WO2010057977A1

WO2010057977A1 - Wash and cleaning composition

Info

Publication number: WO2010057977A1
Application number: PCT/EP2009/065554
Authority: WO
Inventors: Luc E. Feyt; Geneviève BONNECHÈRE - DELSTANCHE; Touria El Mekeddem
Original assignee: Thermphos Trading Gmbh
Priority date: 2008-11-21
Filing date: 2009-11-20
Publication date: 2010-05-27

Abstract

The invention relates to a wash and cleaning composition for cleaning surfaces and subjects, preferably for the use in industrial and institutional applications, comprising a mixture of: - aminotrimethylene phosphonic acid ("ATMP") and/or the salt of ATMP as one component, and - as the second component - diethylene triamine penta (methylene phosphonic acid) ("DETPMPA"), and/or the salt of DETPMPA, and optionally and additionally as a third component - (i) phosphonobutane tricarboxylic acid ("PBTC") and/or the salt of PBTC, or (ii) homopolymer maleic anhydride ("HPMA") and/or the salt of HPMA, or (iii) a mixture of (i) and (ii); or - N-oxide of ATMP and/or the salt of the N-oxide of ATMP as one component, and PBTC and/or the salt of PBTC as a second component; or - hexamethylenediamine tetra(methylene phosphonic acid) ("HDTMP") and/or the salt of HDTMP as one component, and - as a second component - (i) N,N'-bis-(3- aminopropyl)-ethylenediamine hexa methylene phosphonic acid ("NEHMP"), and/or the salt of NEHMP, or (ii) bis(hexamethylene) triamine phosphonic acid ("BHMT") and/or the salt of BHMT, or (iii) a mixture of (i) and (ii). The wash and cleaning composition shows at least the same good effect in chelating calcium compared with NTA and EDTA, and the chemicals used for substituting NTA as well as EDTA show even better washing and cleaning properties when used in much lower concentration.

Description

Wash and Cleaning Composition

The invention relates to a wash and cleaning composition for cleaning surfaces and subjects, preferably for the use in industrial and institutional applications, comprising a mixture of certain components being essentially free of nitrilotriacetic acid and its salts, such as nitrilotriacetic trisodium salt, hereinafter said acid and its salts collectively called "NTA" and, further, being essentially free of ethylene diamine tetraacetic acid and its salts, such as ethylene diamine tetraacetic acid tetrasodium salt, hereinafter said acid and its salts collectively called "EDTA". Further, the invention relates to a method for washing and cleaning surfaces and subjects (articles) using a wash and cleaning composition comprising a mixture of components being essentially free of NTA and EDTA, preferably in the field of industrial and institutional applications, and to the use of said mixture of components in wash and cleaning compositions.

The term "industrial applications" comprises any cleaning application made in the industry, including without limitation the cleaning and washing of vehicles, walls, floors, tiles and the like, stainless steel surfaces, toilets, machines including, for example, storage tanks, tubes and pipelines, as used in the industry, subjects in processing and production facilities, such as used in the food processing industry, canteen kitchens, or slaughter houses.

The term "institutional applications" comprises any cleaning application made outside industry, including without limitation the cleaning and washing of subjects in housekeeping, hotels, hospitals, airports and the like, such as cleaning and washing of walls, floors, tiles and the like, stainless steel surfaces, toilets, plates and dishes, silverware, pots and pans, china and crystalware.

Wash and cleaning compositions are generally used to remove dirt, grease, oil and other unwanted substances from a wide range of surfaces and consist primarily of surfactants performing the main cleaning function, and of builders that soften water in order to increase the cleaning power of the surfactants. In addition to these two main components wash and cleaning compositions may also contain a number of other ingredients depending on their purpose. These may include bleaching agents and enzymes to remove dirt, organic solvents to help remove oils and grease, acids and alkali to achieve desired pH levels, in addition to fragrants, preservatives and colorants.

NTA and EDTA are often used as sequestering agents and detergent builders in commercial wash and cleaning compositions for industrial and institutional applications.

