selected from alkali metal halides or sulphates and ammonium halides or sulphates. Suitable such salts include sodium chloride, sodium sulphate, potassium sulphate, potassium chloride, ammonium chloride and the like.
- Arquad 16-50 which is hexadecyltri- methyl ammonium chloride or Arquad S-50 which is a mixture of octadecanyl and octadecadienyl trimethyl ammonium chloride.
- Arquad is a trade mark of Armour Hess Chemicals.
- compositions of the invention may be added to compositions of the invention depending on their end use.
- germicides surfactants including anionic, nonionic, cationic and amphoteric, sequestering agents, corrosion inhibitors, perfumes and colouring agents may be added.
- a principal advantage of the present invention is that an aqueous acid or acidic salt solution may be readily and easily thickened.
- steps of obtaining such thickened compositions will be - (a) add an appropriate amount of acid or acidic salt to water and stir to dissolve, (b) add a thickening agent of the present invention to the solution and stir until dissolved and (c) added other ingredients if required, stirring to dissolve.
- the thickening agent of the present invention is defined to be soluble in the selected acidic salt or acid solution, and as it will generally be easily wet, the step (b) above will be relatively rapid unlike many of the prior art thickening agents, which whilst they may be soluble are frequently difficult to wet.
- thickening agents of the present invention are relatively inexpensive and in use produce smooth, homogeneous immediate thickening. Furthermore, thickened compositions are stable with respect to viscosity. For example, the present inventor has found that a citric acid composition thickened with Farmin O had no substantial change in viscosity when stored at room temperature for 12 months.
- compositions of the invention have some surfactant and corrosion inhibition properties.
- the former finding means that water immiscible substances such as fragrances may be directly solubilized in a composition of the invention without requiring the addition of emulsifiers or auxilliary solvents, and in compositions in which the surface active properties are required, potentially less or no additional surfactant would be required.
- the present inventor has also found that if only sufficient of an acid or an acidic salt is present to just dissolve a thickening agent of the present invention, then a composition of near neutral pH may be obtained.
- Farmin O may be used to thicken lactic acid at a pH of 6.5.
- the advantage of this finding is that it may be used in aqueous liquid cleaners in general.
- an acid or acidic salt which is usually considered to be water insoluble at room temperature may be brought into solution through the use of a thickening agent of the present invention, with thickening occurring.
- the viscosity may be increased through the use of a strong ionic salt such as sodium chloride.
- a strong ionic salt such as sodium chloride.
- compositions of this type include ethylenediaminetetraacetic acid with Genamin S0302D as the thickening agent, potassium hydrogen tartrate with Genamin TA302D as thickening agent and pentetic acid with Farmin O as thickening agent.
- examples 1 to 60 of the present invention, together with comparative examples 1A and 1B, in which the viscosity, in centipoise, of each was determined using a Brookfield RVT viscometer using a spindle and speed as appropriate at 25°C. Note that the thickening agent is asterixed in each case. All of these examples (except Nos. 27, 46 and 51) were produced by bringing the acid or acidic salt into solution, adding the thickening agent and mixing until dissolved, and then adding the other ingredients with mixing until dissolved.
- Examples 27, 46 and 51 were prepared by dispersing the acid or acid salt in water, adding the thickening agent and mixing until solution occurred, followed by sodium chloride (if required) until a satisfactory viscosity was achieved.
- Example 1 when compared with the viscosity of water (1A) and 5% w/w citric acid (1 B), is substantially greater. A comparison with an aqueous solution of the thickening agent in this case was not possible as the thickening agent is water insoluble.
- the examples 1 to 60 disclosed herein may be used for example as toilet bowl cleaners, metal cleaners and brighteners and the like as well as applications such as gel batteries
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Abstract
the thickened aqueous composition has a viscosity of not less than 30 centipoise at 25°C when measured with a Brookfield RVT viscometer at 50 rpm using a No. I spindle.
Description
- The present invention relates to aqueous compositions of acids or acidic salts and more particularly to novel compositions of these acids or acidic salts which include a thickening agent.
- As used in the specification acidic salts refer to those compounds which in an aqueous solution liberate protons.
- Aqueous solutions of acids and acidic salts have long been used in compositions for cleaning. Such compositions include toilet bowl cleaners, metal cleaners and brighteners, rust stain removers, denture cleansers, metal descalers, general hard surface cleaners and disinfectants.
- It has been found that a desirable property of many of the aforementioned compositions is that they have sufficient viscosity so as to allow the composition to be effectively applied to surfaces, for example, by brushing, or to allow the composition to remain in contact with the surface for a sufficient time to act. The latter function has particular relevance to the cleaning of angular surfaces such as those found in toilet bowls where prolonged contact between the composition and the bowl is required for effective cleaning.
