AU602707B2 - Amine acid thickening compositions - Google Patents

Abstract

A thickened aqueous composition comprising at least one compound acid or acidic salt, a thickening agent which is at least one of the compounds selected from the group consisting of compounds of the formula: <CHEM> wherein R, R1 R2, R3, R4 and R5 are specified substituent groups, and optionally a strong ionic salt, the thickening agent and the acid or acidic salt being together substantially water soluble, and wherein the thickened aqueous composition has a viscosity of not less than 30 centipoise at 25 DEG C when measured with a Brookfield RVT viscometer at 50 rpm using a No. 1 spindle.

Description

A T' COMMONWEALTH OF AUSTRALI Patent Act 1952 0 2 COMPLETE SPE C I F I C A T ION

(ORIGINAL)

Class Int. Class Application Number PH06989 Lodged 17 July 1986 Complete Specification Lodged Accepted Published to 0 2 SPriority: o 0 0 s Related Art c o C This document contains the amendments made under Section 49 and is correct for printing.

Name of Applicant c I 6Ce C VC C ccAddress of Applicant Cr Ce Actual Inventor c c R C PRODUCTS PTY. LIMITED 845 Pacific Highway, CHATSWOOD. NEW SOUTH WALES.

COMMONWEALTH OF AUSTRALIA.

RAYMOND NEVILLE SILVESTER F.B. RICE CO., Patent Attorneys, 28A Montague Street, BALMAIN. 2041.

i Complete Specification for the invention entitled: "Amine Acid Thickening Compositions" The following statement is a full description of this invention including the best method of performing it known to Us:-

I

2 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 Cof the aforementioned compositions is that they have 1 5 sufficient viscosity so as to allow the composition to be 94 C4 effectively applied to surfaces, for example, by brushing, or to allow the composition to remain in contact with the C a" surface for a sufficient time to act. The latter function C egg has particular relevance to the cleaning of angular surfaces such as those found in toilet bowls where cc prolonged contact between the composition and the bowl is t required for effective cleaning.

C There are many such com,,).itions known in the art

I

4 V 0 It I I 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:cellulose derivatives exemplified by sodium carboxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, methyl cellulose, hydroxypropylmethyl cellulose, hydroxybutylmethyl cellulose; gums such as xanthan gum, acrylic acid polymers such as Carbopol (Registered Trade Mark of B.F. Goodrich) nonionic surfactants such as nonyl phenol ethoxylates; -3poly(ethylene oxide) resins such as Polyox (Registered Trade Mark of Union Carbide); anionic surfactants such as alkylbenzene sulfonates and alkyl ether sulfates; and 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 C viscosity, need to be neutralized with a fairly strong I i alkali.

Nonionic surfactants have the disadvantage that usually high levels of about 5-10% 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 2 composition viscosity and additionally, in some acid solutions show significant instability.

Sodium silicates are able to produce aqueous acid or cc" 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 -4the art which relate to an aqueous acid and/or acidic salt compositions include: GBl,443,244 (Reckitt Colman Products Limited) which discloses a thickening agent of the formula: 7A), z-

N.

y- H

CC

C

C CC C C

I

C C for thickening aqueous compositions of mineral acids and acid salts of strong inorganic acids.

GB2,071,688 (Jeyes Limited) which discloses as a thickening agent a mixture of: a substantially acid insoluble compound of the formula or (II) and a substantially acid soluble cationic or nonionic surfactant, for thickening aqueous compositions of 20 inorganic acids or acid salts of strong inorganic acids.

R

Z-R

CC

C C C CCC

C

CCC CCC C C

R

1 R 0 (I I) j 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 all, resulting mixture until cold.

0 sitUS 4,021,377 (Borchert et al) which discloses a 2 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 0 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 12-45% W/W and the citric acid, 19.2% W/W. Further, only the amines monoethanolamine, diethanolamine and C 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 6 liquid cleaning composition having 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, which composition comprises at least one acid or acidic salt, optionally a strong ionic salt in an amount up to a molar equivalent of 3% w/w sodium chloride and, as the sole organic agent to thicken the composition and impart said viscosity to the composition in an amount of from 0.1 to 10% w/w, at least one compound of the formula.

