AU659640B2 - Cast cleaning and/or deodorizing composition - Google Patents

Description

OPI DATE 21/12/92 APPLN. ID 16525/92 1111111111 E i 1111|||1| AOJP DATE 28/01/93 PCT NUMBER PCT/EP92/00936 11111 1111111111 II il1 AU9216525 INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 5 (11) International Publication Number: WO 92/19712 Cu1D 17/00, 9/00, 10/04 Al A61L 9/01 (43) International Publication Date: 12 November 1992 (12.11.92) (21) International Application Number: PCT/EP92/00936 (74) Agents: HUBERT, Philippe et al.; Cabinet Beau de Lomenie, 55, rue d'Amsterdam, F-75008 Paris (FR).

(22) International Filing Date: 27 April 1992 (27.04.92) (81) Designated States: AT (European patent), AU, BE (Euro- Priority data: pean patent), CA, CH (European patent), DE (Euro- 91/05268 29 April 1991 (29.04.91) FR pean patent), DK (European patent), ES (European patent), FR (European patent), GB (European patent), GR (European patent), IT (European patent), JP, LU (Euro- (71) Applicant (for all designated States except US): S.C. JOHN- pean patent), MC (European patent), NL (European pa- SON SON, INC. [US/US]; 1525 Howe Street, Racine, tent), SE (European patent), US.

WI 53403-5011 (US).

(72) Inventors; and Published Inventors/Applicants (for US only) FERRANDO, Jean- With international search report.

Christophe [FR/GB]; South Lodge, Milton Park, Stroude Road, Egham, Surrey TW20 9UH MAZ- IER, Henri [FR/FR]; 7, rue du Sergent-Bobillot, F- 37000 Tours (54) Title: CAST CLEANING AND/OR DEODORIZING COMPOSITION (57) Abstract The present invention relates to a solid cast composition containing no paradichlorobenzene, usable notably as cleaning and/or deodorizing product. The composition according to the invention, which is preoared by melting the constituents under stirring and casting the resulting molten mixture in cooling molds, comprises 3 to 15 by weight of a behenic acid soap obtained by reacting behenic acid with at least one saponifying agent selected from the group including alkaline metal hydroxides, alkanolamines, alkanamines, alkaline or alkalino-earth carbonates or silicates.

SWb 92/19712 PCT/EP92/00936 CAST CLEANING AND/OR DEODORIZING COMPOSITION The present invention relates to a novel solid cast composition, usable notably as cleaning and/or deodorizing product, and to its preparation process.

production of devices for the automatic cleaning of toilets, such as for example W.C. blocks or containers designed to be immersed in the flushing tank, or to the production of air fresheners.

It is recalled that a W.C. block is a product which, after each flushing of the bowl, ensures the cleaning and deodorizing of toilet bowls. This product is generally constituted of a solid active block placed and held inside the bowl, for example in a perforated cage-like container equipped with a hook.

After each flushing of the bowl, these products clean the toilet bowl, ensure the formation of foam on the water in the bowl and deodorize.

For the consumer, these blocks have a duration of use corresponding to about 400-600 flushes.

The main properties required for these products are a good stability in time and under heat. Moreover, they are required to have a relatively high melting point (generally higher than 0 C) in order to withstand the varied conditions of use and principally of storage.

Currently, there are three important types of products on the toilet block market.

First of all, there are the products formed by compression and extrusion of solid and non-readily fusible materials (surfactants, such as alkylbenzenesulfonate or laurylsulfate; mineral fillers), and of liquids (perfume, solvents, 8 surfactants).

There are also the "cast" products containing paradichlorobenzene.

These products are prepared by melting the constituents and casting the resulting molten mixture in cooling molds.

Paradichlorobenzene is used: on the ine hand, as structuring agent since it enables the WO 92/19712 PCT/EP92/00936 2 retention of certain constituents (surfactants and perfume) and the production of a solid block; on the other hand, for controlling the wear caused by use, seeing that, given its hydrophobic properties, it permits a progressive release of the surfactants.

However, it is suspected that paradichlorobenzene is carcinogenic, so that the products of this second type tend to disappear from the market.