- There are many such compositions known in the art that have the requisite viscosity characteristics. Most of such compositions achieve their viscosity through the use of one or more of the following thickening agents:-
- (a) cellulose derivatives exemplified by sodium carboxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, methyl cellulose, hydroxypropylmethyl cellulose, hydroxybutylmethyl cellulose;
- (b) gums such as xanthan gum,
- (c) acrylic acid polymers such as Carbopol (Registered Trade Mark of B.F. Goodrich)
- (d) nonionic surfactants such as nonyl phenol ethoxylates;
- (e) poly(ethylene oxide) resins such as Polyox (Registered Trade Mark of Union Carbide);
- (f) anionic surfactants such as alkylbenzene sulfonates and alkyl ether sulfates; and
- (g) sodium silicates such as sodium metasilicate.
- Most of these thickeners whilst able to effectively increase the viscosity of aqueous acid or acidic salt compositions do have some disadvantages in use.
- The cellulose derivatives and gums tend to hydrolyse on storage which results in a reduction in viscosity of the composition. They are also generally difficult to dissolve, in some cases intensive mixing being required in order to bring them into solution.
- Acrylic acid polymers are generally only useful in solutions which have a pH near neutral and above. They also tend to hydrolyse on storage and to achieve viscosity, need to be neutralized with a fairly strong alkali.
- Nonionic surfactants have the disadvantage that usually high levels of about 5-100/o are required to achieve satisfactory viscosity, thus making them expensive to use.
- The poly(ethyleneoxide) water soluble resins also require generally high levels to achieve desirable composition viscosity and additionally, in some acid solutions show significant instability.
- Sodium silicates are able to produce aqueous acid or acidic salt gel compositions. However, in developing viscosity in a composition, it has been noted that the viscosity generally develops over a long period of time, for example, as much as twelve hours. In commercial manufacturing processes, this is often inconvenient. It is also to be noted that on storage, such gels tend to break down into small pieces which in many instances is undesirable.
- Other thickening agents and compositions disclosed in the art which relate to an aqueous acid and/or acidic salt compositions include:-
- GB1,443,244 (Reckitt & Colman Products Limited) which discloses a thickening agent of the formula:
-
- GB2,071,688 (Jeyes Limited) which discloses as a thickening agent a mixture of: (a) a substantially acid insoluble compound of the formula (I) or (11); and
- (b) a substantially acid soluble cationic or nonionic surfactant, for thickening aqueous compositions of inorganic acids or acid salts of strong inorganic acids.
- US 3,786,091 (Bolsing) which discloses a phosphoric acid containing base paste, produced by preparing a finely divided aqueous dispersion of a long chain amine, preheating this dispersion, introducing preheated phosphoric acid thereinto with vigorous agitation, at elevated temperature until neutral and then stirring the resulting mixture until cold.
- US 4,021,377 (Borchert et al) which discloses a citric acid-amine reaction product obtained by mixing citric acid and water soluble or water dispersible amine in water until all the citric acid is dissolved. Generally the reaction is accompanied by a rise in temperature to about 40° C over an hour. The resultant solution containing amine salts of citric acid and citric acid amides is viscous. It is to be noted that the concentrations of citric acid and the amines exemplified are particularly high, the amines exemplified being in the range 12-4.5% W/W and the citric acid, 19.2% W/W. Further, only the amines monoethanolamine, diethanolamine and triethanolamine are exemplified.
- The present inventor has recognized the difficulties of the prior art thickening agents for such aqueous acid or acidic salt compositions. Accordingly, the present invention seeks to provide alternative compositions to those of the prior art.
- The present invention consists in a thickened aqueous composition comprising at least one compound selected from the group consisting of acids and acidic salts, a thickening agent which is at least one of the compounds selected from the group consisting of compounds of the formula:
said thickened aqueous composition has a viscosity of not less than 30 centipoise at 25°C when measured with a Brookfield RVT viscometer at 50 rpm using a No. 1 spindle. - In a second aspect, the present invention consists in a method of forming a thickened aqueous solution, comprising dissolving in water (a) at least one compound selected from the group consisting of acids and acidic salts (b) a thickening agent which is at least one of the compounds selected from the group consisting of compounds of the formula:
[A]x-H and [A]y-H where A is either ethoxy or propoxy and X, Y are independently 1, 2 or 3, and optionally (c) a strong ionic salt, said thickening agent and the at least one compound selected from the group consisting of acids and acidic salts being together substantially water soluble, in amounts sufficient to produce a viscosity of not less than 30 centipoise at 25° C when measured with a Brookfield RVT viscometer at 50 rpm using a No. spindle. - In the context of this specification, substantially water soluble means that a thickening agent and an acid or acidic salt selected in accordance with the invention, will together either be soluble in water at 25° C or at most will form a hazy soluble that does not separate into two phases during normal storage.