R I- R N 0 8 o a t 0 0 1 0 t" i It

I

ic Iec

S

IC tiI i c I II I S t i S* C I a I

S

in which R contains at least 6 carbon atoms and 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, or R 1 and R 2 when taken together comprise a substituted or 25 unsubstituted heterocyclic ring, provided that if either R, R 1 or R 2 is an alkyl or alkenyl derived from a fatty acid obtained from a natural oil or fat or an equivalent synthetic fatty acid, or is an alkaryl group containing from 8 to 12 carbon atoms in the alkyl moiety, 30 then the other substituents are not respectively of the formulae: H and H where A is either x y ethoxy or propoxy and x, y are independently 1, 2 or 3, the thickening agent and the acid or acidic salt being together substantially water soluble (as hereinbefore defined).

a 7 In a second aspect, the present invention consists in a method for the preparation of a thickened aqueous solution of an acid or acidic salt comprising, including in water a thickening agent which is at least one of the compounds selected from the group consisting of compounds of the formula: R N

I

ix o 9 o e9 o o o •9 o 9 o 99.

e o 9 o o 0 0 o o 9 090 oe o Q a o o 9 o o o oo o o o 15 in which R contains at least 6 carbon atoms and 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 20 alkyl, aryl, alkaryl, aralkyl or alkenyl group, or R and R 2 when taken together comprise a substituted or unsubstituted heterocyclic ring, provided that if either R, R 1 or R 2 is an alkyl or alkenyl group derived from a fatty acid obtained from a natural oil or fat or an equivalent synthetic fatty acid, or is an alkaryl group containing from 8 to 12 carbon atoms in the alkyl moiety, then the other substituents are not respectively of the formulae: [A]x-H and [A]y-H 30 where A is either ethoxy or propoxy and X, Y are independently 1, 2 or 3, an acid or acidic salt in an amount at least sufficient to neutralise the thickening agent; and optionally a strong ionic salt; the thickening agent 7 7a and acid or acidic salt being together substantially water soluble (a hereinbefore defined), and neutralizing the thickening agent with the acid or acidic salt to form a thickened aqueous solution, the amount of said thickening agent, acid or acidic salt and strong ionic salt being chosen such that said aqueous solution 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.

ct C rf

CC

t C C f tc ct 5 t t t 8 V 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 0 C or at most will form a hazy solution 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 catiornic or nonionic surfactant to achieve thickening.

By contrast the present invention is limited to amines which together with the selected acid or acidic salt are substantially water soluble, without a cationic or nonionic surfactant being required 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 f e Tj

Z~TRQ

ofQ -9solution of an inorganic acid or acid salt will cause thickening.

It will also be appreciated that the aforemention-~d 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 amine~s 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 t etc produced aqueous solutions containing 5% w/w citric acid anhydizous and 2% w/w mono-, di- or tri-ethanolamine. No thickening was noted in any of these solutions.

9 V25 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.

IThus, Bolsing in the simplest embodiment of his invention disperses the selected amine in water, heats the dispersion to between 40 0 C and 100 0 C and then adds to it at least a neutralising amount of phosphoric acid, preheated to between 40 0 C and 120 0 C. Stirring is continued until the temperature falls to between 5 0 C and 25 0 C and the resultant composition is a paste consisting

A

I,

4j

U

-~=I-ie~41

I

r 10 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 20 and the present inventor believes that amines additional to those of Bolsing are operative.

is- r-e-ti the bove formulae I or II C t

C

C C t C 8tO~ 4 4 tC

C

either of the groups R or R3 contains at least six carbon atoms. More preferably, either of the grpps R or

R

3 contains from 8 to 24 carbon atoms. Mos referably either of the groups R or R 3 contains f m 8 to 24 carbon atoms in an unsubstituted a 1 or alkenyl group.

Preferably, the groups R nd R 2 are independently a hydrogen m or a lower unsubstituted alkyl group, where lo r refers to groups containing 1 to 4 carbon atoms or, substituted alkyl group. More preferably t groups R 1 and R2 are independently a hydrogen om or a lower unsubstituted alkyl group. Most pref ably, the groups R 1 and R2 are independently a ogen atom or a methyl group.

C,

Qi Preferably, the group R contains from 8 to 24 carbon atoms. Most preferably the group R contains from 8 to 24 carbon atoms in an unsubstituted alkyl or alkenyl group.

Preferably, 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 1 and R 2 are independently a hydrogen atom or a lower unsubstituted alkyl Most preferably, the groups R i and R are independently a 1 2 hydrogen atom or a methyl group.

