CA2108555A1

CA2108555A1 - Cast cleaning and/or deodorizing composition

Info

Publication number: CA2108555A1
Application number: CA002108555A
Authority: CA
Inventors: Jean-Christophe Ferrando; Henri Mazier
Original assignee: Individual
Current assignee: SC Johnson and Son Inc
Priority date: 1991-04-29
Filing date: 1992-04-27
Publication date: 1992-10-28
Also published as: FR2675814B1; EP0582613A1; JPH06506964A; FR2675814A1; AU659640B2; AU1652592A; WO1992019712A1

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 prepared 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.

Description

WOg2/19712 2108~r 5 PCr/EPg2/00936 CAST CLEANING AND/OR DEODORIzING ccMPosmoN
The present nvention relates to a novel solid east composition, usable notably as eleaning and/or deodorizing produet, and to its preparation proeess.
The invention is partieularly applieable to the 05 produetion of devices for the automatic cleaning of toilets, such as for exsmple W.C. blocks or eontainers designed to be immersed in the flushing tank, or to the produetion of air fresheners.
It is recalled that a W.C. bloek i8 a product which, after ach nushing of the bowl, ensures the clesning and ~deodorizing of toilet bowls. This produet is generally constituted ~ ~ of a solid sctive ~bloek plaeed and held inside the bowl, for `~ example in a perforated csge-like eontainer equipped with a hook.
After eaeh flushing of the bowl, these produets clesn the toilet~ bowl, ensure the formation of foam on the water in the bowl 5 '~ and deodorize.
For the eonsumer, these bloeks have a duration of use eorresponding to about 400-600 flushes.
he main properties required for these produets are a good stability in time and under heat. Moreover, they are required to have a relatively high melting point (generally higher than 50C) in order to withstand the varied conditions of use and prineipally of storage.
Currently, there are three important types of produets on the toilet bloek market.
First of all, there sre the products formed by eompression and extrusion of solid and non-readily fusible materials (surfactants, such as alkylbenzenesulfonate or lauryl-sulfate; mineral fillers), and of liquids (perfume, solvents, surfaetants).
There are also the "east" produets containing paradiehlerobenzene.~
These~ products are prepared by melting the eonstituents and easting the resùlting molten mixture in cooling molds.
Paradiehlorobenzene is used:
- on the one hand, as structuring agent since it enables the WO 92/lg712 PCT/EP92/00936 , e ~F~C~5 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 penmits a 05 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 ' 10 ere cast products containing no peradichlorobenzene~
`
Yet, the currently known products of this type have at least one of the following disadvantages :
vlsry poor quantity of foaming in the bowl;
melting point too low;
- limited~period of use;
behevior degrading with time (toilet bowl staining).
;~ Furthermore, the known products of ths three types mentioned previously necessarily have a limited perfume content ~(less than or equal to about 15% by weight).
~ lndeed, perfumes, when incorporated in a proportion higher than lS% by weight, soften up the compositions obtained by extrusion and render them unsuitable for use.
In addition, the cast products (with or without dichloro-benzene) which contain more than 15% by weight of perfume have a me~ting point which is too low and incompatible with the severe storage conditions which are normally encountered.
It 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 aforemehtioned 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 W O 92/lg7l2 21 0 8 ~ 5 ~ PCTlEPg2/OOg36 behenic acid soap.
