WO2007122128A1

WO2007122128A1 - Cleaning composition for hard surface cleaning and method of use

Info

Publication number: WO2007122128A1
Application number: PCT/EP2007/053683
Authority: WO
Inventors: Alexander Mantler; Olof Wallquist; Oliver Reich
Original assignee: Ciba Holding Inc.
Priority date: 2006-04-26
Filing date: 2007-04-16
Publication date: 2007-11-01

Abstract

Cleaning compositions for cleaning hard surfaces of a substrate are provided which comprise indicator compounds and a dye which show improved colour forming or colour change when coming into contact with ions responsible for water hardness. The cleaning process can be facilitated and total purity of the hard surfaces can be reached.

Description

Cleaning composition for hard surface cleaning and method of use

The present invention relates to a cleaning composition for cleaning of hard surfaces of substrates and a method of treating/cleaning hard surfaces.

In cleaning processes for hard surfaces of a substrate it is always a problem to reach complete cleaning, especially when ions responsible for water hardness are present, i.e. when their corresponding water-insoluble salts being deposited on the surface. This deposited soil is as a rule more or less colourless, often not easy to detect by the eye and simulates purity of the surface although such purity is not really existent.

In order to solve this problem of incomplete cleaning, it is proposed to use cleaning compositions comprising an organic compound indicating metal ions responsible for water hardness, denoted as 'indicator compounds' or 'colour change compounds' hereinafter and in addition a dye which shows an absorption maximum in a different wavelength region as compared to the indicator compound before and after the indicating absorption change.

The additional dye ensures an improved visibility of the colour change and an improved aspect of the cleaning composition before its use.

The indicator compound - when coming into contact with the ions responsible for water hardness - shows an observable colour forming or colour change indicating the impurities (caused by hard water deposits) on the hard surfaces of the substrate.

The present invention accordingly provides as main object a cleaning composition for cleaning the hard surface of a substrate which comprises a) an organic indicator compound for metal ions responsible for water-hardness, which indicates said metal ions by a change of light absorption; and b) a dye with an absorption maximum different from that of the organic indicator compound for metal ions.

The metal ions (cations) responsible for water hardness are present on the hard surface, e.g. in form of their salts. For instance the organic indicator compound indicates the presence of the metal ions by observable colour forming or colour change.

For example the absorption maximum of the indicator compound in the absence of metal ions is between 550 and 680 nm, preferably between 580 and 650 nm and the absorption maximum in the presence of metal ions is between 480 and 550 nm preferably between 500 and 550 nm.

For example the indicator compound has aromatic and/or heterocyclic hydrocarbon ring structure.

In particular the indicator compound of aromatic and/or heterocyclic hydrocarbon ring structure contains at least one OH-group bonded to a carbon atom of said ring structure.

As mentioned, suitable indicator compounds are organic compounds of aromatic and/or heterocyclic hydrocarbon ring structure, especially those organic compounds containing at least one OH-group bonded to a carbon atom of said ring structure; mesomeric structures of the OH-group, viz. -O^" and =0 are also comprised.

Preferred indicator compounds are those of the following chemical formulae (1 ) to (9): (1 )

wherein R1to R8 is independently from each other -SO₃X, with X being H, Na, K, C₁-C18 - tetraalkylammonium or a polymeric quaternary ammonium (polyquat); further R1 to R8 are independently from each other hydrogen, -C_rCi₂Alkyl, -NO₂ -Cl, -Br, -CH₃, -OC₂H₅, -COOX, -CH₂N(CH₂COOX)₂ or an annelated phenyl which can be substituted with R1 to R8; preferred substituents R1 to R8 are-SO₃H, -SO₃Na, hydrogen, -NO₂, -Cl,- Br₁-CH₃ or -OCH₃; Examples for X being a polymeric quaternary ammonium (polyquat) (in the compounds of this formula and also in those of the following formulae (2) to (5)) may be found in WO 01/42015 and EP-A-467'472.