- It will be appreciated that the compositions of the present invention may be readily distinguished over those disclosed in the aforementioned patent application GB2071688 (Jeyes Limited) in that the compositions claimed therein are directed towards substantially acid insoluble amines or amine oxides, which require a substantially acid soluble cationic or nonionic surfactant to achieve thickening.
- By contrast the present invention is limited to either amines or amine oxides which together with the selected acid or acidic salt are substantially water soluble, without a cationic or nonionic surfactant being required in the case of the amines to achieve solution and thickening, and in the case of the amine oxides, without the use of a cationic, nonionic or anionic surfactant, particulary an alkyl sulphate to achieve solution and thickening. It is also to be noted that in GB2071688 it is stated that neither of the amine, amine oxide, cationic surfactant or nonionic surfactant alone with an aqueous solution of an inorganic acid or acid salt will cause thickening.
- It will also be appreciated that the aforementioned US 4,021,377 (Borchert et al) does not disclose, nor does it suggest that thickening will occur in compositions envisaged by the present invention without recourse to heating the amine with citric acid to form various reaction products. The present inventor believes that the disclosure in this US patent that the reaction products of citric acid and an amine are viscous in solution was merely an observation by the inventors, and perhaps not unexpected in view of the high concentration of reactants employed. In fact, there is no disclosure in this US patent that the inventors are aware that levels of amines as low as those preferred and exemplified in the present invention will form thickened compositions with acid or acidic salt solutions. The real thrust of this patent is a method of producing a concentrated solution of desired reaction products which happen in this high concentration to be viscous.
- In order to demonstrate this, the present inventor produced aqueous solutions containing 5010 w/w citric acid anhydrous and 20/o w/w mono-, di- or tri-ethanolamine. No thickening was noted in any of these solutions. Similarly, in US 3,786,091 (Bolsing), it is taught that it is necessary to obtain the reaction products between the selected amine and phosphoric acid by heating them together to produce a paste.
- Thus, Bolsing in the simplest embodiment of his invention disperses the selected amine in water, heats the dispersion to between 40°C and 100°C and then adds to it at least a neutralising amount of phosphoric acid, preheated to between 40°C and 120°C. Stirring is continued until the temperature falls to between 5°C and 25° C and the resultant composition is a paste consisting of the reaction products between phosphoric acid and selected amine. Bolsing also discloses that other acids such as sulphuric, hydrochloric, tartaric, oxalic, hydrofluoric and nitric may be used as an additive to a base paste of his invention. He further discloses that other amines may also be used as additives.
- The present invention may be distinguished over Bolsing when it is considered that the amines of the Bolsing invention must be derivatives of substituted or unsubstituted hydrocarbons having 8-24 carbon atoms, the selected amine must be reacted by heating with phosphoric acid to achieve viscosity and there is no hint or suggestion that acids other than phosphoric acid are operative. Additionally, with respect to acidic salts, it is noted that Bolsing refers to ammonium chloride as an auxilliary.
- In contrast, the present invention teaches that thickening can be achieved with a range of acids and acidic salts, no heating is required to obtain thickening and the present inventor believes that amines additional to those of Bolsing are operative.
- It is preferred that in the above formulae I or II, either of the groups R or Rs contains at least six carbon atoms. More preferably, either of the groups R or R3 contains from 8 to 24 carbon atoms. Most preferably either of the groups R or R3 contains from 8 to 24 carbon atoms in an unsubstituted alkyl or alkenyl group. Preferably, the groups R1 and R2 are independently a hydrogen atom or a lower unsubstituted alkyl group, where lower refers to groups containing 1 to 4 carbon atoms or a substituted alkyl group. More preferably the groups Ri and R2 are independently a hydrogen atom or a lower unsubstituted alkyl group. Most preferably, the groups R1 and R2 are independently a hydrogen atom or a methyl group.
- Preferably, the groups R4 and Rs are independently a lower unsubstituted alkyl group, where lower refers to groups containing 1 to 4 carbon atoms or a substituted alkyl group. More preferably, the groups R4 and Rs are independently a lower substituted or unsubstituted alkyl group. Most preferably the groups R4 and Rs are independently a methyl, or hydroxyethyl, or hydroxy propyl group.
