EP0027083A1 - Process for cleaning vehicles and composition therefor - Google Patents

Abstract

1. Process for cleaning vehicles, by putting into operation, in an acid medium, notably at a pH less than 3, in the presence of at least one surface-active agent, preferably non-ionic or anionic, notably at ordinary temperature, an effective quantity of a mono- or dialkylphosphoric ester the alkyl group or groups of which each contain from one to three carbon atoms, characterized by the fact that simultaneously an effective quantity of at least one compound chosen from the alkanephosphonic acids and their esters with the formula : see diagramm : EP0027083,P5,F3 in which R1 is an alkyl radical containing from one to eight carbon atoms, possibly substituted by at least one of the substituents of the group containing the halogens, the hydroxyl radical, other phosphonic groups and amino groups with the formula : see diagramm : EP0027083,P6,F1 in which each of R2 and R3 , which can be identical or different from one another, represents a hydrogen atom or the significances of R1 , and each of R4 and R5 , which are identical or different from one another, represents a lower alkyl radical containing from one to four carbon atoms, or a hydrogen atom, is put into operation.

Description

The subject of the invention is a method for cleaning vehicles of the kind of railway wagons, buses and trucks.

It also relates, as an industrial product, to the composition used in the context of the process.

The cleaning of vehicles of the kind in question includes not only the washing of the windows but also that of the bodywork from which it is advisable to remove, on the one hand, dirt of any origin and in particular the metallic particles coming from the abrasion of the rails, wheel tires, brake shoes, contact wires, silicate soiling, grease, oil and fume black particles, on the other hand, traces of oxide and even rust both on metal parts only on paints.

It has already been proposed for this type of cleaning, whether manually or by jet with brushing, to use compositions based on oxalic acid. These compositions give all satisfaction in terms of effectiveness except with regard to the panes on which a veil remains after rinsing, but are dangerous for the user and pose rejection problems.

It has also been proposed to use compositions based on mono- and di-alkylphosphoric esters with short C ₁ to C ₃ chains. These products do not have all the drawbacks of compositions based on oxalic acid but are not sufficiently effective, this efficiency being appreciated by a set of aptitudes for removing dirt, for deoxidizing rusty parts, window cleaning both in manual operation and by jet followed by brushing.

The object of the invention is therefore, above all, to remedy these drawbacks and to provide a method and a composition which are satisfactory on all levels.

However, the Applicant Company found, after his research, that, unexpectedly, the implementation simultaneously with that of the above mono- and di-alkylphosphoric esters of an effective amount of alkanephosphonic acid made it possible to record results comparable to those obtained with the compositions based on 'oxalic acid without having the drawbacks thereof and without leaving a veil on the panes after rinsing. This result is all the more surprising since it is greater than the sum of the effects recorded with phosphoric esters, on the one hand, and alkanephosphonic acids, on the other hand, the latter having not yet been proposed. for the cleanings targeted by the process according to the invention.

et leurs esters, formule dans laquelle R₁ est un radical alcoyle en C₁ à C₈ ou un radical aryle éventuellement substitués par au moins l'un des substituants du groupe comprenant les halogènes, le radical hydroxyle, d'autres groupements phosphoniques et les groupements amino de formule : -

dans laquelle R₂ et R₃, qui peuvent être identiques ou différents l'un de l'autre, représentent un atome d'hydrogène ou les significations de R₁, le milieu acide, véhicule de ces principes actifs, renfermant également au moins un agent tensio-actif, de préférence non ionique ou anionique.It follows that the subject of the invention is a method of cleaning by manual operation or by jet followed by brushing of vehicles of the kind in question, characterized in that in an acid medium, in particular at a pH below 3, used simultaneously, in particular at ordinary temperature, an effective amount of mono- or dialkylphosphoric ester at C ₁ to C ₃ and an effective amount of at least one compound chosen from alkanephosphonic acids of formula:

and their esters, formula in which R ₁ is a C ₁ to C ₈ alkyl radical or an aryl radical optionally substituted with at least one of the substituents from the group comprising halogens, the hydroxyl radical, other phosphonic groups and the amino groups of formula: -

in which R ₂ and R ₃ , which may be identical or different different from each other, represent a hydrogen atom or the meanings of R ₁ , the acid medium, vehicle of these active principles, also containing at least one surfactant, preferably nonionic or anionic.

• - de 10 à 30% en poids d'un ester phosphorique mono-ou dialcoylé en C₁ à C₃,
• - de 1 à 20% en poids, de préférence de 2 à 10% en poids, d'au moins un composé choisi parmi les acides al- canephosphoniaues de formule :
  
  et leurs esters, formule dans laquelle R₁ a les significations susmentionnées,
• - de 1 à 20% en poids d'un agent tensio-actif, de préférence non ionique ou anionique, notamment de la série des alcoylarylsufonates,
• - éventuellement des agents séquestrants tels que l'acide citrique et des solvants tels que les alcools et polyols.

