DE60114422T2 - CLEANING PROCEDURE OF HARD SURFACES - Google Patents

Description

These The invention relates to a method for cleaning a hard surface which deposits lime.

at Bath cleaners are mainly acidic compounds, the fight against Calcium deposits are provided. On the other hand it is at kitchen cleaners mainly around alkaline compositions used to combat fatty deposits are provided. However, there are situations in which to clean of baths an alkaline composition is required, and in which for cleaning kitchens an acidic cleaning composition is required. The consumer has to decide if he has a fullness on different products for Buying different cleaning applications, or making a compromise received. It would be good to show a single composition containing the deposits, which are attacked by acidic cleaning compositions, and the deposits caused by alkaline cleaning compositions be attacked, fight but the difficulty in achieving this is obvious.

The patent US 4,522,738 also solves the problem of removing limescale from toilet bowls. It discloses toilet bowl cleaners with inner and outer water soluble wraps. The inner wrapper contains basic material and the outer wrapper acidic material that dissolves first, after which the inner wrapper dissolves. The amounts are selected such that the pH changes release carbon dioxide gas, thereby stirring the water in the bowl and thus improving the cleaning process.

The British patent GB 2 000 177 discloses alkaline washing carbonate based laundry compositions which change the pH from acidic to alkaline. The removal of lime on hard surfaces is not mentioned.

It would be beneficial to provide a cleaning composition effective for effecting a Cleaning initially acidic or alkaline, but to prevent damage to the Substrate and, if desired, to effect a second cleaning stage not in this state remains.

According to one The first aspect of the present invention is a method of cleaning a hard surface, on which deposits lime, provided, the method the application of a cleaning composition comprising reactants, after exposure to the hard surface of a chemical reaction undergo, including on the hard surface, taking the reaction such is that a delayed change the pH is generated on the hard surface by the Composition initially an alkaline liquid and after a period of time to an effective in controlling lime acidic liquid becomes.

According to one second aspect of the present invention is a cleaning composition provided that has the property that the place when Acting on a hard surface to be cleaned acidic or alkaline or is neutral and alkaline after a period of time or neutral (if original acidic) or acidic or neutral (if originally alkaline) or acidic or alkaline (if original neutral).

The Composition according to one of the aspects may have the property the surface containing the composition is initially an acidic liquid is and after a period of time to an alkaline liquid becomes.

The Composition according to one of the aspects may have the property the site containing the composition is initially an alkaline liquid is and becomes a sour liquid after a period of time.

Preferably finds the pH change of at least two pH units after an induction period (i.e. a period after exposure of the composition to the place) of at least 10 seconds, stronger preferably at least 20 seconds, more preferably at least 60 seconds and especially at least 100 seconds instead.

Suitably, the induction peroxide is not more than 12 hours, preferably not more than 1200 seconds, more preferably not more than 600 seconds, most preferably not more than 400 Seconds and in particular not more than 300 seconds.

A Composition of the invention could a single pack composition, wherein the reactants are optionally kept in stasis. In such embodiments, the ongoing pH change be initiated by adding an agent, before which the reactants previously protected were. For example, could this is water or oxygen or carbon dioxide or Act light.

In another embodiment could the reactants, e.g. in a tablet or in a detachable sachet with two or more zones, depending on the tablet or bag type can act around layers, parts or encapsulated sections, or in a double-bottle or double-tablet package physically separated from each other. In all such embodiments this is the key factor because the reactants are only combined at the time of cleaning become.

The Composition can be provided in a package, the composition as a spray, foam, gel or jet of liquid ejects. at the packaging may suitably be a pump spray or preferably an aerosol container act. A spray launching Packaging of the composition, in particular an aerosol container forms another aspect of the invention. In other embodiments becomes a wipeable one Product, e.g. a sponge or cloth impregnated with a composition.

at The composition may be a product for use dilute or a product in ready to use form. Lies the product for dilution before, this may be a solid, e.g. a powder or a tablet or a liquid or act a gel.

The Composition may be in a single unit dose delivery Be provided composition-providing packaging.

The Composition may be such that the chemical reaction is a color change causes. One or more of those responsible for the change in pH Reactants can e.g. when you use up a color change cause, or a separate dye or a separate colorant may be included in the composition due to the pH change or the presence of an oxidant species or reductant species or a temperature change reacts in the event of an exothermic reaction.

Other Means for indicating a chemical change other than the color may be used. For example, could the system be arranged so that it takes place when the Reaction e.g. by including a bicarbonate in a system, which becomes acidic after the induction period bubbles. Another in the case of an exothermic reaction useful method sets one Perfume, which is made volatile by a temperature increase.

Of the The term "cleaning" can, as used here, Include: Removal of dirt deposits, prevention of dirt formation, Bleaching, fighting of allergens and fighting including microbes by one or more effects of an antiseptic agent, Disinfectant, bactericidal agent, sporicidal agent, fungicidal agent and viricidal agent.

Preferably the composition is antimicrobial. Preferably, an antimicrobial Effect by the reaction, e.g. by temperature increase, if the reaction is exothermic, and / or by the pH change in the field and / or by preparing an antimicrobial chemical in generates the reaction. Preferably, the antimicrobial chemical by changing the pH Reaction and therefore generated in situ with the same delay. The For example, an antimicrobial chemical can be an iodate, bromate, thiocyanate or chlorate.