(2):

wherein R1to R10 is independently from each other SO₃X, with X being H, Na, K, C₁-C₁8- tetraalkylammonium or a polymeric quaternary ammonium (polyquat); further R1 to R10 are independently from each other hydrogen, -C_rCi₂Alkyl, -NO₂ -Cl, -Br, -OCH₃, -OC₂H₅, -COOX or -CH₂N(CH₂COOX)₂; preferred subtituents R1 to R10 are SO₃H, -SO₃Na, hydrogen, -NO₂, -Cl, -Br, -CH₃ or -OCH₃; (3)

wherein R1to R6 is independently from each other SO₃X, with X being H, Na, K, C₁-C₁8- tetraalkylammonium or a polymeric quaternary ammonium (polyquat); further R1 to R6 are independently from each other hydrogen, -C_rCi₂Alkyl, -NO₂ -Cl, -Br, -OCH₃, -OC₂H₅, -COOX or -CH₂N(CH₂COOX)₂; preferred substituents R1 to R6 are -SO₃H, -SO₃Na, hydrogen, -NO₂, -Cl, -Br, -CH₃ or -OCH₃ ;

(4) - A -

0

wherein R1to R10 is independently from each other SO₃X, with X being H, Na, K, C₁-C₁8- tetraalkylammonium or a polymeric quaternary ammonium (polyquat); further R1 to R10 are independently from each other hydrogen, -CrCi₂Alkyl, -NO₂ -Cl, -Br, -OCH₃, -OC₂H₅, -COOX, -CH₂N(CH₂COOX)₂ or an annelated phenyl which can be substituted with R1 to R10; preferred substituents R1 to R10 are -SO₃H, -SO₃Na, hydrogen,-NO₂, -Cl, -Br, -CH₃ or -OCH₃ ;

(5)

wherein R1to R9 is independently from each other SO₃X, with X being H, Na, K, C₁-C₁8- tetraalkylammonium or a polymeric quaternary ammonium (polyquat); further R1 to R9 are independently from each other hydrogen, -C_rCi₂Alkyl, -NO₂ -Cl, -Br, -OCH₃, -OC₂H₅,

-COOX, -CH₂N(CH₂COOX)₂, an annelated phenyl which can be substituted with R1 to R9 or

-N=N-Phenyl, where Phenyl can be substituted with R1-R9; preferred substituents R1 to R9 are -SO₃H, -SO₃Na, hydrogen, -NO₂, -Cl, -Br, -CH₃ -OCH₃ , -COOH or -CH₂N(CH₂COOH)₂;

(ammonium salt of purpuric acid)

Of special interest are the indicator compounds of formula (1). A typical representative is 1',2-dihydroxy-6-nitro-1 ,2'-azonaphtalene-4-sulfonic acid (Eriochrome^R Black T). The indicator compounds of formulae (1 ) to (9) are known compounds that can be prepared by known manufacturing processes.

The amount of the indicator compound used in the inventive cleaning compositions comprises a broad range of e.g. from 0.001 to 2.0% by weight, preferably from 0.01 to 1.0% by weight, based on the weight of the cleaning composition.

In order to achieve best indication results the indicator dyes have to be"activated' by exposing to an alkaline solution of, for example, NaOH or monoethanolamine. The pH of the solution should be in the range between 8-14, preferably between 9 and 12.

The dye, component b) is preferably water soluble. The dye is not a fluorescent dye.

By the expression with absorption maximum different from that of the organic indicator compound for metal ions it is meant, that the absorption maximum is different from the indicator compound in the absence and presence of metal ions.

For example the dye may be selected from the yellow dyes, when the indicator compound is a blue compound, which changes colour to red when complexing metal ions. The resulting overall colour change will then be from green to orange which is significantly better visible.

For instance the dye has an absorption maximum between 400 and 450 nm and the indicator compound between 550 and 680 nm.

For example the dye, component b), is selected from the group consisting of the acid dyes or direct dyes.

For instance the chemical class of the dye, component b), is selected from the group consisting of azo dyes, bis azo dyes, triphenyl methane dyes and anthraquinone dyes.

Suitable dyes are commercially available and are summarized, for example, in the Colour Index of the Society of Dyers and Colourists.

