BRPI0907384B1 - SURFACE TREATMENT COMPOSITION CONTAINING PHOSPHONIC ACID COMPOSITE, USE OF THE SAME AND METHOD TO TREAT A SURFACE. - Google Patents

Description

(54) Title: COMPOSITION FOR SURFACE TREATMENT CONTAINING PHOSPHONIC ACID COMPOUND, USE OF THE SAME AND METHOD FOR TREATING A SURFACE.

(51) lnt.CI .: C11D 3/36 (30) Unionist Priority: 22/01/2008 EP 08 100756.9 (73) Holder (s): ITALMATECH CHEMICALS S.P.A.

(72) Inventor (s): PATRICK NOTTÉ; ALBERT DEVAUX; LUC E. FEYT (85) National Phase Start Date: 7/21/2010

DESCRIPTION REPORT FOR THE COMPOSITION FOR SURFACE TREATMENT CONTAINING PHOSPHONIC ACID COMPOUNDS, USE OF THE SAME AND METHOD FOR TREATING A SURFACE.

The present invention relates to surface treatment, in particular cleaning, compositions containing active surface agents, selected phosphonic acid compounds, and optionally conventional additives and additional components, exhibiting desirable properties in a wide range of applications. The surface treatment compositions can be used in known applications, including laundry detergent compositions, dishwashing compositions, fabric softening compositions and rigid surface cleaning products. The surface treatment compositions at present include, as a major component, generally 99.9% to 40% of an active surface agent and 0.1% to 60% of a phosphonic acid compound.

The use of surface cleaning compositions containing active surface agents, in combination with a wide variety of individual additives and optional components is widespread and is therefore recognized in the art. This applies, inter alia (among other things), to combinations of surfactants and phosphonic acid compounds. Increasingly demanding performance criteria and other important parameters, including economy, component compatibility and environmental acceptability, created an imperative need to provide new, different from existing, active ingredients, which are eminently appropriate to meet existing needs and supply additional distribution benefits possibly due to synergies between the ingredients of the treatment composition.

U.S. 2007/0015678 describes polymers of modified polysaccharides, in particular oxidized polymers containing up to 70% moiety of carboxylic groups and up to 20% moiety of aldehyde groups. The modified polysaccharides can be used in a variety of applications, including water treatment. The modified polysaccharides can also be used in blends with other chemical substances, including from 02/07/2018, p. 8/18 conventional phosphonates. EP 1 090 980 describes tissue rejuvenation technologies, including compositions and methods. Phosphonates are used as builders and as metal hijackers. 2phosphonobutane-1,2,4-tricarboxylic acid is preferred in this regard. EP 1 035 198 teaches the use of phosphonates as detergent tablet builders. Phosphonates are also used in the tablet coating composition.

EP 0 892 039 refers to liquid cleaning compositions containing a nonionic surfactant, a polymer, such as a vinyl pyrrolidone homopolymer or copolymer, a polysaccharide, such as a xanthene gum, and an amphoteric surfactant. Conventional phosphonates, for example, diethylene penta triamine (methylene phosphonic acid) (DTPMP) can be used as chelating agents. EP 0 859 044 relates to the rigid surface cleaning liquid containing diencapsulated polyalkoxylene glycols capable of imparting debris removal properties to the surface to which the cleaner has been applied. The cleaning compositions may contain phosphonates, for example, DTPMP, to thereby provide chelating properties.

Oxygen bleach detergent technology / compositions containing heavy metal scavengers, such as phosphonobutane tricarboxylic acid, are described in EP 0 713 910. Dishwasher bleach compositions are illustrated in EP 0 682 105. DTPMP is used as a hijacker heavy metal ions.

The technique mainly aims to combine the cumulative functionalities, to thereby yield additive results, without providing to any substantial degree, particularly within the context broadly for applications for surface treatment, the desirable benefits, without being subject to negative (secondary) incidental performances and / or without the use of multi-component systems, which in addition to the benefits may be subject to random economic, environmental and / or acceptability deficiencies.

It is a main objective of the present invention, to provide surface treatment technology, in particular compositions, capable of providing superior performance. It is another objective of this invention to provide effective treatment compositions, capable of providing significant benefits, at least equivalent or better than the technique, with significant decrease in environmental profiles and / or acceptability. Yet another objective of the present invention is to generate laundry compositions capable of offering superior performance with markedly reduced, for example, environmental, shortcomings. Yet, another objective of the present invention aims to generate surface treatment technology capable of providing, in addition to the functionalities established in the technique, additional functionalities to, in this way, generate additional benefits coupled with the structural configuration of specific ingredients in relation to other ingredients in the composition.

The foregoing and other objectives of this invention can now be met by providing surface treatment compositions widely comprising surface active agents and combinations with specifically defined compounds of phosphonic amino alkylene acid.

The term percentage or used throughout this application represents, unless otherwise defined, percentage by weight or% by weight. The terms phosphonic acid and phosphonate are also used interchangeably, depending, of course, on the prevailing conditions of alkalinity / acidity of the medium. Both terms include free acids, salts and esters of phosphonic acids. The terms active surface and surfactant ’’ are used interchangeably. The term ppm means part per million.

Surface treatment compositions containing active surface agents, optionally conventional additives and additional components, and an amino alkylene phosphonic acid compound have now been covered. In more detail, the compositions of this invention relate to surface treatment compositions, comprising:

(a) from 99.9 to 40% by weight (based on the sum of (a) and (b)) of a surface-active agent; and (b) from 0.1 to 60% by weight (based on the sum of (a) and (b)) of a phosphonic acid compound selected from the group:

(I) phosphonic alkylene amino acid acids having the formula

A ¹ - (B) _X where A ¹ has the formula

HOOC-A-NH ₂ where A is independently selected from a linear, branched, cyclic or aromatic C2-C20 hydrocarbon moiety, optionally substituted by linear, branched, cyclic or aromatic C1-C12 hydrocarbon groups, optionally substituted by OH, COOH and / or portion of NH ₂ , and

B is a portion of alkylene phosphonic acid having 1 to 6 carbon atoms in the alkyl group and X is an integer from 1 to 10;

(II) amino acid of alkylene phosphonic acids having the formula A ² By

Where A ² has the formula

HOOC-C (NH ₂ ) (R) (R) where R and R 'are independently selected from linear, branched, cyclic or aromatic C1-C20 hydrocarbon moieties, optionally substituted by linear Ci-C ₁₂ hydrocarbon groups , branched, cyclic or aromatic, optionally substituted by OH, NH ₂ and / or COOH, and one of R or R 'can be hydrogen, with the exclusion clause:

compounds in which R and / or R 'are electron-rich moieties containing at least a single electron pair, the moiety of which is directly linked to an aromatic moiety by a covalent bond, or aromatics in which at least one of the carbon atoms it was replaced by a heteroatom; and compounds, in the case where R is -C (X) (R'j (R ') and R', R and R 'are hydrogen where X is an electron removal group selected from NO ₂ , CN, COOH , SO _s H, OH and halogen, and with the additional clause that when:

A ² is L-lysine, at least one amino radical L-iisine carries 2 (two) halves of alkyl phosphonic acid, and when A ² is Lgiutamic acid, the term giutamic acid phosphonate represents a combination of 50 to 90% by weight of carboxylic acid pyrrolidone N-methenenophosphonic acid and 10 to 50% by weight of L-glutamic acid diphosphonic acid, expressed on the basis of the reaction products and

B is a portion of alkylene phosphonic acid having 1 to 6 carbon atoms in the alkyl group and Y is an integer from 1 to 10;

(III) a phosphonate compound of the general formula:

T-B where B is a phosphonate-containing portion having the form:

-X ~ N (W) (ZPO3M2) where X is selected from a linear, branched, cyclic or aromatic C2-C50 hydrocarbon option, optionally substituted by a linear, branched, cyclic or aromatic C1-C12 group, ( whose portion and / or whose group can be) optionally substituted by portions of OH, COOH, F, OR 'and SR ¹ , where R' is a linear, branched, cyclic or aromatic portion of CrC-iz hydrocarbon, and [A -0] _X -A where A is a linear, branched, cyclic or aromatic C2-C9 hydrocarbon portion and _x is an integer from 1 to 200;

Z is a C-i-Ce alkylene chain;

M is selected from H, portions of linear, branched, cyclic or aromatic C1-C20 hydrocarbon and from alkaline, alkaline earth products and ammonium ions and from protonated amines;