- Preferred thickening agents of the present invention that are primary amines include Farmin O (Farmin is a registered trade mark of Kao Soap Co.) or Genamin OL-100D (Genamin is a registered trade mark of Hoechst), both of which are mainly oleylamine and Farmin T or Genamin TA100D, both of which are tallow fatty amine distilled. These thickening agents are able to thicken organic acids including formic, acetic, DL lactic, adipic, glycollic, malonic, succinic, pentetic, ascorbic, chloroacetic, citric and propionic acids. In some cases a small addition of a strong ionic salt such as sodium chloride is required to achieve adequate composition viscosity in the preferred concentration range of thickening agent. Naturally, increasing the concentration of thickening agent will increase viscosity in many cases. However, because of the relatively low cost of such salts, it is preferred to use a mixture of thickening agent and strong ionic salt to achieve the desired viscosity. However, it must also be considered that the addition of extra thickening agent may increase the pH and thereby decrease the efficiency of a composition.
- Preferred thickening agents of the present invention that are tertiary amines include Genamin S0302D (dimethyl soya bean oil fatty amine distilled) and Genamin TA302D (dimethyl tallow fatty amine distilled). These amines are able to thicken organic acids including citric acid, L tartaric acid, formic acid, DL malic acid, acetic acid, DL lactic acid, adipic acid, maleic acid, ethylenediaminetetraacetic acid, glycollic, malonic, succinic and propionic acid and inorganic acids including sulfamic acid, phosphoric acid, boric, hydrofluoric and sulphuric acid. Generally, for reasons outlined above, these amines require the addition of a strong ionic salt, such as sodium chloride in order to achieve adequate composition viscosity in the preferred concentration range of thickening agent.
- Preferred thickening agents of the present invention that are tertiary amines able to thicken acidic salts include Genamin TA302D and Genamin S0302D. Genamin TA302D is able to thicken aqueous solutions of monosodium citrate, and potassium hydrogen tartrate with the addition of a strong ionic salt such as sodium chloride. Genamin S0302D is able to thicken aqueous solutions of aluminium sulphate, sodium hydrogen sulphate, sodium dihydrogen orthophosphate, disodium ethylenediaminetetraacetate and aluminium potassium sulphate with a small addition of a strong ionic salt such as sodium chloride required in some cases; the sodium chloride being required to achieve adequate composition viscosity as previously described.
- Preferred thickening agents of the present invention that are primary amines able to thicken acidic salts include farmin O, genamin OL-100D, Farmin T and Genamin TA-100D. These amines are able to thicken aqueous solutions of aluminium acetate.
- Other amines considered by the present inventor to be within the scope of this invention include:
- Farmin DMON (Dimethyl oleylamine),
- Kao-DBA (dimethyl benzylamine) ;
- N-lauryl morpholine;
- N-Coco morpholine;
- N-cetylmorpholine; and
- Onamin 1416 (N-alkyl C14-CI6 dimethylamine)
- Genamin 14R302D (tetradecyl dimethylamine distilled);
- Genamin 16R302D (hexadecyl dimethylamine distilled);
- Genamin 14R100D tetradecylamine distilled);
- Genamin 16R100D (hexadecylamine distilled);
- The following amines obtainable from KenoGard-
- Amine 2MOL (dimethyloleylamine)
- Amine 28 (dioctylamine)
- Amine 210 (didecylamine)
- Amine M28 (methyldioctylamine) and
- Amine M210 (methyldidecylamine).
- It is to be noted that the abovementioned preferred amines are in fact mixtures of a number of amines with one amine being predominant. The present inventor believes that the predominant amine may function to solubilize the minor amines in compositions of the present invention.
- For example, Farmin O is predominantly oleylamine having an approximate alkyl content of 6% C14, 13% C16 and 81% C18, whilst Genamin S0302D has an approximate average chain length distribution of 2% C14, 15% C16 and 83% C18 and Genamin TA302D has an approximate average chain length distribution of 5% C14, 30% C16 and 65% Cis.
- Preferred thickening agents of the present invention that are amine oxides include Aromox T/12 (bis[2-hydroxyethyl]tallow amine oxide) and Ammonyx MCO (mixture of myristyl and cetyl dimethyl amine oxides). Aromox is a trade mark of Armour Hess and Ammonyx is a trade mark of Onyx Chemicals Co. Aromox T/12 is able to thicken citric, phosphoric and sulphuric acids.
- An example of a composition containing Ammonyx MCO was prepared to contain:
- Ammonyx MCO (30% active) 6.67%
- Sulphuric acid 3.83% w/w
- Sodium chloride 0.7% w/w
- Water 88.8% w/w
- It was observed that whilst the viscosity was not determined, it appeared to be thick and viscous. Futhermore, it is to be noted that whilst Ammonyx MCO water soluble, its viscosity is water thin, even in a 6.67% aqueous solution additionally containing solely 2% sodium chloride.
