The invention relates to detergent compositions, particularly detergent compositions for automatic dishwashing, particularly for automatic dishwashing. Thus, the invention provides a detergent composition without phosphate comprising at least one non-ionic non-sulfonated surface-active compound and a water-soluble non-sulfonated copolymer prepared in particular by reaction of polymerization of acrylic acid or methacrylic acid, an ester of a acrylic or methacrylic acid, itaconic acid or maleic acid and a compound of formula (I):

The invention also relates to the use of this water-soluble copolymer as non-sulfonated anti-scaling agent or anti-drip agent, and a cleaning method.

EP 324568 discloses a detergent composition comprising a water soluble polymer. EP 995 791 also discloses a polymer for a detergent composition. EP 2468843 discloses a detergent composition comprising a HASE copolymer. EP 2935358 discloses a copolymer HASE thickener useful as anti-settling agent for paint compositions. The detergent compositions of the state of the art have a number of problems. In particular, the presence of phosphates in detergent compositions leads to environmental problems.

There are compositions for automatic dishwashing are phosphate-free. are known in particular such compositions, however, including water-soluble copolymers prepared from phosphate monomers. Thus, the presence of phosphate residues within these copolymers can be problematic.

Besides the presence of such residues in phosphate copolymers used in detergent compositions known, these detergent compositions do not always allow for significant performance improvements when washing and especially when washing the dishes. Thus, such detergent compositions do not always prevent the formation of scale or water marks on the dishes, especially during automatic dishwashing. Such problems are particularly to be avoided when washing glasses or glass crockery.

Indeed, limescale formation and occurrence of water spots on dishes lead to aesthetic problems but can also lead to other problems during the subsequent use of the dishes.

Known detergent compositions without phosphates or low concentration of phosphates which include residues sulfonated copolymers. Such detergent compositions fail to provide fully satisfactory performance against phosphate detergent compositions. In particular, such detergent compositions without said phosphate and copolymers comprising residues sulfonated these defects during dishwashing as regards the washing efficiency for the ability to avoid traces of tartar or traces of drops.

Thus, the substances generally used as a substitute for phosphates in detergent compositions do not provide acceptable or satisfactory result.

Moreover, insoluble or sparingly soluble materials leading to the formation of limescale deposits on dishes, including carbonates or magnesium silicates or calcium salts, also lead to problems when washing the laundry.

There is therefore a need for a polymeric phosphate free detergent composition having improved properties. In particular, there is a need for a detergent composition without phosphate to fight against the pie deposits and with a good forming efficiency or reduce or eliminate traces of drops during automatic dishwashing.

The invention provides a solution to all or some of the problems encountered with polymeric phosphate free detergent compositions of the state of the art. In particular, the invention helps fight against against the nucleation and crystal growth leading to the formation of tartar.

Thus, the invention provides a detergent composition without phosphate comprising:

at least one water soluble non-sulfonated copolymer prepared by polymerization reaction:

a) 55 to 93% mole of at least one acid selected from acrylic acid, methacrylic acid, their mixtures and their salts,

b) from 2 to 25 mol% of at least one ester of a compound an acid derivative selected from acrylic acid, methacrylic acid, itaconic acid and maleic acid and

c) from 5 to 20 mol% of at least one compound of formula (I):

R 1

V (D

in which :

R 1 and R 2 , identical or different, independently represent H or CH 3 , L 1 independently represents a group selected from C (O), CH 2 , CH 2 -CH 2 and 0-CH 2 -CH 2 -CH 2 - CH 2 ,

L 2 independently represents a group selected from (CH 2 -CH 2 0) x , (CH 2 CH (CH 3 ) 0) y (CH (CH 3 ) CH 2 0) z , and combinations thereof and

x, y and z, which are identical or different, independently represent an integer or decimal number between 0 and 150, x is strictly greater than y + z, and x + y + z is between 10 and 150 and

at least one nonionic surfactant compound non-sulfonated.