W is selected from Η, ZPO3M2 and [V - N (K)] _N K, where V is selected from: a linear, branched, cyclic or aromatic C ₂ -C ₅ hydrocarbon portion, optionally substituted by groups C1-C12 linear, branched, cyclic or aromatic (whose portions and / or groups are) optionally substituted by portions of OH, COOH, F, OR 'or SR' where R 'is a portion of linear, branched CrC ^ hydrocarbon, cyclic or aromatic, and from [A - 0] χ-Α where A is a linear, branched, cyclic or aromatic C2-C9 hydrocarbon portion and x is an integer from 1 to 200, and

K is ZPO3M2 or H and n is an integer from 0 to 200; and where T is a selected portion of the group:

(i) MOOC-X-N (U) -;

(ii) MOOC-C (X ² ) 2-N (U) -;

(iii) MOOC-X-S-;

(iv) [X (HO) _n · (NU) (v) UN (U) - [XN (U) k (vi;) DS-;

(vii) CN-;

(viii) MOOC-X-O-;

(ix) MOOC-C (X ² ) 2-O-;

(x) NHR-; and (xi) (DCO) ₂ -N-;

where Μ, Z, W and X are as defined above, U is selected from portions of linear, branched, cyclic or aromatic C1-C12 hydrocarbon, H and XN (W) (ZPO3M2); X ² is independently selected from H, portions of linear, branched, cyclic or aromatic C1-C20 hydrocarbon, optionally substituted by linear, branched, cyclic or aromatic C1-C12 hydrocarbon groups, optionally substituted by OH, COOH, R'O, R'S and / or portions of NH2; n ', ne ri are independently selected from integers 1 to 100, D and R are independently selected from portions of linear, branched, cyclic or aromatic C1-C50 hydrocarbon, optionally substituted by a Ci-C _{12 group} linear, branched, cyclic, or aromatic, (whose portion and / or group may be) optionally substituted by OH, COOH, F, OR 'and SR' portions, where R 'is a linear C1-C12 hydrocarbon portion, branched, cyclic or aromatic; and ΑΌ - [A-0] _X A where A is a linear, branched, cyclic or aromatic C ₂ -C ₉ hydrocarbon portion, x is an integer from 1 to 200 and A 'is selected from a portion of linear, branched, cyclic or aromatic C1-C50 hydrocarbon, optionally substituted by a linear, branched, cyclic or aromatic C1-C12 group (whose portion and / or group can be) optionally substituted by OH, COOH, F, OR ' and portions SR ', where R' has the meaning given above, with the additional clause that D can also be represented by H;

(IV) linear or branched hydrocarbon compounds having from 6 to 2.10® carbon atoms containing amino groups substituted by substituents of alkylene phosphonic acid and / or -XN (W) (ZPO ₃ M ₂ ), in relation to the hydrocarbon group , in any terminal or branched positions in which the molar ratio of the substituents of phosphonic aminoalkylene acid to the number of carbon atoms in the hydrocarbon chain is from 2: 1 to 1: 40 where at least 30% of the available NH functionalities have been converted into corresponding phosphonic aminoalkylene acid, and / or in substituted groups -XN (W) (ZPO ₃ M ₂ ) and in which the alkylene portion is selected from Cre and X, W, Z and M alkylene has the same meaning as given above ; and (V) alkylene alkylamino phosphonate compounds having the formula:

y [xn (W) (ZPO ₃ M _{2)] s} the structural elements having the following meaning:

X is selected from C ₂ -C ₅ linear, branched, cyclic or aromatic hydrocarbon moieties, optionally substituted by a linear, branched, cyclic or aromatic Ci-Ci ₂ group (whose half and / or group can be) optionally substituted by OH, COOH, F, OR ', R ² 0 [A-0] x-, where R ² is a linear, branched, cyclic or aromatic C 1 -C 50 hydrocarbon portion and SR', where R 'is a portion of linear, branched, cyclic or aromatic C1-Cgo hydrocarbon, optionally substituted by linear, branched, cyclic or aromatic C1-C ₁₂ hydrocarbon groups (said portions and / or groups may be) optionally substituted by COOH, OH, F, OR 'and SR'; and [A-0] _X -A where A is a linear, branched, cyclic or aromatic C ₂ -C ₉ hydrocarbon portion and ex is an integer from 1 to 200;

Z is a C ₁ -C ₆ alkylene chain;

M is selected from H, portions of linear, branched, cyclic or aromatic Ci-C ₂₀ hydrocarbon and of alkaline, alkaline earth products and ammonium and protonated amine ions;

W is selected from Η, ZPO3M2 and [VN (K)] _n K, where V is selected from: a portion of linear, branched, cyclic or aromatic C2-C50 hydrocarbon, optionally substituted by linear C1-C12 groups, branched, cyclic or aromatic (whose portions and / or groups can be) optionally substituted by OH, COOH, F, OR ', R ² 0 [A-0] x_, where R ² is a portion of linear Ci-C50 hydrocarbon , branched, cyclic or aromatic and SR 'portions, and [A-0] _X -A where A is a linear, branched, cyclic or aromatic C210 C ₉ hydrocarbon portion and _x is an integer from 1 to 200;

K is ZPO3M2 or H and n is an integer 0 to 200, and Y is a portion selected from NH ₂ , NHR ', N (R') ₂ , NH,

N, OH, OR ', S, SH, SS where R' is as defined above with the proviso of 15 that, when Y is OH or OR ', X is at least C4 and s is 1 in the case of Y representing NH ₂ , NHR ', N (R') ₂ , HS, OR ', or OH; s is 2 if Y represents NH, NR ', S or SS, and s is 3 if Y represents N.

α-specific amino acids not suitable for use within the 20 claimed phosphonic acids (II) are: tyrosine, tryptophan, asparagine, aspartic acid and serine. This unsuitable clause is not applicable to phosphonic acids (lll) such as, for example, those represented by species (lll) (ii).

In the definition of A, R, R ', Μ, V, A', U, x2, D, and R, the linear or branched portion of hi25 drocarbon C _x -C _y is preferably linear or branched alkanyl diyl with a respective chain length. The cyclic hydrocarbon moiety is preferably C3-Cw-cycloalkane-di-yl. The aromatic hydrocarbon moiety is preferably C ₆ -C | 2-arene-diyl. When the above hydrocarbon moieties are replaced, it is preferably with straight or branched alkyl of a respective chain length, C ₃ -C ₁₀ cycloalkyl, or C ₆ -Ci2-aryl. All of these groups can also be replaced with the groups listed with their respective symbols.

Most and particularly preferred chain lengths for alkane moieties are listed with specific symbols. A cyclic portion is more preferred a cyclohexane portion, in the case of cyclohexane-di-yl in particular, a cyclohexane-1,4-di-yl portion. An aromatic moiety is preferably phenylene or phenyl, as the case may be, for phenylene, 1,4-phenylene is particularly preferred.

The compositions of the invention comprise one or more, preferably one to five, phosphonic acid compounds (b).

The compositions of the invention comprise one or more, preferably one to ten, surface active compounds (a).

The treatment compositions can be used, in a conventional manner, for application in relation to all types of surfaces, in particular for cleaning. Similar applications can be represented by: textile laundry; fabric softening, fabric bleaching, rigid surface treatment; domestic and industrial use for dishwashing; glass cleaning and other well-known applications in the field of technology.

The cleaning compositions comprise, as main constituent, from 99.9% to 40% of a surface active agent, and from 0.1% to

60% of a compound selected from phosphonic acid amino alkylene, these levels being expressed in relation to the sum of the constituents. The cleaning compositions of this invention often contain 2 to 50% surfactant ingredients, more preferably 3 to 40% surfactants. The phosphonate ingredient herein can be used, in the actual treatment compositions, at subadditive levels of 0.0001 to 5%, preferably 0.001 to 2%. The phosphonate exhibits, in the context of the actual cleaning composition, conventional phosphonate functionalities, such as chelating, sequestering, threshold scale inhibiting, dispersant and oxygen bleach with similar properties, but, in addition, it can provide, in part due to the particularities structural effects of the essential phosphonate ingredient, additional synergistic features with respect to, for example, optional ingredients such as aesthetics, for example perfumes, optical brighteners, dyes and catalytic enhancers for enzymes, and also to provide improved storage stability for, for example , bactericides, thus allowing a reformulation of the composition without adversely affecting performance objectives. The essential phosphonate constituent, which is very important, can greatly facilitate the environmental and regulatory acceptance of the cleaning compositions contained in this document.

The cleaning compositions also optionally comprise conventional additives and other components that are used at levels established in the art and for their known functionality.