Consequently, there is a third type of products, which are cast products containing no paradichlorobenzene.

Yet, the currently known products of this type have at least one of the following disadvantages very poor quantity of foaming in the bowl; melting point too low; limited period of use; behavior degrading with time (toilet bowl staining).

Furthermore, the known products of the three types mentioned previously necessarily have a limited perfume content (less than or equal to about 15% by weight).

Indeed, perfumes, when incorporated in a proportion higher than 15% by weight, soften up the compositions obtained by extrusion and render them unsuitable for use.

In addition, the ccst products (with or without dichlorobenzene) which contain more than 15% by weight of perfume have a melting point which is too low and incompatible with the severe storage conditions which are normally encountered.

SIt is therefore the object of the present invention to solve the technical problem consisting in providing a new solid cast composition containing no paradichlorobenzene, usable in particular as cleaning and/or deodorizing product, which shows none of the aforementioned disadvantages and which can contain a very high proportion of perfume (up to 35% by weight).

The solution proposed by the present invention to solve said technical problem consists in a solid cast composition characterized in that it comprises 3 to 15% by weight of at least a i WO 92/19712 PCT/EP92/00936 3 behenic acid soap.

It has indeed been found, and this is the basis of the Spresent invention, that the use of a behenic acid soap instead of paradichlorobenzene, in solid cast compositions, makes it possible to obtain cleaning and/or deodorizing products of which the duration of use is comparable to that of blocks containing paradichlorobenzene and is optionally adjustable; products which form a rich and stable foam in the bowl and no unwanted ptaining of the toilet bowl during use.

It is moreover possible, when using behenic acid soaps, to incorporate to the solid cast compositions a very high proportion of perfume, reaching up to 35% by weight.

The various findings which constitute the basis of the present invention are surprising and unexpected.

Indeed, it is a known fact that soaps, which are excellent structuring agents, confer to the solid cast compositions, high melting points which can be corrected or reduced by addition of solvent. On the other hand, the "conventional" fatty acid soaps containing between 12 and 18 carbon atoms (lauric, myristic acids), considerably reduce the stability of the foam produced in the bowl, because of their insoluble nature. As a matter of fact, soaps are generally used as foam-suppressing agents in washing powders.

And also, fatty acid soaps containing between 12 and 18 carbon atoms cause an important reduction of the wearing time compared with blocks containing paradichlorobenzene; they also cause staining of the bowl during use.

The man skilled in the art could not, therefore, have been in any way tempted to look for a solution to the technical problem raised in the field of fatty acid soaps.

The benehic acid salts contained in the solid compositions according to the invention are generally obtained by saponification of the behenic acid.

The behenic (or n-docosanoic) acid is a saturated aliphatic fatty acid containing 22 carbon atoms, naturally found in u m* L i1:y i: WO 92/19712 PCT/EP92/00936 colza and mustard oils, in carnauba wax and in animal sphingolipids.

The industrially available behenic acid is in fact constituted by a mixture of pure behenic acid and other fatty acids in lesser quantity, such as for example the palmitic, stearic, arachidic and lignoceric acids.

It is possible, according to the present invention, to use the behenic acid pure or taken from a raw material, for example a colza extract.

It is, however, important for such raw material to contain the highest possible proportion of behenic acid, at least to 90% by weight.

Indeed, as indicated hereinabove, it is preferable to avoid incorporating, in quantities higher than about 20% by weight (and preferably higher than 10% by weight), other fatty acids naturally found in raw materials of natural origin, as these would make the finished product lose the advantages obtained from using behenic acid (poor and unstable foaming, staining of the bowl).

Suitable saponifying agents according to the invention include, in general, all basic agents reacting with behenic acid.

These agents can be used in pure form or in solution, alone or mixed.

Among suitable saponifying agents, there are in particular, alkaline metal hydroxides, such as sodium hydroxide and potassium hydroxide; alkanolamines, such as monoethanolamine, diethanolamine, triethanolamine; alkanamines; as well as alkaline or alkaline-earth carbonates and silicates.

Said saponifying agents will be used in equimolar quantity with respect to behenic acid.