The invention also provides a detergent composition without phosphate comprising: at least one water soluble non-sulfonated copolymer prepared by polymerization reaction:

d) 55 to 93% by weight of at least one acid selected from acrylic acid, methacrylic acid, their mixtures and their salts,

e) from 2 to 25% by weight of at least one ester of a compound an acid derivative selected from acrylic acid, methacrylic acid, itaconic acid and maleic acid and

f) from 5 to 20% by weight of at least one compound of formula (I):

R 1

^L^ (I)

in which :

R 1 and R 2 , identical or different, independently represent H or CH 3 , L 1 independently represents a group selected from C (O), CH 2 , CH 2 -CH 2 and 0-CH 2 -CH 2 -CH 2 - CH 2 ,

L 2 independently represents a group selected from (CH 2 -CH 2 0) x , (CH 2 CH (CH 3 ) 0) y (CH (CH 3 ) CH 2 0) z , and combinations thereof and

x, y and z, which are identical or different, independently represent an integer or decimal number between 0 and 150, x is strictly greater than y + z, and x + y + z is between 10 and 150 and

at least one nonionic surfactant compound non-sulfonated.

Thus, and particularly advantageously for the composition according to the invention, the monomers (a), (b) and (c) used in preparing the copolymer and the surface active compound is non-sulfonated compounds.

The water-soluble non-sulfonated copolymer used according to the invention results from the implementation of at least three kinds of monomers, the monomers (a), (b) and (c) are different from each other.

This is a different copolymer of a HASE copolymer. The copolymer used according to the invention is water soluble, in particular in acidic medium.

This water-soluble non-sulfonated copolymer may also be characterized by its molecular weight (Mw). Preferably, it has a molecular weight ranging from 2000 g / mol to 100 000 g / mol or 5000 g / mol to 50 000 g / mol or even 7000 g / mol to 20 000 g / mol. Such copolymers of M wof 8000 g / mol, 9000 g / mol, 10,000 g / mol, 11,000 g / mol or 12,000 g / mol are particularly preferred. According to the invention, the molecular weight of the copolymers is determined by Steric Exclusion Chromatography (CES) or English "Gel Permeation Chromatography" (GPC). This technique uses a Waters brand liquid chromatograph equipped with a detector. This detector is a refractive concentration detector Waters brand. This liquid chromatography apparatus has a size exclusion column to separate the different molecular weights of the copolymers studied. The elution liquid phase is an aqueous phase adjusted to pH 9.00 by means of 1N sodium hydroxide containing 0.05 M NaHC0 3 , 0.1 M NaN0 3, 0.02 M triethanolamine and 0.03% NaN 3 .

In a first step, 0.9% dry diluted copolymer solution in the ESC of the solubilization solvent, which corresponds to the elution liquid phase of the ESC to which is added 0.04% of dimethylformamide playing the role of flow marker or internal standard. Then, filtered to 0.2 μιη. 100 μΐ ^ are then injected into the chromatograph (eluent: an aqueous phase adjusted to pH 9.00 by N sodium hydroxide containing 0.05 M NaHC0, NaN0 0.1M, 0.02M triétanolamine and 0.03% NaN 3 ).

The liquid chromatography apparatus contains an isocratic pump (Waters 515) whose flow rate is set at 0.8 mL / min. The chromatography apparatus further comprises an oven which itself comprises in series the following column system: a type precolumn Guard Column Waters Ulrahydrogel 6 cm in length and 40 mm internal diameter and a linear column type Ulrahydrogel Waters 30 cm long and

7.8 mm internal diameter. The detection system consists of a refractometric detector type RI Waters 410 The furnace is heated to a temperature of 60 ° C and the refractometer is heated to a temperature of 45 ° C.

The apparatus of chromato graphy is calibrated using sodium polyacrylate standards powder of different molecular weights certified by the supplier: Polymer Standard Service or Polymers American Standards Corporation.

Preferably to the invention, the acid (a) is acrylic acid or a salt of acrylic acid. Also preferably to the invention, the copolymer is prepared by reacting from 55 to 90 mol%, preferably 60 to 85 mol%, more preferably 65 to 80 mol% of (a), in particular of acrylic acid or a salt of acrylic acid.