As for example, WO 1997/029175 describes a detergent composition containing NTA for use in the institutional market. Although NTA is known to chelate Calcium ions and consequently boosts the cleaning performance of wash and cleaning formulations, it may have a negative effect on human health and is a suspected cause of cancer and tumors if used in higher quantities. On the other hand, although EDTA chelating properties are acknowledged to enhance the performance of cleaning formulations, it is under suspicion to increase the heavy metal ions mobility in the environment.

It is therefore an object of this invention to provide a wash and cleaning composition wherein NTA as well as EDTA shall be substituted because of their negative influence on human health and environment, respectively. Despite the absence of NTA and EDTA, the wash and cleaning composition shall show at least the same good effect in chelating calcium, and the chemicals used for substituting NTA as well as EDTA shall show even better washing and cleaning properties when used in much lower concentration.

It is a further object of this invention to create a wash and cleaning composition suitable for that purpose showing improved scale inhibition effect which means preventing from forming insoluble crystals with hardness ions like calcium and magnesium, and improved soil and scale dispersion properties.

It is also an object of the invention to create a method for washing and cleaning surfaces and subjects, preferably in the field of industrial and institutional applications, by using that improved wash and cleaning composition.

Surprisingly, these objects are achieved by a wash and cleaning composition for cleaning surfaces and subjects, preferably for the use in industrial and institutional applications, comprising a mixture of

(a) aminotrimethylene phosphonic acid ("ATMP") and/or the salt of ATMP as one component, and - as the second component - diethylene triamine penta

(methylene phosphonic acid) ("DETPMPA"), and/or the salt of DETPMPA, and optionally and additionally as a third component - (i) phosphonobutane tricarboxylic acid ("PBTC") and/or the salt of PBTC, or (ii) homopolymer maleic anhydride ("HPMA") and/or the salt of HPMA, or (iii) a mixture of (i) and (ii); or

(b) N-oxide of ATMP and/or the salt of the N-oxide of ATMP as one component, and PBTC and/or the salt of PBTC as a second component; or

(c) hexamethylenediamine tetra(methylene phosphonic acid) ("HDTMP") and/or the salt of HDTMP as one component, and - as a second component - (i) N,N'-bis-(3-aminopropyl)-ethylenediamine hexa methylene phosphonic acid ("NEHMP"), and/or the salt of NEHMP, or (ii) bis(hexamethylene) triamine phosphonic acid ("BHMT") and/or the salt of BHMT, or (iii) a mixture of (i) and (ii).

These objects are further achieved by a method for washing and cleaning surfaces and subjects preferably in the field of industrial and institutional applications by using the wash and cleaning composition of the invention. The method of the invention comprises the step of contacting the surface and/or subject with a wash and cleaning composition of the invention. In the method of the invention the wash and cleaning composition is applied either in undiluted or diluted form. The diluent is preferably water.

Additionally, these objects are achieved by the use of a mixture consisting of

(c) hexamethylenediamine tetra(methylene phosphonic acid) ("HDTMP") and/or the salt of HDTMP as one component, and - as a second component - (i) N,N'-bis-(3-aminopropyl)-ethylenediamine hexa methylene phosphonic acid ("NEHMP"), and/or the salt of NEHMP, or (ii) bis(hexamethylene) triamine phosphonic acid ("BHMT") and/or the salt of BHMT, or (iii) a mixture of (i) and (ii);

or a preferred embodiment thereof in a wash and cleaning composition cleaning surfaces and subjects, preferably for industrial and institutional purposes.

The wash and cleaning composition is suitable for cleaning surfaces and subjects, preferably for the use in industrial and institutional applications. Preferably, it is essentially free of NTA and EDTA which means that the content of NTA as well as that of EDTA is limited to traces, but in any event shall be less than 5 %, preferably less than 3 % of the total weight of the wash and cleaning composition. More preferred the wash and cleaning composition of the invention is free of NTA and EDTA. Of course the advantageous properties of the wash and cleaning composition of the invention make it also suitable for use in mixture with NTA and/or EDTA should that be desired in a specific application, however the maximum amount of NTA and/or EDTA shall be less than 5%.