It has indeed been found, and this is the basis of the present invention, that the use of a behenic acid soap instead of paradichlorobenzene, in solid cast compositions, makes it possible 05 to obtain cleaning and/or deodorizing products of which the duration of use iæ comparable to that of blocks conteining paradichlorobenzene and is optionally adjustable; products which form a rich and stable foam in the bowl and no unwanted staining of the toilet bowl during use.
, 10 It i8 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.
he various findings which constitute the basis of the prssent~invention are surprising and unexpected.
Indeed, it is a known fact that soaps, which are ~` excell~nt~ 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 ~8 carbon atoms (lauric, myristic acids), considerably reduce the stability of the foam produced in the bowl, because of their insolùble nature. As a matter of fact, soaps are generally used ss 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 ~lso 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.
he benehic acid salts contained in the solid compositions according to the invention are generally obtained by aponification of the behenic acid.
The behenic (or n-docosanoic) acid is a saturated aliphatic fatty acid containing 22 carbon atoms, naturally found in ~ ~ 0 ~ ~ ~ 4 colza and mustard oilsl 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 05 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 b-henic acid pure or taken from a raw material, I~or example a colza extract.
It is, howeYer, important for such raw material to contain the highest possible proportion of behenic acid, at least 80 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 ake 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 particul~r, alkaline metal hydroxides, such as sodium hydroxide and potassium hydroxide; alkanolamines, such as monoethanolamine, diethanolamine, triethsnolamine; 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.
- 30 Among the aforesaid saponifying agents, the preferredones are sodium hydroxide, potasæium hydroxide and alkanolamines which give harder products than the other saponifying agents.
According to a particular characteristic, a solid cast composi:ion ~ccording to the invention further comprises :
- up to 70% by weight, and preferably 15 to 5o% of at least one W0 92/19712 2 1 0 8 ~ 5 S PCT/EP92/00936 non-ionic surfactsnt;
- up to 6o% by weight, and preferably 15 to ~0%, of at least one anionic or amphoteric surfactant;
- up to 50X by weight, and preferably between l5 and 30X, of at 05 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 20X, of at least one perfume;
up to 25X by weight of at least one dye;
- up to 5X 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 sccording 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 lO0 moieties of ethylene oxide.
These non-ionic surfactants can be in liquid, paste or solid form, and they are generally used pure or in solut-ion.
Advantageously, the non-ionic surfactant used will be an ethoxylated fstty alcohol of which the straight or branched alkyl 2S part contains 8 to l5 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 present invention, to ~0 use as anionic or amphoteric surfactant, any one of the conventional amphoteric or anionic surfactants, as well as mixtures thereof.
Suitable anionic surfactants include : alkyl benzene sulfonates, C~-olefin sulfonates, paraffin sulfonates, alkyl ether ~sulfates, alkyl sulfates, fatty acid sarcosinates, fatty acid , , ~ ~ .