Preferably to the invention, the acid (a) is acrylic acid or a salt of acrylic acid. Also preferably to the invention, the copolymer is prepared by reacting 55 to 90% by weight, preferably from 60 to 85% by weight, more preferably 65 to 80% by weight of acid (a), in particular acrylic acid or a salt of acrylic acid.

According to the invention, the ester (b) may be an anionic ester or a nonionic ester. According to the invention, the ester (b) may also be a hydrophilic or a hydrophobic ester ester, preferably it is a hydrophobic ester. Also preferably, the ester (b) is an ester of acrylic acid, preferably methyl acrylate, ethyl acrylate, butyl acrylate, hydroxypropyl acrylate, the acrylate, ethylene glycol acrylate, propylene glycol, more preferably ethyl acrylate; or an ester of methacrylic acid, preferably methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxypropyl methacrylate, ethylene glycol methacrylate. Also preferably to the invention, the copolymer is prepared by reacting from 5 to 20 mol%, preferably 7 to 15 mol% of ester (b), in particular methyl acrylate, acrylate ethyl, hydroxy propyl acrylate or butyl acrylate, preferably ethyl acrylate or hydroxypropyl acrylate. Also preferably to the invention, the copolymer is prepared by reacting 5 to 20% by weight, preferably 7 to 15% by weight of ester (b), in particular methyl acrylate, ethyl, hydroxy propyl acrylate or butyl acrylate, preferably ethyl acrylate or hydroxypropyl acrylate. the copolymer is prepared by reacting from 5 to 20 mol%, preferably 7 to 15 mol% of ester (b), in particular methyl acrylate, ethyl acrylate, hydroxypropyl acrylate or butyl acrylate, preferably ethyl acrylate or hydroxypropyl acrylate. Also preferably to the invention, the copolymer is prepared by reacting 5 to 20% by weight, preferably 7 to 15% by weight of ester (b), in particular methyl acrylate, ethyl, hydroxy propyl acrylate or butyl acrylate, preferably ethyl acrylate or hydroxypropyl acrylate. the copolymer is prepared by reacting from 5 to 20 mol%, preferably 7 to 15 mol% of ester (b), in particular methyl acrylate, ethyl acrylate, hydroxypropyl acrylate or butyl acrylate, preferably ethyl acrylate or hydroxypropyl acrylate. Also preferably to the invention, the copolymer is prepared by reacting 5 to 20% by weight, preferably 7 to 15% by weight of ester (b), in particular methyl acrylate, ethyl, hydroxy propyl acrylate or butyl acrylate, preferably ethyl acrylate or hydroxypropyl acrylate. hydroxypropyl acrylate or butyl acrylate, preferably ethyl acrylate or hydroxypropyl acrylate. Also preferably to the invention, the copolymer is prepared by reacting 5 to 20% by weight, preferably 7 to 15% by weight of ester (b), in particular methyl acrylate, ethyl, hydroxy propyl acrylate or butyl acrylate, preferably ethyl acrylate or hydroxypropyl acrylate. hydroxypropyl acrylate or butyl acrylate, preferably ethyl acrylate or hydroxypropyl acrylate. Also preferably to the invention, the copolymer is prepared by reacting 5 to 20% by weight, preferably 7 to 15% by weight of ester (b), in particular methyl acrylate, ethyl, hydroxy propyl acrylate or butyl acrylate, preferably ethyl acrylate or hydroxypropyl acrylate.

According to the invention, a compound (c) of formula (I) preferred for preparing the non-water-soluble sulfonated copolymer is a compound wherein:

R 1 and R 2 represent H or CH 3 or

L 1 represents a group chosen from C (O) and CH 2 or

L 2 represents a group combining (CH 2 -CH 2 0) x and (CH 2 CH (CH3) 0) y or (CH (CH 3 ) CH 2 0) z or

x represents a whole or decimal number between 10 and 140 or

y + z is an integer or decimal number between 10 and 140 or x is strictly greater than y + z, and x + y + z is between 10 and 150. According to the invention, a compound (c) of the formula (I) more preferred is a compound in which R 1 and R 2 are H, L 1 represents a group chosen from C (O) and CH 2 , L 2 represents a group combining (CH 2 -CH 2 0) x and ( CH 2 CH (CH 3 ) 0) y or (CH (CH 3 ) CH 2 0) zX represents a whole or decimal number between 10 and 140, y + z is an integer or decimal number between 10 and 140 and x is strictly greater than y + z, and x + y + z is between 10 and 150.