99 O0 SOft 4.

fot o t *0 O; 4 11 Preferred thickening agents of the present invention that are primary amines include Farmin 0 (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 15 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 I ionic salt to achieve the desired viscosity. However, it must also be considered that the addition of extra S 20 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 l -12 12 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 S 15 of a strong ionic salt such as sodium chloride. Genamin S0302D is able to thicken aqueous solutions of aluminium Ssulphate, 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 0, 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 Genamin 14R302D (tetradecyl dimethylamine distilled); 13 Genamin 16R302D (hexadecyl dimethylamine distilled); Genamin 14.100D (tetradecylamine distilled); Genamin 16R100D (hexadecylamine distilled); L The following amines obtainable from KenoGard- Amine 2MOL (dimethyloleylamine) Amine 28 (dioctylamine) Amine 210 (didecylamine) Amine M28 (methyldioctylamine) and Amine M210 (methyldidecylamine).

The following amine is obtainable from Onyx Chemicals Corp- Onamine 1416 (N-alkyl C 14

-C

16 dimethylamine).

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 0 is predominantly oleylamine having an approximate alkyl content of 6% C 14 13% C 16 and 81% C 18 whilst Genamin S0302D has an approximate average chain length distribution of 2% C 14 15% C 16 and 83% C18 and Genamin TA302D has an approximate average chain length distribution of 5% C 14 30% C 16 and 65% C 1 8 1i.

i IICL~1IEI~II-~IC~ 14 Amines 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 hexadecenoic 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, lactic, propionic, citric, malic, tartaric, adipic, maleic, ethylenediaminetetraacetic, malonic, glycollic, I r i i i: a ~i I~ I

I

I

I

15 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, 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.

15 In other cases, the concentration of acid or acidic salt may be in excess of 90% w/w.

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 cov,,position 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 trtt(r

I

"I

16 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 hexadecyltrimethyl ammonium chloride or Arquad S-50 which is a mixture of octadecanyl and octadecadienyltrimethyl 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 a 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 Icinol and the like (Icinol is a trade mark of ICI) and Dowanol DPM (dipropyleneglycol methylether. Dowanol is a trade mark of Dow Chemicals). Such an addition of salt, 1 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 25 compositions of the invention depending on their end use.

bacter1icdes Thus, qrjefEi'iE surfactants including anionic, nonionic, cationic and amphoteric, sequestering agents, corrosion inhibitors, perfumes and colouring agents may be added.

t A principal advantage of the present invention is 30 that an aqueous acid or acidic salt solution may be readily and easily thickened. Generally the steps of obtaining such thickened compositions will be add an appropriate amount of acid or acidic salt to water and stir to dissolve, add a thickening agent of the present invention to the solution and stir until dissolved I t It

I

ii i.: 11 r It I: I It

I

1 17 and add 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 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 30 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 The advantage of this finding is that it may be used in aqueous liquid cleaners in general.

35 The present inventor has further found that an acid 2 0' i tr ttr

C'

t r C C: r

J

I

18 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 5 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 acidic 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 of the examples were prepared under standard laboratory conditions.

1.J: -i

A

19 Example 1

I

I

Citric Acid Anhydrous Farmin 0 Water Viscosity (Spindle No. 2, speed 20 rpm, at 25 0

C)

pH Comparative Example 1A Water Viscosity Spindle 1 Spindle 2 w/w 1.8 93.2 670 cps 2.2 Speed 20 rpm Speed 50 rpm Speed 20 rpm Speed 50 rpm 3.5 cps 6.5 cps 0 cps 5.5 cps 0 cps 5.5 cps Example 1B Aqueous 5% w/w Citric Acid Anhydrous solution Viscosity Spindle 2 Speed 20 rpm Speed 50 rpm Example 2 w/w Citric Acid Anhydrous Farmin 0 Vantoc CL (Benzalkonium Chloride BP 50% w/v Vantoc is a trade mark of ICI) Sodium Chloride Perfume Dye Water Viscosity (Spindle No. 1, speed 50 rpm, at 25 0

C)

2.2 0.7 0.2 0.005 89.9 54 cps 2.3 t t

_T~

I r r? 20 Example 3 DL-Lactic Acid 88% Farmin 0 Sodium Chloride Water Viscosity (Spindle No. 2, speed 20 rpm, at 250C) pH Example 4 DL-Lactic Acid 88% Farmin 0 Vantoc CL (Benzalkonium Chloride BP 50% w/v Vantoc is a trade mark of ICI) Sodium Chloride Perfume Dye Water Viscosity (Spindle No. 2, speed 20 rpm, at 25 0