0 ~ S 6 methyl laurates, fatty acid isethionates, dialkyl sulfoccinates;
these compounds being for example in sodium salt form.
Suitable amphoteric surfàctants include alkylbetaines, alkylhydrosulfobetains.
05All these surfactents 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 thsn 90C.
Suitable solvents include:
glycerol;
15- polyethylen glycols (PEG) of all molecular masses;
:~:
~ lycols such as for example propylene glycol, dipropylene glycol, - ~ hexylene glycol;
- glycol ethers such as for example diethylene glycol methyl ether, diethylene glycol ethyl ether, diethyl~eglycol n-butyl ether, 20tripropylene glycol methyl ether.
All said solvents are liquid at room temperature, with the exception of the polyethylene glycols of molecular ~ass higher than 1000 of which the melting point varies between 25 and 55C.
Suitable perfumes and dyes according to the present 25invention include all the compounds known in that application, provided that they are stable in basic medium (pH between 9 and ~, 11).
Finally, additives, adapted to confer additional properties to these compositions, may be advantageously 30incorporated 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 35said compositions, such as for example phosphonates, certain :: :

W 0 92/l9712 21 0 8 5 5 5 PCT/EP92/00936 polycarboxylic polymsrs or tetra-acetic ethylenedismine 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 05 resulting molten mixture in cooling molds.
The present invention further relates to the use of behenic aeid- in the preparation of a solid east composition partieularly usable as eleaning and/or deodorizing produqt.
But other objeets, eharacteristics and advantages of the ~ ~im ention will~merge on reading the following detailed description of a~number of _bodiments of the invention, given solely by way of illustration and non-restrietively.
Except otherwi-e ~stated in these examples, the pereentages are given by weight.
15~ Example 1 The s~olid east~eomposition according to the invention of h the~ formula i given in Table 1 hereafter, was prepared as follows :~
polyethyleneglyeol (PEG 600) is introdueed in a closed ~stainless~ steel vat, equipped with heating, heat-controlling and stirring sy~t~ms, and heatèd to 60C~
` The ethoxylated fatty alcohol iæ then addad and the temperature of the mixture is brought to 70C under stirring.
- The lauryl ether sulfate is added, also under stirring, and the temperature of the resulting mixture is brought to 80C.
The behenic acid is added under stirring while keeping the temperature at 80C, 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 80C.
The resulting mixture is kept under stirring at 80C 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 bet~een~75;~and~80C,~until eomplete homogenizing.
35~ The final mixture then obtained is brought, from the W O 92/lg712 pcT/Ep92/oos36 2108~ 5 production vat, to an automatic measuring device, via pipes thermo-regulated at 80C.
This device then delivers into aluminium molds, calibrat-ed qvantities of the mixture, generally between 20 and lOOg, 05 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 stresm 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.

Formula Example 1 Example 2 Example 6 _______________________________ __________________________________ Behenic acid 6% - 7%
Stearic acid - 6%
Bodium hydroxide at 20% 3.6% 4.Z% 4.2%
Water 6% 6% 7.4%
Ethoxyl~ted fatty alcohol 30% 30% - 24.39%
Lauryl ether sodium sulfate 18% 18% 2Z%
PEG 600 28.4% 27.8%
Perfume 7.99% 7-99% 30%
Dye O.01% 0.01% 0.01%
Glycerine - - 5~
________________________________________________________._________ 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 ~; 35 ethoxylated fatty alcohol used is a product containing an alkyl WO 92/1g712 21 0 8 ~ 5 5 PCT/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 70%.
The properties of the compositions of Examples 1 and 2, 05 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 9 per liter of water, - ~ - water temperature : 15C, - hardness of the water : 25f, weight of the products : 50 9.
- , `-3~ As shown il Table 2, the composition of Example 2 which ~ contains stearic acid has a relatively low melting point and rather poor~fos~ing and wearing performances, and it stains the bowl through wesr.
Co~parable result8 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 performa~cesof the composition according to Example 1 are quite comparable if not slightly better than those of compositions found on the market which contain paradichlorobenzene.

.

, WO 9Vlg712 PCI~/EP92/OOg36 " 10 ~o~

Measured Properties Example 1 Example 2 Example 6 05 ------_-___________________________________________________________ Melting point of finished product 71C 58C 60C
Foam height time z 0 7.0 cm 7.0 cm 5.5 cm ~ time - 5 min. 7.0 cm 1.5 cm 5.0 em 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 (nu bbr of flushings) 600 250 500 ~Product behavior ` through wear correct bowl correct staining Examples 3 to 5 Three solid cast compositions according to the invention with different behenic acid contents were prepared by ~he method of Example 1.
Table 3 below ~ives 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 60%.
The propert1es of these different compositions were measured~and :the resul*s~obtained are giYen 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.

~"

WO 92/lg712 PCI`/EP92/00936 210~5~

In all cases, the properties obtained are acceptable and compatible with the normal condieions of use.

.
Formulae Example 3 Example 4Example 5 Behenic acid 3% 8% 13%
- ' 10 Sodium hydroxide at 20% 1.8% 4.8X g%: Water 3% 8% 15%
Ethoxylated fatty alcohol 15X 15% ~5%
Sodiu~para~fin sulfonate 35% 35% 35%
Glycol propylene 30.ZX 17.Z% 3%
15~ Perfume ll.9g% 11.99%11.99%
: ~ Dye O.OlX 0 01%0 01%