According to the invention, a compound (c) of formula (I) more preferred is a compound wherein R 1 is CH 3 , R 2 is H, L 1 is C (O), L 2 represents a group combining ( CH 2 -CH 2 0) x and (CH 2 CH (CH 3 ) 0) y or (CH (CH 3 ) CH 2 0) z , x represents a whole or decimal number between 10 and 140, y + z represents an integer or decimal number between 10 and 140 and x is strictly greater than y + z, and x + y + z is between 10 and 150.

According to the invention, a compound (c) of formula (I) also more preferred is a compound wherein R 1 is CH 3 , R 2 is CH 3 , L 1 is C (O), L 2 represents a group combining (CH 2 -CH 2 0) x and (CH 2 CH (CH 3 ) 0) y or (CH (CH 3 ) CH 2 0) zX represents a whole or decimal number between 10 and 140, y + z is an integer or decimal number between 10 and 140 and x is strictly greater than y + z, and x + y + z is between 10 and 150.

According to the invention, a compound (c) of formula (I) also more preferred is a compound in which R 1 and R 2 are H, L 1 is C (O), L 2 is (CH 2 CH 2 0) x and x is 1.

According to the invention, a compound (c) of formula (I) also more preferred is a compound in which R 1 and R 2 are H, L 1 is C (O), L 2 is (CH 2 CH (CH 3 ) 0) y or (CH (CH 3 ) CH 2 0) z and y + z is 1.

According to the invention, a compound (c) of formula (I) also more preferred is a compound wherein R 1 is CH 3 , R 2 is H, L 1 is C (O), L 2 represents a group (CH2- CH 2 0) x and x is 1.

According to the invention, a compound (c) of formula (I) also more preferred is a compound wherein R 1 is CH 3 , R 2 is H, L 1 is C (O), L 2 represents a group (CH 2 CH (CH 3 ) 0) y or (CH (CH 3 ) CH 2 0) z and y + z is 1.

According to the invention, a compound (c) of formula (I) also more preferred is a compound wherein R 1 is CH 3 , R 2 is H, L 1 is CH 2 , L 2 represents a group combining (CH 2 - CH 2 0) x and (CH 2 CH (CH 3 ) 0) y or (CH (CH 3 ) CH 2 0) zX represents a whole or decimal number between 10 and 140, y + z is an integer or decimal number between 10 and 140 and x is strictly greater than y + z, and x + y + z is between 10 and 150.

According to the invention, a compound (c) of formula (I) also more preferred is a compound wherein R 1 is CH 3 , R 2 is H, L 1 is CH 2 , L 2 is (CH 2 -CH 2 0 ) x , x is an integer or decimal number between 10 and 140.

According to the invention, a compound (c) of formula (I) also more preferred is a compound in which R 1 and R 2 are H, L 1 is O-CH2-CH2-CH2-CH2, L 2 is (CH 2 -CH 2 0) x , x is an integer or decimal number between 10 and 140.

Within particularly preferred manner, the compound (c) of formula (I) is a compound wherein:

x represents a whole or decimal number between 15 and 140,

- y + z is an integer or decimal number between 10 and 135 and

x is strictly greater than y + z, and x + y + z is between 10 and 150. More preferably, the compound (c) is a compound of formula (I) in which x represents a whole or decimal number between 15 and 80 and y + z is an integer or decimal number between 10 and 65, preferably a compound of formula (I) in which x represents a whole or decimal number between 30 and 65 and y + z is an integer or decimal number between 15 and 40, in particular a compound of formula (I) in which x represents a whole or decimal number between 40 and 60 and y + z is an integer or decimal number between 20 and 30, e.g. a compound of formula (I) wherein x is 50 and y is 25.

