WO2009092740A1

WO2009092740A1 - Surface treatment composition containing sugar phosphonates

Info

Publication number: WO2009092740A1
Application number: PCT/EP2009/050670
Authority: WO
Inventors: Henricus W.C. Raaijmakers; Luc E. Feyt; Albert Devaux; Arjen Postma; Eric Hoets
Original assignee: Thermphos Trading Gmbh; Koninklijke Coöperatie Cosun U.A.
Priority date: 2008-01-22
Filing date: 2009-01-21
Publication date: 2009-07-30
Also published as: EP2090645A1

Abstract

This invention discloses surface treatment, in particular cleaning, compositions containing, as a core ingredient combination, a binary active system comprising, expressed in relation to the sum (100 %) of the actives in said binary systema major level ofsurface active agenttogether with a lower level of a selected sugar phosphonate. The compositions can contain, usually contain, conventional additives and additives in art established levels for their known functionalities.

Description

Surface Treatment Composition containing Sugar Phosphonates

This invention relates to surface treatment, particularly cleaning, compositions, containing surface-active agents, selected sugar phosphonates and conventional additives and optional components, exhibiting a range of desirable properties over a broad range of applications. The surface treatment compositions can be used in by known applications including detergent laundry compositions, dishwashing compositions, textile treatment compositions including textile softening compositions, hard surface cleaners, bleaching compositions and compositions suitable for use in industrial textile treatment applications and other conventional surface treatment compositions well known in the relevant domain. The surface treatment compositions herein comprise as a major constituent a binary active system containing, expressed in relation to the sum (100 %) of the components of the binary active system, usually from 99.9 % to 40 % of a surface-active agent and from 0.1 % to 60 % of a sugar phosphonate.

The use of surface-treatment compositions containing surface- active agents in combination with a large variety of individual additives and optional components is widespread and is accordingly acknowledged in the art. This applies, inter alia, to combinations of surfactants and phosphonic acids and also combinations of selected sugars and surface-active agents. Ever more demanding performance criteria and other major parameters including economics, component compatibility and environmental acceptability have created an overriding need for providing novel active ingredients which are eminently suitable for meeting the technological needs. EP 1 431 381 discloses fabric treatment compositions containing, among others, cationic ammonium-based fabric softening compounds and cationic guar gums.

US 2007/0015678 describes modified polysaccharide polymers, in particular oxidized polymers containing up to 70 mole % carboxyl groups and up to 20 mole % 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 chemicals including conventional phosphonates . EP 1 090 980 discloses fabric rejuvenating technologies including compositions and methods. Phosphonates are used as builders and as metal sequestrants . 2-Phosphonobutane-l, 2, 4- tricarboxylic acid is preferred in that respect. EP 1 035 198 teaches the use of phosphonates as builders in detergent tablets. Phosphonates are also used in the tablet coating composition .

EP 0 892 039 pertains to liquid cleaning compositions containing a non-ionic surfactant, a polymer, such as a vinyl pyrrolidone homopolymer or copolymer, a polysaccharide, such as a xanthan gum, and an amphoteric surfactant. Conventional phosphonates e.g. diethylene triamino penta (methylene phosphonic acid) (DTPMP) can be used as chelating agents. EP 0 859 044 concerns liquid hard surface cleaners containing dicapped poly alkoxylene glycols capable of conferring soil removal properties to the surface to which the cleaner has been applied. The cleaner compositions can contain phosphonates e.g. DTPMP, to thus provide chelating properties.

Oxygen bleach detergent technology/compositions containing heavy metal sequestrants, such as phosphonobutane tricarboxylic acid, are described in EP 0 713 910. Bleaching machine dishwashing compositions are illustrated in EP 0 682 105. DTPMP are used as heavy metal ion sequestrants .

The art chiefly aims at combining cumulative functionalities to thus yield additive results without providing, to any substantial degree, particularly within the context of surface treatment applications broadly, desirable benefits without being subject to incidental (secondary) performance negatives and/or without using multi component systems, which in addition to benefits can be subject to aleatory economic, environmental and/or acceptability shortcomings.

