WO2007141635A2

WO2007141635A2 - Detergents formulations with low impact on the environment

Info

Publication number: WO2007141635A2
Application number: PCT/IB2007/001505
Authority: WO
Inventors: Silvia Palladini
Original assignee: Silvia Palladini
Priority date: 2006-06-07
Filing date: 2007-05-30
Publication date: 2007-12-13
Also published as: ITCR20060016A1; WO2007141635A3

Abstract

Detergents formulations with low impact on environment and human health, together with good cleaning efficacy, particularly for laundry, crockery or hard surfaces, containing at least one surfactant and at least one sequestering agent, in which at least one sequestering agent is selected from the group consisting of: - iminodisuccinic acid tetrasodium salt (IDS); - N,N-diacetic glutamic acid tetrasodium salt (GLDA); - sodium glucoheptonate; sodium gluconate; and mixtures thereof.

Description

"Detergents formulations with low impact on the environment"

DESCRIPTION INVENTION OBJECT

The present invention relates to formulations of detergents for laundry, dishwashers, washing-up, hard surfaces cleaning, containing one or more surfactants, if necessary one or more electrolytes and one or more sequestering agents. The main features of these formulations concern toxicology and environmental toxicology, as well as cleaning efficacy.

BACKGROUND ART Generally, a detergent formulation is based on a surfactant, if necessary an electrolyte and a sequestering agent, or a set of them. An example is

EP1137752 (Unilever) which considers, among other components, either IDS or HIDS (0,05 - 1 ,5 % by weight) for laundry detergents without bleaching agents, aimed to preserve fabrics colours. Two very important matters associated with household detergents are environmental impact and toxicological hazard.

Surfactants are sometimes toxic, as it was recently demonstrated for ethoxylated nonylphenols, almost ubiquitous until they were recognized as likely endocrine disruptors and fast taken off the market. Tensides can also create various problems in aquatic environments: they act on water surface tension and some of them are foam boosters, so they promote the formation of persistent foams upon rivers and lakes surfaces either preventing oxygen-carbon dioxide exchanging or permeating natural membranes.

Further concern for both toxicity and environmental impact is represented by sequestering agents. Generally used nonbiodegradable complexing agents are: EDTA and sodium salt (C.A.S. 60-00-4 and 64-02-8), phosphonates (ATMP - C.A.S. 6419-19- 8; EDTMP - C.A.S. 1429-50-1 ; HDTMP - C.A.S. 23605-74-5; DTPMP - C.A.S. 15827- 60-8; HEDP, etidronic acid - C.A.S. 2809-21-4) and polycarboxylated (acrylic acid omopolymers - C.A.S. 9003-04-7 and 9003-01-4; acrylic acid and maleic anhydride copolymers - C.A.S. 52255-49-9). All of them can easily transfer and concentrate heavy metals (among them lead, cadmium and mercury) into various organisms of the food chain.

EDTA and its salts are very little biodegradable: recently it was experienced a slow biodegradation at alkaline pH and without heavy metals, but these particular conditions are likely neither in surface waters nor in activated sludge plants (European Union - Risk Assessment Report Vol.49: Εdetic acid (EDTA)", 2004).

Polycarboxylated are very little biodegradable aerobically and aren't at all anaerobically; in sewage treatment plants, they are adsorbed upon sludges (Danish EPA: "Environmental and Health Assessment of Substances in Household and Cosmetic Detergent products", 100-103, 615-2001).

Phosphonates are very little biodegradable aerobically (HERA - Human & Environmental Risk Assessment on ingredients of European household cleaning products: "Phosphonates", 2004) and almost nonbiodegradable anaerobically (Danish EPA: "Environmental and Health Assessment of Substances in Household and Cosmetic Detergent products", 96-100, 615-2001); in particular conditions (catalysis made by some transition metals ions, at specific pH ranges) they're photodegradable; nevertheless, in real environments photodegradation is prevented by other physico- chemical mechanisms, such as low exposition to sun light (for example: muddy or deep waters) and, above all, absorbance in soil and sediments, which is reversible only after treatment either with strong acids or with more concentrated salted solutions. These are all conditions very far from real conditions (FISCHER K: "Distribution and elimination of HEDP in aquatic test systems", WATER RES; 27 (3). 1993. 485-493).