The The composition preferably produces a bleaching effect. Preferably the bleaching effect is determined by the reaction, e.g. by the temperature, when the reaction is exothermic and / or by the pH change in situ and / or by the production of a bleaching chemical in generates the reaction. Preferably, a bleaching agent through the changing the pH Reaction and therefore generated in situ with the same delay. To the For example, the composition may be acidic forming sodium chloride, sodium hydroxide and chlorine dioxide. consequently For example, a bleaching agent and an alkaline agent can be formed.

suitably For example, the composition may be hydrogen peroxide or a precursor thereof as bleach and / or reactant.

The Composition may include one or more surfactants. One Surfactant used in the present invention may be selected from one or more surface-active Agents which are anionic, cationic, nonionic or amphoteric (zwitterionic) surfactants.

at a class of non-ionic surfactants used in of the present invention are alkoxylated Alcohols, especially alkoxylated fatty alcohols. These include ethoxylated and propoxylated fatty alcohols, as well as ethoxylated and propoxylated Alkylphenols, both of which are alkyl groups of 7 to 16, more preferred Have 8 to 13 carbon chains in length.

Examples for alkoxylated Close alcohols certain ethoxylated alcohol compositions currently used in the Trade of Shell Oil Company (Houston, TX) among the general Brand name NEODOL (trademark) are available, which are described as such are that these are linear alcohol ethoxylates, and certain compositions currently marketed by Union Carbide Company (Danbury, CT) under the general trade mark TERGITOL (Trade Mark), which are described as being secondary alcohol ethoxylates one.

Examples for alkoxylated Close alkylphenols certain compositions currently marketed by Rhone-Poulenc Company (Cranbury, NJ) under the general brand name IGEPAL (Brand) available are and are described in such a way that these are octyl and nonylphenols.

Other Classes of nonionic surfactants used can be are sorbitol esters of fatty acids, typically fatty acids with 10 to 24 carbon atoms, e.g. Sorbitan.

Examples for anionic surfactants Agents which can be used in the present invention include alkali metal salts, Ammonium salts, amine salts, aminoalcohol salts or the magnesium salts of one or more of the following compounds: alkyl sulfates, Alkyl ether sulfates, alkylamidoether sulfates, alkylaryl polyether sulfates, Monoglyceride sulfates, alkyl sulfonates, alkyl amide sulfonates, alkylaryl sulfonates, Olefin sulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, Alkyl amide sulfosuccinates, alkyl sulfosuccinamate, alkyl sulfoacetates, Alkyl phosphates, alkyl ether phosphates, acyl sarcosinates, acyl isothionates and N-acyl taurates, but are not limited thereto. in the Generally, the alkyl or acyl group in these various includes those Compounds a carbon chain containing 12 to 20 carbon atoms contains.

Other anionic surface-active Means that can be used shut down Fatty acid salts, including salts of oleic, ricinoleic, palmitic and stearic acids, copra oils or hydrogenated cocoa acid and Acyllactylate whose acyl group contains 8 to 20 carbon atoms.

ein, wobei R eine hydrophobe Gruppe ist, die eine Alkylgruppe, enthaltend 10 bis 22 Kohlenstoffatome, vorzugsweise 12 bis 18 Kohlenstoffatome, eine Alkylaryl- oder Arylalkylgruppe, enthaltend eine ähnliche Anzahl an Kohlenstoffatomen, wobei ein Benzolring als Äquivalent mit etwa 2 Kohlenstoffatomen behandelt wird, und ähnliche Strukturen, die durch Amido- oder Etherbindungen unterbrochen sind, ist; jedes R₁ eine Alkylgruppe, enthaltend 1 bis 3 Kohlenstoffatome, ist; und jedes R₂ eine Alkylengruppe, enthaltend 1 bis 6 Kohlenstoffatome, ist.Amphoteric surfactants which can be used in the present invention include amphoteric betaine surface active compounds of the following general formula

wherein R is a hydrophobic group containing an alkyl group containing 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms, an alkylaryl or arylalkyl group containing a similar number of carbon atoms, with a benzene ring treated as an equivalent of about 2 carbon atoms, and similar structures interrupted by amido or ether bonds; each R _{1 is} an alkyl group containing 1 to 3 carbon atoms; and each R _{2 is} an alkylene group containing 1 to 6 carbon atoms.

A or more such betaine compounds may be used in the compositions to be included in the invention.

gekennzeichnet sind, ein, wobei mindestens einer der Reste R₁, R₂, R₃ und R₄ eine hydrophobe, aliphatische, arylaliphatische oder aliphatische Arylgruppe, enthaltend 6 bis 26 Kohlenstoffatome, ist, und der gesamte kationische Teil des Moleküls ein Molekulargewicht von mindestens 165 aufweist. Die hydrophoben Gruppen können langkettiges Alkyl, langkettiges Alkoxyaryl, langkettiges Alkylaryl, halogensubstituiertes langkettiges Alkylaryl, langkettiges Alkylphenoxyalkyl oder Arylalkyl sein. Die übrigen anderen Gruppen an den Stickstoffatomen als die hydrophoben Reste sind im Allgemeinen Kohlenwasserstoffgruppen, die gewöhnlich insgesamt nicht mehr als 12 Kohlenstoffatome enthalten. R₁, R₂, R₃ und R₄ können geradkettig oder verzweigt sein, sind jedoch vorzugsweise geradkettig und können eine oder mehrere Amid- oder Esterbindungen einschließen. X kann eine beliebige salzbildende anionische Einheit sein.Examples of cationic surfactants which can be used in the present invention include quaternary ammonium compounds and salts thereof, including quaternary ammonium compounds which also have a germicidal effect and which are governed by the general structural formula