It is a major object of this invention to provide surface treatment technology, in particular compositions, capable of delivering superior performance. It is another object of this invention to provide effective treatment compositions capable of providing significant benefits, at least equivalent or better than the art, with significantly decreased environmental and/or improved acceptability profiles. Yet another object of this invention aims at generating laundry compositions capable of delivering superior performance with markedly reduced incidental e.g. environmental shortcomings. Yet another object of this invention aims at generating surface treatment technology capable of providing, in addition to the art established functionalities, additional functionalities to thus generate further benefits attached to the structural configuration of specific ingredients in relation to other ingredients in the composition.

The foregoing and other objects of this invention can now be met by the provision of surface treatment compositions broadly comprising surface-active agents in combination with specifically defined amino alkylene phosphonic acid compounds. The term "percent" or "%" as used throughout this application stands, unless defined differently, for "percent by weight" or "% by weight". The terms "phosphonic acid" and "phosphonate" are also used interchangeably depending, of course, upon medium prevailing alkalinity/acidity conditions. Both terms comprise the free acids as well as salts and esters of the phosphonic acids. The terms "surface active" and "surfactant" are used interchangeably. "Da" stands for Dalton which is an alternative name for the atomic mass unit. "DS" means degree of substitution i.e. the number of substituents per monosaccharide unit. "Average DP" means the average number of monosaccharide units in the sugar polymer. "DE" stands for Dextrose Equivalent and represents the percentage of reducing end groups in the starch expressed as percent monosaccharide on dry weight basis.

Surface-treatment, particularly cleaning, compositions containing surface-active agents, conventional additives and optional components and an alkylene phosphonic acid substance have now been discovered. In more detail, the compositions of this invention concern surface treatment, particularly cleaning, compositions comprising a binary active system, expressed in relation to the sum (100 %) of the actives of the components (a) and (b) in said binary system, namely:

(a) from 99.9 to 40 % by weight of a surface-active agent; and

(b) from 0.1 to 60 % by weight of a sugar phosphonate having the formula

T-(B) wherein T is a carbohydrate selected from the group of:

polysaccharides having a molecular weight of up to about 350 kDa, selected from the group of: cellulose; starch; fructan; galactomannan; arabinan; agar; chitosan; arabinogalactan; xylan; alginic acid and derivatives thereof selected from carboxyl; carboxyalkyl with from 1 to 6 carbon atoms in the alkyl chain; C₂-Cs linear or branched hydroxyalkyl substituents; with the index a being from 0.01 to 3 expressed on the basis of the monosaccharide unit in the polysaccharide;

saccharides, which are substantially free of aldehyde and keto groups, with the index a being from 1 to 11;

sugar alcohols with a being from 1 to 9; and

monosaccharides having protected anomeric centers with the index a being from 1 to 4;

B is a phosphonate moiety selected from the group of:

(i) -X-PO₃M₂; and

(ii) -X-N(W) (ZPO₃M₂) ;

wherein X, for each (i) and (ii) , is selected from C₂-C₅O and, in addition Ci for (i) , linear, branched, cyclic or aromatic hydrocarbon moiety, optionally substituted by a Ci-Ci₂ linear, branched, cyclic, or aromatic group, (which moiety and/or which group can be) optionally substituted by OH, COOH, F, OR', SO₃H and SR' moieties, wherein R' is a Ci-Ci₂ linear, branched, cyclic or aromatic hydrocarbon moiety; and [A-O]_x-A wherein A is a C₂-Cg linear, branched, cyclic or aromatic hydrocarbon moiety and x is an integer from 1 to 200; provided that when the carbohydrate moiety is starch, X is C3-C50 with the additional proviso that when X is substituted by OH, the latter moiety can be attached to any carbon atom other than the second carbon atom starting from T;

Z is a Ci-Cε alkylene chain;

M is selected from H, C1-C20 linear, branched, cyclic or aromatic hydrocarbon moieties and from alkali, earth alkali and ammonium ions and from protonated amines;