Usually powder laundry detergents contain zeolites (C AS. 1318-02-1) too; they are water insoluble aluminosilicates which act as ionic exchangers. Zeolites precipitate onto rivers bottom and in some cases cover it at all; they create problems in sewage and wastewater plants too, because they raise sludges to be wasted at the end of the cycle.

There are many other chemicals with low or no biodegradability at all, commonly used as detergents ingredients. Among them, sylicone based antifoaming agents. Although they're relatively chemically inert, their action may damage aquifers and natural membranes.

To improve fabrics look after washing, laundry detergents usually contain optical brighteners. Although they're not a concern toxicologically, (HERA: "Fluorescent

Brightener FWA-T, 2004; "Fluorescent Brightener FWA-5", 2003), they are completely useless from the washing power point of view; their temporary action has only commercial profit.

Antiredeposition agents generally contained in detergents behave in various ways: some of them (acrylic polymers and acrylic-maleic copolymers) have low acute toxicity, but are very slowly biodegradable; instead, carboxymethylcellulose (CMC, C.A.S. 9004- 32-4) is readily biodegradable, but last studies (RTECS database) testify carcinogenicity (subcutaneous route) and mutagenicity in reproductive system (oral route) in rats at relatively low dosages (140 mg/Kg).

Preservatives and perfumes have heavy outcomes both on the environment and human health : generally both kind of chemicals are very slowly biodegradable, very toxic on aquatic organisms and sensitizing. For example: 5-chloro-2-methyl-2H- isothiazolin-3-one and 2-methyl-2H-isothiazolin-3-one are mutagens according to the Ames test; 2-Bromo-2-nitropropane-1 ,3-diol (Bronopol) is quite biodegradable, but byproducts are carcinogens (nitrosamines).

Fragrances may contain sensitizing or allergizing chemicals, even if in small concentrations; such chemicals are often toxic or very toxic for aquatic organisms. For example: limonene [(r)-p-mentha-1 ,8-diene, C.A.S. 5989-27-5; labelling: Xi, N R10-38-

43-50/53], 2,4,6-trinitro-1,3-dimethyl-5-terz-butylbenzene (C.A.S. 81-15-2, labelling: N

R44, R51/53), hydroxycitronellal (C.A.S. 107-75-5; labelling: Xi R36, R43), cinnamyl alcohol (C.A.S. 104-54-1 , labelling: Xi R43), diphenil etere (C.A.S. 101-84-8, labelling: Xi, N, R38, 51/53).

Taking into consideration all of these features, we can see what an impact may have large quantities of detergents put every year into rivers or lakes water. In addition, for some kinds of detergents there's also a direct or indirect toxicological impact because they get in touch with users, for example washing-up detergents (direct contact with the skin), or dishwasher and laundry detergents (indirect contact due to machines incomplete rinsing of dishes surface or clothes).

A lot of toxic or polluting raw materials are not written upon detergents labels or safety data sheets, because their concentrations are lower than law limits (Dir 1999/45/CE relating to the classification, packaging and labelling of dangerous preparations); in fact such chemicals are present and those with low biodegradability tend to accumulate in the environment and may get into the food chain.

This situation is getting a little better thank to the recent Reg 2004/648/CE, which obliges detergents producers (with the exception of dispensations) to use only rapidly (aerobically) biodegradable surfactants; it is restricted to surfactants without considering all other chemicals, in many cases more harmful to the environment and to human health. It seems to be more and more important to search for low environmental impact and low toxicity formulations. Recently, the most careful consumers are looking for ecologic products. So, household detergents market offers many products defined "environmentally friendly"; in our opinion, this definition is seldom supported by facts.