The wash and cleaning composition contains the inventive mixture consisting of at least two components at least one of which is a phosphonate derivative. The wash and cleaning composition is harmless with respect to effects on human health compared with NTA, and is not under suspicion to increase the heavy metal ion leaching in the environment, and additionally shows improved crystal inhibition effects and excellent soil and scale dispersion properties. When comparing, on the one side, wash and cleaning compositions containing NTA, or EDTA respectively, and, on the other side, the inventive mixture of specific components in terms of such properties, the wash and cleaning composition of the invention shows better effects even in lower concentration compared with the respective concentrations of NTA and EDTA to be used to reach optimal results.

Preferably, the term "the wash and cleaning composition contains the inventive mixture consisting of at least two components..." means that the composition of the invention may contain further ingredients, but that the number of phosphonate derivatives in the composition is limited to the said mixture, i.e. that the composition does not comprise any further phosphonate derivatives. In one preferred embodiment the mixture is mixture (a), especially mixture (a) consisting of the first and the second component. In a further preferred embodiment the mixture is mixture (b). In yet a further preferred embodiment the mixture is mixture (c).

Salts of the components are generally alkali, ammonia, and/or amine salts, preferably the respective sodium and/or potassium salts.

The minimum amount of each component in said mixture is generally 5 %, preferably 10 %, and the maximum amount of each component is 80 %, preferably 60 %, based on the total weight of the mixture of components .

All percentage values mentioned herein and related to the components of the mixture of components are made in weight percent referring to the total weight of the mixture of components.

Preferably the components of the said mixtures comprise,

10 to 60 % of ATMP (first component), 90 to 35 %, preferably 40 to 90 % or 35 to 60 %, of DETPMPA (second component), or in case there is a third component 10 to 60 % of ATMP (first component), 35 to 90 %, preferably 35 to 60 % or 40 to 90 %, of DETPMPA (second component), and 5 to 60 % of PBTC, and/or 25 to 50 % of HPMA, and/or its salts (third component);

40 to 60 % of N-oxide of ATMP, and 60 to 5 %, preferably 60 to 40 %, of PBTC;

5 to 60 % of HDTMP (first component), 30 to 80 % of NEHMP, and/or 5 to 60 % of BHMT (second component(s), respectively).

Each of these components may be present as its salt, generally as its alkali, ammonia, and/or amine salts, preferably as its sodium or potassium salt within the same range of weight percentages.

In further preferred embodiments the amounts of components and/or their respective salts are as follows:

5 %, preferably 10 %, to 80 %, preferably 60%, PBTC; 5 %, preferably 10 %, to 80 %, preferably 60 %, ATMP;

5 %, preferably 10 %, in particular 25 % to 80 %, preferably 60 %, in particular 50 %, HPMA;

5 %, preferably 10 %, more preferred 35 %, in particular 40 %, to 90 %, preferably 80 %, in particular 60 %, DETPMPA;

5 %, preferably 10 %, in particular 40 %, to 80 %, in particular 60%, of N-oxide of ATMP;

5 %, preferably 10 %, to 80 %, preferably 60 % of BHMT;

5 %, preferably 10 %, to 80 %, preferably 60 % of HDTMP; and

5 %, preferably 10 %, in particular 30 %, to 80 %, preferably 60 % NEHMP.

The cleaning and washing composition according to the present invention may contain a combination of known detergent ingredients used for their known functionality depending on their purpose in art established levels. As suitable ingredient consists of detergent surfactants, including, nonionic, anionic, cationic, zwitterionic or amphoteric surfactants, or mixtures of such surfactants, can be used. Typical surfactant levels are in the range of from 1 to 80 %, usually from 5 to 40 %. Anionic surfactants can be represented by anionic sulfonates and sulfates. Individual examples of such anionic surfactants are C 12- 18 alkanesulfonates, C7-15 alkylbenzenesulfonates, olefinesulfonates, C 10- 16 alkylsulfates, and anionic surfactants derived from C12-18 fatty alcohols such as coconut-, lauryl-, myristyl-, cetyl- or stearylalcohol. Nonionic surfactants can be represented by the reaction products of aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides having from 2 to 6 carbon atoms in the alkyl chain. Suitable alkylene species can be represented by ethylene oxides, propylene oxides and/or butylenes oxides.