Dyes according to the present invention are for example: natural or synthetic organic dyes or pigments , pigments may be in a pre-dispersed form disperse dyes or solvent dyes which may be solubilized in solvents , soluble dyes, preferably anionic dyes (acid dyes, direct dyes, reactive dyes) or cationic dyes (basic dyes) as listed in International Cosmetic Ingredient Dictionary and Handbook, 7^th edition 1997 , or in the Color Index International for Society of Dyers and Colourists.

Generally, for the coloration of household- and body care products all substances are suitable which have an absorption in the visible light of electromagnetic radiation (wavelength of ca. 400 to 700 nm). The absorption is often caused by the following chromophores:

Azo- (mono-, di, tris-, or poly-)stilbene-, carotenoide-, diarylmethan-, triarylmethan-, xanthen-, acridin-, quinoline, methin- (also polymethin-), thiazol-, indamin-, indophenol-, azin-, oxazin, thiazin-, anthraquinone-, indigoid-, phtalocyanine- and further synthetic, natural and/or inorganic chromophores.

Typical individual dyes are, for example, Acid Yellow 17, Acid Yellow 23, Food Yellow 3, Food Yellow 13, Pigment Yellow 1 , Pigment Yellow 3, Pigment Yellow 13, Food Green 3, Acid Green 25, Pigment Green 7, Acid Blue 9, Food Blue 5, Acid Blue 74, Acid Blue 225, Acid Blue 182, Direct Blue 99, Direct Blue 86, Pigment Blue 15, Pigment BLue 15:3, Acid Red 33, Food Red 17, Food Red 1 , Acid Red 18, Acid Red 14, Acid Red 27, Pigment Red 5, Pigment Red 57.1 , Acid Violet 43, Pigment Violet 19 and Pigment Violet 23.

The amount of the dye used in the inventive cleaning compositions comprises a broad range of e.g. from 0.001 to 2.0% by weight, preferably from 0.01 to 1.0% by weight and in some cases from 0.7 to 2%, based on the weight of the cleaning composition.

The ratio between the indicator compound and the dye may vary in a wide range, for example, from 100:1 to 1 to 20, preferably from 100: 1 to 10:1.

The amount of indicator compounds and dyes is based on the active substance, for example, when commercial products are used.

The metal ions responsible for water hardness and the corresponding depositons on the hard surfaces may be e.g. the cations of metals of the second group of the Periodic System of Chemical Elements (Mg, Ca, Sr, Ba), preferably the cations of Ca and Mg, and further, those of iron (Fe) and manganese (Mn) may be mentioned. These metal ions can be present in form of their salts, which are for example the corresponding carbonates and hydrogencarbonates, the sulfates, phosphates, silicates and also some chlorides, nitrates or oxides and hydroxides; further also the water-insoluble salts (Ca-,Mg-salts) of tensides, comprising e.g. the salts of C₆-C₂₂-, preferably C₈-Ci₈-fatty acids.

It is assumed that the colour forming/colour change of the indicator compounds depends on the forming of salts of said metal ions with the indicator compounds. But this invention is not bound by this theory.

Preferably, the inventive cleaning compositions for hard surface cleaning are household cleaning compositions, such as kitchen, bathroom or toilet cleaners. They may be in pulverulent form (to be dissolved for use), preferably however they are aqueous or alcoholic (for example ethanol or isopropanol ) solutions which generally contain one or more of the following components:

- anionic, nonionic, amphoteric and/or cationic surfactants,

- soaps, prepared by saponification of animal and vegetable greases, like coconut and tallow grease,

- inorganic and organic acids, like hydrochloric acid, phosphoric acid, citric acid, acetic acid or sulfuric acid,

- for basic products inorganic (NaOH or KOH) or organic bases like triethanolamine,

- abrasives for improved cleaning of surfaces, such as silicas, seed kernel or polyethylene - waxes and/or silicones for maintenance and protection of surfaces,

- polyphosphates,

- substances, which eliminate hypochlorite or halogens;

- peroxides comprising bleaching activators like TAED, for example sodium perborate, H₂O₂ or hypochlorite; - enzymes;

- cleaning agents based on wax may comprise solvents selected from benzine, turpentine and/or paraffines and emulsifiers based on wax;

- filling agents like silicates, polyphosphates, such as sodium or potassium tripolyphosphate, zeolithes for powdery cleaning agents; - pigments, lakes or soluble dyes;

- perfumes; and

- light stabilizers, antioxidants, antimicrobials, UV-absorbers and chelating agents (cf. for example WO 2004/050815)

These components as well as their use in cleaning compositions are well known in the art. As to the surfactants and soaps reference is made for example to the well known textbooks 'Surface Active Agents" Vol. I by Schwartz and Perry, and "Surface Active Agents and Detergents" Vol. Il by Schwartz, Perry and Berch.