Measured Pr~pert es Example 3 Ex~mple 4Example 5 Melting Point 57C 75C 82C
Foam height time = 0 7.5 cm 7.0 cm 6.0 cm time - 5 min. 7.0 cm 6 cm 5.5 cm time = 10 min. 6.5 cm 5.5 cm 5.0 cm time = ~5 min. 6.5 cm 5.5 cm 5.0 cm Product wearing time (number of flushes) 300 700 1200 8ehavior of products : through~wear correct correct correct ~ ------------------_--__________ ~ 35 W O 92/t9712 PCT/EP92/00936 2 1 0 ~ ~ 5 S 12 Example 6 A composition according to the invention having the formula indicated in Table 1 above, is prepared by the method deseribed in Example 1. The surfaetants used in this example are 05 the same 8S those used in Examples 1 and 2.
The properties of this eomposition were measured and the results obtained are giwn in Table 2. The performances of the eomposition are perfectly satisfaetory.
Further tests, of whieh the results are not given here, 0 have shown that it was also possible to incorporste up to 35X by w ight of perfume in eompositions eontaining between 3 and 15% by weight of behenîe aeid, without their physieal properties being altered. `~
Ali the results obtained, the main ones of whieh are ~reported ~herein, show that it is for the first time possible to ~ prepare solid east eompositions without paradiehlorobenzene whieh ;~ ~ have a high and readily adjustable melting point, good foamingproperties (rieh and stable foam) despite the use of a soap as strueturing ~gent, whose behavior during use is very satisfactory eontrory to the products eontaining other soaps eausing staining in the bowl, and whose wearing time is readily adjustable within' a ~- very wide ran~e reaching ùp to 1500 flushes.
- Finally, said eompositions ean eontain a very high proportion of perfume, and the obtained produets ean be eonsidered as room deodorizers.

~ ~ , ~ 30 :,.

~ 35~ ~

Claims

13

1. Solid cast composition usable notably as cleaning and/or deodorizing products, characterized in that it comprises 3 to 15%
by weight of at least a behenic acid soap.

2. Composition according to claim 1, characterized in that said soap is a product from the reaction of the behenic acid with at least one saponifying agent selected from the group comprising alkaline-metal hydroxides, alkanolamines, alkanamines, alkaline or alkaline-earth silicates or carbonates.

3. Composition according to claim 1 or 2, characterized in that it further comprises:
- up to 70% by weight, and preferably 15 to 50% of at least one non-ionic surfactant;
- up to 60% by weight, and preferably 15 to 60% of at least one anionic or amphoteric surfactant;
- up to 50% by weight, and preferably 15 to 30% of at least one organic solvent, - up to 25% by weight, and preferably 3 to 15% of water;
- up to 35% by weight, and preferably 5 to 20% of at least one perfume;
- up to 15% by weight of at least one dye; and - up to 5% by weight of at least one additive selected from the group comprising the bactericidal agents and the antitartar agents.

4. Composition according to claim 3, characterized in that said non-ionic surfactant is an ethoxylated fatty alcohol of which the hydrophobic alkyl part, which is straight or branched, comprises 8 to 18, and preferably 8 to 15 carbon atoms, and of which the hydrophilic part comprises 5 to 100, and preferably 5 to 35 moieties of ethylene oxide.

5. Composition according to claim 3 or 4, characterized in that said anionic surfactant is selected from the group comprising alkyl benzene sulfonates,.alpha.-olefin sulfonates, paraffin sulfonates, alkyl ether sulphates, alkyl sulphates, fatty acid sarcosinates, fatty acid methyl laurates, fatty acid isethionates, dialkyl sulphosuccinates and in that said amphoteric surfactant is selected from the alkyl betaines and alkyl hydroxy sulpho betaines.

6. Composition according to one of claims 3 to 5, characterized in that said solvent is selected from the group comprising glycerol, polyethylene glycols, glycols, glycol ethers.

7. Process for the preparation of a solid cast composition according to one of claims 1 to 6, characterized in that it consists in melting the various constituents under stirring and casting the resulting molten mixture in cooling molds.

8. Process according to claim 7, characterized in that the behenic acid soap is formed in situ during said melting operation.

9. Use of the behenic acid for preparing a solid cast composition, useful in particular as cleaning and/or deodorizing product.