The compositions herein can furthermore contain any one, or combinations of, detergent ingredients selected from builders, solvents, perfumes, optical brighteners, dispersing agents, pH adjusting agents, fiber softeners, suds regulants, dyes, dye transfer inhibitors, enzymes and redeposition agents, bleaching agents, fragrant, preservatives, and additional detergent components, well known in the art. Any of such components is used for its known functionality in known levels. The choice of any such component will, of course, very depending upon the physical state, pH and application properties of a given composition.

Accordingly, in a preferred embodiment the wash and cleaning composition according to the invention comprises 1 to 80 %, preferably 5 to 50 %, by weight of one or more surfactants, and further comprises one or more ingredients selected from non-phosphonate builders, solvents, perfumes, optical brighteners, dispersing agents, pH adjusting agents, fiber softeners, suds regulants, dyes, dye transfer inhibitors, enzymes and redeposition agents, bleaching agents, fragrant, and preservatives.

Detergent builders - different from the mixture of the invention - are typically used in levels ranging from 5 to 50 %, in liquid compositions frequently from 5 to 30 %. Examples of suitable builders include polyphosphates, such as tripolyphosphates, pyrophosphates and polymeric meta-phosphates, alkali metal silicates, carbonates, polycarboxylates, such as oxydisuccinates, copolymers of maleic acid with ethylene or vinyl methyl ether, fatty acids, such as lauric - stearic acids, and combination of such builders. Another class of suitable detergent builders is represented by zeolites such as synthetic crystalline aluminosilicate ion exchange materials known under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS, Zeolite MAP and mixtures thereof.

Suitable enzymes for use herein can be proteases, amylases, lipases, cellulases, esterases, possibly peroxidases, and mixtures thereof. The enzymes are generally present in levels in the range from 0.05 to 4 %.

Fiber (fabric) through-the -wash softeners can be represented in quaternary ammonium softeners, impalpable smectic clays and by mixtures thereof. Such softener materials are, in accordance with needs, typically used at levels in the range of from 0.5 to 10 %. Suitable suds suppressors can be represented by salts of monocarboxylic fatty acids having preferably from 12 to 18 carbon atoms in the hydrocarbyl chain.

Low molecular weight primary and secondary alcohols such as methanol, ethanol, propanol and isopropanol, are suitable for use in connection with liquid compositions of this invention.

In preferred embodiments the wash and cleaning composition of the invention is selected from laundry detergents, hard surface cleansers, dishwashing agents, textile cleaning agents and compositions for cleaning cars and/or other vehicles. Compositions for dishwashing and for cleaning cars and/or other vehicles are particularly preferred.

The cleaning and washing composition may have any beneficial physical form generally used in industrial and institutional applications including liquids, powders, solidified bricks, granules and tablets. Processing is made in any conventional manner.

Examples

The following examples demonstrate, without limiting the scope of the claimed invention, preferred embodiments of the invention. Preferred examples of mixtures contain the following components:

(1) 6:1 DETPMPA /ATMP mixture

(2) 1 :1 DETPMPA / ATMP mixture

All components are known per se and available in the market.

The mixture (1) is incorporated in a wash and cleaning composition suitable for dish washing, the mixture (2) is incorporated in a wash and cleaning composition suitable for cleaning cars and other vehicles in a car wash site and the two compositions were compared with a wash and cleaning composition wherein said mixtures are substituted by NTA (active acid 40%) in terms of crystal growth inhibition, dispersion properties and cleaning efficiency on selected soils.

NTA as well as EDTA show no crystal growth inhibition and no dispersion properties. To ensure full chelation of calcium, stoichiometric amounts of NTA or EDTA, respectively, must be applied. The CaCO₃ scale inhibition is measured in water at 38° FH, using 380 ppm CaCO₃ equivalent to 152 ppm Ca⁺⁺' at 60° C at pH 10, 11 and 12.