Particularly preferably, the copolymer is prepared by reaction of 7-18 mol%, preferably 7 to 15 mol%, compound (c) of formula (I). Also preferably, the copolymer is prepared by reaction of 7-18% by weight, preferably 7 to 15% by weight, compound (c) of formula (I).

In addition to the monomers (a), (b) and (c) the water soluble non-sulfonated copolymer used according to the invention may also be prepared by polymerization reaction also implementing a monomer (d).

Preferably according to the invention, the monomer (d) is selected from maleic acid, itaconic acid, crotonic acid, mixtures thereof and salts thereof. Also preferably, the monomer (d) is implemented in an amount by weight of from 1/20 to 1/3, relative to the amount of monomer (a).

The copolymer prepared according to the invention is obtained by a polymerization reaction. This reaction may be a radical polymerization reaction, for example an emulsion polymerization reaction, in dispersion or in solution. The polymerization may be conducted in water or in a solvent in the presence of at least one initiator compound. Examples of initiator compounds are known persulfate salts, particularly ammonium persulfate, sodium persulfate, potassium persulfate.

According to the invention, the amounts of non-water-soluble copolymer sulfonated and non-sulfonated nonionic surfactant compound can vary quite broadly. Preferably, the detergent composition of the invention comprises from 1 to 15% by weight, preferably 2 to 10% by weight of non-water-soluble sulfonated copolymer. More preferably, it comprises from 4 to 8% by weight, for example 6% by weight, non-water-soluble sulfonated copolymer.

According to the invention, the amounts of monomers, particularly the amounts of monomers (a), (b) and (c) used are expressed in molar percentage, or by weight based on the total amount of monomers used in the preparation of the water-soluble copolymer non-sulfonated.

In addition to the non-sulfonated particular water-soluble copolymer, the detergent composition of the invention also comprises at least one nonionic surfactant compound which is non-sulfonated. Preferably, the nonionic surfactant compound comprises ethoxylated or propoxylated chains or chains combining ethoxylated and propoxylated chains channels. More preferably, it is a block copolymer comprising ethoxylated propoxylated chains and chains.

Preferably, the nonionic surface-active compound present in the detergent composition of the invention is a block copolymer which is nonionic and non-foaming. This surfactant compound is non-sulfonated.

Examples of non-ionic non-sulfonated surfactant compounds include synthetic alcohols ethoxylates, ethoxylates of alcohols of natural origin, tributyl phenol ethoxylates, nonyl phenol ethoxylates, block polymers of ethylene oxide and propylene oxide, adducts of ethoxylated-propoxylated alcohols, fatty acid ethoxylates, fatty amine ethoxylates, ethoxylates of castor oil, tristyryl phenol ethoxylates, polyglycosides alkyls. A preferred group of nonionic surface-active compounds non-Ones tallow comprises block polymers of ethylene oxide and propylene oxide comprising 10% ethylene oxide, adducts of ethoxylated-propoxylated fatty alcohols C10-C12, adducts of

Preferably, the detergent composition of the invention comprises from 0.3 to 30% by weight of nonionic surface active compound, more preferably from 0.5 to 20% by weight or from 1 to 8% by weight.

According to the invention, the detergent composition may also comprise at least one detergency adjuvant (builder in English) or one or more substances chosen from: at least one filler, in particular a solid filler, for example a zeolitic filler,

- a whitening or bleaching agent,

a catalyst agent or bleach activator,

an enzyme,

a control agent the corrosion of glass,

a perfume and

- a disintegrating agent for tablets.