- As in the case of the amines of the invention, the preferred amine oxides falling within the scope of this invention are mixtures of amine oxides. Thus, AromoxT/12 has an average chain length distribution of 1% C12, 3% C14, 27% C16, 240/0 C18, 1% C14 (unsat), 40/0 C16 (unsat) 39% C18 (unsat), 1% C18 (double unsat). Similarly, the amine oxides of the invention, may require a small addition of a strong ionic salt to achieve adequate composition viscosity, as previously described.
- Other amine oxides considered by the present inventor to be within the scope of this invention include:
- bis (2-hydroxy ethyl) soya bean oil amine oxide;
- dimethyl tallow amine oxide;
- dimethyl oleyl amine oxide;
- dimethyl soya bean oil amine oxide;
- bis (2-hydroxy ethyl) oleyl amine oxide.
- Additionally, amines or amine oxides of the invention may be generally derived from natural or synthetic sources of tallow, soya bean oil, oleic acid, palmitic acid, myristic acid, linoleic acid, linolenic acid, ricinoleic acid or hexadecanoic acid.
- Generally the acids to which the present invention is directed include inorganic acids such as sulphuric hydrofluoric, boric, sulphamic and phosphoric acids and the organic acids Formic, acetic, DL lactic, propionic, citric, DL malic, L tartaric, adipic, maleic and ethylenediaminetetraacetic acid, malonic, glycollic, succinic, ascorbic, pentetic and chloroacetic acids.
- The acidic salts to which the present invention is directed include the acid salts of inorganic or organic acids such as monosodium citrate, sodium hydrogen sulphate, sodium dihydrogen orthophosphate, disodium ethylenediaminetetraacetate, aluminium acetate and potassium hydrogen tartrate, aluminium sulphate and aluminium potassium sulphate.
- The concentration of acid or acidic salt may be varied over a wide range depending on the end use of the composition. In some cases, particularly where a strong acid such as hydrofluoric acid is used and a near neutral product is required, the concentration of acid or acidic salt may be as low as 0.01% w/w.
- In other cases, the concentration of acid or acidic salt may be in excess of 90%.
- Generally, the concentration of acid or acidic salt will lie in the range of from 0.1 to 30% w/w.
- In use, generally the thickening agent will be present in a concentration in the composition of from 0.1 to 10% w/w. Preferably, the concentration in the composition will lie in the range of from 0.4 to 5.0% w/w. In order to achieve a desired viscosity in the composition, the concentration of the thickening agent may be varied appropriately. However, in some cases, it has been found that it is not possible to achieve sufficient composition viscosity for some applications. In such cases, the addition of a salt which has high ionic strength has been found to enhance the viscosity of these compositions. In most cases however, the concentration of thickening agent and high ionic strength salt will be optimized in order to produce a cost effective composition of the desired viscosity. Generally, the ionic salts will be selected from alkali metal halides or sulphates and ammonium halides or sulphates. Suitable such salts include sodium chloride, sodium sulphate, potassium sulphate, potassium chloride, ammonium chloride and the like.
- Alternatively, the present inventor believes that certain long chain quaternary ammonium compounds may achieve similar thickening to the aforementioned salts. An example is Arquad 16-50 which is hexadecyltri- methyl ammonium chloride or Arquad S-50 which is a mixture of octadecanyl and octadecadienyl trimethyl ammonium chloride. Arquad is a trade mark of Armour Hess Chemicals.
- It has further been found that in some cases whilst the composition is thick, clear and stable at room temperature, in order to achieve a satisfactory upper and lower cloud point for a composition, it is necessary to add another ingredient such as salt with a strong ionic effect of the type mentioned above, a cationic, nonionic or amphoteric surfactant or a solvent miscible with the composition, for example ethanol, isopropanol butyl lcinol and the like (Icionol is a trade mark of ICI) and Dowanol DPM (dipropyleneglycol methylether. Dowanol is a trade mark of Dow Chemicals). Such an addition of salt, surfactant or solvent insures that a composition will remain stable under hot and cold weather conditions.
- A variety of other ingredients may be added to compositions of the invention depending on their end use. Thus, germicides, surfactants including anionic, nonionic, cationic and amphoteric, sequestering agents, corrosion inhibitors, perfumes and colouring agents may be added.
- A principal advantage of the present invention is that an aqueous acid or acidic salt solution may be readily and easily thickened. Generally the steps of obtaining such thickened compositions will be - (a) add an appropriate amount of acid or acidic salt to water and stir to dissolve, (b) add a thickening agent of the present invention to the solution and stir until dissolved and (c) added other ingredients if required, stirring to dissolve. It will be appreciated that since the thickening agent of the present invention is defined to be soluble in the selected acidic salt or acid solution, and as it will generally be easily wet, the step (b) above will be relatively rapid unlike many of the prior art thickening agents, which whilst they may be soluble are frequently difficult to wet.