Mixtures (1) and (2) can substitute NTA or EDTA at chelant/Ca ions ratios much lower than NTA and EDTA, respectively. For example, when using pH 12, it can be shown that

100 parts of NTA 40% « as is » can be replaced by 55 parts of mixture (1) corresponding to a molar ratio 0.25 : 1 , and 25 parts of mixture (2) corresponding to a molar ratio 0.50 to 1. Each of the mixtures was tested in water at 38° FH, using 380 ppm CaCO₃ equivalent to 152 ppm Ca⁺⁺at 60° C and at pH 12 to check its ability to keep a turbidity- free solution. Different mol ratios of the respective mixture and of NTA for comparison were applied between 0.25 and 1.0 and the turbidity was assessed virtually and also measured with an instrument (Hach Turbidimeter).

200 ml of water was introduced in 250 ml beaker with the selected amount of the respective chelant, which means one of said mixtures and for comparison of NTA, and heated to 60° C. Then the pH was adjusted to 12 with NaOH and the turbidity observed. The results are reported in the following table.

The data reported in the above table demonstrate that mixture (1) and (2) have better scale inhibition properties than NTA.

Soil removal was assessed for mixture (1) on tea, red wine and coffee soil made on melamine tiles, for mixture (2) on hard water spotting on car metallic painting.

Red wine, tea and coffee soil removal was assessed as following. Soiled melamine tiles (10 x 12 cm) where purchased from the Center for Test Materials (the Netherlands). Each soiled melamine tile was divided in three area of same surface. The middle area of the respective tile was left unexposed to any treatment while the two remaining areas were respectively exposed for 5 minutes to aqueous solutions heated to 6O⁰C of 10 % NTA (40 % active), of 10 % EDTA (40% active) and of 5.44 % of (1) (32 % active). The soil removal was assessed by visual grading. Solution (1) provides considerable better soil removal (tea, coffee and red wine stains) than the NTA solution, and noticeable better soil removal (coffee and red wine stains) than the EDTA solution. This higher soil removal indicates that mixture (1) has considerable better washing and cleaning properties than NTA and noticeable better washing and cleaning properties than EDTA.

Hard water spotting removal was assessed as following. Hard water (38 dH) was sprayed on a metallic surface coated with dark blue car metallic painting. The metallic painting was then dried for 10 minutes at 6O⁰C. After cooling down of the metallic plate, the metallic surface was divided in three equal parts. The middle surface was left unexposed to any treatment. The two remaining surfaces were respectively sprayed with aqueous solution adjusted to pH 11 of 10 % NTA (40% active) and of 2.62 % of (2) (50 % active). After 100 seconds, the metallic plate was rinsed under tap water. The result was assessed by visual grading. The area treated with solution (2) and NTA exhibit complete removal of spotting. The spotless result obtained with a reduced concentration of mixture (2) (compared to NTA) demonstrates the higher efficacy in scale inhibition and dispersion.

Claims

1. A wash and cleaning composition for cleaning surfaces and subjects, comprising a mixture of

- aminotrimethylene phosphonic acid ("ATMP") and/or the salt of ATMP as one component, and - as the second component - diethylene triamine penta (methylene phosphonic acid) ("DETPMPA"), and/or the salt of DETPMPA, and optionally and additionally as a third component - (i) phosphonobutane tricarboxylic acid ("PBTC") and/or the salt of PBTC, or (ii) homopolymer maleic anhydride ("HPMA") and/or the salt of HPMA, or (iii) a mixture of (i) and (ii); or

- N-oxide of ATMP and/or the salt of the N-oxide of ATMP as one component, and PBTC and/or the salt of PBTC as a second component; or

- hexamethylenediamine tetra(methylene phosphonic acid) ("HDTMP") and/or the salt of HDTMP as one component, and - as a second component - (i) N,N'-bis-(3- aminopropyl)-ethylenediamine hexa methylene phosphonic acid ("NEHMP"), and/or the salt of NEHMP, or (ii) bis(hexamethylene) triamine phosphonic acid ("BHMT") and/or the salt of BHMT, or (iii) a mixture of (i) and (ii).

2. The wash and cleaning composition according to claim 1, wherein the minimum amount of each component of said mixture is 5 %, and the maximum amount of each component is 80 %, based on the total weight of the mixture of components.