When UV-absorbers are used, colour stability during storage of the cleaning composition is improved. Examples for suitable UV-absorbers are given below.

1. 2-(2'-Hvdroxyphenyl)benzotriazoles, for example 2-(2'-hydroxy-5'-methylphenyl)-benzo- triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphe- nyl)benzotriazole, 2-(2'-hydroxy-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di- tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphe- nyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'- hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy- 5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyl- oxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2- methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-meth- oxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonyl- ethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxy- phenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert-butyl- 2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylene-bis[4-(1 , 1 ,3,3- tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterification product of 2-[3'-tert-bu- tyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol

300; [R-CH₂CH₂-COO-CH₂CH₂-^- , where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotri-

azol-2-ylphenyl, 2-[2'-hydroxy-3'-(α,α-dimethylbenzyl)-5'-(1 ,1 ,3,3-tetramethylbutyl)-phenyl]- benzotriazole; 2-[2'-hydroxy-3'-(1 ,1 ,3,3-tetramethylbutyl)-5'-(α,α-dimethylbenzyl)-phenyl]ben- zotriazole. 2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.

3. Esters of substituted and unsubstituted benzoic acids, for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben- zoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzo- ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxyben- zoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphe- nylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinna- mate, butyl α-cyano-β-methyl-p-methoxy-cinnamate, methyl α-carbomethoxy-p-methoxycin- namate, N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline, neopentyl tetra(α-cyano-β,β-di- phenylacrylate.

5. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'- di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.

6. 2-(2-Hvdroxyphenyl)-1 ,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2- (2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2,4-bis(2-hydroxy-4-propyl- oxyphenyl)-6-(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4- methylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2- [2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1 ,3,5-triazine, 2-[2- hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1 ,3,5-triazine, 2-[4- (dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-

1 ,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl- phenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1 ,3,5-triazine, 2-(2-hydr- oxy-4-methoxyphenyl)-4,6-diphenyl-1 ,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydro- xypropoxy)phenyl]-1 ,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1 ,3,5- triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-di- methylphenyl)-1 ,3,5-tιϊazine, 2,4-bis(4-[2-ethylhexyloxy]-2-hydroxyphenyl)-6-(4-methoxyphe- nyl)-1 ,3,5-triazine.

The amount of UV-absorber used is typically from 0.01 to 2% by weight, based on the weight of the cleaning composition.

The indicator compound, the dye and optionally the other ingredients may be incorporated into these compositions or at least one of their components by known methods, such as by mixing it with the cleaning composition or by mixing it previously with one component or plural components thereof at room temperature (e.g.15 to 30°C) or higher temperatures (e.g. 30 to 100°C) with stirring. In the latter case, the cleaning composition is completed by adding the other component(s).

For bringing the inventive liquid cleaning compositions containing the compound indicating metal ions responsible for water hardness into contact with the hard surfaces of substrates, various methods are possible.

Examples of such cleaning methods include dipping type cleaning (dipping in the cleaning solution, e.g. in a cleaning tank), spraying type cleaning (spraying on the hard surface), pouring, rinsing and the like. Optionally, these methods can be combined with a method of employing a physical force, such as brushing or scouring, and the like.

The cleaning process may be carried out at normal (room) temperature (ca. 15 to 30°C) or at higher temperatures (ca. 30 to 80°C) in order to improve the cleaning effect.

The observable/detectible colour forming or colour change effect can occur between about 1 second and about 2 minutes, preferably between about 5 seconds and about 30 seconds.