- Other advantages of the thickening agents of the present invention are that they are relatively inexpensive and in use produce smooth, homogeneous immediate thickening. Furthermore, thickened compositions are stable with respect to viscosity. For example, the present inventor has found that a citric acid composition thickened with Farmin O had no substantial change in viscosity when stored at room temperature for 12 months.
- A still further advantage is that the present inventor has found that the compositions of the invention have some surfactant and corrosion inhibition properties. The former finding means that water immiscible substances such as fragrances may be directly solubilized in a composition of the invention without requiring the addition of emulsifiers or auxilliary solvents, and in compositions in which the surface active properties are required, potentially less or no additional surfactant would be required.
- The present inventor has also found that if only sufficient of an acid or an acidic salt is present to just dissolve a thickening agent of the present invention, then a composition of near neutral pH may be obtained. Thus, Farmin O may be used to thicken lactic acid at a pH of 6.5. The advantage of this finding is that it may be used in aqueous liquid cleaners in general.
- The present inventor has further found that an acid or acidic salt which is usually considered to be water insoluble at room temperature may be brought into solution through the use of a thickening agent of the present invention, with thickening occurring. The viscosity may be increased through the use of a strong ionic salt such as sodium chloride. To prepare such compositions, the acid is dispersed in the water and the thickening agent added with mixing. It is observed that as the acid and thickener go into solution, the solution increases in viscosity.
- Preferred compositions of this type include ethylenediaminetetraacetic acid with Genamin S0302D as the thickening agent, potassium hydrogen tartrate with Genamin TA302D as thickening agent and pentetic acid with Farmin O as thickening agent.
- Hereinafter are a number of examples, 1 to 60, of the present invention, together with comparative examples 1A and 1B, in which the viscosity, in centipoise, of each was determined using a Brookfield RVT viscometer using a spindle and speed as appropriate at 25°C. Note that the thickening agent is asterixed in each case. All of these examples (except Nos. 27, 46 and 51) were produced by bringing the acid or acidic salt into solution, adding the thickening agent and mixing until dissolved, and then adding the other ingredients with mixing until dissolved.
- Examples 27, 46 and 51 were prepared by dispersing the acid or acid salt in water, adding the thickening agent and mixing until solution occurred, followed by sodium chloride (if required) until a satisfactory viscosity was achieved.
- Note that all examples were prepared under normal laboratory conditions.
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- It is to be noted that the viscosity of Example 1, when compared with the viscosity of water (1A) and 5% w/w citric acid (1 B), is substantially greater. A comparison with an aqueous solution of the thickening agent in this case was not possible as the thickening agent is water insoluble.
- The examples 1 to 60 disclosed herein may be used for example as toilet bowl cleaners, metal cleaners and brighteners and the like as well as applications such as gel batteries
Claims (19)
wherein the thickened aqueous composition has a viscosity of not less than 30 centipoise at 25° C when mesured with a Brookfield RVT viscometer at 50 rpm using a No.1 spindle.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT87306355T ATE64753T1 (en) | 1986-07-17 | 1987-07-17 | AMINO ACID THICKENING AGENT. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU6989/86 | 1986-07-17 | ||
AUPH698986 | 1986-07-17 |
Publications (4)
Publication Number | Publication Date |
---|---|
EP0253676A2 true EP0253676A2 (en) | 1988-01-20 |
EP0253676A3 EP0253676A3 (en) | 1988-09-21 |
EP0253676B1 EP0253676B1 (en) | 1991-06-26 |