The surface active agents described herein can be represented by conventional species selected from, for example, cationic, anionic, non-ionic, ampholytic and zwitterionic surfactants and mixtures thereof. Typical examples of similar conventional detergent components are mentioned. Useful surfactants include Cn-20 alkyl benzene sulfonates, C ₁₀ _ ₂ q alkyl sulfate, C 12 - 20 alkyl alkoxide sulfates containing, for example, 1 to 6 ethoxy groups and C _w _ 2 -Soaposols may also be suitable. represented by amine oxides having the formula R, R ', RN -> 0 where R, R', R can be alkyl having 10 to 18 carbon atoms. Cationic surfactants include quaternary ammonium surfactants such as C ₆ _ 16 N-alkyl surfactants or alkenyl ammonium surfactants.

Cleaning compositions in general are well known and have found commercial applications for a long time. The ingredients of such compositions are eminently well known, including both quantitative and qualitative parameters. We would like to briefly exemplify some of the matrices of treatment compositions to which the essential phosphonate ingredient can be added. Solid dishwasher composition containing a surfactant selected from cationic, anionic, non-ionic and ampholytic and zwitterionic species and mixtures thereof at a level of 2 to 40%, a builder largely at a level of 5 to 60 %. Suitable building species include water-soluble salts of polyphosphates, silicates, carbonates, polycarboxylates, for example, citrates and sulphates and mixtures thereof, and also water-insoluble species, such as zeolite builders. The dishwashing composition can also include a peroxide bleach (peroxybleach) and an activator for that purpose, such as TAED (ethylene tetra acetate diamine). Conventional additives and optional components, including enzymes, proteases and / or lipases and / or amylases, foam regulating agents, foam suppressants, perfumes, optical bleaches and possibly coating agents for selected individual ingredients. These additives and optional ingredients are generally used for their functionality established at the levels established in the art.

The various types of cleaning compositions are generally well known and have found widespread commercial application. Specific examples of individual compositions according to this invention are mentioned below.

Laundry detergent Liquid for industrial use.

Fatty acids C10-22 Parts by weight. 10 Nonionic surfactant 10 Anionic surfactant 15 Potassium hydroxide (50%) 3 Propane-1,2-diol 5 Sodium citrate 5 Ethanol 5 Enzymes 0.2 to 2 Phosphonate 1 to 3 Minors and water balance to 100 Powdered powder. Parts by weight Zeolite Builder 25 Nonionic surfactant 10 Anionic surfactant 10 Calcium carbonate 10

Target SiSodium Sodium Percarbonate TAED

Optical Bleach Polyvinyl pyrrolidone Carboxymethyl cellulose Acrylic Copolymer Enzymes Perfumes Phosphonates Sodium Sulphate Fabric softener.

Parts by weight.

Phosphoric acid

0.2

0.2 to 2 0.2 to 0.4 0.1 to 2 balance to weight

Distearyl dimethyl ammonium chloride at 20

Amino stearyl ethoxylate 1 to 3

Magnesium chloride (10%) 3

Perfume; dye 0.5

Phosphonate 0.1 to 2

Water Balance for 100

Automatic dishwasher powder.

Parts by weight

Sodium Tripolyphosphate 40

Non-tonic surfactant (low foaming) 3 to 10

Sodium Carbonate 10

Sodium metasilicate 3

Sodium Percarbonate 15

TAED 5

Acrylic Copolymer 2

Zinc Sulfate 0.1 to 2

Enzymes 0.2 to 2

Phosphonate 0.1 to 2

Sodium Sulfate balance to 100

Rigid surface cleaner (Industrial).

Parts by weight.

5 Sodium Hydroxide (5O '%) Low non-ionic surfactant foaming 5 to 20 40 Sodium carbonate 2 to 5 Phosphonate 0.1 to 3 10 Water Multipurpose kitchen cleaner Low non-ionic surfactant foaming 2 to 5 balance to 100 Parts by weight. 15 Potassium hydroxide (50%) 1 a3 Fatty acid C10-22 2a5 Propane-1,2-diol 3a5 Sodium metasilicate 1 a2 Phosphonate 0.1 to 2 20 Color and Perfume 0.1 to 0.5

Balance water to 100

Bottle washing.

Parts by weight.

Low to non-ionic surfactant 5 to 15

25 Phosphoric Acid (85%) Isopropanol Phosphonate Water 30 to 40 2a5 0.5 to 5 balance to 100

In a further aspect of the invention, the use of a composition, as described above, is provided for the treatment of surfaces, in particular for washing fabrics, treating textiles and industrial fabrics, such as softening, bleach and finishing , cleaning specifically for rigid surface treatment, industrial dishwashing and household applications.

In addition, a method is provided for treating a surface comprising the step of applying a composition of the invention to that surface.

The essential phosphonic acid compound is selected from the groups (I) to (V) mentioned above:

(I): amino acid, instead of a, alkylene phosphonic acids;

(II): α-amino acids of alkylene phosphonic acid;

(III): phosphonate compounds containing a group of phosphonic alkylene aminic acid, linked to a hydrocarbon chain, coupled to a portion selected from 11 structures;

(IV): hydrocarbon compounds containing alkylene phosphonic amino acid substituents, and (V): phosphonic amino alkylene acids attached to a hydrocarbon compound containing a selected portion of N, 0 or S.

Suitable species of phosphonic alkylene (I) amino acid are represented by:

aminoeptanoic acid; - 6 - aminoexanoic acid; aminopentanoic acid; - 4 - aminobutyric acid, and -β - alanine;

thus x is 2 in each species.

The α-amino acid alkylene phosphonic (II) acids can, in preferred embodiments, be selected from:

-D, L-alanine where y is 2;

-L-alanine where y is 2;

-L-phenylalanine where y is 2;

-L-lysine where y is 2 to 4;

-L-arginine where y is 2 to 6;

-L-threonine where y is 2;

-L-methionine where y is 2;

-L-cysteine where y is 2; and L-glutamic acid where y is 1 to 2.

It has been found that L-gSutamic acid composed of phosphonic alkylene, as it is, due to insufficient performance and stability, is not suitable for use in the method of this invention. Depending on the conditions of the formation reaction, the L-giutamic acid of alkylene phosphonic acid resulting from the methylene phosphonation of L-glutamic acid can be represented by a substantially binary mixture containing, based on the mixture (100%), the majority of a mono- phosphonic methylene derived from a carboxylic acid-substituted pyrrolidone, and a relatively lower level of a dimethylene phosphonic acid glutamic acid compound. It was found that, in a beneficial embodiment, the reaction product often contains 50% to 90% of the N15 phosphonic acid scale inhibitor of pyrrolidone carboxylic acid and 10% to 50% of bi (phosphonic alkylene acid) compound L-glutamic acid. The sum of the diphosphonate and monophosphonate inhibitors formed during the reaction often exceeds 80%, based on the glutamic acid starting material. The binary mixture can also be prepared by admixing the individually prepared phosphonic acid compounds separately. In another preferred embodiment, the L-lysine carrying a group of alkylene phosphonic acid coupled to the amino radical (s) represents no more than 20% moles of the sum of L-lysine carrying one and two groups of phosphonic alkylene acid coupled to the amino radical (s). In another preferred embodiment, the L-lysine of alkylene phosphonic acid is represented by a mixture of L-lysine carrying two groups of alkylene phosphonic acid coupled to (di-lysine) and L-lysine of amino radical (s) (individual) carrying four groups of alkylene phosphonic acid (tetra lysine), so the ratio of tetra Usina to di lysine is from 9: 1 to 1: 1, even more preferred 7; 2 to 4: 2.

The phosphonate compound (III) can, in preferred embodiments, be represented by a phosphonate moiety attached to a T portion of the formula:

(i) MOOC-X-N (U) -;

(ii) MOOC-C (X ² ) z-Ν (U) -;

(iv) [X (HO) _n - (NU) _n .] _n · .-;

(v) U-N (U) - [X-N (U)] n ”-;

(viii) MOOC-X-O-;

(ix) MOOC-C (X ² ) 2-0-;

(x) NHR ¹ _and (xi) (DCO) ₂ -N-,

Hydrocarbon compounds containing alkaline phosphonic amino acids (IV) are, in preferred embodiments, characterized by a molar ratio of alkylene phosphonic amino acid substituents to carbon atoms in the hydrocarbon group from 2: 1 to 1: 8, more preferably to from 2; 1 to 1: 4. In preferred embodiments, the hydrocarbon group contains from 6 to 500000, more preferably from 6 to 100000 carbon atoms.

The amino alkylene phosphonic acid (V) compounds preferably contain a portion containing N and / or 0 atoms largely substituted or unsubstituted, more preferably a selected portion of NH, NeOH.