Among the aforesaid saponifying agents, the preferred ones are sodium hydroxide, potassium hydroxide and alkanolamines which give harder products than the other saponifying agents.

According to a particular characteristic, a solid cast composition according to the invention further comprises up to 70% by weight, and preferably 15 to 50% of et least one WO 92/19712 PCT/EP92/00936 non-ionic surfactant; up to 60% by weight, and preferably 15 to 30%, of at least one anionic or amphoteric surfactant; up to 50% by weight, and preferably between 15 and 30%, of at least one organic solvent; up to 25% by weight, and preferably between 3 and 15%, of water; up to 35% by weight, and preferably between 5 and 20%, of at least one perfume; up to 25% by weight of at least one dye; up to 5% by weight of at least one additive selected from the group comprising the bactericidal agents and antitartar agents.

The non-ionic agents suitable for use according to the invention are generally ethoxylated fatty alcohols with an alkyl chain of hydrophobic nature and a polyoxyethylated chain of hydrophylic nature.

The hydrophobic alkyl part may be straight or branched, of natural or synthetic origin and it can contain for example 8 to 18 carbon atoms.

The hydrophilic polyoxyethylated part can contain 5 to 100 moieties of ethylene oxide.

These non-ionic surfactants can be in liquid, paste or solid form, and they are generally used pure or in solution.

Advantageously, the non-ionic surfactant used will be an ethoxylated fatty alcohol of which the straight or branched alkyl part contains 8 to 15 carbon atoms and of which the polyoxyethylated part is composed of 5 to 35 moieties of ethylene oxide. It has indeed been found that such products give a solid composition with a very high cleaning and foaming power.

It is possible, according to the presen invention, to use as aniolic or amphoteric surfactant, any one of the conventional amphoteric or anionic surfactants, as well as mixtures thereof.

Suitable anionic surfactants include alkyl benzene sulfonates, O(-olefin sulfonates, paraffin sulfonates, alkyl ether sulfates, alkyl sulfates, fatty acid sarcosinates, fatty acid 6 methyl laurates, fatty acid isethionates, dialkyl sulfoccinates; these compounds being for example in sodium salt form.

Suitable amphoteric surfactants include alkylbetaines, alkylhydrosulfobetains.

J 05 All these surfactants may be in liquid, solid or gel form, and will be used either pure or in solution.

Any conventional organic solvent can be used according to the present invention if they are compatible with the other constituents of the composition and with the conditions of production.

In general, said solvents must have a flash point higher than 90 0

C.

Suitable solvents include: glycerol; polyethylen glycols (PEG) of all molecular masses; glycols such as for example propylene glycol, dipropylene glycol, hexylene glycol; glycol ethers such as for example diethylene glycol methyl ether, diethylene glycol ethyl ether, diethyleeglycol n-butyl ether, tripropylene glycol methyl ether.

All said solvents are liquid at room temperature, with the exception of the polyethylene glycols of molecular mass higher than 1000 of which the melting point varies between 25 and 55 0

C.

Suitable perfumes and dyes according to the present invention include all the compounds known in that application, provided that they are stable in basic medium (pH between 9 and 11).

Finally, additives, cdapted to confer additional properties to these compositions, may be advantageously incorporated to the solid compositions according to the invention.

In particular, bactericidal agents may be added to said compositions, such as for example formaldehyde or phenol derivatives, in order to confer a disinfectant effect thereto.

Antitartar or sequestering agents may also be added to said compositions, such as for example phosphonates, certain

L.

Li L WO 92/19712 PCT/EP92/00936 7 polycarboxylic polymers or tetra-acetic ethylenediamine acid.

The solid cast compositions according to the invention can be obtained by conventional processes which include melting under stirring of the different constituents and casting of the resulting molten mixture in cooling molds.

The present invention further relates to the use of behenic acid in the preparation of a solid cast composition particularly usable as cleaning and/or deodorizing product.

But other objects, characteristics and advantages of the invention will emerge on reading the following detailed description of a number of embodiments of the invention, given solely by way of illustration and non-restrictively.

Except otherwise stated in these examples, the percentages are given by weight.