C)

pH Example DL-Lactic Acid 88% Farmin 0 Sodium Chloride Water Viscosity (Spindle No. 2, speed 20 rpm, at 250C) w/w 0.3 92.7 820 cps 2.9 w/w 0.4 0.35 0.2 0.005 92.05 530 cps 2.9 w/w 0.85 0.1 97.05 740 cps *0 o 0r 4 *44 t 44 I' tI 4 4 Itr 21 Example 6 w/w i" j ji:

I

j r i i ii

I

i ~9"rj Formic Acid 88% Farmin 0 Sodium Chloride Water Viscosity (Spindle No. 1, speed 50 rpm, at 25 0

C)

pH 4.1 0.05 93.85 58 cps Example 7 Formic Acid 88% Genamin TA100D Sodium Chloride Water Viscosity (Spindle No. 1, speed 50 rpm, at 250C) pH w/w 4.1 0.05 93.85 30 cps 2.45 Example 8 Acetic Acid (Glacial) Farmin 0 Sodium Chloride Water Viscosity (Spindle No. 2, speed 50 rpm, at 25°C) pH w/w 4.7 0.25 93.05 160 cps 3.6 1 t.t I t I t 22 Example 9 Acetic Acid (Glacial) Farmin 0 Vantoc CL (Benzalkonium Chloride BP 50% w/v Vantoc is a trade mark of ICI Sodium Chloride Perfume Dye Water Viscosity (Spindle No. 2, speed 50 rpm, at 25 0

C)

pH Example Acetic Acid (Glacial) Genamin TA100D Sodium Chloride Water Viscosity (Spindle No. 2, speed 20 rpm, at 25 C) pH Example 11 Propionic Acid Farmin 0 Sodium Chloride Water Viscosity (Spindle No. 1, speed 50 rpm, at 250C) w/w 4.7 0.4 0.35 0.2 0.005 92.35 180 cps 3.6 w/w 4.7 0.3 93.0 660 cps 3.6 iP

I~

t1 t t A I a t I L It t( w/w 5.8 0.3 91.9 58 cps 3.7 -Y3PXIILI II~ R~UX~~ ~X 23 Example 12 Citric Acid Anhydrous Genamin S0302D Sodium Chloride Perfume Water Viscosity (Spindle No. 2, speed 50 rpm, at 25 0

C)

pH Example 13 Citric Acid Anhydrous Genamin TA302D Sodium Chloride Perfume Water Viscosity (Spindle No. 2, speed 50 rpm, at 25 0

C)

pH w/w 0.2 90.8 220 cps 2.35 w/w 0.2 90.8 240 cps 2.35 I3

I

Example 14

(I

r

P

o L-Tartaric Acid Genamin S0302D Sodium Chloride Perfume Dye Water Viscosity (Spindle No. 2, speed 20 rpm, at 250C) w/w 5.9 1.4 0.2 0.005 90.5 625 cps 2.15 pi IILr rrm m U I s 24 Example L-Tartaric Acid Genamin TA302D Sodium Chloride Perfume Water Viscosity (Spindle No. 2, speed 20 rpm, at 25 0

C)

pH w/w 5.9 1.4 0.2 90.5 1065 cps 2.1 Example 16 Formic Acid 88% Genamin S0302D Sodium Chloride Dye Water Viscosity (Spindle No. 2, speed 50 rpm, at 25 0

C)

pH w/w 4.1 1.3 0.005 92.6 160 cps 2.4 Example 17 ji Cr I 4 rt Formic Acid 88% Genamin TA302D Sodium Chloride Water Viscosity (Spindle No. 2, speed 20 rpm, at 25 0

C)

w/w 4.1 1.6 92.3 500 cps r i

I

j N::i nl~,scs~t~i~~ 25 Example 18 DL-Malic Acid Genamin S0302D Sodium Chloride Dye Water Viscosity (Spindle No. 1, speed 20 rpm, at 25 0

C)

pH Example 19 DL-Lactic Acid 88% Genamin 16R302D Sodium Chloride Perfume Dye Water Viscosity (Spindle No. 1, speed 20 rpm, at 250C) pH Example Sulphamic Acid Genamin S0302D Sodium Chloride Water Viscosity (Spindle No. 1, speed 50 rpm, at 250C) w/w 5.2 1.6 0.005 91.2 97 cps 2.45 i