Most of these products contain chemicals with very low biodegradability.

For example: dishwasher "ecologic" detergents contain polyacrylates or polyacrylates- sulphonates and phosphonates, sometimes CMC too; laundry "ecologic" detergents contain phosphonates, polyacrylates, zeolite, acrylic-maleic copolymers, silycone- paraffine mixture, optical brightener, CMC; in multipurpose "ecologic" detergents are present phosphonates, polycarboxylates, non biodegradable preservatives (methylisothiazolinone) and allergizing fragrances (limonene). Such components are present in relatively low concentrations, but these low values must be parametrized to the large quantities poured in water every day and their tendency to accumulate. SUMMARY OF THE INVENTION

The present invention is aimed to detergents formulations with low impact on environment and human health, together with good cleaning efficacy.

In order to reach these features, only rapidly biodegradable chemicals are used, according to OECD Tests A-F and equivalent tests (see also Reg CE/2004/648), together with low tendency to bioaccumulate (Log Kow < 3 and other toxicological data (low acute and chronic human toxicity, low toxicity for aquatic organisms).

Those features don't concern mineral electrolytes, such as alkali metals hydroxides, carbonates, hydrogencarbonates, silicates and chlorides, which are made with chemicals naturally present in the environment; in addition, their pH tends to neutralize simply for diluition into wastewater.

Since all chosen organic chemicals are rapidly biodegradable, microorganisms naturally present in the environment are able to degrade the detergents residuals in a reasonable time, even if wastewaters don't flow to a sewage treatment plant. This feature is added to the low toxicity of molecules and to the good cleaning performance.

Formulations here described are preferably water based and can be liquid or gel/paste shaped. They include at least one surfactant, or a collection of surfactants, if needed an electrolyte and at least a sequestering agent, chosen into the following group: iminodisuccinic acid tetrasodium salt (IDS), N,N-diacetic glutamic acid tetrasodium salt (GLDA), sodium glucoheptonate, sodium gluconate.

DETAILED DESCRIPTION OF THE INVENTION

In the following paper, the invention is thoroughly described, with specific reference to the surfactants and sequestering agents used, together with some examples of formulations. Surfactants

The surfactants used may belong to 3 categories: anionic, non-ionic and amphoteric/zwitterionic.

The first selection we made was about both the impact on the environment and the toxicity: in addition to be rapidly biodegradable (according to complete biodegradability standard required by Reg CE/2004/648), they had to be anaerobically biodegradable and to have a low toxicity on aquatic organisms (LC50 > 1mg/l), considering that any surfactant - soap too - is quite toxic for fishes. This is one of the reasons why it is important for a tenside to be rapidly biodegradable. Preferably, in this invention are used: - alkali metals alkyl ether sulfates (<= 4 EO);

- alkali metals alkyl isethyonates;

- alkali metals soaps;

- ethoxylated fatty alcohol (<= 6 EO); - cocodiethanolamide;

- alkylpolyglucosides (preferably: alkyl = C4 - C11), as hydrotrope;

- alkyliminodipropionate, as hydrotrope;

- alkylamidopropyl betaine.

In the following table are listed average acute toxicity values [from Danish EPA: "Environmental and Health Assessment of Substances in Household and Cosmetic Detergent products", 17-93, 615-2001 , and from US National Library of Medicine - SIS (Specialized Information Services)]:

Among the group of surfactants, some are non persistently foam boosters. This feature allows to see very well where the detergent is acting (for ex.: during washing-up), anyhow losing foam consistency when reaching the wastewater. In this way, even if wastewater don't flow up to a sewage treatment plant, the danger to damage natural ecosystems with floating foams is minimized. Sequestering agents / Builders In detergency, a sequestering agent acts mainly as a calcium ad magnesium lime controller, in order to avoid lime to precipitate upon clothes and hard surfaces both as carbonates and as insoluble fatty acids esters. Moreover, they complex heavy metals ions (Fe³⁺, Cu²⁺, etc.), which may create coloured stains upon clothes and surfaces.