Generally, a detergency builder combines several properties such as eliminating or chelate ions Ca 2+ and Mg 2+ present in the wash water and articles to wash, basify the medium, improving the performance of surface-active compounds, desorbing dirt and keep them in the cleaning medium. Preferably according to

the invention, the detergent composition comprises at least one adjuvant of non-phosphate detergency builders, inorganic or organic. More preferably, it is selected from sodium salt of nitrilotriacetic acid (NTA), sodium aluminosilicates or zeolite, carbonates such as sodium carbonates, citrates such as sodium citrates, especially sodium tricitrate, silicates such as sodium silicate , gluconic acid and its salts, in particular sodium salts, glutamic acid and its salts, sodium salt quadruple of N, N-diacetic acid, EDTA (ethylenediaminetetraacetic acid), MGDA (méthylglycindiacétate), EDDS (ethylenediamine-N , N'-disuccinic acid), IDSA (iminodisuccinic acid), sodium salt of iminosuccinique acid and mixtures thereof.

WE CLAIMS

1. A detergent composition without phosphate comprising:

at least one water soluble non-sulfonated copolymer selected from:

o a water-soluble non-sulfonated copolymer prepared by polymerization reaction:

a) 55 to 93% mole of at least one acid selected from acrylic acid, methacrylic acid, their mixtures and their salts,

b) from 2 to 25 mol% of at least one ester of a compound an acid derivative selected from acrylic acid, methacrylic acid, itaconic acid and maleic acid and

c) from 5 to 20 mol% of at least one compound of formula (I):

in which :

R 1 and R 2 , identical or different, independently represent H or CH 3 , L 1 independently represents a group selected from C (O), CH 2 , CH 2 -CH 2 and 0-CH 2 -CH 2 -CH 2 - CH 2 ,

L 2 independently represents a group selected from (CH 2 -CH 2 0) x , (CH 2 CH (CH 3 ) 0) y (CH (CH 3 ) CH 2 0) z , and combinations thereof and

x, y and z, which are identical or different, independently represent an integer or decimal number between 0 and 150, x is strictly greater than y + z, and x + y + z is between 10 and 150 and

o a water-soluble non-sulfonated copolymer prepared by polymerization reaction:

a) from 55 to 93% by weight of at least one acid selected from acrylic acid, methacrylic acid, their mixtures and their salts,

b) from 2 to 25% by weight of at least one ester of a compound an acid derivative selected from acrylic acid, methacrylic acid, itaconic acid and maleic acid and

c) from 5 to 20% by weight of at least one compound of formula (I):

R 1

in which :

R 1 and R 2 , identical or different, independently represent H or CH 3 , L 1 independently represents a group selected from C (O), CH 2 , CH 2 -CH 2 and 0-CH 2 -CH 2 -CH 2 - CH 2 ,

L 2 independently represents a group selected from (CH 2 -CH 2 0) x , (CH 2 CH (CH 3 ) 0) y (CH (CH 3 ) CH 2 0) z , and combinations thereof and

x, y and z, which are identical or different, independently represent an integer or decimal number between 0 and 150, x is strictly greater than y + z, and x + y + z is between 10 and 150 and

at least one nonionic surfactant compound non-sulfonated.

2. A detergent composition according to claim 1:

for which the acid (a) is acrylic acid or a salt of acrylic acid or wherein the copolymer is prepared by reacting from 55 to 90 mol%, preferably 60 to 85 mol%, more preferably from 65 to 80 mol% of (a) or

wherein the copolymer is prepared by reacting 55 to 90% by weight, preferably from 60 to 85% by weight, more preferably 65 to 80% by weight of acid (a).

3. A detergent composition according to one of Claims 1 and 2:

for which the ester (b) is an anionic or nonionic ester or is a hydrophilic or a hydrophobic ester ester, preferably a hydrophobic ester, preferably the ester (b) is an ester of acrylic acid, preferably methyl acrylate, ethyl acrylate, hydroxypopyle acrylate or butyl acrylate, more preferably ethyl acrylate or acrylate hydroxypopyle or wherein the copolymer is prepared by reaction of 5 to 20 mol%, preferably 7 to 15 mol% of ester (b) or

wherein the copolymer is prepared by reacting from 5 to 20% by weight, preferably 7 to 15% by weight of ester (b).