The cleaning compositions targeted by the invention and used in the context of the above process are characterized in that, in the concentrated state, they comprise, within an acidic aqueous solution in particular at pH <3,

• - from 10 to 30% by weight of a mono-or dialkylated phosphoric ester at C ₁ to C ₃ ,
• from 1 to 20% by weight, preferably from 2 to 10% by weight, of at least one compound chosen from alkanephosphonic acids of formula:
  
  and their esters, formula in which R ₁ has the abovementioned meanings,
• from 1 to 20% by weight of a surfactant, preferably nonionic or anionic, in particular from the series of alkylarylsufonates,
• - optionally sequestering agents such as citric acid and solvents such as alcohols and polyols.

The compositions in accordance with the invention, ready to be used in the context of the above process, are obtained by aqueous dilution from the concentrates defined above, in particular in a proportion of 1 to 5.

• - l'acide hydroxyméthylphosphonique
• - l'acide hydroxypropylphosphonique
• - l'acide chloroéthylphosphonique
• - l'acide octylphosphonique
• - l'acide éthyl- et butylphosphonique
• - l'acide 1-hydroxyéthylidène-1,1-diphosphonique
• - l'acide amino-tri (méthylène phosphonique) ainsi que les esters phosphoniques de formule :
  
  dans laquelle R1 a les significations susindiquéés alors que R₄ et R₅, qui sont identiques ou différents l'un de l'autre, représentent un radical alcoyle court en C₁ à C₄ ou un hydrogène.

The phosphonic acids which have given good results in the context of the above processes and compositions are in particular those of the group comprising:

• - hydroxymethylphosphonic acid
• - hydroxypropylphosphonic acid
• - chloroethylphosphonic acid
• - octylphosphonic acid
• - ethyl- and butylphosphonic acid
• - 1-hydroxyethylidene-1,1-diphosphonic acid
• - amino-tri acid (methylene phosphonic) as well as the phosphonic esters of formula:
  
  in which R1 has the abovementioned meanings whereas R ₄ and R ₅ , which are identical or different from each other, represent a short C ₁ to C ₄ alkyl radical or a hydrogen.

The invention can be understood even better with the aid of the additional description which follows.

• - à une composition à base d'acide oxalique,
• - à une composition à base d'esters mono- ou dialcoyl- phosphoriques,
• - à diverses compositions selon l'invention.

A set of comparative tests was carried out using:

• - a composition based on oxalic acid,
• - a composition based on mono- or dialkylphosphoric esters,
• - various compositions according to the invention.

• - 4% en poids d'acide oxalique,
• - 1,4% d'un tensio-actif non ionique,
• - 3% de polyglycol,
• - 1,1% de tensio-actif anionique,
• - 91,5% d'eau.

The diluted composition based on oxalic acid (test No. I) included:

• - 4% by weight of oxalic acid,
• - 1.4% of a nonionic surfactant,
• - 3% polyglycol,
• - 1.1% anionic surfactant,
• - 91.5% water.

• - 20% en poids d'ester méthylique de l'acide phosphorique,
• - 5% d'agent tensio-actif constitué par un nonyl- phénol à 10 unités d'oxyde d'éthylène connu sous la marque "CEMUSOL NP 10" (RHONE PROGIL),
• - 5% d'agent tensio-actif anionique connu sous la marque "HOSTAPUR SAS 60" (HOECHST), du type alcanesulfonate de sodium,
• - q.s.p. 100% en poids d'eau.

The composition based on phosphoric esters included in the concentrated state (composition A):

• - 20% by weight of methyl ester of phosphoric acid,
• - 5% of surfactant consisting of a nonylphenol with 10 units of ethylene oxide known under the brand "CEMUSOL NP 10" (RHONE PROGIL),
• - 5% of anionic surfactant known under the brand name "HOSTAPUR SAS 60" (HOECHST), of the sodium alkanesulfonate type,
• - qs 100% by weight of water.

• - 2% en poids d'acide hydroxyméthylphosphonique (composition B)
• - 5% en poids d'acide hydroxyméthylphosphonique (composition C)
• - 5% en poids d'acide chloroéthylphosphonique (composition D)
• - 5% en poids d'acide amino-tri (méthylène phosphonique) (composition E)
• - 10% en poids d'acide amino-tri (méthylène phosphonique) (composition F).

The concentrated compositions in accordance with the invention were obtained from the composition based on phosphoric ester which has just been defined, to which we make com take respectively:

• - 2% by weight of hydroxymethylphosphonic acid (composition B)
• - 5% by weight of hydroxymethylphosphonic acid (composition C)
• - 5% by weight of chloroethylphosphonic acid (composition D)
• - 5% by weight of amino-tri acid (methylene phosphonic) (composition E)
• - 10% by weight of amino-tri acid (methylene phosphonic) (composition F).