Example 1 The solid cast composition according to the invention of which the formula is given in Table 1 hereafter, was prepared as follows polyethyleneglycol (PEG 600) is introduced in a closed stainless steel vat, equipped with heating, heat-controlling and stirring systems, and heated to 60 0

C.

The ethoxylated fatty alcohol is then added and the temperature of the mixture is brought to 70 0 C under stirring.

The lauryl ether sulfate is added, also under stirring, and the temperature of the resulting mixture is brought to 80 0

C.

The behenic acid is added under stirring while keeping the temperature at 80 0 C, until complete melting of the acid.

Then the mixture water-sodium carbonate is added slowly, care being taken to keep the temperature of the mixture at 80 0

C.

The resulting mixture is kept under stirring at 80 0 C for about half-an-hour, until the saponification reaction is completed.

The perfume and dye are then added, and the final mixture is kept for about half-an-hour, under moderate stirring, at between 75 and 80 0 C, until complete homogenizing.

The final mixture then obtained is brought, from the WO 92/19712 PCT/EP92/00936 8 production vat, to an automatic measuring device, via pipes thermoregulated at 80 0

C.

This device then delivers into aluminium molds, calibrated quantities of the mixture, generally between 20 and 100g, corresponding to the weight of the finished product.

The molten mixture is rapidly cooled and solidified inside the molds, giving solid blocks.

The solidification phenomenon can be speeded up by subjecting the molds, after filling, to a stream of cold air.

Then the blocks can be removed from the molds and packed as a function of the proposed use.

A noteworthy fact is that the behenic acid salt is formed in situ, during the melting operation.

TABLE 1 Formula Example 1 Example 2 Example 6 Behenic acid 6% 7% Stearic acid 6% Sodium hydroxide at 20% 3.6% 4.2% 4.2% Water 6% 6% 7.4% Ethoxylated fatty alcohol 30% 30% 24.39% Lauryl ether sodium sulfate 18% 18% 22% PEG 600 28.4% 27.8% Perfume 7.99% 7.99% Dye 0.01% 0.01% 0.01% Glycerine Example 2 A solid composition containing stearic acid instead of behenic acid, was prepared according to the method described in Example 1.

The formula of this composition is given in Table 1.

It should be noted that, in Examples 1 and 2, the ethoxylated fatty alcohol used is a product containing an alkyl WO 92/19712 IPCr/EP92/00936 radical with 14 carbon atoms and an ethoxylated chain including 12 moieties of ethylene oxide. Similarly, the lauryl ether sulfate used is a fluid gel, with an active material content of The properties of the compositions of Examples 1 and 2, and in particular the foaming performances have been compared.

Table 2 sums up the obtained results.

The foaming performances were measured according to the AFNOR NFT-73-404 norm in the following conditions: concentration of the tested products: 0.1 g per liter of water, water temperature 15 0

C,

hardness of the water 25 0 f, weight of the products 50 g.

As shown in Table 2, the composition of Example 2 which contains stearic acid has a relatively low melting point and rather poor foaming and wearing performances, and it stains the bowl through wear.

Comparable results are obtained when replacing the stearic acid by other fatty acids with 12 to 18 carbon atoms.

By contrast, a definite improvement of all the properties is noted when using behenic acid (see Example 1).

Further tests have shown that the performancesof the composition according to Example 1 are quite comparable if not slightly better than those of compositions found on the market which contain paradichlorobenzene.

iAil i, WO 92/19712 PCT/EP92/00936 TABLE 2 Measured Properties Example 1 Example 2 Example 6 Melting point of finished product 71 0 C 58 0 C 60 0

C

Foam height time 0 7.0 cm 7.0 cm 5.5 cm time 5 min. 7.0 cm 1.5 cm 5.0 cm time 10 min. 6.5 cm 1.0 cm 4.5 cm time 15 min. 6.0 cm 1.0 cm 4.0 cm Product wearing time (number of flushings) 600 250 500 Product behavior through wear correct bowl correct staining Examples 3 to Three solid cast compositions according to the invention with different behenic acid contents were prepared by the method of Example 1.

Table 3 below gives the formulae of said compositions.