In this invention, formulations contain all rapidly biodegradable sequestering agents with low toxicological impact, chosen among the following:

• iminodisuccinic acid tetrasodium salt (IDS), also called N-(1 ,2-dicarboxyethyl)-aspartic acid tetrasodium salt, having the following molecular formula (I):

• N,N-diacetic glutamic acid tetrasodium salt (GLDA), having the following molecular formula (II):

• sodium glucoheptonate, having the following molecular formula (III):

sodium gluconate, having the following molecular formula (IV):

In the following table are listed average acute toxicity values, taken from Safety Data Sheets provided from the products suppliers:

The use of one or more than one sequestering agents could be accompanied by the use of a builder chosen among alkali metal orthophosphate, diphosphate and triphosphate.

Phosphates, if used in very small quantities, give a little contribute to eutrophication, with regard to detergents used in the past or to current other uses (such as agricultural ones). Instead, using few quantities may allow to avoid to use more pollutant chemicals. The described above sequestering agents may be matched with an additional sequestering/antiredeposition agent selected from the group consisting of citric acid, citric acid tri alkali metals salt, polyaspartate, alkali metals orthophosphate, diphosphate and/or triphosphate and mixture thereof. Other components In these formulations may be present other chemicals with the same toxycological and eco-toxycological features described above, for example the following: solvents (short chain alcohols, esters, etc.), thickening agents, antiredeposition agents, perfumes, colouring agents, preservatives, antibacterial agents, bleaching agents with or without bleach activators, scrubbing agents, bittering agents, etc.. The phrase "other components" is generally used referring to those components, but sometimes the formulations report some specific chemicals selected from this group. EXAMPLES

The following paper reports some examples of preferred formulations, used as laundry detergent, dishwasher, multipurpose, etc. For each use, two or more formulations are written, called A, B, C, ... For each component, a preferred concentration range and a single value (between brackets) are written; the single value is related to an even more preferred formulation. All concentrations are expressed as %, that is the dry chemical weight (in grams) in comparison to 100 grams of the aqueous formulations.

EXAMPLE 1: detergent for laundry machine or washing clothes by hand; particularly, formulation E is preferably used for delicate laundry wash.

In formulation E, it is particularly preferred either the formulation with 2 wt% or the formulation with 5 wt% Sodium lactate.

EXAMPLE 2: Washing-up and/or hard surfaces degreasing detergents.

EXAMPLE 3: alkaline machine dishwasher / glasswasher / potwasher, also suitable for certain hard surfaces other than cooking tools (ex. car spareparts, etc.).

In formulation A, it is particularly preferred either the formulation with 7 wt% N,N-diacetic glutamic acid sodium salt and 4 wt% Polyaspartate, or the formulation with 8 wt% N, N- diacetic glutamic acid sodium salt and 3 wt% Polyaspartate. In formulation E, it is particularly preferred either the formulation with 3 wt% N,N-diacetic glutamic acid sodium salt and 3 wt% lminodisuccinic acid sodium salt, or the formulation with 5 wt% N₁N- diacetic glutamic acid sodium salt and 5 wt% lminodisuccinic acid sodium salt; both formulations E are suitable to contain preferably either 6 wt% or 12 wt% alkali hydroxide.

EXAMPLE 4: rinse-aid for dishwasher / glasswasher / potwasher and/or anti-lime for hard surfaces.

EXAMPLE 5: multipurpose detergents for hard surfaces.

EXAMPLE 6: pretreating detergents for laundry.

Claims

1. Detergent formulation, particularly for laundry, crockery or hard surfaces, containing at least one surfactant and at least one sequestering agent, characterized in that at least one sequestering agent is selected from the group consisting of: - iminodisuccinic acid tetrasodium salt (IDS), having the following molecular formula (I):

- N,N-diacetic glutamic acid tetrasodium salt (GLDA), having the following molecular formula (II):

(II) sodium glucoheptonate, having the following molecular formula (III):

H

(III) sodium gluconate, having the following molecular formula (IV):

(IV) and mixtures thereof.