M is selected from H, portions of linear, branched, cyclic or aromatic C1-C20 hydrocarbon and alkali, alkaline earth and ammonium ions and protonated amines.

In more detail, the essential phosphonate compound here at present can be neutralized, depending on the degree of acidity / acidity required by conventional agents, including alkali hydroxides, alkaline earth hydroxides, ammonia and / or amines. Beneficial amines can be represented by alkyl, dialkyl and trialkyl amines having, for example, from 1 to 20 carbon atoms in the alkyl group, said groups being in the linear and / or branched configuration. Alkanol amines, such as ethanol amines, ethanol di- and tri-amines can be a preferred class of neutralizing agents. Cyclic alkyl amines, such as cyclohexyl amines and morpholine, polyamines, such as 1,2-ethylene diamine, polyethylene imine and mono polyalkoxy and polyamines can also be used.

Phosphonic acid compounds for use in the inventive arrangement can be prepared by reacting one or more of the available NH functions of the amine radical with phosphoric acid and formaldehyde, in the presence of hydrochloric acid, in an aqueous medium having a pH generally below 4 by heating that reaction mixture, at a temperature normally above 70 ° C for a sufficient time to complete the reaction. This type of reaction is conventional and well known in the field of technology and examples of the new phosphonate compounds have been synthesized, as described below, via the hydrochloric acid pathway.

In another approach, phosphonic acid compounds can be prepared with substantial exclusion of hydroalogenic acid and corresponding by-products and intermediates. Specifically, phosphonic acids can be made in the presence of not more than 0.4%, preferably less than 2000 ppm of hydrohalogenic acid, expressed in relation to the phosphoric acid component (100%) by the reaction of phosphoric acid, an amine and formaldehyde in conventional proportions of reagent in the presence of a catalyst acid having a pKa equal to or less than 3.1, followed by recovery, in a known manner, of the phosphonic acid reaction product. The catalyst, which is preferably homogeneously compatible with the reaction medium, that is, without precipitation or separation phase, can be represented by sulfuric acid, sulfurous acid, trifluoro acetic acid, trifuluoro methane sulfonic acid, methane sulfonic acid, oxalic acid, acid mayonic acid, p-toluene sulfonic acid, naphthalene sulfonic acid. In another variation of the homogeneous catalytic method, phosphonic acid compounds can also be prepared by replacing the homogeneous catalyst with a heterogeneous one, with respect to the reaction medium, Broensted acid catalyst selected from solid acidic metal oxide combinations, such such as, or supported on a vehicle material, a cation exchange resin comprising aromatic copolymers functionalized so that graft SO3H portions for the aromatic group and perfluorinated resins carrying groups of carboxylic and / or sulfonic acids, and a derivative acid catalyst of the interaction of a solid support ten18 of a solitary pair of electrons in which a Broensted organic acid or a compound having a Lewis acid site is deposited.

The synthesis of examples of phosphonic acid compounds of the invention is described in the examples below.

Examples

Throughout the examples section, the following abbreviations are used:

PIBMPA represents bis propyl imino (methylene phosphonic acid). EIBMPA represents imino ethyl bi (methylene phosphonic acid).

(A) Examples of syntheses

165.19 g (1 mol) of L-phenyl alanine are mixed with a solution of 164 g (2 mol) of phosphoric acid in 147.8 g of 37% aqueous solution of hydrochloric acid (1.5 mol) and 250 cc of water. The mixture is heated, with stirring at 110 ° C. 180.5 g of a 36.6% (2.2 mol) aqueous solution of formaldehyde are added over a period of 110 minutes, while maintaining the reaction temperature between 106 ° C and 107 ° C. Upon completion of the formaldehyde addition, the reaction mixture is maintained for an additional 90 minutes at a temperature of 107 ° C to 108 ° C. The ³¹ P NMR analysis of the crude product showed the presence of 68% L-phenyl alanine bi (methylene phosphonic acid).

131.17 g (1 mol) of L-isoleucine are mixed with a solution of 164 g (2 mol) of phosphorous acid in 147.8 g of a 37% aqueous solution of hydrochloric acid (1.5 mol) and 150 cc of water. The mixture is heated, with stirring at 110 ° C. 180.5 g of a 36.6% aqueous formaldehyde solution (2.2 mo25 les) are added over a period of 100 minutes, while maintaining the reaction temperature at 110 ° C. Upon completion of the formaldehyde addition, the reaction mixture is maintained at 110 ° C for an additional 110 minutes. The analysis of ³¹ P NMR of the crude product showed the presence of 69.7% of Lysoleucine bi (methylene phosphonic acid).

131.17 g (1 mol) of D, L-leucine are mixed with a solution of 164 g (2 moles) of phosphorous acid in 147.8 g of aqueous hydrochloric acid solution (1.5 moles) and 150 cc of Water. The mixture is heated, under stirring, to 105 ° C. 180.5 g of a 36.6% aqueous solution of formaldehyde (2.2 mois) are added over a period of 100 minutes, while maintaining the reaction temperature between 105 ° C and 110 ° C. Upon completion of the formaldehyde addition, the reaction mixture is maintained at 110 ° C for an additional 60 minutes. ³¹ P NMR analysis of the crude product showed the presence of 69.7% of D, L-leucine bis (methylene phosphonic acid).

117.15 g (1 mol) of L-valine are mixed with a solution of 164 g (2 moles) of phosphorous acid in 147.8 g of 37% hydrochloric acid (1.5 mol) and 150 g of water. The mixture is heated, with stirring, to 110 ° C. 180.5 g of 36.6% aqueous formaldehyde (2.2 mois) are added in 85 minutes, while maintaining the reaction temperature at 107 ° C. Upon completion of the formaldehyde addition, the reaction mixture is maintained at 107 ° C for an additional 60 minutes. The ³¹ P NMR analysis of the reaction product, as it is, showed the presence of 70.3% L-valine bi (methylene phosphonic acid).

g (1 mol) of 2-pyrrolidone are mixed with a solution of 164 g (2 mol) of phosphorous acid in 118.4 g of hydrochloric acid (1.2 mol) at 37% and 100 g of water. The mixture is heated, with stirring, to 100 ° C. 172.1 g of 36.6% aqueous formaldehyde (2.1 mois) are added over a period of 135 minutes, while maintaining the reaction temperature between 100 ° C and 114 ° C. Upon completion of the formaldehyde addition, the reaction mixture is maintained at 110 ° C for an additional 90 minutes. The ³¹ P NMR analysis of the reaction product, as it is, showed the presence of 91.2% 4-amino butanoic acid bi (methylene phosphonic acid).

113.1 g (1 mol) of G-caprolactam are mixed with 164 g (2 mol) of phosphorous acid in 118.4 g of 37% aqueous hydrochloric acid solution (1.2 mol) and 100 g of water. The mixture is heated, with stirring, to 100 ° C. 172.1 g of 36.6% aqueous formaldehyde (2.1 mois) are added over a period of 105 minutes, while maintaining the reaction temperature between 100 ° C and 112 ° C. Upon completion of the formaldehyde addition, the temperature of the reaction mixture is maintained for an additional 75 minutes, at a temperature of 110 ° C. The ³¹ P NMR analysis of the reaction product showed the presence of 89% 6-amino hexanoic acid bi (methylene phosphonic acid).

92.27 g (0.65 mol) of 2 azocyclononanone are mixed with 106.6 g (1.3 mol) of phosphoric acid in 96.07 g of 37% aqueous hydrochloric acid solution (0.97 mol) and 65 g of water. The mixture is heated, with stirring, to 100 ° C. 114 g of 36.6% aqueous formaldehyde (1.39 mois) are added in 70 minutes, while maintaining the reaction temperature between 104 ° C to 106 ° C. Upon completion of the formaldehyde addition, the temperature of the reaction mixture is maintained at 107 ° C for an additional 60 minutes. The ³¹ P NMR analysis of the reaction product showed the presence of 84% bi-8-amino octanoic acid (methylene phosphonic acid).

g (1 mol) of L-alanine are mixed with 164 g (2 moles) of phosphorous acid in 147.81 g of 37% aqueous hydrochloric acid solution (1.5 ml) and 150 g of water. The mixture is heated, with stirring, to 110 ° C. 180.51 g of aqueous formaldehyde (2.2 mois) at 36.6% are then added over a period of 120 minutes, while maintaining the temperature of the reaction mixture between 110 ° C and 115 ° C. Upon completion of the formaldehyde addition, the temperature of the reaction mixture is maintained at 106 ° C for an additional 60 minutes. The ³¹ P NMR analysis of the reaction product showed the presence of 77.6% L-alanine bis (methylene phosphonic acid).