For the comparative tests (II to VII), the above-mentioned concentrated compositions A to F were respectively diluted at a rate of 1 to 5 with water.

• - enduction à la brosse des parties à nettoyer, le temps d'action chimique étant de 15 minutes,
• - action mécanique de brossage pendant 10 minutes,
• - rinçage à l'eau du robinet.

All the diluted compositions were used in the following manner:

• - brush coating of the parts to be cleaned, the chemical action time being 15 minutes,
• - mechanical brushing action for 10 minutes,
• - rinsing with tap water.

A l'examen de ces résultats, on constate que les performances des compositions conformes à l'invention sont comparables à celles enregistrées avec l'acide oxalique sans présenter les inconvénients de celui-ci.The results (effectiveness as defined above, that of the composition with oxalic acid being taken equal to 100, and presence or absence of a veil on the panes) are collated in the following table:

On examination of these results, it can be seen that the performances of the compositions in accordance with the invention are comparable to those recorded with oxalic acid without present the disadvantages of it.

The compositions of tests I to VII were used using an automatic machine and after having diluted a new liver in a proportion of 1 to 6. The speed of travel of the train was 5 km / h and the results recorded are located respectively in the same way as in the case of the non-automatic application defined above.

Following what and whatever the embodiment adopted, there is thus a method and a composition for cleaning vehicles, the characteristics of which result from the above and which are devoid of the disadvantages inherent in the methods and compositions of prior art.

As goes without saying and as it moreover already follows from the above, the invention is in no way limited to those of the modes of application and of embodiments which have just been envisaged; on the contrary, it embraces all its variants.

Claims (4)

1. A method of cleaning vehicles of the kind of railway wagons, buses and trucks, characterized in that in an acid medium, in particular at a pH below 3, a simultaneous implementation, in particular at ordinary temperature, effective amount of C ₁ to C ₃ mono- or dialkylphosphoric ester and an effective amount of at least one compound chosen from alkanephosphonic acids of formula:

and their esters,
formula in which R ₁ is a C ₁ to C ₈ alkyl radical or an aryl radical optionally substituted with at least one of the substituents from the group comprising halogens, the hydroxyl radical, other phosphonic groups and amino groups of formula:

in which R ₂ and R ₃ , which may be the same or different from each other, represent a hydrogen atom or the meanings of R ₁ , the acid medium, vehicle of these active ingredients, also containing at least one surfactant, preferably nonionic or anionic. 2. Composition for cleaning vehicles of the kind of railway wagons, buses and trucks, in particular implemented within the framework of the method according to claim 1, characterized in that in the centered state it comprises, within of an acidic aqueous solution, in particular at pH <3, - from 10 to 30% by weight of a mono-or dialkylated phosphoric ester at ^C ₁ to C ₃ , - from 1 to 20% by weight, preferably from 2 to 10% by weight, of at least one compound chosen from alkanephosphonic acids of formula:

and their esters,
formula in which R ₁ is a C ₁ to C ₈ alkyl radical or an aryl radical optionally substituted with at least one of the substituents from the group comprising halogens, the hydroxyl radical, other phosphonic groups and the amino groups of formula :

in which R ₂ and R ₃ , which may be the same or different from each other, represent a hydrogen atom or the meanings of R ₁ , from 1 to 20% by weight of a surfactant, preferably nonionic or anionic, in particular from the series of alkylarylsulfonates, - optionally sequestering agents such as citric acid and solvents such as alcohols and polyols. 3. Method according to claim 1, characterized in that the alkanephosphonic acids used are chosen from the group comprising: - hydroxymethylphosphonic acid - hydroxypropylphosphonic acid - chloroethylphosphonic acid - octylphosphonic acid - ethyl- and butylphosphonic acid - 1-hydroxyethylidene-1,1-diphosphonigue acid - amino-tri acid (methylene phosphonic) as well as the phosphonic esters of formula:

in which R ₁ has the abovementioned meanings whereas R ₄ and R ₅ , which are identical or different from each other, represent a short C ₁ to C ₄ alkyl radical or a hydrogen. 4. Composition according to claim 2, characterized in that the alkanephosphonic acid is chosen from the group comprising: - hydroxymethylphosphonic acid - hydroxypropylphosphonic acid - chloroethylphosphonic acid - octylphosphonic acid - ethyl- and butylphosphonic acid - 1-hydroxyethylidene-1,1-diphosphonic acid - amino-tri acid (methylene phosphonic) - as well as the phosphonic esters of formula:

in which R ₁ has the abovementioned meanings whereas R ₄ and R ₅ , which are identical or different from each other, represent a short C ₁ to C ₄ alkyl radical or a hydrogen.