2. Formulations according to Claim 1, characterized in that at least one surfactant selected from the group consisting of alkali metals alkylsulfates, alkali metals alkyl ether sulfates, alkali metals alkyl isethyonates, alkali metals soaps, ethoxylated fatty alcohol, cocodiethanolamide, alkylpolyglucosides, alkyliminodipropionate, alkylamidopropyl betaine and mixtures thereof.

3. Formulation according to Claim 1 or Claim 2, characterized in that it contains also solvents, thickening agents, antifoam agents, antiredeposition agents, perfumes, colouring agents, preservatives, antimicrobial agents, bleaching agents with or without bleach activators, scrubbing agents, bittering agents, alone or in mixture.

4. Formulation as claimed in any of the preceding claims, particularly suitable for laundry machine or washing clothes by hand, characterized in that it comprises (dry wt%):

Sodium lauryl sulfate 0,05 - 3,5 Potassium soap 5,5 - 9,5 Ethoxylated fatty alcohol 5,0 - 9,0 Amphoteric surfactant 0,05 - 3,5 Sodium gluconate 0,5 - 4,5 Sodium carbonate 2,0 - 6,0 Sodium chloride 0,05 - 3,5 Other components, water to 100%

5. Formulation as claimed in any of the Claims 1 to 3, particularly suitable for laundry machine or washing clothes by hand, characterized in that it comprises (dry wt%):

Sodium lauryl sulfate 0,01 - 3,0 Sodium alkyl ether sulfate 5,0 - 9,0 Potassium soap 5,5-9,5 ethoxylated fatty alcohol 5,0-9,0 Amphoteric surfactant 0,05-3,5 - Sodium gluconate 0,5-4,5

Sodium carbonate 2,0-6,0

Sodium chloride 0,05 - 3,5

Other components, water to 100%

6. Formulation as claimed in any of the Claims 1 to 3, particularly suitable for laundry machine or washing clothes by hand, characterized in that it comprises (dry wt%):

Potassium soap 7,0-12,0 ethoxylated fatty alcohol 5,5-10,5 Hydrotrope surfactant 1,0-4,0

Sodium gluconate 0,5-5,5 - Sodium carbonate 2,0-6,0

Sodium chloride 0,05 - 3,5

Other components, water to 100%

7. Formulation as claimed in any of the Claims 1 to 3, particularly suitable for laundry machine or washing clothes by hand, characterized in that it comprises (dry wt%): - ethoxylated fatty alcohol 2,5-7,5

Hydrotrope surfactant 0,5 - 4,5

Sodium gluconate 2,5 - 7,5

N, N-diacetic glutamic acid sodium salt 0,05-4,0 lminodisuccinic acid sodium salt 1,6- 4,0 - sodium citrate dihydrated 2,5 - 7,5

Sodium lactate 0,5 - 7,0

Sodium carbonate 3,0-7,0

Sodium chloride 0,05 - 3,5

Other components, water to 100%

8. Formulation as claimed in any of the Claims 1 to 3, particularly suitable for laundry machine or washing clothes by hand, preferably used for delicate laundry wash, characterized in that it comprises (dry wt%):

Sodium alkyl ether sulfate 0,5 - 5,5 - ethoxylated fatty alcohol 2,5 - 7,5

Hydrotrope surfactant 0,5 - 4,5

Sodium gluconate 0,5 - 5,5 lminodisuccinic acid sodium salt 1 ,6 - 4,0 Sodium lactate 0,5 - 7,0 - Sodium chloride 0,05 - 3,5

Citric acid or lactic acid 0,01 - 1,5

Other components, water to 100%

9. Formulation as claimed in any of the Claims 1 to 3, particularly suitable for washing- up /hard surfaces degreasing detergents, characterized in that it comprises (dry wt%):