wherein at least one of R ₁ , R ₂ , R ₃ and R _{4 is} a hydrophobic, aliphatic, arylaliphatic or aliphatic aryl group containing 6 to 26 carbon atoms, and the entire cationic portion of the molecule has a molecular weight of at least 165 has. The hydrophobic groups can be long-chain alkyl, long-chain alkoxyaryl, long-chain alkylaryl, halogen-substituted long-chain alkylaryl, long-chain alkylphenoxyalkyl or arylalkyl. The remaining groups on the nitrogen atoms other than the hydrophobic groups are generally hydrocarbon groups, usually containing not more than 12 carbon atoms in total. R ₁ , R ₂ , R ₃ and R ₄ may be straight chain or branched, but are preferably straight chain and may include one or more amide or ester linkages. X can be any salt-forming anionic unit.

Examples for quaternary ammonium salts within the above description include alkyl ammonium halides such as cetyltrimethylammonium bromide, alkylarylammonium halides such as Octadecyldimethylbenzylammonium bromide and N-alkylpyridinium halides such as N-cetylpyridinium bromide. Other suitable types of quaternary ammonium salts shut down those in which the molecule is contains either amide or ester bonds, such as octylphenoxyethyldimethylbenzylammonium chloride and N- (laurylcocoaminoformylmethyl) pyridinium chloride. Other effective types of quaternary Ammonium compounds useful as germicides, shut down those in which the hydrophobic moiety is as in the case of lauryloxyphenyltrimethylammonium chloride, Cetylaminophenyltrimethylammonium methosulfate, dodecylphenyltrimethylammonium methosulfate, Dodecylphenyltrimethylammonium chloride and chlorinated dodecylphenyltrimethylammonium chloride are characterized by a substituted aromatic nucleus.

ein, wobei R₂ und R₃ gleiches oder verschiedenes C₈-C₁₂-Alkyl sind oder R₂ C₁₂-C₁₆-Alkyl, C₈-C₁₈-Alkylethoxy, C₈-C₁₈-Alkylphenolethoxy ist und R₃ Benzyl ist, und X ein Halogenid, z.B. Chlorid, Bromid oder Iodid, oder Methosulfat ist. Die Alkylgruppen R₂ und R₃ können geradkettig oder verzweigt sein, sind jedoch vorzugsweise im Wesentlichen linear.Preferred quaternary ammonium compounds which act as germicides and are useful in the present invention include those of the structural formula

in which R ₂ and R _{3 are the} same or different C ₈ -C ₁₂ -alkyl or R _{2 is} C ₁₂ -C ₁₆ -alkyl, C ₈ -C ₁₈ -alkylethoxy, C ₈ -C ₁₈ -alkylphenolethoxy and R _{3 is} benzyl and X is a halide, eg, chloride, bromide or iodide, or methosulfate. The alkyl groups R ₂ and R ₃ may be straight or branched, but are preferably substantially linear.

One Mixture of two or more surfactants may as well be used. Other known surfactants described above are not specifically described, may also be used. Such surface-active Means are in McCutcheon's Detergents and Emulsifiers, North American Edition, 1982; Kirk-Othmer, Encylopaedia of Chemical Technology, 3rd Edition, Vol. 22, pp. 346-387.

The Compositions of the present invention may be one or more organic solvent such as lower alkyl alcohols, lower alkyl diols or glycol ethers therein lock in. Such compounds can act as cleaning agents of the compositions and based on the absence of their tendency to smearing in glass cleaners especially useful be.

Preferably the composition is such that its temperature after exposure increased to a place to be cleaned which is preferably due to the pH-changing Reaction and therefore caused with the same delay. consequently is that for the change the pH responsible reaction is preferably exothermic.

The Composition may be such that the pH after a pH change change in the reverse direction can. For example, a composition can change from acid to alkaline and back after acid or from alkaline to sour and back to alkaline. It is possible, that such compositions further pH changes can undergo. Every pH change preferably takes over an induction period as defined above.

• Oscillation, Waves and Chaos in Chemical Kinetics, S. K. Scott, Oxford University Press, 1995.
• Design of pH-Regulated Oscillators, G. Rabai et al., Acc. Chem. Res., 1990, 23, 258–263.
• A General Model for pH Oscillators, Y. Luo et al., J. Am. Chem. Soc., 1991, 113, 1518–1522.
• Temperature compensation in the oscillatory hydrogen peroxide-thiosulfate-sulphite flow system, G. Rabai et al., Chem. Commun., 1999, 1965–1966.
• Kinetic Role of CO₂ in the Oscillatory H₂O₂-HSO₃ ^–-HCO₃ ^– Flow System – G. Rabai et al., J. Phys. Chem. A1999, 103, 7224–7229.
• Chaotic pH oscillations in hydrogen peroxide-thiosulfate sulphite flow system, G. Rabai et al., J. Phys. Chem. A1999, 103, 7268–7273.