Arginine was reacted, in a conventional manner, with phosphorous acid and formaldehyde in the presence of hydrochloric acid. The crude reaction was found to be substantially complete, 72.7%, represented by a derivative of bi (alkylene phosphonic acid). This reaction product was used in the usage examples.

91.33 g (0.5 mol) of L-iisine hydrochloride are mixed with 164 g (2 mol) of phosphorous acid in 73.91 g of 37% aqueous hydrochloric acid solution (0.75 mol) and 120 g of water. The mixture is heated, with stirring, to 105 ° C. 180.51 g of aqueous formaldehyde (2.2 moles) at 36.6% are added over a period of 120 minutes, while maintaining the reaction temperature between 106 ° C and 109 ° C. Upon completion of the formaldehyde addition, the temperature of the reaction mixture is maintained at 106 ° C for an additional 50 minutes. The ³¹ P NMR analysis of the reaction product showed the presence of 72.2% 5 tetra L-lysine (methylene phosphonic acid) and 14% 2-amino 6-imino bi (methylene phosphonic acid) hexanoic acid. This preparation was used in the examples of use, under the name tetraphfonate.

273.98 g (1.5 ml) of L-lysine hydrochloride are mixed with 5 369 g (4.5 ml) of phosphoric acid in 221.72 g of aqueous HCI (2.25 ml) at

37% and 400 g of water. The mixture is heated with stirring at 106 ° C. 404.14 g of 36.6% aqueous formaldehyde (4.95 mois) are added over a period of 180 minutes, while maintaining the reaction temperature between 106 and 112 ° C. Upon completion of the formaldehyde addition, the reaction mixture is heated for an additional 60 minutes at 110 ° C. ³¹ P NMR analysis of the crude product shows the presence of 52.1% tetra L-lysine (methylene phosphonic acid), 19.7% 2-amino-6-imino bis (methylene phosphonic acid) hexanoic and 22% N- Me L-lysine diphosphonate. This composition corresponds to an approximate average of two methylene phosphonic acid groups per L15 lysine fraction. This preparation was used in the examples of use, under the name diphosphonate.

147.13 g (1 mol) of L-glutamic acid are mixed with a solution of 164 g (2 mol) of phosphoric acid in 147.8 g of 37% aqueous HCI (1.5 mol) and 120 ml of water . This mixture is heated, with stirring, to

110 ° C. 180.5 g of 36.6% aqueous formaldehyde (2.2 mois) are added over a period of 105 minutes, while maintaining the reaction temperature around 110 ° C. Upon completion of the formaldehyde addition, the temperature of the reaction mixture is maintained at 110 ° C for another 30 minutes. The ³¹ P NMR analysis of the reaction product shows the presence of 20.1% of L-glutamic acid bi (methylene phosphonic acid) and 51.5% of 2-pyrrolidone-5-carboxylic acid N-methylene phosphonic acid.

173.5 g (1 mol) of 4 - aminomethyl 1.8 - octane diamine were mixed under stirring to 492 g (6 mois) of phosphoric acid, 413.87 g (4.2 mois) of 37% hydrochloric acid and 200 ml of water. The mixing result is heated to 110 ° C. 541.52 g of 36.6% aqueous solution (6.6 mol) of formaldehyde were added in 300 minutes, while maintaining the reaction temperature around 113 ° C. Upon completion of the formaldehyde addition, the reaction mixture is heated for an additional 60 minutes at 114 ° C. The ³¹ P NMR analysis of the crude product shows 93.2% 4-aminomethyl - octane 1,8 - hexa diamine (methylene phosphonic acid).

222.67 g (1 mol based on the monomer unit), 32.2% w / w polyvinyl 5 formamide (Lupamin 4500 from BASF) were mixed with stirring to 164 g (2 moles) of phosphoric acid, 221, 71 g (2.25 mois) of 37% hydrochloric acid and 50 ml of water. The resulting mixture was heated to 110 ° C. 168 ml of 36.6% formaldehyde (2.2 mol) aqueous solution were added in 120 minutes, while maintaining the reaction temperature between 10 and 108 and 110 ° C. Upon completion of the formaldehyde addition, the reaction mixture was heated for an additional 60 minutes at 105 ° C. The analysis of ³¹ P NMR of the crude reaction product showed the presence of 60% of polyvinyl amine bi (methylene phosphonic acid) in the mixture of the reacted product.

6-amino hexanoic acid PIBMPA (mixture of mono- and bi-product of alkylation)

Slurry 1 is prepared by mixing 22.63 g (0.2 moles) of C-caprolactam with 50 ml of water and 64 g (0.8 moles) of a 50% NaOH solution in water and heated for 3 hours at 100 ° C. The slurry is prepared by mixing 117.3g (0.4 moles) of 96% pure 3-chloro propyl imino bis (methylene phosphonic acid) and 150 cc of water. 64 g (0.8 moles) of 50% NaOH solution in water diluted to 150 ml with water are gradually added to this suspension at 5 to 10 ° C. Solution 2 thus obtained is mixed with Solution 1 at 8 to 10 ° C. At the end of the addition, 16 g of the 50% NaOH solution (0.2 moles) in water are added before heating the resulting mixture to 105 ° C for 6 hours. The ³¹ P NMR analysis of the crude reaction mixture shows 68% hexanoic acid 6 imino bi [3 - imino propyl bi (methylene phosphonic acid)], 15% molar hexanoic acid 6-amino propyl 3imino bi (methylene phosphonic acid) and 9% bi-molar imino 3-hydroxypropyl (methylene phosphonic acid).

PIBMPA 11-amino undecanoic acid (mixture of mono and bis alkylation product)

Slurry 1 is prepared by mixing at room temperature 40.26 g (0.2 mol) of 11-amino undecanoic acid with 75 ml of water and 64 g (0.8 mol) of a 50% NaOH solution in water. Slurry 2 is prepared by mixing 117.3 g (0.4 moles) of 96% pure 3-chloro propyl imino bi (methylene phosphonic acid) and 150 cc of water. To this slurry, 64 g (0.8 mol) of 50% NaOH solution in water diluted to 150 ml with water, are added gradually between 5 and 10 ° C. Solution 2 thus obtained is mixed with the slurry 1 at 8 to 10 ° C. At the end of this addition, 24 g (0.3 mol) of 50% NaOH solution in water are added to the reaction mixture, along with 2 g of Kl, before heating at 90 ° C for 6 hours. The ³¹ P NMR analysis of the crude reaction mixture shows 54% 11-imino bi [3-imino propyl bi (methylene phosphonic acid)] and 16% 11-amino propyl 3-imino bi ( phosphonic methylene acid).

- PIBMPA (2-amino ethoxy) ethanol (mixture of mono- and bi-alkylating product)

Solution 1 is prepared by mixing 21.03 g at room temperature (0.2 mol) of 2- (2-amino ethoxy) ethanol with 75 ml of water and 80 g (1 mol) of a 50% NaOH solution in water . Slurry 1 is prepared by mixing 117.3 g (0.4 mol) of 96% pure 3-chloro propyl imino (methylene phosphonic acid) and 150 cc of water. To this slurry 48 g (0.6 moles) of 50% NaOH solution in water, diluted with 120 ml of water, are added gradually between 5 and 10 ° C. Solution 2 thus obtained is mixed with Solution 1 at 8 to 10 ° C. At the end of this addition 16 g (0.2 ml) of 50% NaOH solution in water are added and the resulting mixture is heated at 90 ° C for 5 hours. The ³¹ P NMR analysis of the crude reaction mixture shows 55% of 2 - (2-imino ethoxy) bi molar ethanol [propyl 3-imino bis (methylene phosphonic acid)], 19% of 2 - (2-amino ethoxy) propyl ethanol molar 3-imino bi (methylene phosphonic acid) and 16% of the corresponding molar azetidinium salt. Glycine PIBMPA (mixture of mono and bis alkylation product)

Solution 1 is prepared by mixing 15.02 g at room temperature (0.2 mol) of glycine with 75 ml of water and 96 g (1.2 moles) of a 50% NaOH solution in water. Slurry 1 is prepared by mixing

117.3 g (0.4 moles) of 96% pure 3-chloro propyl imino bi (methylene phosphonic acid) and 150 cc of water. To these 48 g (0.6 moles) of 50% NaOH slurry in water, diluted to 100 ml with water are gradually added between 5 and 10 ° C. Solution 2 thus obtained is mixed with Solution 1 at 5 to 10 ° C. At the end of this addition, 8 g (0.1 mol) of 50% NaOH solution in water are added to the mixture, which is heated to 105 ° C for 5 hours. The ³¹ P NMR analysis of the crude reaction mixture shows 67.4% w / w of glycine bi [propyl 3-imino bi (methylene phosphonic acid)]; 2.2% w / w of propyl 3 - imino glycine bi (methylene phosphonic acid) and 3% w / w of the corresponding azetidinium salt.