The hard surface substrate is for example of a metal (steel) or plastic and preferably of glass, enamel or ceramics.

Through the observable colour forming or colour change of the indicator compound, those impurities (deposits) on the hard surfaces of the substrate which are caused by metal ions responsible for water hardness and which are mostly colourless (invisible) can be easily detected and a complete cleaning can be reached.

Another aspect of the invention is the use of an organic indicator compound for metal ions responsible for water-hardness, which indicates said metal ions by a change of light absorption; and a dye with an absorption maximum different from that of the organic indicator compound for metal ions, in cleaning compositions for cleaning hard surfaces of a substrate.

For example the organic indicator compounds of formulae (1 ) to (9) are used.

Yet another aspect of the invention is a method for treating (cleaning) hard surfaces of a substrate with a cleaning composition as described above.

For instance the hard surface treatment includes film forming, polishing and preferably cleaning.

In particular t the hard surface substrate is of metal (steel) or plastic and preferably of glass, ceramics or enamel.

The definitions and preferences described for the composition apply equally for the other aspects of the invention.

The following examples describe the present invention in further detail. However, the present invention is not limited to these examples.

Parts and percentages are by weight, if not otherwise indicated. The temperature is indicated in degrees centigrade.

Examples

Indication of Ca residues on hard surfaces based on formulations containing Eriochrome Black T (RTM)

Activation of Eriochrome Black T (RTM) Ericochrome Black T (RTM) does not best work as a Ca indicator in its supplied, uncomplexed form. It can be "activitated" by exposing it to alkaline conditions before addition to the final formulation. A stock solution is prepared by dissolving Eriochrome Black T in an alkaline medium, for example, in water containing NaOH or monoethanol amine, resulting in a stock solution of the dye with a pH 8-14, preferably pH 9-12.

Visual cue solution:

A 1 % stock solution of Eriochrome^R Black T is added to a commercial disinfection bathroom cleaner formulation. The stock solution is further diluted down to 0.05% with the bathroom cleaner formulation. 0.005% Acid Yellow 17 (VIBRACOLOR Yellow AYE17) is added to the solution, resulting in a bright green colour.

Preparation of a Ca-stearate suspension:

A mixture of 1 to 3 drops of a surfactant for moistening and 60 g of Ca-stearate in 300 g of water are carefully stirred until a stable suspension is obtained. The suspension is then heated up to 60°C; a thick paste is obtained.

Application test.

Approximately 3 g of said Ca-stearate paste are distributed as a film on a glass plate (25 cm x 25 cm). After 5 minutes the film is dried. The visual cue solution containing 0.05% of Eriochrome^R Black T and 0.005% Acid Yellow 17 is sprayed onto the dried Ca-stearate film. After a few seconds a clear colour change of the Ca-stearate film from green to orange is observed.

Example formulations:

Formulation 1

0.5% Sodium salt Ethylenediamine Tetraacetic acid (40% active - EDTA);

2% butoxyethanol (EB);

0.8% Nonionic (C12-16 + 9 EO); 0.05% Ericochrome Black T

0.001 % Vibracolor Yellow AYE 17 (Acid Yellow 17)

0.10% Cibafast H Liquid Formulation 2

0.5% Sodium salt Ethylenediamine Tetraacetic acid (40% active - EDTA);

2% butoxyethanol (EB);

0.8% Nonionic (C12-16 + 9 EO);

0. 10% Ericochrome Black T

0.005% Puricolor Yellow AYE23 (Acid Yellow 23)

Formulation 3 0.5% Sodium salt Ethylenediamine Tetraacetic acid (40% active - EDTA);

2% butoxyethanol (EB);

0.8% Nonionic (C12-16 + 9 EO);

0. 05% Ericochrome Black T

0.10% Cibafast H Liquid

Claims

Claims:

1. A cleaning composition for cleaning the hard surface of a substrate which comprises a) an organic indicator compound for metal ions responsible for water-hardness, which indicates said metal ions by a change of light absorption; and b) a dye with an absorption maximum different from that of the organic indicator compound for metal ions.

2. The cleaning composition according to claim 1 , wherein the organic indicator compound indicates the presence of the metal ions by observable colour forming or colour change.