Consequently, cleaning compositions based on pH oscillation systems can be envisaged. Suitable systems may include those described in the following references:

• Oscillation, Waves and Chaos at Chemical Kinetics, SK Scott, Oxford University Press, 1995.
• Design of pH-Regulated Oscillators, G. Rabai et al., Acc. Chem. Res., 1990, 23, 258-263.
• A General Model for pH Oscillators, Y. Luo et al., J. Am. Chem. Soc., 1991, 113, 1518-1522.
• Temperature compensation in the oscillatory hydrogen peroxide-thiosulfate-sulphite flow system, G. Rabai et al., Chem. Commun., 1999, 1965-1966.
• Kinetic Role of CO ₂ in the Oscillatory H ₂ O ₂ -HSO ₃ ^- -HCO ₃ ^- Flow System - G. Rabai et al., J. Phys. Chem. A1999, 103, 7224-7229.
• Chaotic pH oscillations in hydrogen peroxide thiosulfate sulfite flow system, G. Rabai et al., J. Phys. Chem. A1999, 103, 7268-7273.

Thus, the compositions may preferably contain ingredients that provide an abrupt pH step. The autocatalytic species for the reaction are H ⁺ (or more rarely OH ^- ), and the pH steps can take place when a solution of a weak acid is oxidized to provide a strong acid such that the H ⁺ concentration increases with the reaction volume.

The chemical composition of a typical pH-step system an oxidizing agent and a reducing agent. Typically is the reducing agent is the salt of a weak acid and the corresponding oxidizing agent a strong acid. Naturally For example, a reaction can involve a variety of oxidants and / or a Include a variety of reducing agents.

Lots different species can be used as a partner in these redox systems. In the search suitable species is a guideline for total reaction stoichiometry because the reducing agent release more protons per electron should be consumed as the oxidizer.

In of the present literature the following species are identified and purified in cleaning compositions be used:

Potential oxidizers:

• I peroxo compounds (eg BrO ₃ ^- , IO ₃ ^- , ClO ₃ ^- , ClO ₂ ^- , S ₂ O ₈ ^2- , ClO ₂ , H ₂ O ₂ or a precursor thereof)
• II Oxidizing metal compounds that are stable in alkaline solutions (eg [Fe (CN) ₆ ] ^3- ).

Potential reducing agents:

• I All oxyanions of sulfur containing SS bonds (eg, S ₂ O ₃ ^2- , S ₄ O ₆ ^2- , S ₂ O ₄ ^2- , S ₂ O ₆ ^2- ).
• II reducing agents, which are significantly more basic than their oxidized counterparts (eg, SO ₃ ^2- , HSO ₃ ^- , AsO ₃ ^3- , S ₂ O ₃ ^2- , S ₄ O ₆ ^2- , N ₂ H ₅ ⁺ , [Fe ( CN) ₆ ] ^4- ).

wobei „Ja" auf einen etablierten Beweis für das pH-Schrittverhalten und „Nein" auf keine beobachtete Reaktion unter den bis heute untersuchten Verbindungen hinweist.Based on the reactions described in the published literature, a raster pattern of combinations of some of these species can be constructed:

where "yes" indicates established evidence of pH pacing, and "no" indicates no observed response among compounds tested to date.

The most widely studied pH stepping reactions are those embodied by the Landolt-Clock reaction wherein the oxidant has the formula XO _n ^- , where X is Cl, Br or I and n is 3 when X is Is Br or I and 2, 3 or 4 when X is Cl; and the reducing agent is SO ₃ ^2- / HSO ₃ ^- . The classic Landolt system employs IO ₃ ^- as an oxidizing agent and SO ₃ ^2- / HSO ₃ ^- as the reducing agent. The reaction is autocatalytic in I ^- (depending on the second power of the iodide ion concentration) and a pH step reaction system even in buffered solution. In unbuffered solution, the reaction is also autocatalytic in H ⁺ .

Among these combinations mentioned above, there are reports of pH step reactions with associated pH changes involving the following reagents:
Permanganation as an oxidizing agent, wherein the reducing agent is sulfite, nitrite, selenite, arsenite thiosulfate + iodide + H ₂ O ₂ or a precursor thereof.

Examples for precursors of Close hydrogen peroxide Urea hydrogen peroxide (UHP) and a cyclodextrin, e.g. complexed with an organic peroxyacid as described in EP-A-895777 is a. An example is β-cyclodextrin, that with an organic peroxyacid, e-phthalimidoperoxyhexanoic acid (PAP), is complexed. This product is under the mark EURECO HC of Wacker Chemie GmbH available.

The Add a second reducing agent to a Landolt system ("mixed Landolt system ") create a pH step reaction in which the pH at the end an induction period from high to low and then on a longer timescale back pivots to a high pH.

An example of a pH-step reaction system that starts at low pH and changes to a high pH at the end of an induction period involves reduction of H ₂ O ₂ (which can be delivered by a precursor as described above) various multidentate complexes of Fe (II) or Co (II) ions, in particular using Fe (CN) ₆ ^4- as anion species, as described in G. Rabai et al., J. Am. Chem. Soc., 1989, III, p. 3870.

cleaning structures of the invention e.g. For Textile materials, including Carpets and garments be used. You can in dishwashing detergent compositions and clothes washing compositions. The pH change can e.g. the resolution the coating of a washing tablet or one in a washing tablet cause in each case a delayed Release of the ingredients is provided.

at a preferred cleaning composition of the present invention It is a cleaner for hard surfaces to Cleaning of ceramics, glass, stone, plastics and wood and in particular for cleaning hard surfaces in baths and kitchens, e.g. of sinks, bowls, toilets, paneling, Tiles and work surfaces. When acid, it is especially effective in controlling lime. In alkaline state, it is especially when fighting fat and protein Deposits effective.