Imino bis (EIBMPA) (mixture of mono- and bi-alkylating product)

Solution 1 is prepared by mixing between 5 and 8 ° C 111.4 g (0.4 moles) of 96% pure 2-chloro ethyl imino bi (methylene phosphonic acid); 300 ml of water and 30 g (0.375 moles) of a 50% solution of a solution of NaOH in water. Solution 2 is prepared by mixing 130 g (1.625 moles) of 50% aqueous sodium hydroxide with water to obtain a final volume of 250 ml. Ammonia solution is prepared by mixing 13.6 g (0.8 moles) of 25% ammonia solution in water with 200 ml of water. Solutions 1 and 2 are gradually added to the ammonia solution, with good stirring between 80 ⁰ and 12 ⁰ C. This mixture is heated to 80 ° C for 5 hours. The ³¹ P NMR analysis of the crude reaction mixture shows 56.2% w / w imino bi [ethyl 2-imino bi (methylene phosphonic acid)], 22.2% w / w amino ethyl 2-imino bi ( methylene phosphonic acid) and 11.8% w / w nitrile tri [ethyl 2-imino bi (methylene phosphonic acid)].

EIBMPA glycine (mixture of mono and alkylation bi-product)

A glycine solution is prepared by mixing at room temperature 7.51 g (0.1 moles) of glycine with 30 ml of water and 8 g (0.1 moles) of a 50% NaOH solution in water. Slurry 1 is prepared by mixing 55.72 g (0.2 moles) of 96% pure 2-chloro ethyl imino bis (methylene phosphonic acid) and 150 cc of water. To this slurry 15 g (0.1875 mol) of 50% NaOH in water, diluted to 100 ml with water, are gradually added between 5 and 10 ° C. Solution 1 is prepared by diluting 53 g (0.6625 moles) of 50% NaOH in water to a total volume of 110 ml. Solution 1 and slurry 1 are gradually added, with stirring to the glycine solution at 8 to 12 ° C. At the end of this addition 4 g (0.25 moles) of a 50% NaOH solution in water are added to the mixture which is heated to

100 ° C for 5 hours. The ³¹ P NMR analysis of the crude reaction mixture shows

74.5% w / w of glycine bi [ethyl 2-imino bi (methylene phosphonic acid)], 7.1% w / w of ethyl glycine 2 - imino bi (methylene phosphonic acid) and 4.8% w / p of ethyl 2hydroxy imino bi (methylene phosphonic acid).

The benefits associated with the compositions according to this invention can be illustrated, directly and / or indirectly, by means of specific test procedures, some of which are shown in the following usage examples.

Usage Examples

The effectiveness of clay dispersion is a significant parameter in many surface treatments, such as cleaning textiles. This property is demonstrated with the aid of the following test procedure. Dispersion of clay.

This test is used to determine and compare the effectiveness of the phosphonate agents of this invention.

One liter of 0.15% w / w solution of the selected phosphonate is prepared in tap water. The pH of the solution is brought to 11.5 by the addition of 50% aqueous sodium hydroxide solution. Caolin (Ig) is added and the liquid is stirred at room temperature until a homogeneous suspension is obtained. The suspension is then introduced into an I25 mhoff cone. Gradually, the second phase appears at the bottom of the cone and its level is recorded at regular intervals (5, 15, 30, 60 and 120 minutes). The appearance and color of the two phases were also recorded at the same intervals. The percentage of dispersion provided by the tested product, after 120 minutes, is calculated as follows by reference to a blank test that does not contain a phosphonate.

% Dispersion = 100 - (level of the bottom phase (in ml) x 100 / level of the background of the test blank (in ml)).

Calcium Tolerance

This test is used to measure and compare the calcium tolerance of phosphonate compounds. Tolerance to calcium is an indirect parameter (qualification), to use phosphonate compounds selected in the presence of high levels of water hardness, for example, calcium and magnesium.

A solution of the tested product is prepared in 1200 ml of water, so as to correspond to a solution of active acid of 15 ppm in 1320 ml. The solution is heated to 60 ° C and its pH adjusted to 10 by adding a 50% sodium hydroxide solution. Turbidity is measured with a Hach spectrophotometer, model DR 2000, manufactured by Hach Company, P.O.Box 389, Loveland, CO 80539, USA and reported in FTU units (*). The calcium concentration in the tested solution is gradually increased by 200 ppm increments of calcium based on the tested solution. After each addition of calcium, the pH is adjusted to 10 by the addition of a 50% sodium hydroxide solution and turbidity is measured 10 minutes after the addition of calcium. A total of six calcium solution additions are made.

(*) FTU = Formazina Turbidity Units.

Stain removal

This test is used to determine and compare the stain removal performance of selected detergent formulations.

A typical detergent-based formulation is prepared by mixing 12 g of C ₁₃ -C ₁₅ of ethoxylated oxo alcohol with 8 moles of ethylene oxide, 10 g of C ₈ -C ₁₈ of coconut fatty acid, 6 g of triethanamine, 4 g of 1,2-propanediol, 15 g of linear C10-C13 alkylbenzene sulfonate sodium salt, 3 g of ethanol and 50 g of water. The first four ingredients are added in the order indicated and heated to 50 ° C until a uniform liquid is obtained before adding the other ingredients.

The stain removal test is conducted at 40 ° C in a tergotometer using one liter of running water, per wash, to which 5 g of base detergent formulation and 50 ppm as active acid of the tested phosphonate are added. Soil coupons are added to the liquid which is stirred at 100 rpm for 30 minutes. After the wash cycle, the samples are rinsed with running water and dried in the oven for 20 minutes at 50 ° C. The whiteness of the samples is measured with Elrepho 2000, made by Datacolor from Dietlikon, Switzerland. The equipment is standardized, in a conventional way, with black and white patterns before measuring the washed samples. The chromatic value of Rz is recorded for each sample before and after the wash cycle. The percentage of stain removal for a specific stain and formulation is calculated as follows:

ÍRz ^ j Rz /)% stain removal = - xl00 (100-Jfeí) legend:% stain removal with

Rz _w = Rz value for the washed sample

Rz, = Rz value for the sample not washed.

Calcium carbonate scale inhibition procedure

These methods are used to compare the relative capacity of selected phosphates to inhibit the formation of calcium carbonate scales in, for example, laundry applications.

The following solutions are prepared:

- Buffer PH: a 10% solution of NH ₄ C1 in deionized water is adjusted to pH 9.5 with 25% aqueous solution of NH ₄ 0H.

- Buffer pH: a 10% solution of NH ₄ C1 in deionized water is adjusted to PH 10.0 with 25% aqueous solution of NH ₄ OH.

- Inhibiting mother solution 1: a solution such as 1% of each inhibitor is prepared. These solutions contain 10,000 ppm of inhibitor as is.

- Inhibiting mother solution 2: a solution such as 10% of each inhibitor is prepared. These solutions contain 100,000 ppm of inhibitor as is.

Inhibitor test solution 1: weigh 1 g of mother inhibitor solution 1 in a 100 ml glass bottle and adjust to 100 g with deionized water. These solutions contain 100 ppm of inhibitor as is.

Inhibitor test solution 2: Weigh accurately 1 g of mother inhibitor solution 2 in a 100 ml glass bottle and adjust to 100 g with deionized water. These solutions contain 100 ppm of inhibitor as is.

- 2N sodium hydroxide solution.

The test is performed as follows:

in a 250 ml glass flask, 75 g of 38 ⁰ water with French hardness are placed; appropriate levels of mother inhibitor or test solutions corresponding to 0, 5, 10, 20, 50, 200, 500, 1000, 2500 and 5000 ppm of inhibitor as is and 5 ml of the pH 9.5 buffer solution. The pH of the mixture is adjusted to 10, 11 or 12 by adding 2N sodium hydroxide and an appropriate amount of deionized water is added to adjust the total net weight to 100 g of solution.

The vial is immediately capped and placed on a controlled shaker at 50 ° C for 20 hours. After 20 hours, the vials are removed from the shaker and 50 ml of the hot solution is filtered, using a syringe with a 0.45 micron filter. This filtrate is diluted with 80 ml of deionized water and stabilized with 1 ml of the pH 10 buffer solution. Calcium solution is titrated with a 0.01 M EDTA solution and a selective calcium electrode combined with a calomel electrode.