Sodium lauryl sulfate 3,5 - 7,5 ethoxylated fatty alcohol 1 ,5 - 5,5 alkylamidopropyl betaine 0,05 - 4,0 lminodisuccinic acid sodium salt 0,05 - 2,5 - Citric acid 0,01 - 1 ,5

Sodium chloride 0,05 - 4,0

Other components, water to 100%

10. Formulation as claimed in any of the Claims 1 to 3, particularly suitable for washing- up /hard surfaces degreasing detergents, characterized in that it comprises (dry wt%):

Sodium lauryl sulfate 7,5 - 11 ,5 ethoxylated fatty alcohol 7,0 - 11 ,0 alkylamidopropyl betaine 0,05 - 4,0

Potassium stearic soap 0,05 - 3,0 Citric acid 0,01 - 1 ,5

Sodium gluconate 0,5 - 4,5

Sodium chloride 0,05 - 4,0

Other components, water to 100%

11. Formulation as claimed in any of the Claims 1 to 3, particularly suitable for washing- up /hard surfaces degreasing detergents, characterized in that it comprises (dry

Ό : ethoxylated fatty alcohol 0,5 - 5,5

Sodium alkyl ether sulfate 2,5 - 7,5 - alkylamidopropyl betaine 0,05 - 3,0

Hydrotrope surfactant 0,05 - 3,0

Sodium lactate 1 ,5 - 6,5 lminodisuccinic acid sodium salt 0,05 - 3,0

Citric acid or lactic acid 0,01 - 1 ,5 - Sodium chloride 0,05 - 3,5

Other components, water to 100%

12. Formulation as claimed in any of the Claims 1 to 3, particularly suitable for washing- up /hard surfaces degreasing detergents, characterized in that it comprises (dry wt%): - ethoxylated fatty alcohol 3,5 - 8,5

Sodium alkyl ether sulfate 2,5 - 7,5 alkylamidopropyl betaine 0,05 - 3,0

Hydrotrope surfactant 2,0 - 6,0

Sodium lactate 1 ,5 - 6,5 - lminodisuccinic acid sodium salt 0,05 - 3,5

Citric acid or lactic acid 0,01 - 1 ,5

Sodium chloride 0,05 - 3,5

Other components, water to 100%

13. Formulation as claimed in any of the Claims 1 to 3, particularly suitable for washing- up /hard surfaces degreasing detergents, characterized in that it comprises (dry

%,: ethoxylated fatty alcohol 0,5 - 5,5

Hydrotrope surfactant 2,0 - 7,0 - Sodium lactate 1 ,5 - 6,5 lminodisuccinic acid sodium salt 0,05 - 4,0 Citric acid or lactic acid 0,01 - 3,0

Sodium gluconate 2,5 - 7,5

Sodium chloride 0,05 - 3,5 - Other components, water to 100%

14. Formulation as claimed in any of the Claims 1 to 3, particularly suitable for machine dishwasher / glasswasher / potwasher, also suitable for certain hard surfaces other than cooking tools (ex. car spareparts, etc.). characterized in that it comprises (dry wt%): - N,N-diacetic glutamic acid sodium salt 5,0 - 10,0

Sodium citrate dihydrated 5,0 - 10,0

Hydrotrope surfactant 0,05 - 3,0

Ethoxylated fatty alcohols 0,05 - 3,0

Sodium hydroxide 0,05 - 3,5 - Sodium metasilicate 3,0 - 7,0

Polyaspartate 2,0 - 7,0

Other components, water to 100%

15. Formulation as claimed in any of the Claims 1 to 3, particularly suitable for machine dishwasher / glasswasher / potwasher, also suitable for certain hard surfaces other than cooking tools (ex. car spareparts, etc.). characterized in that it comprises (dry wt%):

N, N-diacetic glutamic acid sodium salt 8,0 - 13,0 Sodium citrate dihydrated 5,0 - 10,0