I

Ii w/w 0.2 0.005 88.8 100 cps 2.75 I, 5 I t 4 4 1 4r w/w 7.6 1.1 89.3 77 cps 0.8 -j -26 Example 21 i% w/w Sulphamic Acid 7.6 Genamin TA302D Sodium Chloride 1.7 Water 88.7 Viscosity (Spindle No. 2, speed 20 rpm, at 250C) 390 cps pH 0.9 Example 22 w/w Phosphoric Acid 85% 5.9 Genamin S0302D Sodium Chloride 1.1 Water 91.0 Viscosity (Spindle No. 2, speed 50 rpm, at 250C) 170 cps pH 1.35 Example 23 w/w Phosphoric Acid 85% 5.9 Genamin TA302D Sodium Chloride Water 90.6 Viscosity (Spindle No. 2, speed 20 rpm, at 250C) 395 cps S H 1.35 SExample 24 w/w Sulphuric Acid conc. 3.83 Genamin S0302D Water 94.17 Viscosity (Spindle No. 2, speed 20 rpm, at 25 0 C) 890 cps pH 0.85 7, I; 27 Example Sulphuric Acid conc.

Genamin TA302D Water Viscosity (Spindle No. 2, speed 20 rpm, at 25 0

C)

pH Example 26 Monosodium Citrate Genamin TA302D Sodium Chloride Water Viscosity (Spindle No. 2, speed 20 rpm, at 250C) pH Example 27 Ethylenediaminetetraacetic Acid Genamin S0302D Sodium Chloride Water Viscosity (Spindle No. 2, speed 20 rpm, at 25 C) pH Example 28 Al 2

(SO

4 3 .16H 2 0 Genamin S0302D Sodium Chloride w/w 3.83 94.2 375 cps 0.9 w/w 8.35 87.65 430 cps 3.75 i i i i:; i r i:- 1r i ;1 i i i i; w/w 0.8 1.7 95.5 730 cps 5.65 Water Viscosity (Spindle No. 2, speed 20 rpm, at 25 0

C)

pH w/w 6.7 0.3 91.0 390 cps 3.65 Ilrar ~u*l~u~-aul-~h

I

28 Example 29 AlK (SO 4 2 .12H 2 0 Genamin S0302D Sodium Chloride Water Viscosity (Spindle No. 2, speed 50 rpm, at 25 0

C)

pH w/w 10.0 0.1 87.9 240 cps 3.75 Example C t C- V -r Sodium Hydrogen Sulphate Genamin S0302D Water Viscosity (Spindle No. 2, speed 20 rpm, at 250C) pH w/w 88.5 1500 cps 0.9 Example 31 w/w :nC 1~ tt Sodium Dihydrogen Orthophosphate Dihydrate Genamin S0302D Water Viscosity (Spindle No. 2, speed 20 rpm, at 250C) pH Example 32 Adipic Acid Genamin S0302D Sodium Chloride Water Viscosity (Spindle No. 2, speed 50 rpm, at 250C) 12.0 86.0 585 cps 5.2 w/w 95.0 255 cps 4.55 7

+L

29 Example 33 Adipic Acid Farmin 0 Water Viscosity (Spindle No. 2, speed 5 rpm, at 25 0

C)

pH w/w 1.4 96.6 4095 cps 3.95 Example 34 Maleic Acid Genamin S0302D Sodium Chloride Water Viscosity (Spindle No. 1, speed 20 rpm, at 250C) pH w/w 96.5 113 cps 2.6 Example w/w Disodium Ethylenediaminetetraacetate Genamin S0302D Sodium Chloride Water Viscosity (Spindle No. 2, speed 20 rpm, at 25 0

C)

6.6 1.7 89.7 785 cps 5.8 i-rTh -e 1 i :r :1 t 30 Example 36 DL-Lactic Acid 88% Genamin TA100D Sodium Chloride Water Viscosity (Spindle No. 2, speed 20 rpm, at 250C) pH Example 37 Formic Acid 88% Farmin 0 Vantoc CL (Benzalkonium Chloride BP 50% w/v Vantoc is a trade mark of ICI Sodium Chloride Perfume Dye Water Viscosity (Spindle No. 1, speed 50 rpm, at 25 0

C)

pH w/w 0.6 89.4 1255 cps 2.7 w/w 4.1 0.4 0.15 0.2 0.005 93.15 89 cps

I.