4. A detergent composition according to one of claims 1 to 3, wherein the compound (c) of formula (I) is a compound wherein:

R 1 and R 2 represent H or CH 3 or

L represents a group selected from C (O) and CH 2 or

L 2 represents a group combining (CH 2 -CH 2 0) x and (CH 2 CH (CH3) 0) y or (CH (CH 3 ) CH 2 0) z or

x represents a whole or decimal number between 10 and 140, preferably x is an integer or decimal number between 15 and 140 or

y + z is an integer or decimal number between 10 and 140, preferably y + z is an integer or decimal number between 10 and 135 or x is strictly greater than y + z, and x + y + z is in the range between 10 and 150.

5. A detergent composition according to one of claims 1 to 4, wherein the compound (c) of formula (I) is a compound wherein:

R 1 and R 2 represent H,

L 1 represents a group chosen from C (O) and CH 2 ,

L 2 represents a combining group (CH 2 -CH 2 0) x and (CH 2 CH (CH 3 ) 0) y or (CH 2 (CH 3 ) CH 2 0) z ,

x represents a whole or decimal number between 10 and 140, preferably x is an integer or decimal number between 15 and 140,

y + z is an integer or decimal number between 10 and 140, preferably y + z is an integer or decimal number between 10 and 135 and

- x is strictly greater than y + z, and x + y + z is between 10 and 150.

6. A detergent composition according to one of claims 1 to 5, wherein the compound (c) is:

a compound of formula (I) in which x represents a whole or decimal number between 15 and 80 and y + z is an integer or decimal number between

10 and 65, preferably

a compound of formula (I) in which x represents a whole or decimal number between 30 and 65 and y + z is an integer or decimal number between 15 and 40, including

- a compound of formula (I) in which x represents a whole or decimal number between 40 and 60 and y + z is an integer or decimal number between 20 and 30, e.g.

a compound of formula (I) wherein x is 50 and y is 25.

7. A detergent composition according to one of claims 1 to 6, wherein the compound (c) is selected from

• a compound of formula (I) wherein R 1 is CH 3 , R 2 is H, L 1 is C (O), L 2 represents a group combining (CH 2 -CH 2 0) x and (CH 2 CH (CH 3 ) 0) y or (CH (CH 3 ) CH 2 0) z , x represents a whole or decimal number between 10 and 140, y + z is an integer or decimal number between 10 and 140 and x is strictly greater than y + z, and x + y + z is between 10 and 150,

• a compound of formula (I) wherein R 1 is CH 3 , R 2 is CH 3 , L 1 is C (O), L 2 represents a group combining

(CH 2 -CH 2 0) x and (CH 2 CH (CH 3 ) 0) y or (CH (CH 3 ) CH 2 0) z , x represents a whole or decimal number between 10 and 140, y + z represents a whole or decimal number between 10 and 140 and x is strictly greater than y + z, and x + y + z is between 10 and 150,

"A compound of formula (I) wherein R 1 and R 2 are H, L 1 represents

C (O), L 2 is (CH 2 CH 2 0) x and x is 1,

• a compound of formula (I) wherein R 1 and R 2 are H, L 1 is C (O), L 2 is (CH 2 CH (CH 3 ) 0) y or (CH (CH 3 ) CH 2 0 ) z and y + z is 1,

• a compound of formula (I) wherein R 1 is CH 3 , R 2 is H, L 1 is C (O), L 2 represents a group (CH 2 -CH 2 0) x and x is 1,

• a compound of formula (I) wherein R 1 is CH 3 , R 2 is H, L 1 is C (O), L 2 represents a group (CH 2 -CH (CH 3 ) 0) y or (CH ( CH 3 ) CH 2 0) z and y + z is 1,

• a compound of formula (I) wherein R 1 is CH 3 , R 2 is H, L 1 is CH 2 , L 2 represents a group combining (CH 2 -CH 2 0) x and

(CH 2 CH (CH 3 ) 0) y or (CH (CH 3 ) CH 2 0) z , x represents a whole or decimal number between 10 and 140, y + z is an integer or decimal number between 10 and 140 and x is strictly greater than y + z, and x + y + z is between 10 and 150,

· A compound of formula (I) wherein R 1 is CH 3 , R 2 is H, L 1 is CH 2 , L 2 is (CH 2 -CH 2 0) x , x is an integer or decimal number between 10 and 140

• a compound of formula (I) wherein R 1 and R 2 are H, L 1 is O-CH2-CH2-CH2-CH2, L 2 is (CH2-CH20) X , x represents a whole or decimal number between 10 and 140.