Hydrotrope surfactant 0,01 - 2,5 Ethoxylated fatty alcohols 0,01 - 2,5

Sodium hydroxide 9,0 - 13,0

Polyaspartate 2,0 - 7,0

Other components, water to 100%

16. Formulation as claimed in any of the Claims 1 to 3, particularly suitable for machine dishwasher / glasswasher / potwasher, also suitable for certain hard surfaces other than cooking tools (ex. car spareparts, etc.). characterized in that it comprises (dry wt%):

N,N-diacetic glutamic acid sodium salt 0,5 - 5,5 - lminodisuccinic acid sodium salt 0,5 - 5,5

Sodium citrate dihydrated 5,0 - 11 ,0

Sodium gluconate 2,5 - 7,5

Sodium carbonate 0,01 - 3,0

Hydrotrope surfactant 0,05 - 3,0 - Ethoxylated fatty alcohols 0,01 - 2,5

Sodium hydroxide 0,05 - 3,5

Sodium metasilicate 3,0 - 7,0

Other components, water to 100%

17. Formulation as claimed in any of the Claims 1 to 3, particularly suitable for machine dishwasher / glasswasher / potwasher, also suitable for certain hard surfaces other than cooking tools (ex. car spareparts, etc.). characterized in that it comprises (dry wt%):

N,N-diacetic glutamic acid sodium salt 0,1 - 8,5 lminodisuccinic acid sodium salt 0,1 - 8,5 - Sodium citrate dihydrated 5,0 - 11 ,0

Sodium gluconate 2,5 - 7,5

Sodium carbonate 0,01 - 3,0

Hydrotrope surfactant 0,1 - 3,5

Ethoxylated fatty alcohols 0,1 - 3,5 Sodium hydroxide 0,05 - 3,5

Sodium metasilicate 3,0 - 7,0

Other components, water to 100%

18. Formulation as claimed in any of the Claims 1 to 3, particularly suitable for machine dishwasher / glasswasher / potwasher, also suitable for certain hard surfaces other than cooking tools (ex. car spareparts, etc.). characterized in that it comprises (dry wt%):

Sodium gluconate 2,5 - 7,5

Sodium carbonate 0,01 - 3,0

Hydrotrope surfactant 0,05 - 3,0

Ethoxylated fatty alcohols 0,01 - 2,5 - Sodium hydroxide 5,0 - 15,0

Sodium metasilicate 3,0 - 7,0

Other components, water to 100%

19. Formulation as claimed in any of the Claims 1 to 3, particularly used as rinse-aid for dishwasher / glasswasher / potwasher and/or anti-lime for hard surfaces, characterized in that it comprises (dry wt%): lminodisuccinic acid sodium salt 0,05 - 2,5

Citric acid monohydrated 3,0 - 7,0

Hydrotrope surfactant 9,0 - 13,0

Ethoxylated fatty alcohols 9,0 - 13,0 - Alcohols 5,0 - 9,0

Ethyl lactate 0,05 - 3,0

Other components, water to 100%

20. Formulation as claimed in any of the Claims 1 to 3, particularly used as rinse-aid for dishwasher / glasswasher / potwasher and/or anti-lime for hard surfaces, characterized in that it comprises (dry wt%): lminodisuccinic acid sodium salt 0,05 - 2,5 Citric acid monohydrated 10,0- 14,0

Ethoxylated fatty alcohols 16,0 - 21 ,0 - Alcohols 11 ,0 - 16,0

Other components, water to 100%

21. Formulation as claimed in any of the Claims 1 to 3, particularly used as rinse-aid for dishwasher / glasswasher / potwasher and/or anti-lime for hard surfaces, characterized in that it comprises (dry wt%): - lminodisuccinic acid sodium salt 0,05 - 3,0

Citric acid monohydrated 10,0 - 14,0

Hydrotrope surfactant 0,05 - 3,0

Alcohols 3,0 - 7,0

Other components, water to 100%

22. Formulation as claimed in any of the Claims 1 to 3, particularly used as rinse-aid for dishwasher / glasswasher / potwasher and/or anti-lime for hard surfaces, characterized in that it comprises (dry wt%): lminodisuccinic acid sodium salt 0,05 - 2,5 Citric acid monohydrated 10,0 - 14,0 - Lactic acid 0,1 - 4,0