3. The cleaning composition according to claim 1 , wherein the indicator compound has aromatic and/or heterocyclic hydrocarbon ring structure

4. The cleaning composition according to claim 3, wherein the indicator compound of aromatic and/or heterocyclic hydrocarbon ring structure contains at least one OH-group bonded to a carbon atom of said ring structure.

5. The cleaning composition according to claim 4, wherein the indicator compound comprises the chemical compounds of the following chemical formulae (1 ) to (9): (1 )

wherein R1to R8 is independently from each other SO₃X, with X being H, Na, K, -C₁-C18- tetraalkylammonium or a polymeric quaternary ammonium (polyquat); further R1 to R8 are independently from each other hydrogen, -CrCi₂Alkyl,- NO₂ -Cl, -Br, -OCH₃, -OC₂H₅, -COOX, -CH₂N(CH₂COOX)₂ or an annelated phenyl which can be substituted with R1 to R8; (2)

wherein R1to R10 is independently from each other SO₃X, with X being H, Na, K, C₁-C₁8- tetraalkylammonium or a polymeric quaternary ammonium (polyquat); further R1 to R10 are independently from each other hydrogen, -C_rCi₂Alkyl, -NO₂ -Cl, -Br, -OCH₃, -OC₂H₅, -COOX or -CH₂N(CH₂COOX)₂;

(3)

wherein R1to R6 are independently from each other SO₃X, with X being H, Na, K, C_rCi8- tetraalkylammonium or a polymeric quaternary ammonium (polyquat); further R1 to R6 are independently from each other hydrogen, -C_rCi₂Alkyl, -NO₂ -Cl, -Br, -OCH₃, -OC₂H₅, -COOX or -CH₂N(CH₂COOX)₂;

0

(4)

wherein R1to R10 is independently from each other SO₃X, with X being H, Na, K, C₁-C₁8- tetraalkylammonium or a polymeric quaternary ammonium (polyquat); further R1 to R10 are independently fromeach other hydrogen, -Ci-Ci₂Alkyl, -NO₂ -Cl, -Br, -OCH₃, -OC₂H₅, -COOX, -CH₂N(CH₂COOX)₂ or an annelated phenyl which can be substituted with R1 to R10;

(5)

wherein R1to R9 is independently from each other SO₃X, with X being H, Na, K₁CrCi₈- tetraalkylammonium or a polymeric quaternary ammonium (poyquat); further R1 to R9 are independently from each other hydrogen, -d- Ci₂Alkyl, -NO₂ -Cl, -Br, -OCH₃, -OC₂H₅, -COOX, -CH₂N(CH₂COOX)₂, an annelated phenyl which can be substituted with R1 to R9 or -N=N-Phenyl, where Phenyl can be substituted with R1-R9;

(7)

6. The cleaning composition according to claim 1 , wherein the amount of the indicator compound is from 0.001 to 2.0 % by weight, based on the weight of the cleaning composition.

7. The cleaning composition according to claim 1 wherein the dye, component b), is selected from the group consisting of the acid dyes or direct dyes.

8. The cleaning composition according to claim 1 , wherein the dye, component b), is selected from the group consisting of azo dyes, bis azo dyes, triphenyl methane dyes and anthraquinone dyes.

9. The cleaning composition according to claim 1 in pulverulent form.

10. The cleaning composition according to claim 1 in liquid form, preferably as aqueous solution.

1 1. The cleaning composition according to claim 1 which is a household cleaning composition.

12. Use of an organic indicator compound for metal ions responsible for water-hardness, which indicates said metal ions by a change of light absorption; and a dye with an absorption maximum different from that of the organic indicator compound for metal ions in cleaning compositions for cleaning hard surfaces of a substrate.

13. Use according to claim 12 wherein the organic compound from those of formulae (1 ) to (9).

14. A method for treating (cleaning) hard surfaces of a substrate with a cleaning composition according to claim 1.

15. The method according to claim 14, wherein the hard surface treatment includes film forming, polishing and preferably cleaning.

16. The method according to claim 14, wherein the hard surface substrate is of metal (steel) or plastic and preferably of glass, ceramics or enamel.