EP0253676B2 EP0253676B2 (en) | 1994-08-03 |
Family
ID=3771719
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87306355A Expired - Lifetime EP0253676B2 (en) | 1986-07-17 | 1987-07-17 | Amine-acid thickening compositions |
Country Status (21)
Country | Link |
---|---|
EP (1) | EP0253676B2 (en) |
JP (1) | JPS6324000A (en) |
KR (1) | KR950006289B1 (en) |
AT (1) | ATE64753T1 (en) |
AU (1) | AU602707B2 (en) |
BR (1) | BR8703747A (en) |
DE (1) | DE3771008D1 (en) |
DK (1) | DK170538B1 (en) |
EG (1) | EG18545A (en) |
ES (1) | ES2022360T5 (en) |
GR (1) | GR3002573T3 (en) |
IE (1) | IE60070B1 (en) |
IN (1) | IN172271B (en) |
MX (1) | MX170920B (en) |
MY (1) | MY102871A (en) |
NO (1) | NO175967C (en) |
NZ (1) | NZ221105A (en) |
PT (1) | PT85352B (en) |
ZA (1) | ZA875279B (en) |
ZM (1) | ZM5787A1 (en) |
ZW (1) | ZW13287A1 (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0486113A2 (en) * | 1990-11-16 | 1992-05-20 | Akzo Nobel N.V. | Biodegradable fabric softeners derived from aspartic acid or glutaminic acid |
WO1994028108A1 (en) * | 1993-06-01 | 1994-12-08 | Ecolab Inc. | Thickened hard surface cleaner |
DE4331942A1 (en) * | 1993-09-21 | 1995-03-23 | Loeffler Karl Gmbh & Co Kg | Composition for cleaning and disinfecting articles and the use thereof in a cleaning process |
WO1996013565A1 (en) * | 1994-10-28 | 1996-05-09 | The Procter & Gamble Company | Hard surface cleaning compositions comprising protonated amines and amine oxide surfactants |
US5624891A (en) * | 1994-06-07 | 1997-04-29 | Reckitt & Colman Inc. | Drain opening compositions thickened with N-alkyl-N-acyl amino acids and myristyl/cetyl dimethyl amine oxides |
US5639722A (en) * | 1993-01-13 | 1997-06-17 | The Clorox Company | Acidic aqueous cleaning compositions |
WO1997025401A1 (en) * | 1996-01-03 | 1997-07-17 | S.C. Johnson & Son, Inc. | Cleaning compositions |
EP0808892A1 (en) * | 1996-05-21 | 1997-11-26 | The Procter & Gamble Company | Acidic cleaning compositions |
EP0808891A1 (en) * | 1996-05-21 | 1997-11-26 | The Procter & Gamble Company | Acidic cleaning compositions |
US6617293B2 (en) | 2001-08-06 | 2003-09-09 | 3M Innovative Properties Company | Thickening on dilution liquid soap |
WO2021023415A1 (en) * | 2019-08-07 | 2021-02-11 | Beiersdorf Ag | Comestic nanoemulsion |
US11395484B2 (en) | 2003-05-28 | 2022-07-26 | Agquam R&D, Llc | Manufacture and use of agricultural spray adjuvants for hard water conditions |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MX169902B (en) * | 1986-07-10 | 1993-07-30 | Colgate Palmolive Co | IMPROVEMENTS TO FABRIC CONDITIONING COMPOSITIONS THROUGH WASHING |
US4743395A (en) * | 1986-09-12 | 1988-05-10 | The Drackett Company | Thickened acid cleaner compositions containing quaternary ammonium germicides and having improved thermal stability |
US4869836A (en) * | 1988-05-03 | 1989-09-26 | Colgate-Palmolive Co. | Wash cycle fabric conditioning compositions: tertiaryamine-multi-functional carboxylic acid complex |
FR2897611B1 (en) * | 2006-02-20 | 2008-05-30 | Gilles Allard | TREATMENT PRODUCT FOR A TANK AND A WATER HUNTING BOWL |
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GB2071688A (en) | 1980-03-13 | 1981-09-23 | Jeyes Ltd | Liquid Cleaning and Descaling Compositions |
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- 1987-07-16 DK DK372187A patent/DK170538B1/en not_active IP Right Cessation
- 1987-07-16 KR KR1019870007740A patent/KR950006289B1/en not_active IP Right Cessation
- 1987-07-16 MX MX007379A patent/MX170920B/en unknown
- 1987-07-16 MY MYPI87001031A patent/MY102871A/en unknown
- 1987-07-16 EG EG417/87A patent/EG18545A/en active
- 1987-07-17 EP EP87306355A patent/EP0253676B2/en not_active Expired - Lifetime
- 1987-07-17 ZA ZA875279A patent/ZA875279B/en unknown
- 1987-07-17 IN IN614DE1987 patent/IN172271B/en unknown
- 1987-07-17 AU AU75787/87A patent/AU602707B2/en not_active Ceased
- 1987-07-17 IE IE194387A patent/IE60070B1/en not_active IP Right Cessation
- 1987-07-17 BR BR8703747A patent/BR8703747A/en not_active IP Right Cessation
- 1987-07-17 JP JP62177332A patent/JPS6324000A/en active Pending
- 1987-07-17 NO NO873000A patent/NO175967C/en unknown