Another preferred cleaning composition is useful for cleaning artificial dentition (usually polyacrylic material) and therefore is effective in removing stains and / or plaque sam.

A Another preferred cleaning composition is for cleaning suitable for toilet bowls, and for For this purpose, the cleaning composition may be dissolved in an ITB (in the key) or ITC (cistern) device preferably in one of the edge of the bowl or cistern hanging down Holder be packed. In the case of chemical reactants, the desirably kept away from each other until the reaction takes place Preferably, the reactants are in separate form Kept containers liquids or solids contained in separate tablets (e.g., compressed Powders or granules or gel blocks) or in a tablet with separate zones for the different reactants are formulated. Naturally can the reactants are mixed in some systems and only when used react, in which case a single vessel or a simple tablet can be used.

A other useful Cleaning composition is for effective cleaning of marble surfaces suitable. Such Composition is acidic when applied to certain But attacking stains and dirt becomes alkaline before any resolution of the marble can occur. In the alkaline state, it attacks others Stains and other dirt, especially grease.

The Invention will now be described by way of example with reference to the following examples described. Unless otherwise stated, the solutions of Reactants are mixed in distilled water at ambient temperature and with a magnetic stirrer touched, while the pH and the temperature are monitored were. Cationic species were sodium ions.

example 1

The variations of the induction period (the period between the mixing of reactants and the start of swinging of the pH) and the swirling of the pH with initial reactant concentrations for a dilute solution of bromate and sulfite ions mixed as solutions at ambient temperature and Use of concentrated sulfuric acid to adjust the pH was determined in a series of experiments. As is apparent from Table 1 below, the induction period can t _ind from 4 hours to 2 minutes varied _ind where t is approximately inversely proportional to the initial combinations both of BrO ₃ ^- and H ⁺ and independent of the initial concentration of SO ₃ ^2- is. The initial sulfite concentration appears to determine the swing in pH, which is typically on the order of 4 to 5 pH units. The reaction occurs for compositions having initial pH's in the range of 6.6 to 8.9.

Table 1 [BrO ₃ ^- ] ₀ = 0.06 M, [SO ₃ ^2- ] ₀ = 0.054 M

The initial Experiments were repeated by comparing the initial concentration of bromate ions in a sequence with constant initial pH and sulfite concentration were varied. This resulted in how Variations in the induction period shown in Table 2 below.

Table 2

wobei [BrO₃ ^–]₀ = 0,06 M und ein anfänglicher pH-Wert = 7,0.The initial experiments were then repeated with variations in the concentration of reducing agent species sulfate with constant bromate and initial pH. The effect of this on the induction period and the swirling of the pH is set forth in Table 3 below. Table 3

where [BrO ₃ ^- ] ₀ = 0.06 M and an initial pH = 7.0.

Consequently, the induction period and the pivoting of the pH in these experiments were of [SO ₃ ^2-] ₀ relatively insensitive.

All in all The results showed that the system was the basis for a new one Cleaning composition is valuable.

Example 2

A A series of experiments was conducted with significantly higher concentrations of the reactants as used in Example 1, wherein the Objective to use the concentration dependence to reduce the Induction period while maintaining a larger swing of the pH acted. Likewise, the required initial pH was used rather retain a suitable mixture of sulphite and bisulphite salts, as the initial one pH after dissolution the reactant was adjusted with concentrated sulfuric acid. The Variations with initial ones Reductant concentrations of the induction period, the final pH and the peak temperature that during was observed in the reaction are shown in Table 4 below. The results showed that the system is the basis of a promising could provide new cleaning composition.

Table 4

Example 3

In this example, the classical iodate sulfate / bisulfite-Landolt reaction was investigated. It is known that the induction period is inversely proportional to the initial iodine ion concentration and independent of the initial sulfite ion concentration (provided that the initial pH is kept constant). The dependence of t _ind on the initial pH is less well understood, therefore these data were determined in the present program. The solutions consisted of a concentration of 0.01 M iodate (fixed) and 0.02-0.002 M bisulfite. The results are set forth in Table 5 below. In all cases, the final pH was 2.2-2.3.

Table 5

Example 4

Chlorination ClO ₃ ^- can be used as an oxidant in Landolt type systems. A number of experiments were carried out by this system. The reaction does not appear to occur when starting at pH's greater than about 5.0, therefore the initial pH for the experiments discussed below using concentrated H ₂ SO _{4 was} reduced to a range of 4.5- 5.0 set. The concentration is highly exothermic, and even for relatively dilute solutions significant temperature increases (self-heating) take place. The results are set forth in Tables 6 and 7 below.

Table 6 - Variation of induction period with initial chlorate concentration [SO ₃ ^2- ] ₀ = 0.44 M, initial pH = 4.5

Table 7 - Dependence on initial sulfite concentration [ClO ₃ ^- ] ₀ = 0.290 M, initial pH = 4.5

These Data indicate that the induction period is inversely proportional to the initial concentration of Chloration and effectively independent from the sulphite concentration. The peak temperature increase drops, when the system is diluted becomes. The system is of potential value as a cleaning composition.

Example 5

A series of experiments were carried out in which the chloride ion was added to the bromate-sulfite reaction system to see if the latter could drive the production of ClO ₂ after a suitable induction period. The experimental data set forth in Table 8 below was collected.