Sa

SC

se 0 *o 50 *c 00

II

Example 38 ,'4 Formic Acid 88% Farmin O Vantoc CL (Benzalkonium Chloride BP 50% w/v Vantoc is a trade mark of ICI Sodium Chloride Perfume Dye Water Viscosity (Spindle No. 2, speed 20 rpm, at 25 0

C)

w/w 0.4 0.2 0.2 0.005 91.7 450 cps 2.05 i i i I 31 Example 39 Glycollic Acid 70% Farmin O Sodium Chloride Water Viscosity (Spindle No. 2, speed 20 rpm, at 25 C) pH w/w 0.2 89.3 660 cps Example I S o f v t t Glycollic Acid 70% Genamin SO 302D Sodium Chloride Water Viscosity (Spindle No. 2, speed 50 rpm, at 250C) pH Example 41 Malonic Acid Farmin O Water Viscosity (Spindle No.2, speed 50 rpm, at 250C) pH w/w 1.8 87.7 290 cps 2.3 n

I

rr r r w/w 94.0 185 cps '1 1 Example 42 Malonic Acid Genamin SO 302D Sodium Chloride Water Viscosity (Spindle 1, speed 50 rpm, at 25 0

C)

w/w 1.6 92.4 69 cps 1.9 S- 32 Example 43 Succinic Acid Farmin O Sodium Chloride Water Viscosity (Spindle No. 2, speed 50 rpm, at 250C) pH w/w 4.6 0.1 93.3 230 cps 3.1 Example 44 K tr

I

I

UK1.

Ittr U I I I

I

4 1 K iI rI

I

Succinic Acid Genamin SO 302D Sodium Chloride Water Viscosity (Spindle No. 1, speed 50 rpm, at 25°C) pH w/w 4.6 2.4 91.0 105 cps 3.1 Example ~7~t; L(+)-Ascorbic Acid Farmin 0 Sodium Chloride Water Viscosity (Spindle No. 2, speed 20 rpm, at 25 C) pH w/w 13.75 83.75 705 cps 2.9 Example 46 D.T.P.A.(Pentetic Acid) Farmin O Water Viscosity (Spindle No. 2, speed 20 rpm, at 25 0

C)

pH w/w 1.3 96.7 1185 cps 3.2 33 Example 47 w/w Chloroacetic Acid 8.6 Farmin O Water 89.4 Viscosity (Spindle No. 1, speed 50 rpm, at 25 0 C) 96 cps pH 1.7 Example 48 w/w Hydrofluoric Acid 50% 3.1 Genamin SO 302D Sodium Chloride 0.6 Water 94.3 Viscosity (Spindle No. 2, speed 50 rpm, at 250C) 370 cps pH 1.2 Example 49 w/w Boric Acid Genamin SO 302D Sodium Chloride 1.4 Water 91.6 Viscosity (Spindle No. 1, speed 20 rpm, at 250C) 280 cps pH 6.2 Example w/w Aluminium Acetate 5.3 Farmin 0 Water 92.7 Viscosity (Spindle No. 2, speed 20 rpm, at 25 0 C) 1055 cps pH 5.2

I

-4 i 1111~ 7 34 Example 51 Potassium Hydrogen Tartrate Genamin TA 302D Sodium Chloride Water Viscosity (Spindle No. 1, speed 50 rpm, at 25°C) pH w/w 1.1 0.7 96.2 78 cps 6.3 Example 52 Sulphuric Acid conc.

Genamin 14R302D Genamin 16R302D Sodium Chloride Water Viscosity (Spindle No. 1, speed 20 rpm, at 250C) pH Example 53 Sulphuric Acid conc.

Genamin 16R302D Water Viscosity (Spindle No. 2, speed 20 rpm, at 250C) pH w/w 3.83 1.00 1.00 3.00 91.17 212 cps 0.4 w/w 7.7 90.3 556 cps 0.15

UI

L

,~,~innrxarrrmmn~ ra~~r;rrc~:~ 35 Examle 54 Hydrochloric acid 30% technical Genamin 14R302D Sodium Chloride Water Viscosity (Spindle No. 1, speed 50 rpm, at 25°C) pH w/w 85.5 105 cps 0.1 Example Hydrochloric acid 30% technical Genamin TA302D Water Viscosity (Spindle No. 2, speed 50 rpm, at 250C) w/w 53.0 45.0 380 cps Example 56 Genamin TA302D Hydrochloric acid 30% Sodium chloride Water Viscosity (Spindle No. 1, speed 50 rpm, at 250C) w/w 0.50 0.20 1.20 98.10 50 cps t;, ~tt 1 r n

I

a u~~kii

I

*1 36 Example 57 *Genamin S0302D Hydrochloric acid 50% Sodium chloride Water Viscosity (Spindle No. 1, speed 50 rpm, at 250C) pH w/w 0.30 0.06 1.40 98.24 32 cps 4.3 4 i 's' .444

I(

1tt Example 58 Genamin S0302D Hydrochloric acid 50% Sodium chloride Water Viscosity (Spindle No. 1, speed 50 rpm, at 25 C) pH w/w 0.50 0.10 1.40 98.00 49 cps 4.6

I

I

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 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.