It should be noted that the ethoxylated fatty alcohol used in these examples contains an alkyl radical with 12 carbon .atoms and an ethoxylated chain containing 20 moieties of ethylene oxide.

Moreover, the paraffin sulfonate used is a fluid gel with an active material content of The properties of these different compositions were measured and the results obtained are given in Table 4.

Said results show the effect of the behenic acid content on the product wearing time and on the melting point of the finished products,

I

VIft WO 92/19712 PCEP92/00936 11 In all cases, the properties obtained are acceptable and compatible with the normal conditions of use.

TABLE 3 Formulae Example 3 Example 4 Example Behenic acid 3% 8% 13% Sodium hydroxide at 20% 1.8% 4.8% 9Y Water 3% 8% Ethoxylated fatty alcohol 15% 15% Sodium paraffin sulfonate 35% 35% Glycol propylene 30.2% 17.2% 3% Perfume 11.99% 11.99% 11.99% Dye 0.01% 0.01% 0.01% TABLE 4 Measured Properties Exai.ple 3 Example 4 Example ii Melting Point Foam height time 0 time 5 min.

time 10 min.

time 15 min.

Product wearing time (number of flushes) Behavior of products through wear 57 0

C

7.5 cm 7.0 cm 6.5 cm 6.5 cm 300 correct 75 0

C

7.0 cm 6 cm 5.5 cm 5.5 cm 700 correct 820C 6.0 cm 5.5 cm 5.0 cm 5.0 cm 1200 correct .I I I- I WO 92/19712 PCT/EP92/00936

I

LI

1] i;

I/

LI

a, Example 6 A composition according to the invention having the formula indicated in Table I above, is prepared by the method described in Example 1. The surfactants used in this example are the .ame as those used in Examples I and 2.

The properties of this composition were measured and the results obtained are given in Table 2. The performances of the composition are perfectly satisfactory.

Further tests, of which the results are not given here, have shown that it was also possible to incorporate up to 35% by weight of perfume in compositions containing between 3 and 15% by weight of behenic acid, without their physical properties being altered.

All the results obtained, the main ones of which are reported herein, show that it is for the first time possible to prepare solid cast compositions without paradichlorobenzene which have a high and readily adjustable melting point, good foaming properties (rich and stable foam) despite the use of a soap as structuring agent, whose behavior during use is very satisfactory contrary to the products containing other soaps causing staining in the bowl, and whose wearing time is readily adjustable within a very wide range reaching up to 1500 flushes.

Finally, said compositions can contain a very high proportion of perfume, and the obtained products can be considered as room deodorizers.

Claims (15)

1. Solid cast composition useable notably as a cleaning or deodorising product or both, characterized in that it comprises 3 to 15% by weight of at least a behenic acid soap and lacks paradichlorobenzene.

2. Composition according to claim 1, characterized in that said soap is a product from the reactio', of said behenic acid with a saponifying agent being at least one of an alkaline- metal hydroxide, an alkanolamine, an alkanamine, an alkaline or alkaline-earth silicate or a carbonate.

3. Composition according to claim 1 or claim 2, characterized in that it further comprises: up to by weight of at least one non-ionic surfactant; up to 60% by weight of at least one anionic or amphoteric surfactant; up to 50% by weight of at least one organic solvent; up to 25% by weight of water; up to 35% by weight of at least one perfume; up to 25 by weight of at least one dye; and up to 5 by weight of an additive comprising at least one of a bacterial agent or an antitartar agent.

4. Composition according to claim 3 comprising 15 to 50% of said non-ionic surfactant. Composition according to claim 3 or claim 4 comprising 15 to 30% of said anionic or amphoteric surfactant.

6. Composition according to any one of claims 3 to 5 comprising 15 to 30% of said organic solvent.

7. Composition according to any one of claims 3 to 6 comprising 3 to 15% of water.

8. Composition according to any one of claims 3 to 7 comprising 5 to 20% of said perfume.

9. Composition according to any one of claims 3 to 8, characterized in that said non- ionic surfactant is an ethoxylated fatty alcohol, the hydrophobic alkyl part of which is straight or branched and comprises 8 to 18 carbon atoms and the hydrophilic part of which comprises 5 to 100 moieties of ethylene oxide. Composition according to claim 9 wherein said hydrophobic alkyl part of said alcohol comprises 8 to 15 carbon atoms.