Inhibitor performance is calculated as follows:

Vi-Vo% = _ Inhibition

V2 scale - Vo where: Vo is the volume of the EDTA solution needed for the blank

V2 is the volume of the EDTA solution required for 100% inhibition and is determined by titrating a solution containing 10 ml of the inhibitory mother solution 2 diluted in deionized water to 100 g of total weight.

Vi is the volume of the EDTA solution needed for the test sample.

Peroxide stabilization is tested as follows.

Peroxide stabilization procedure

In a 250 ml glass bottle filled with 200 ml of deionized water stabilized at 40 ° C, add the following ingredients: 0.4 g of iron, 35 ppm of the bleach stabilizer tested, 0.53 g of sodium bicarbonate, 0.42 g of sodium carbonate, 0.14 g of sodium perborate tetrahydrate and 0.06 g of tetraacetyl ethylene diamine (TAED). Dissolve the ingredients in the water using an ultrasound bath. After one minute of such treatment, the vial is transferred to the water bath set at 40 ° C and the samples (10 ml each) are removed from test vial 2, 6, 10, 15, 20 and 30 minutes later. 10 ml of 1 M of potassium iodide and 10 ml of 20% aqueous sulfuric acid are added to these samples before immediate titration with a standardized 0.01 N thiosulfate solution.

The test results were as follows.

Clay dispersion.

Time (min) Neutron test L-Lysine-ph. D, L-Alanine-ph. ml (I) (2) ml (l) (2) ml (I) (2) 5 5.5 0.1 0.2 White clear White cloudy White cloudy Yellow Yellow Yellow 15 5.5 0.2 0.4 White clear White cloudy White cloudy Yellow Yellow Yellow 30 5.5 0.3 0.6 White clear White cloudy White cloudy Yellow Yellow Yellow 60 5 0.5 0.9 White clear White cloudy White cloudy Yellow Yellow Yellow 120 5 0.8 1.1

Light white Cloudy white White Yellow cloudy Yellow Yellow % dispersion 0.0 84.0 78.0 Time (min) Hexanoic-ph. ml (I) (2) Triamine-ph. ml (I) (2). 5 0.3 White Yellow cloudy 0.2 White Yellow cloudy 15 0.5 White Yellow cloudy 0.4 White Yellow cloudy 30 0.7 White Yellow cloudy 0.5 White Yellow cloudy 60 0.9 White Yellow cloudy 0.9 White Yellow cloudy 120 1 White Yellow cloudy 1 White Yellow cloudy % dispersion 80.0 83.3

(1) = bottom phase;

(2) = upper phase;

L-Lysine-ph. = tetra L-lysine (methylene phosphonic acid); D, LAlanina-ph. = D, L-alanine bis (methylene phosphonic acid); Hexanoic-ph. = Hexanoic acid 6-imino bis (methylene phosphonic acid);

Triamine-ph. = Hexa triaminonone (methylene phosphonic acid).

Clay Dispersion

Time (Min) Neutral test Hexanoic acid 6-Amino Glycine PIBMPA

ml (1) (2) GDPMPA ml (1) (2) ml (1) (2) 5 6 cloudy 0.15 cloudy 0.4 turbid 15 7 cloudy 0.4 turbid 0.6 cloudy 30 6 cloudy 0.55 cloudy 0.9 cloudy 60 6 clear 0.8 cloudy 1.1 cloudy 120 6 clear 1 cloudy 1.2 cloudy % Dispersion 0.0 82 78 Time (Min) Neutral test mi (1) (2) Glycine EIBMPA ml (1) (2) 2- (2-Amino ethoxy) ethane] PIBMPA ml (1) (2) 5 6 cloudy 0.2 cloudy 0.5 cloudy 15 7 cloudy 0.5 cloudy 0.75 cloudy 30 6 cloudy 0.7 cloudy 1.0 cloudy 60 6 clear 1.0 cloudy 1.0 cloudy 120 6 clear 1.2 cloudy 1.4 cloudy % Dispersion 0.0 78 74

Time (Min) Neutral test ml (1) (2) Imino bis ml (1) (2) (EIBMPA) 11-Amino acid undecanoico PIBMPA ml (1) (2) 5 6 cloudy 0.2 cloudy 0.4 turbid 15 7 cloudy 0.3 cloudy 0.7 cloudy 30 6 cloudy 0.5 cloudy 1.0 cloudy 60 6 clear 0.7 cloudy 1.2 cloudy 120 6 clear 0.9 cloudy 1.3 cloudy % Dispersion 0.0 80 71

Calcium carbonate scale inhibition.

L-Lysine tetra (methylene phosphonic acid)

Addition of phosphonate Ppm level as is Calcium carbonate scale % inhibition a pH 12 pH 10 pH 11 0 17, 63 2 1.7 5 100 24 14 10 100 57 30 20 74 75 45 50 72 86 55 200 66 68 47 500 49 59 49 1000 86 63 96 2500 97 98 95 5000 100 99 91

Hexanoic acid 6-imino bis (methylene phosphonic acid)

Phosphonate addition level % scale inhibition of calcium carbonate □ pm how are you □ H 10 pH 11 pH 12 0 5 10 20 39, 83 1.74 1.77 50 73.36 3, 10 5, 11 200 100.00 13.60 13, 81 500 80.77 86, 54 80.80 1000 100.00 88.31 81.36 2500 100.00 92, 17 82.05 5000 100.00 99.20 83, 55

D, L- Alanine phosphonic methylene bisaccharide)

Phosphonate addition level ppm how are you % carbonate scale inhibition of calcium pH 10 pH 11 pH 12 0 28.40 2.00 1.70 5 66, 80 4.30 3.00 10 96.20 3.00 3.20 20 97, 80 6.00 10.50 50 95, 30 82, 30 36, 30 200 100.00 76, 80 76, 10 500 95, 40 80.00 76.4 1000 98.00 94, 80 72.70 2500 96.00 91.00 85.50 5000 71.00 96.00 90, 40

Phosphonic methylene hexacid triaminonone)

Phosphonate addition level ppm how are you % carbonate scale inhibition calcium to pH 10 pH 11 pH 12 0 57.00 17.00 2.00 5 96.00 8.00 9.00 10 100.00 10.00 11.00 20 93.00 57.00 20.00 50 92.00 79.00 34.00 200 89.00 67.00 51.00 500 83.00 55.00 27.00 1000 70.00 37.00 61.00 2500 75.00 82, 00 80.00 5000 85.00 82, 00 80.00

Example II 1. 2-aminoetoxy 2 ppm ethanol PIBMPA full scale 2. 11-amino acid 2 ppm undecanoic PIBMPA full scale 3. Glycine PIBMPA 2 ppm full scale 4. 6-Hexanoic Amino 2 ppm

Ca tolerance in deionized water at 60 ° C and pH 10

Products tested at 15 ppm active acid in 1320 ml Ca * ² added (ppm) Turbidity (FTU) Appearance after addition Hexa Triaminononana (acid 0 08 Of course phosphonic methylene) 200 itself. cloudy 400 8 itself. cloudy 600 8 itself. cloudy

Products tested at 15 ppm active acid in 1320 ml Ca * ² added (ppm) Turbidity (FTU) Appearance after addition 800 9 itself. cloudy 1000 7 itself. cloudy 1200 7 itself. cloudy Tetra L-Lysine (methyl 0 09 clear in phosphonic) 200 itself. cloudy 400 10 itself. cloudy 600 10 itself. cloudy 800 10 itself. cloudy 1000 10 itself. cloudy 1200 10 itself. cloudy D, L-Alanine bis (methyl acid 0 0 0 clear clear phosphonic lene) 200 400 0 clear 600 0 clear 800 0 clear 1000 0 clear 1200 0 clear 6-Imino Hexanoic Acid 0 0 clear Bi (methylene acid Phosphonic) 200 0 clear 600 0 clear 800 0 clear 1000 0 clear

Products tested at 15 ppm active acid in 1320 ml Ca ⁺² added (ppm) Turbidity (FTU) Appearance after addition 1200 0 clear

Stain removal property% stain removal with test stains (*) _

Detergent Base Tea Oil Clay Grass Wine

10020 10050 10055 EMPA 164 10031

Neutral detergent base 26.3 44.2 51.3 14.5 51 ”+ 50 ppm L-lysine-ph 37.6 58 52.5 14.9 54.2 + 50 ppm Hexanoic-ph. 30.2 44.1 51 12.9 53

+ 50 ppm Triamine-ph. 29.5 46.6 46 16 51.7 (*) All test samples are WFK except EMPA

164.