-j

I

~II~I1I 37 The examples 1 to 68 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.

*a o o 0 *0t 0$ 0o o 040 o .4* iioi

I

Claims (42)

1. A thickened aqueous liquid cleaning composition having a viscosity of not less than 30 centipoise at C when measured with a Brookfield RVT viscometer at rpm using a No. 1 spindle, which composition comprises at least one acid or acidic salt, optionally a strong ionic salt in an amount up to a molar equivalent of 3% w/w sodium chloride and, as the sole organic agent to thicken the composition and impart said viscosity to the composition in an amount of from 0.1 to 10% w/w, at least one compound of the formula. I R N ij i ii Ito in which R contains at least 6 carbon atoms and 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, or R 1 and R 2 when taken together comprise a substituted or unsubstituted heterocyclic ring, provided that if either R, R 1 or R 2 is an alkyl or alkenyl derived from a fatty acid obtained from a natural oil or fat or an equivalent synthetic fatty acid, or is an alkaryl group containing from 8 to 12 carbon atoms in the alkyl moiety, then the other substituents are not respectively of the formulae: H and H where A is either x y ethoxy or propoxy and x, y are independently 1, 2 or 3, the thickening agent and the acid or acidic salt being together substantially water suluble (as hereinbefore defined). 4 A i' -39-

2. A composition as in claim 1, wherein the thickening agent is water insoluble.

3. A composition as in claim 1 or 2, wherein the pH of the composition is not more than

4. A composition as in claim 3, wherein the group R contains from eight to twenty four carbon atoms.

A composition as in any one of claims 1 to 4, wherein the group R is an unsubstituted alkyl or alkenyl group.

6. A composition as in claim 5, wherein R is derived from either a natural or synthetic source of tallow, soya bean oil, oleic acid, palmitic or myristic acid.

7. A composition as in claim 5, wherein R is derived from either a natural or synthetic source of linolenic, ricinoleic, linoleic, or hexadecenoic acid.

8. A composition as in any one of claims 1 to 7, wherein the groups R 1 and R 2 are independently a hydrogen atom, a lower unsubstituted alkyl group containing one to four carbon atoms, or a substituted alkyl group.

9. A composition as in claim 8 wherein the groups R 1 and R 2 are independently a hydrogen atom or a lower unsubstituted alkyl group. A composition as in claim 9, wherein the groups R 1 and R 2 are independently a hydrogen atom or a methyl group.

I, OW a

11. A composition as in any one of claims 1 to 10 wherein the thickening agent is a mixture of compounds.of the formula I.

12. A composition as in any one of claims 1 to 11 wherein the acid is selected from the group consisting of phosphoric, sulphuric, boric, sulphamic, tartaric, citric, lactic, formic, acetic, glycollic, pentetic, ethylenediaminetetraacetic, propionic, malic, adipic, maleic, malonic, succinic, hydrofluoric, ascorbic, hydrochloric and chloroacetic acids.

13. A composition as in any one of claims 1 to 12, wherein the acidic salt is selected from the group consisting of monosodium citrate, sodium hydrogen sulphate, sodium dihydrogen orthophosphate, disodium ethylenediaminetetraacetate, aluminium potassium sulphate, aluminium acetate, potassium hydrogen tartrate and aluminium sulphate.

14. A composition as in any one of claims 1 to 13, wherein the concentration of thickening agent is in the range of from 0.1 to 10% w/w.

A composition as in any one of claims 1 to 14, wherein the concentration of thickening agent is in the range of from 0.4 to 5.0% w/w.

16. A composition as in any one of claims 1 to wherein the concentration of acid or acidic salt is not less than 0.01% w/w.

17. A composition as in any one of claims 1 to 16, S*wherein the concentration of acid or acidic salt is in the 3 range of from 0.1 to 30% w/w. %i 41

18. A composition as in any one of claims 1 to 17, additionally including a perfume, dye, sequestering agent, surfactant or bactericide.

19. A composition as in claim 18, wherein the bactericide is a quaternary ammonium compound.

A composition as in any one of claims 1 to 19, wherein the strong ionic salt is selected from the group consisting of alkali metal halides or sulphates and ammonium halides or sulphates.

21. A composition as in any one of claims 1 to 19, wherein the strong ionic salt is a long chain quaternary ammonium compound.