- 1987-07-17 ES ES87306355T patent/ES2022360T5/en not_active Expired - Lifetime
- 1987-07-17 PT PT85352A patent/PT85352B/en not_active IP Right Cessation
- 1987-07-17 ZW ZW132/87A patent/ZW13287A1/en unknown
- 1987-07-17 DE DE8787306355T patent/DE3771008D1/en not_active Expired - Lifetime
- 1987-07-17 AT AT87306355T patent/ATE64753T1/en not_active IP Right Cessation
- 1987-07-17 NZ NZ221105A patent/NZ221105A/en unknown
- 1987-07-17 ZM ZM57/87A patent/ZM5787A1/en unknown
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1991
- 1991-08-19 GR GR91401221T patent/GR3002573T3/en unknown
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US3786091A (en) | 1969-06-23 | 1974-01-15 | Boelsing F | Phosphoric acid salts of long chain amino compounds |
GB1443244A (en) | 1972-11-27 | 1976-07-21 | Reckitt & Colmann Prod Ltd | Liquid cleaning and descaling compositions |
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Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0486113A3 (en) * | 1990-11-16 | 1992-07-08 | Akzo N.V. | Biodegradable fabric softeners derived from aspartic acid or glutaminic acid |
EP0486113A2 (en) * | 1990-11-16 | 1992-05-20 | Akzo Nobel N.V. | Biodegradable fabric softeners derived from aspartic acid or glutaminic acid |
US5639722A (en) * | 1993-01-13 | 1997-06-17 | The Clorox Company | Acidic aqueous cleaning compositions |
US6268324B1 (en) | 1993-06-01 | 2001-07-31 | Ecolab Inc. | Thickened hard surface cleaner |
WO1994028108A1 (en) * | 1993-06-01 | 1994-12-08 | Ecolab Inc. | Thickened hard surface cleaner |
US6630434B2 (en) | 1993-06-01 | 2003-10-07 | Ecolab Inc. | Thickened hard surface cleaner |
DE4331942A1 (en) * | 1993-09-21 | 1995-03-23 | Loeffler Karl Gmbh & Co Kg | Composition for cleaning and disinfecting articles and the use thereof in a cleaning process |
US5645648A (en) * | 1993-09-21 | 1997-07-08 | Karl Loffler GmbH & Company KG | Process for cleaning and disinfecting devices in the brewing industry |
US5624891A (en) * | 1994-06-07 | 1997-04-29 | Reckitt & Colman Inc. | Drain opening compositions thickened with N-alkyl-N-acyl amino acids and myristyl/cetyl dimethyl amine oxides |
WO1996013565A1 (en) * | 1994-10-28 | 1996-05-09 | The Procter & Gamble Company | Hard surface cleaning compositions comprising protonated amines and amine oxide surfactants |
WO1997025401A1 (en) * | 1996-01-03 | 1997-07-17 | S.C. Johnson & Son, Inc. | Cleaning compositions |
EP0808891A1 (en) * | 1996-05-21 | 1997-11-26 | The Procter & Gamble Company | Acidic cleaning compositions |
EP0808892A1 (en) * | 1996-05-21 | 1997-11-26 | The Procter & Gamble Company | Acidic cleaning compositions |
US6617293B2 (en) | 2001-08-06 | 2003-09-09 | 3M Innovative Properties Company | Thickening on dilution liquid soap |
US11395484B2 (en) | 2003-05-28 | 2022-07-26 | Agquam R&D, Llc | Manufacture and use of agricultural spray adjuvants for hard water conditions |
WO2021023415A1 (en) * | 2019-08-07 | 2021-02-11 | Beiersdorf Ag | Comestic nanoemulsion |
Also Published As
Publication number | Publication date |
---|---|
ATE64753T1 (en) | 1991-07-15 |
KR880001797A (en) | 1988-04-26 |
MY102871A (en) | 1993-03-31 |
NO873000L (en) | 1988-01-18 |
NO873000D0 (en) | 1987-07-17 |
IN172271B (en) | 1993-05-29 |
GR3002573T3 (en) | 1993-01-25 |
ZW13287A1 (en) | 1987-10-28 |
NZ221105A (en) | 1990-01-29 |
DK372187A (en) | 1988-01-18 |
IE60070B1 (en) | 1994-06-01 |
DK372187D0 (en) | 1987-07-16 |
AU7578787A (en) | 1988-01-21 |
EP0253676B1 (en) | 1991-06-26 |
NO175967C (en) | 1995-01-11 |
DE3771008D1 (en) | 1991-08-01 |
ES2022360B3 (en) | 1991-12-01 |
ES2022360T5 (en) | 1995-08-16 |
AU602707B2 (en) | 1990-10-25 |
ZA875279B (en) | 1988-04-27 |
MX170920B (en) | 1993-09-22 |
EP0253676B2 (en) | 1994-08-03 |
IE871943L (en) | 1988-01-17 |
JPS6324000A (en) | 1988-02-01 |
NO175967B (en) | 1994-10-03 |
PT85352B (en) | 1990-04-30 |
EG18545A (en) | 1993-07-30 |
EP0253676A3 (en) | 1988-09-21 |
ZM5787A1 (en) | 1989-09-29 |
DK170538B1 (en) | 1995-10-16 |
KR950006289B1 (en) | 1995-06-13 |
PT85352A (en) | 1987-08-01 |
BR8703747A (en) | 1988-03-29 |
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