Additional test results are as follows.

Calcium carbonate scale inhibition

6-Hexanoic amino acid P IBM PA

Phosphonate addition level ppm how are you % carbonate scale inhibition calcium a pH 10 pH 11 pH 12 0 6.9 6.75 5.7 1 49.3 6.0 11.3 5 63.9 6.5 11.4 10 100 10 11.4 20 100 26.1 25.9 50 100 63.4 46.9 200 100 86.6 67.6 500 100 100 61.7 1000 100 100 99 2500 100 100 100 5000 100 100 97.3

Glycine PIBMPA

Phosphonate addition level ppm how are you % carbonate scale inhibition calcium a pH 10 pH 11 pH12 0 4.9 6.2 2.0 1 36.3 2.8 4.2 5 63.9 1.4 1.4 10 95.3 15.4 17.4 20 96 27.3 23.8 50 98.6 83.3 51.4 200 98.8 78.4 60.6 500 91.3 74 52.2 1000 84.3 96 96.1 2500 82.5 96.8 90.4 5000 92.3 95.3 81.5

Imino bi (EIBMPA)

Phosphonate addition level ppm how are you % scale inhibition of calcium carbonate at pH 10 pH 11 pH 12 0 8.8 2.0 1.8 1 13.9 1.8 1.7 5 78.3 4.4 17.1 10 70.8 3.7 16.6 20 100 25.6 16.9 50 100 61.3 52.7 200 87.1 90.6 61.2 500 71.4 84.4 52.7 1000 75.5 84.1 75.7 2500 91.3 63.5 71.9 5000 82.4 91.6 62.0

2-2-Amino ethoxy) hey tannin PIBMPA Phosphonate addition level ppm how are you % calcium carbonate scale inhibition at pH 10 pH 11 pH 12 0 53.1 7.9 9.9 1 53.6 2.8 3.0 5 54.5 14.5 11.6 10 100 7.4 12.9 20 100 16.0 34.4 50 100 17.2 34.3 200 100 97.6 31.9 500 100 88.1 65.5 1000 100 97 86.8 2500 100 100 100 5000 100 100 100

11-Undecanoic Amino Acid PIBMPA

Phosphonate addition level ppm how are you % carbonate scale inhibition calcium a pH 10 pH 11 pH 12 0 40.7 1.7 2.0 1 55.1 2.1 2.1 5 66.7 5.9 8.7 10 100 8.6 11.3 20 100 18.9 15.9 50 100 47.6 39.8 200 100 62.8 51.5 500 90.8 70.0 59.6 1000 78.1 56.0 46.7 2500 57.1 84.0 30.4 5000 82.7 44.5 84.0

Stain removal properties% stain removal with test stains

Tea Base Determinant Oil Clay Grass Wine Neutral base detergent 14.7 30.2 47.1 11.1 51.8 + 100 ppm Dequest 2016 28.9 32.7 47.8 13.2 57.0 + 100 ppm Dequest 2066 22.0 31.7 47.2 12.8 56.4 + 100 ppm 6-amino hexa-18.9 acid 36.2 49.8 12.7 56.0 Node PIBMPA + 100 ppm Glycine PIBMPA 21.5 33.8 46.8 14.1 56.4 + 100 ppm lino bis (EIBMPA) 21.1 30.2 45.9 13.3 58.1 + 100 ppm 2- (2-aminoethoxy) eta- 19.1 35.0 48.3 13.0 54.5 nol PIBMPA + 100 ppm 11-amino acid unde- 19.7 32.1 50.3 12.5 54.3

canoe PIBMPA

Peroxide stabilizing properties

Phosphonate tested

none

Time % active oxygen (min) 0 100 2 92 6 80 10 71 15 61 20 53 30 43 0 100 2 100 6 99 10 97

+ 35 ppm Dequest 2066

Phosphonate tested +45.5 ppm 6-amino hexanoic acid PIBMPA +35 ppm Imino bi (EIBMPA) +17.5 ppm Imino bi (EIBMPA) +35 ppm Glycine EIBMPA% active oxygen remaining

100

100

100

91 90 89 100 100

96

94 100 99

96

Phosphonate tested

Time (min)% active oxygen remaining

Claims (9)

1. Surface treatment composition comprising an active surface agent, and, optionally, additional components and additives, characterized by the fact that the composition comprises: (A) from 99.9 to 40% by weight (based on the sum of (a) and (b)) of a surface active agent; and (b) from 0.1 to 60% by weight (based on the sum of (a) and (b)) of a phosphonic acid compound selected from the group of: aquylene phosphonic acids of amino acids having the formula 10 A ² -B _y where A ² has the formula HOOC-C (NH ₂ ) (R) (R ') where R and R' are independently selected from linear, branched, cyclic or aromatic C1-C20 hydrocarbon moieties, optionally substituted by C1-C12 hydrocarbon groups linear, branched, cyclic or aromatic, eventually substituted by OH, NH2 and / or COOH, and one between R or R 'can be hydrogen, with the exclusion of: compounds in which R and / or R 'are electron-rich portions containing at least one electron pair, the portion of which is directly linked to an aromatic portion by a covalent bond, or aromatics in which at least one of the atoms of carbon has been replaced by a heteroatom, and compounds, in the case where R is -C (X) (R) (R '), and R', R and R 'are hydrogen where X is an electron withdrawal group 25 selected from NO2, CN, COOH, SO3H, OH and halogen, and with the additional caveat that when: A ² is L-lysine, at least one L-lysine amino radical which carries 2 (two) portions of alkylene phosphonic acid and, when A ² is L-glutamic acid, the term glutamic acid phosphonate represents a combination of 50 to 90% by weight of carboxylic acid pyrrolidone phosphonic N-methylene acid, and from 10 to 50% by weight of L-glutamic acid diphosphonic acid, expressed as base Petition 870180057105, of 07/02/2018, p. 9/18 of the reaction products; and B is a portion of alkylene phosphonic acid having 1 to 6 carbon atoms in the alkyl group and Y is an integer in the range 1 to 10. 2. Composition according to claim 1, characterized 5 due to the fact that A ² is L-lysine, where L-lysine carrying an alkylene phosphonic acid group attached to the amino radical (s) represents no more than 20% of the moles of the sum of L-lysine carrying one and two groups of alkylene phosphonic acid linked to amine radicals. Composition according to claim 1 or 2, characterized by the fact that A ² is L-lysine, wherein the L-lysine alkylene phosphonic acid is represented by a mixture of L-lysine carrying two groups of phosphonic alkylene acid linked to the amino radicals (bi-lysine) and L-lysine with four alkylene phosphonic acid groups (tetra lysine), in which the weight ratio of tetra lysine to bi lysine is from 9: 1 to 1: 1. 15 4. Composition according to any one of the claims 1 to 3, characterized by the fact that the surfactant is selected from the group of cationic, nonionic, anionic, ampholytic, zwitterionic surfactants and mixtures thereof, and is present at a level of 2 to 40% by weight (based on in the total composition). Composition according to any one of Claims 1 to 4, characterized in that the phosphonic acid compound is selected from the group (II), A ² is - D, L-alanine, and y is 2; - L-alanine, and y is 2; 25 - L-phenylalanine, and y is 2; - L-lysine and y is in the range of 2 to 4; - L-arginine, and y is in the range of 2 to 6; - L-threonine, and y is 2; - L-methionine and y is 2; 30 - L-cysteine, and y is 2 and - L-glutamic acid, and y is 1 to 2. 6. Granular treatment composition according to any Petition 870180057105, of 07/02/2018, p. 10/18 one of claims 1 to 5, characterized by the fact that it contains a detergent buffer at a level of 2 to 60% by weight (based on the total composition). 7. Composition according to any one of the claims 5 1 to 6, characterized by the fact that the surfactant ingredients represent 2 to 50% by weight (based on the total composition). Composition according to any one of claims 1 to 7, characterized in that the surfactant ingredients represent 3 to 40% by weight (based on the total composition) and the phosphonate ingredient 10 represents 0.1 to 5% by weight (based on the total composition). Use of a composition as defined in any of claims 1 to 8, characterized by the fact that it is for surface treatment. 10. Use according to claim 9, characterized by the fact that it is in textile laundry, treatment of textiles and industrial textiles, rigid surface treatment, residential and industrial dishwasher applications. 11. Method for treating a surface, characterized by the fact that it comprises the stage of applying a composition as defined in Any one of claims 1 to 8. Petition 870180057105, of 07/02/2018, p. 11/18