Ethoxylated fatty alcohols 16,0 - 21 ,0

- Alcohols 11 ,0 - 16,0

Other components, water to 100%

23. Formulation as claimed in any of the Claims 1 to 3, particularly used as anti-lime for hard surfaces, characterized in that it comprises (dry wt%): lminodisuccinic acid sodium salt 0,1 - 4,0 Citric acid monohydrated 5,0 - 9,0

Lactic acid 5,0 - 9,0

Sodium alkyl ether sulfate 0,01 - 5,0 Alkylamidopropyl betaine 0,01 - 5,0

Alcohols 5,0 - 9,0

Other components, water to 100%

24. Formulation as claimed in any of the Claims 1 to 3, particularly suitable for multipurpose detergents for hard surfaces, characterized in that it comprises (dry wt%): lminodisuccinic acid sodium salt 0,05 - 2,0 Hydrotrope surfactant 4,0 - 8,0

Ethoxylated fatty alcohols 0,05 - 2,5 - Alcohols 5,0 - 10,0

Ethyl lactate 0,05 - 3,0

Other components, water to 100%

25. Formulation as claimed in any of the Claims 1 to 3, particularly suitable for multipurpose detergents for hard surfaces, characterized in that it comprises (dry wt%): lminodisuccinic acid sodium salt 0,05 - 2,0

Hydrotrope surfactant 0,05 - 3,0

Ethoxylated fatty alcohols 0,05 - 2,5

Alcohols 5,0 - 10,0 - Other components, water to 100%

26. Formulation as claimed in any of the Claims 1 to 3, particularly suitable for multipurpose detergents for hard surfaces, characterized in that it comprises (dry

%): lminodisuccinic acid sodium salt 0,1 - 4,0

Sodium alkyl ether sulfate 0,01 - 3,5

Alcohols 5,0 - 10,0

Alkyl lactate 0,1 - 4,0

Sodium lactate 0,01 - 3,0

Citric acid or lactic acid 0,05 - 2,5 Other components, water to 100%

27. Formulation as claimed in any of the Claims 1 to 3, particularly suitable for multipurpose detergents for hard surfaces, characterized in that it comprises (dry

%.: - lminodisuccinic acid sodium salt 0,1 - 4,0

Hydrotrope surfactant 0,05 - 3,0

Alcohols 5,0 - 10,0

- Alkyl lactate 0,1 - 4,0

Sodium lactate 0,01 - 3,0 - Citric acid or lactic acid 0,05 - 2,5

Other components, water to 100%

28. Formulation as claimed in any of the Claims 1 to 3, particularly suitable for pretreating additive detergents for laundry, characterized in that it comprises (dry

%y. - Potassium soap 14,0 - 22,0

Sodium gluconate 4,0 - 8,0 lminodisuccinic acid sodium salt 0,05 - 3,5

Sodium carbonate 3,0 - 7,0

Other components, water to 100%

29. Formulation as claimed in any of the Claims 1 to 3, particularly suitable for pretreating detergents for laundry, characterized in that it comprises (dry wt%):

Potassium soap 14,0 - 22,0

Sodium gluconate 4,0 - 8,0

N,N-diacetic glutamic acid sodium salt 0,05 - 3,5 - lminodisuccinic acid sodium salt 0,05 - 3,5

Sodium carbonate 3,0 - 7,0

Other components, water to 100%

30. Formulation as claimed in any of the preceding claims, characterized in that it is an aqueous solution, or an aqueous gel/ paste.

31. Formulation as claimed in Claims 14, 15, 16, 17 and 18, characterized in that it is a powder, containing if necessary an additional concentration of sodium carbonate (5 - 50 wt%).

32. Detergent for laundry machine and/or clothes by hand, dishwashers, washing-up, hard surfaces, characterized in that its formulation follows at least one of the preceding claims.