Table 8

These Results indicate that the system for the addition of chloride ion reasonably robust is. The induction period and the pH change are for the chloride ion concentration relatively insensitive, although very high concentrations of the reaction can inhibit.

It is expected that the ClO ₂ ^- decomposes to ClO ₂ upon drop in pH. This was not confirmed quantitatively, but the presence of ClO _{2 was} clearly detectable by its odor after the pH change took place. Consequently, the system is of potential value as a cleaning composition with sterilizing properties.

Example 6

One Trial was carried out to investigate how the bromate and sulfite reactants in dry powder form influence the induction time, the temperature increase and the pH. The experiment was for varying sulphite concentrations at two initial bromate concentrations (0.4 and 0.6 M).

The Reactants were weighed in dry powder form such that they gave the desired concentrations when mixed with 50 ml of water. A foaming was evident when water was added. A comparison was made with reactions using liquid reactants. The Results are shown in Table 9 below.

Table 9

The Table 9 above shows how the induction period changes depending on whether the reactants in solution or in dry powder form. The induction period was for the dry powder increases, but this increase was very high low, and in most cases increased the induction time is only a few seconds. It was not essential Difference in temperature increase and in the beginning and final pH between the experiments with dry powder and solution in front. It turned out, therefore, that a powder system in the present Invention of possible Is worth.

Example 7

One Trial was carried out to investigate how the use of tap water (in The School of Chemistry, University of Leeds, UK) instead of distilled water the induction period, the temperature increase and the pH in a sulfite-bromate system affected. The experiment was for varying sulphite concentrations at two initial bromate concentrations (0.4 and 0.6 M) and a constant bisulfite concentration (0.018 M). The results are shown in Table 10 below.

Table 10

It can be seen from the above results that the use of tap water rather than distilled water has no significant influence on the induction time, the values remaining substantially constant during all experiments. It was also evident that the temperature increase and the initial and final pHs remained substantially constant.

Example 8

In In a bromate sulfate system, the additional addition was typically surfactants used in household cleaning compositions Means examined. A set of initial concentrations became selected (Bromate 0.5 M, sulfate 0.65 M and bisulfite 0.018 M), and a selection at surface-active Means were added as identified in Table 11 below.

Table 11

Sodium lauryl sulfate is a known anionic surfactant. Polytergent ^® SL-62 is a nonionic surfactant, a mixture of ethoxylated and propoxylated fatty alcohols, from BASF. The glycol ether DOWANOL ^® DPnB glycol ethers. Empigen ^® BAC 50 is a cationic surfactant, a benzalkonium chloride, more particularly C _10-16 - (predominantly C _12-14 -) - alkyl dimethylbenzyl ammonium chloride.

It can be seen that none of the surface active agents with the added amounts has a large effect on the induction time. It can be seen that sodium lauryl sulphate slightly increases the induction time, all readily reduced whereas Epigem ^® BAC 50, Polytergent ^® S 162 and glycol n-butyl ether, the induction time. The temperature increase in all cells remains constant. The initial pH is slightly raised when Empigen ^® BAC 50, are Polytergent SL-62 and glycol n-butyl ether was added, but the pivoting of the pH remains virtually constant.

Example 9

One another attempt was made to the effects of the addition of various surface-active To determine more detailed means to the bisulfite / sulfate-bromate reaction mixture.

• i) Bromat 0,5 M, Sulfat 0,65 M und Bisulfit 0,018 M
• ii) Bromat 0,7 M, Sulfat 0,5 M und Bisulfit 0,018 M

Two different sets of initial concentrations were used:

• i) Bromate 0.5 M, sulfate 0.65 M and bisulfite 0.018 M
• ii) bromate 0.7M, sulfate 0.5M and bisulfite 0.018M

A small amount of a common surfactant was added to each experiment in the concentration ranges shown below:
Empigen ^® BAC 50: 1% w / w 5% w / w
Sodium lauryl sulfate: 1% w / w 5% w / w
Polytergent ^® SL-62: 1% w / w 10% w / w
Dipropylene glycol n-butyl ether: 1% w / w 10% w / w

Tables 12 and 13 show the results of the experiments. In any case, the results are the mean results of three replicates. Table 12 shows the results of the initial bromate 0.5 M concentrations, sulfate 0.65 M and bisulfite 0.018 M, and Table 13 shows the results the initial concentrations bromate 0.7 M, Sulft 0.5 M and bisulfite 0.018 M.

The general conclusion that can be drawn from these more detailed experiments is that none of the surface-active agents greatly influences the reaction. The most important observations are that Empigen ^® BAC 50 can slightly decrease the induction time but increase the initial pH by about 0.5 units. The initial pH increases with increasing Empigen ^® -BAC-50 concentration up to 8.6 to (the pH value of Empigen ^® BAC 50). Sodium lauryl sulfate slightly increases the induction time.

Example 10

One Trial was carried out to determine if the dry powder chemicals for the sulfite-bromate system can be stored together and still react when mixed with water.

The Experiments were outlined as above, but over a period of 30 days carried out. "Stirred" and "unstirred" variants were carried out. In the "stirred" variants were the reaction mixtures during The reactions were stirred constantly. In the "unstirred" variants were the reaction mixtures for a duration of 15 seconds touched, then for the rest of the experiments unaffected ditched.