3. The wash and cleaning composition according to claim 1 or 2, wherein the salts of these compounds are the alkali, ammonia, and/or amine salts.

4. The wash and cleaning composition according to any one of claims 1 to 3, wherein the said mixture consists of

- 10 to 60 % of ATMP, and/or its salts (first component), 35 to 90 % of DETPMPA, and/or its salts (second component), 5 to 60 % of PBTC and/or its salts, and/or 25 to 50 % of HPMA, and/or its salts (third component); or - 40 to 60 % of N-oxide of ATMP, and/or its salts, and 60 to 40 % of PBTC and/or its salts; or

- 5 to 60 % of HDTMP, and/ or its salts (first component), 30 to 80 % of NEHMP and/or its salts, and/or 5 to 60 % of BHMT, and/or its salts, (second component(s), respectively).

5. The wash and cleaning composition according to any one of claims 1 to 4, comprising a combination of detergent ingredients.

6. The wash and cleaning composition according to any one of claims 1 to 5, comprising 1 to 80 % by weight of one or more surfactants.

7. The wash and cleaning composition according to claim 6, comprising 5 to 40 % of one or more surfactants.

8. The wash and cleaning composition according to any one of claims 1 to 7, further comprising one or more ingredients selected from non-phosphonate builders, solvents, perfumes, optical brighteners, dispersing agents, pH adjusting agents, fiber softeners, suds regulants, dyes, dye transfer inhibitors, enzymes and redeposition agents, bleaching agents, fragrant, and preservatives.

9. The wash and cleaning composition according to any one of claims 1 to 8, which is free of nitrilotriacetic acid and/or salts thereof, and of ethylendiamine tetraacetic acid and/or salts thereof.

10. The wash and cleaning composition according to any one of claims 1 to 9, which is selected from laundry detergents, hard surface cleansers, dishwashing agents, textile cleaning agents and compositions for cleaning cars and other vehicles.

11. A method for washing and cleaning surfaces and subjects comprising the step of contacting the surface or subject with a wash and cleaning composition according to any one of claims 1 to 10.

12. The use of a mixture consisting of - aminotrimethylene phosphonic acid ("ATMP") and/or the salt of ATMP as one component, and - as the second component - diethylene triamine penta (methylene phosphonic acid) ("DETPMPA"), and/or the salt of DETPMPA, and optionally and additionally as a third component - (i) phosphonobutane tricarboxylic acid ("PBTC") and/or the salt of PBTC, or (ii) homopolymer maleic anhydride ("HPMA") and/or the salt of HPMA, or (iii) a mixture of (i) and (ii); or

- hexamethylenediamine tetra(methylene phosphonic acid) ("HDTMP") and/or the salt of HDTMP as one component, and - as a second component - (i) N,N'-bis-(3- aminopropyl)-ethylenediamine hexa methylene phosphonic acid ("NEHMP"), and/or the salt of NEHMP, or (ii) bis(hexamethylene) triamine phosphonic acid

("BHMT") and/or the salt of BHMT, or (iii) a mixture of (i) and (ii);

as disclosed in any one of claims 1 to 4 in a wash and cleaning composition for cleaning surfaces and/or subjects.

13. The use according to claim 12, wherein the wash and cleaning composition comprises 1 to 80 % by weight of one or more surfactants.

14. The use according to claim 13, wherein the wash and cleaning composition comprises 5 to 40 % of one or more surfactants.

15. The use according to any one of claims 12 to 14, further comprising one or more ingredients selected from non-phosphonate builders, solvents, perfumes, optical brighteners, dispersing agents, pH adjusting agents, fiber softeners, suds regulants, dyes, dye transfer inhibitors, enzymes and redeposition agents, bleaching agents, fragrant, and preservatives.

16. The use according to any one of claims 12 to 15, where the wash and cleaning composition is free of nitrilotriacetic acid and/or salts thereof, and of ethylendiamine tetraacetic acid and/or salts thereof.

17. The use according to any one of claims 12 to 16, where the wash and cleaning composition is selected from laundry detergents, hard surface cleansers, dishwashing agents, textile cleaning agents and compositions for cleaning cars and other vehicles.