8. A detergent composition according to one of claims 1 to 7,

- wherein the copolymer is prepared by reaction of 7-18 mol%, preferably 7 to 15 mol%, compound (c) of formula (I) or

wherein the copolymer is prepared by reaction of 7-18% by weight, preferably 7 to 15% by weight, compound (c) of formula (I).

9. A detergent composition according to one of claims 1 to 8, wherein the non-water-soluble sulfonated copolymer is prepared by polymerization reaction also implementing a monomer (d) selected from maleic acid, itaconic acid, cro tonic acid, their mixtures and their salts, preferably in an amount by weight of from 1/20 to 1/3, relative to the amount of monomer (a).

10. A detergent composition according to one of claims 1 to 9 comprising from 1 to 15% by weight, preferably 2 to 10% by weight, more preferably from 4 to 8% by weight, for example 6% by weight, water soluble non-sulfonated copolymer.

11. Use of at least one water soluble non-sulfonated copolymer according to one of claims 1 to 9 as a scale inhibitor agent, anticalculus or anti-drip and anti-drip, preferably within a detergent composition further comprising at least one surfactant compound non- ionic non-sulfonated, in particular a non-ionic non-sulfonated surfactant compound selected from synthetic alcohols ethoxylates, ethoxylates of alcohols of natural origin, tributyl phenol ethoxylates, nonyl phenol ethoxylates, block polymers of ethylene oxide and propylene oxide, adducts of alcohols ethoxylated-propoxylated fatty acid ethoxylates, fatty amine ethoxylates, ethoxylates of castor oil, tristyryl phenol ethoxylates, polyglycosides alkyls,preferably chosen from block polymers of ethylene oxide and propylene oxide comprising 10% ethylene oxide, adducts of fatty alcohols ethoxylated-propoxylated C10-C12, adducts of ethoxylated-propoxylated fatty alcohols, C12-C14-oxo alcohols adducts ethoxylated-propoxylated C12-C15 alcohol-oxo adducts ethoxylated-propoxylated C12-C18 fatty alcohol ethoxylates in C12-C14 with 10 ethylene oxide groups and terminally butyl function,addition of oxo alcohols ethoxylated-propoxylated C12-C15 alcohol-oxo adducts ethoxylated-propoxylated C12-C18 fatty alcohol ethoxylates of C12-C14 with 10 ethylene oxide moieties and functional terminal butyl,addition of oxo alcohols ethoxylated-propoxylated C12-C15 alcohol-oxo adducts ethoxylated-propoxylated C12-C18 fatty alcohol ethoxylates of C12-C14 with 10 ethylene oxide moieties and functional terminal butyl,

fatty alcohol ethoxylates of C12-C18 with 5 ethylene oxide groups and terminally butyl function, fatty alcohol ethoxylate C 12 -C 18 comprising 10 ethylene oxide moieties and terminal function butyl, oxo-alcohol ethoxylates C12-C15 with 8 ethylene oxide groups, ethoxylates oxoalcohols C12-C15 with 8 ethylene oxide groups, ethoxylates of oxo alcohols comprising C12-C15 10 ethylene oxide groups, poly ( C6-hexyl-glycosides), poly (C8-alkyl-glucosides).

12. Cleaning method comprising the implementation:

at least one detergent composition according to one of claims 1 to 10 or of water and at least one detergent composition according to one of claims 1 to 10, preferably comprising:

o washing with water and at least one detergent composition according to one of claims 1 to 10,

o rinsing and

o drying.

13. A cleaning method according to claim 12, wherein the washing or cleaning is selected from washing a vehicle, in particular automobile, detergency, in particular household detergency, laundry, including automatic washing machine, washing or cleaning the dishwasher, in particular washing or auto dish washing, washing aid, surface cleaning.