It it was noticed that against the latter stages of the experiments orange Spots in powder were evident. Likewise, during the Tried to find that the powder turns into a solid lump settled before performing the experiments had to be broken up.

The Results are shown in Table 14 below.

Table 14

It can be seen from Table 14 that the initial and final pH, with an initial pH of about 8.1 and a final pH of 2.9, were close to zero in both the stirred and the unstirred experiments remained constant. The maximum temperature increase also remained approximately constant at 55 ° C. The mean induction time for the stirred experiments was 260 ± 23.8 sec, but it can be seen to vary in the range of 179 to 261 sec. The induction time in the unstirred case had an average of 276 ± 60 s on, however, the times of 196-386 s varied.

Example 11

Attempts have been made to study a hydrogen peroxide sulfite / bisulfite system suitable for use in the present invention. To release hydrogen peroxide in a stable manner, urea hydrogen peroxide (UHP) CO (NH ₂ ) ₂ H ₂ O _{2 was} used. Sodium sulfite was used in the concentration range of 1 × 10 ^-3 M to 5 × 10 ^-3 M. UHP was used in the concentration range of 1 × 10 ^-2 M to 5 × 10 ^-2 M. The experiments showed that the induction period for a pH change event could be 80 to 2000 seconds, with the lower induction periods being supported by the more concentrated UHP solutions. The pH typically ranged from an initial pH of 7.5 to 8.4 (higher with increasing sulphite concentrations) to a final pH of 5.1, with the UHP concentration having no effect on the initial or final pH and the sulfite concentration had no effect on the final pH. It was concluded that the system was promising as the basis for a cleaning composition.

Example 12

The compatibility of the UHP sulfite system described in Example 11 with a number of surfactants was also investigated. The following surfactants were tested.
Empigen BAC 50: 1% w / w 5% w / w
Sodium lauryl sulfate: 1% w / w 5% w / w
Polytergent SL-62: 1% w / w 10% w / w
Dipropylene glycol n-butyl ether: 1% w / w 10% w / w

The reactants and their initial concentrations were as follows. UHP: 0.3 M Sulfite: 0.01887 M bisulfite: 0.00113 M

The results are in the 1 to 4 explained. In these figures, the left bar of each result block was a control (0% w / w surfactant) and the right bar of each result block indicated the highest level of surfactant employed.

• – Alle oberflächenaktiven Mittel reduzierten den anfänglichen pH-Wert um 0,1 bis 0,2 Einheiten.
• – Dipropylenglycol-n-butylether reduzierte den End-pH-Wert. Alle anderen oberflächenaktiven Mittel erhöhten den End-pH-Wert.
• – Alle oberflächenaktiven Mittel verminderten die Induktionsperiode. Im Falle von Empigen^® BAC 50 war die Verminderung deutlich, indem die Induktionszeit bei seiner niedrigsten Konzentration um bis zu einer Minute vermindert wurde. Dipropylenglycol-n-butylether verminderte die Reaktionszeit letztendlich, arbeitete jedoch noch weiter, um sie um 30 Sekunden bei seiner niedrigsten Konzentration zu vermindern.

The main conclusions were:

• All surfactants reduced the initial pH by 0.1 to 0.2 units.
• - Dipropylene glycol n-butyl ether reduced the final pH. All other surfactants increased the final pH.
• All surfactants reduced the induction period. In the case of Empigen ^® BAC 50, the decrease was significantly by the induction time was reduced at its lowest concentration of up to one minute. Dipropylene glycol n-butyl ether eventually reduced the reaction time, but worked even further to reduce it by 30 seconds at its lowest concentration.

Example 13

The following samples were tested for antimicrobial properties. Sample 1: Sodium bromate (NaBrO ₃ ) - [0.7 M] Sodium sulfite (NaSO ₃ ) - [0.5 M] Sodium bisulfite (NaS ₂ O ₅ ) - [0.025 M] Sample 2: same as Sample 1, but the sodium bisulfite concentration was 0.018M

In the first tests against S. aureus and E. coli, the test (with sample 1) was performed using sterile, purified water in the presence of any organic soil. The second tests (with sample 2) included two additional test organisms (P. aeroginosa and E. hirae) and were performed in hard water (300 ppm CaCO ₃ ) and with addition of organic soil, bovine serum albumin - BSA.

The test procedure for Example 2 was as follows: 1 ml of bacterial suspension (10 ⁷ cfu / ml) of extracted selected bacterium was transferred to a flask containing 1 ml of a 3% BSA suspension. The culture / soil mixture was mixed by vortexing and then shaken on an orbital shaker for a period of 2 minutes. To the culture / soil mixture was added 8 ml of sterile hard water. The mixing was continued for a further minute. Without shaking, the chemical compounds of the respective samples were added in powder form in amounts calculated to give the above-mentioned molarities. 5 minutes after the addition of the sample, shaking was stopped and an aliquot of 1 ml of the test mixture was transferred to 9.0 ml of neutralization medium. After a 5 minute neutralization period, the sample was serially diluted and used to prepare four plates, which were then incubated at 36 ° C for a period of 48 hours prior to counting surviving bacteria. As an inactive control, the test was repeated without the addition of the test sample. The test procedure for Sample 1 was similar but, as stated above, did not use hard water or BSA.

The values of the microbial effect (ME) were calculated as follows:
Log (cfu / ml tested at t = 0) - log (cfu / ml retrievable from the test after 5 minute contact time). The results are shown in Tables 15 and 16 below.