22. A composition as in any one of claims 1 to 21, further including a compound effective in adjusting the upper and/or lower cloud point of the composition.

23. A composition as in claim 22, wherein the compound is I selected from the group consisting of strong ionic salts, t anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, a solvent miscible with the composition, or mixtures thereof.

24. A composition as in claim 23, whe:ein the solvent is ethanol, isopropanol, butoxyethanol or dipropylene glycol methylether.

A composition substantially as defined in any one of examples 2 to 51.

26. A toilet bowl cleaning composition comprising a composition as claimed in any one of claims 1 to 24. i- i ~-"~mrr~i~wn~ 42

27. A method for the preparation of a thickened aqueous solution of an acid or acidic salt comprising,.including in water a thickening agent which is at least one of the compounds selected from the group consisting of compounds of the formula: R N in which R contains at least 6 carbon atoms and 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, or R 1 and R 2 when taken together comprise a substituted or unsubstituted heterocyclic ring, provided that if either R, R 1 or R 2 is an alkyl or alkenyl group derived from a fatty acid obtained from a natural oil or fat or an equivalent synthetic fatty acid, or is an lIkaryl group containing from 8 to 12 carbon atoms in the alkyl moiety, then the other substituents are not respectively of the formulae: [A]x-H and [A]y-H where A is either ethoxy or propoxy and X, Y are independently 1, 2 or 3, i i;L_ 1 I I I I Yi 43 an acid or acidic salt in an amount at least sufficient to neutralise the thickening agent; and optionally a strong ionic salt; the thickening agent and acid or acidic salt being together substantially water soluble (as hereinbefore defined), and neutralizing the thickening agent with the acid or acidic salt to form a thickened aqueous solution, the amount of said thickening agent, acid or acidic salt and strong ionic salt being chosen such that said aqueous solution 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.

28. A method as in claim 27, wherein the acid or acidic salt, the thickening agent and the strong ionic salt are respectively in concentrations of from 0.01 to 90% w/w, 0.1 to 10% w/w, and up to a molar equivalent of 3% sodium chloride in the thickened solution.

29. A method as in claim 27 or claim 28, wherein the thickening agent is water-insoluble.

A method as in any one of claims 27 to 29 wherein the pH of the thickened aqueous solution is not more than

31. A method as in any one of claims 27 to 30 wherein the group R contains from 8 to 24 carbon atoms.

32. A method as in any one 27 to 31 claims, wherein the group R is a substituted or unsubstituted alkyl or alkenyl group.

33. A method as in claim 32, wherein R is derived from either a natural or synthetic source of tallow, soya bean oil, oleic acid, palmitic or myristic acid.

34. A method as in claim 32, wherein R is derived from a natural or synthetic source of linolenic, ricinoleic, linoleic or hexadecenoic acids.

A method as in any one of 27 to 34 claims, wherein the groups R 1 and R 2 are independently a hydrogen atom, a lower unsubstituted alkyl group containing one to four carbon atoms, or a substituted alkyl group.

36. A method as in claim 35 wherein the groups R 1 and R 2 are independently a hydrogen atom or a lower unsubstituted alkyl group. 4 'I 44

37. A method as in claim 36, wherein the groups R 1 and R 2 are independently a hydrogen atom or a methyl group.

38. A method as in any one of 27 to 37 claims, wherein the thickening agent is a mixture of compounds of the formula I.

39. A method as in any one of claims 27 to 38, wherein the acid is selected from the group consisting of phosphoric, sulphuric, boric, sulphamic, tartaric, citric, lactic, formic, acetic, glycollic, pentetic, hydrochloric, ethylenediaminetetraacetic, propionic, malic, adipic, maleic, malonic, succinic, hydrofluoric, ascorbic and chloroacetic acids.

A method as in any one of claims 27 to 39, wherein the acidic salt is selected from the group consisting of monosodium citrate, sodium hydrogen sulphate, sodium dihydrogen orthophosphate, disodium ethylenediaminetetraacetate, aluminium potassium sulphate, aluminium acetate, potassium hydrogen tartrate and aluminium sulphate.

41. A method as in any one of claims 27 to 40, wherein the concentration of thickening agent is in the range of from 0.4 to 5.0% w/w.

42. A method as in any one of claims 27 to 41, wherein the concentration of acid or acidic salt is in the range of from 0.1 to 30% w/w. DATED this 16th day of March 1990 R C PRODUCTS PTY LIMITED Patent Attorneys for the Applicant: 1 i:E s j I 1 j j I:f i, 3 D ii~ F.B. RICE CO. r, 1