11. Composition according to claim 9 or claim 10 wherein said hydrophilic alkyl part of said alcohol comprises 5 to 35 moieties of ethylene oxide.

12. Composition according to any one of claims 3 to 11, characterized in that said anionic surfactant is at least one of an alkyl benzene sulfonate, an a-olefin sulfonate, a paraffin sulfonate, an alkyl ether sulfate, an alkyl sulfate, a fatty acid sarcosinate, a fatty [N:\LIBAA]00251:KEH \Y T 4 Y^ O$X 14 Iy acid methyl laurate, a fatty acid isethionate or a dialkyl sulfosuccinate; and said amphoteric surfactant is at least one of an alkyl betaine or an alkyl hydroxy sulfo betaine.

13. Composition according to any one of claims 3 to 12, characterized in that said solvent is at least one of a glycerol, a polyethylene glycol, a glycol or a glycol ether.

14. Solid cast composition useable notably as a cleaning or deodorising product or both, substantially as hereinbefore described with reference to any one of the examples excluding any comparative examples. Process for the preparation of a solid cast composition according to any one of claims 1 to 14, comprising melting the various constituents under stirring and casting the resulting molten mixture in cooling molds.

16. Process according to claim 15, characterized in that behenic acid soap is formed in situ during said melting operation.

17. Use of the behenic acid for preparing a solid cast composition as claimed in claim 1. Dated 10 March, 1995 S. C. Johnson Son, Inc. Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON ui [N:\LIBAA]00251:KEH -c- on the ine hand, as structuring agent since it enables the I S~I A. I- INTERNATIONAL SEARCH REPORT International Application No PCT/EP ;2/00936 I I. CLASSIFICATION OF SUBJECT MATTER (if several classification symbols apply, indicate all) 6 According to International Patent Classification (IPC) or to both National Classification and IPC C 11 D 17/00 C 11 D 9/00 C 11 D 10/04 A 61 L 9/01 II. FIELDS SEARCHED Minimum Documentation Searched' Classification System Classification Symbols C 11 D A 61 L Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included in the Fields Searched' m. DOCUMENTS CONSIDERED TO BE RELEVANT 9 Category 0 Citation of Document, 1 with indication, where appropriate, of the relevant passages 12 Relevant to Claim No. 3 A Chemical Abstracts, vol. 105, no. 26, 18 August 1 1986, (Columbus, Ohio, US), see abstract no. 232224, JP,A,86185269 (TAIYO PERFUMERY CO., LTD), see abstract A US,A,4149986 (DICKSON) 17 April 1,3 1979, see the whole document A FR,A,1170200 (PROCTER GAMBLE CO.) 1,2 12 January 1959, see the whole document Special categories of cited documents :10 later document published after the international filing date or priority date and not in conflict with the application but document defining the general state of the art which is not cited to uderstand the principle or theory underlying the considered to be of particular relevance invention earlier document but published on or after the international document of particular relevance; the claimed invention filing date cannot be considered novel or cannot be considered to 1' document which may throw doubts on priority claim(s) or involve an inventive step which is cited to establish the publication date of another Y' document of particular relevance; !he claimed invention citation or other special reason (as specified) cannot be considered to involve an inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the international filing date but in the art. later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this International Search Report

24-06-1992 2 07. 92 International Searching Authority Signature of Authorized Officer EUROPEAN PATENT OFFICE Mada Pais P Form PCTISA/210 (tecod Meet)l (Jaunary 1985) i i .A r:- ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. EP 9200936 SA 58949 This annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDP fie on 16/07/92 The European Patent Office is in no way liable for these particulars which are merely given for the purpose of information. Patent document Publication Patent family Publication cited in search report date member(s) date US-A- 4149986 17-04-79 None FR-A- 1170200 BE-A- 551361 CH-A- 347596 DE-B- 1056316 GB-A- 802302 NL-C- 114069 NL-A- 211637 US-A- 2954347 u For more details about this annex see Official Journal of the European Patent Office, No. 12/82