Table 15: Mean ME values (n = 3) for S. aureus and E. coli in preliminary tests

Table 16: Mean ME values (n = 3) for further tests

On From the basis of these preliminary results, it seems that the impact of the reactants on bacteria in a standard suspension test noticeable Reductions in bacterial viability produced. The reduction over one log of 5.0 were for all four test organisms in the presence of organic dirt Bovine serum albumin and hard water and with a 5-minute contact time achieved.

Accordingly, became concluded that the system has good activity as an antimicrobial cleaning composition showed.

Example 14

Experiments were performed on a system which was assumed to cause an increase in pH using urea hydrogen peroxide and Fe (CN) ₆ ^4- .

The Tests tested the effect of the concentration of the above species and hydrogen ion concentration.

tables 17 to 19 summarize the results of the experiments. In each Case, two species were kept at constant concentrations, while the third was varied.

• – UHP = 2 × 10^–3 M
• – Ferrocyanide = 2 × 10^–3 M
• – H+ = 5 × 10^–4 M

Tabelle 17

(Mittelwert von 3 Wiederholungen) Tabelle 18

(Mittelwert von 2 Wiederholungen) Tabelle 19

(Mittelwert von 2 Wiederholungen)Not varied, were the initial species concentrations

• - UHP = 2 × 10 ^-3 M
• Ferrocyanide = 2 × 10 ^-3 M
• - H + = 5 × 10 ^-4 M

Table 17

(Mean of 3 repetitions) Table 18

(Mean of 2 repetitions) Table 19

(Mean of 2 repetitions)

None temperature increase was during observed each of the experiments. A color change from colorless to pale yellow was observed. The mean pH increase varied between 3.5 and 4.9 and was common 4.4.

Example 15

A hard surface cleaning composition has the following composition: TERGITOL ^®, secondary alcohol ethoxylate ethylene glycol n-butyl ether (non-ionic oberflächenaltives agent)) 0.6% w / w Fragrance 0.2% w / w colour track H ₂ O ₂ 0.1% w / w Na ₂ S ₂ O ₃ 0.16% w / w Na ₂ SO ₃ 0.05% w / w H ₂ SO ₄ 0.005% w / w Liquefied petroleum gas (propellant gas) 20% w / w Deionized water at 100% w / w

During the Preparation was the hydrogen peroxide of a solution of three sulfur-containing compounds kept separate. These input solutions were kept free of air before mixing and in the absence of air mixed and bottled in aerosol cans free of air. Just when spraying a surface with this composition for purification, the pH step reaction starts.

Example 16

A hard surface cleaner has the following composition: Ethoxylated fatty alcohol (C _12-14 ; 3EO) (non-ionic surfactant) 1% w / w ethylene glycol 5% w / w perfume 0.1% w / w colour track NaIO ₄ 0.43% w / w Na ₂ S ₂ O ₃ 0.16% w / w Na ₂ SO ₃ 0.06 G / G H ₂ SO ₄ 0.01% w / w Butane (propellant gas) 18% w / w Deionized water at 100% w / w

The Ingredients were mixed and filled into spray cans with the exclusion of air. Just when spraying a surface with this composition for purification, the pH step reaction starts.

Claims (11)

Process for cleaning a hard surface, on which deposits lime, the method applying a A cleaning composition comprising reactants which differs Action on the hard surface undergo a chemical reaction that involves hard surface wherein the reaction is such that a delayed change in pH on the hard surface is produced by the composition initially an alkaline liquid and after a period of time to an effective in controlling lime acidic liquid becomes. The method of claim 1, wherein the composition the property that the composition has after exposure on the hard surface a delayed change of the pH of at least 2 pH units on the hard surface. The method of claim 1 or 2, wherein the composition an oxidizing agent selected from a peroxy compound and a stable in alkaline solutions oxidizing metal compound, and a reducing agent selected from a sulfur containing oxyanion or S-S bonds and a Compound that is substantially more basic than its oxidized counterpart is included. The method of claim 3, wherein the oxidizing agent is selected from the species BrO ₃ ^- IO ₃ ^- , ClO ₃ ^- , ClO ₂ ^- , S ₂ O ₈ ^2- , ClO ₂ , [Fe (CN) ₆ ] ^3- and H ₂ O ₂ or a precursor thereto, and the reducing agent is selected from the species S ₂ O ₃ ^2- , S ₄ O ₆ ^2- , S ₂ O ₆ ^2- , SO ₃ ^2- and N ₂ H ₅ ⁺ , wherein the oxidizing agent and the reducing agent co-participate in pH-fluctuating reactions. Method according to one of the preceding claims, wherein the composition has an antimicrobial effect on the hard surface generated. Method according to one of the preceding claims, wherein the composition produces a bleaching action on the hard surface. Method according to one of the preceding claims, wherein a temperature increase produced by the reactants on the hard surface. Method according to one of the preceding claims, wherein The composition is such that the pH change by a change of color or smell or by bubbling shows. Method according to one of the preceding claims, comprising a surface active Medium. Method according to one of the preceding claims, wherein the composition excluding oxygen and / or water and / or carbon dioxide and / or light is packaged as it is to prevent a pH change is required before use. Method according to one of the preceding claims, wherein the hard surface an aqueous one Environment and the process is the dilution of the cleaning composition in the aqueous Environment includes.