W is selected from H, ZPO₃M₂ and [V-N(K)J_nK, wherein V is selected from: a C2-C50 linear, branched, cyclic or aromatic hydrocarbon moiety, optionally substituted by C1-C12 linear, branched, cyclic or aromatic groups, (which moieties and/or groups are) optionally substituted by OH, COOH, F, OR', SO₃H or SR' moieties wherein R' is a C1-C12 linear, branched, cyclic or aromatic hydrocarbon moiety; and from [A-O]_x-A wherein A is a C2-C9 linear, branched, cyclic or aromatic hydrocarbon moiety and x is an integer from 1 to 200; and

K is ZPO₃M₂ or H and n is an integer from 0 to 200.

The carbohydrate T moiety can be represented by polysaccharides, having a MW of up to about 350 kDa, selected from the group of: cellulose; starch; fructan; galactomannan; agar; chitosan; arabinogalactan; xylan; alginic acid; and derivatives thereof selected from; carboxyl; carboxyalkyl with from 1 to 6 carbon atoms in the alkyl chain; and C₂-Cs linear or branched hydroxyalkyl substituents .

Suitable polysaccharide species have a MW of up to about 350 kDa. It is known that the MW of the individual polysaccharides per se can e.g. in natural state be substantially higher than about 350 kDa. If such a polysaccharide is selected containing a higher MW (than 350 kDa) then it is obvious that a hydrolysate of the selected polysaccharide shall be used or that the polysaccharide polymer shall be depolymerised in a manner routinely known in the relevant domain. The lower number of monosaccharide units is structure induced and thus can the lower limit of the MW vary, in a known manner, depending upon the selected species. The term "about" in relation to the MW can mean up to 20% of 350 kDa i.e. up to 420 kDa, preferably up to 10 % of 350 kDa i.e. up to 390 kDa. The number (a) of phosphonate moieties bound to the polysaccharide T is within the range of from 0.01 to 3, expressed on the basis of the monosaccharide unit in the polysaccharide .

The cellulose polysaccharide has a MW of from 500 Da to 350 kDa. Cellulose is a linear polymer of β- (1→4) -D-glucopyranose units; it may contain sub-additive levels of arabinoxylans .

The starch polysaccharide has a MW of from 700 Da to 350 kDa. Starch consists of amylose and amylopectin which both consist of α-D-glucose units. Amylose consists of mostly unbranched chains of α-l→4-linked-D-glucose units whereas amylopectin is formed by non-random α-l→6 branching of the amylose-type structure. Starch is found in wheat, potatoes, tapioca and corn .

The fructan polysaccharide for use herein comprise all oligo- and poly-saccharides which have a majority of anhydrofructose units. Fructans can have a polydisperse chain length distribution and can be straight-chain or branched. They may be linked by β-2,1 bonds as in inulin or by β-2,6 bonds as in levan. Suitable fructans comprise both products obtained directly from a vegetable or other source and products in which the average chain length has been modified (increased or reduced) by fractionation, enzymatic synthesis or hydrolysis. The fructans have an average chain length (DP) of at least 3 up to about 1000. Suitable fructans have a MW from 500 Da to 350 kDa, preferably from 500 Da to 15 kDa, in particular of from 600 Da to 12 kDa. A particularly preferred fructan is inulin -β-2,1 fructan- or a modified inulin.

Galactomannan has a MW of from 800 Da to 350 kDa. Galactomannan is found in locust bean gum and contains primarily D-galacto-D-mannoglycan with varying ratios of D- galactose to D-mannose in the range from about 1 : 4 to 1 : 10. Galactomannan originating from guaran differs slightly from the material originating from locust bean gum in that the guaran material has a larger number of D-galactosyl units in the side chains.

The agar polysaccharide has a MW of from 600 Da to 350 kDa. Agar is believed to predominantly consist of repeating units of alternating β-D-galactopyranosyl and 3, 6-anhydro-α-L- galactopyranosyl units. Its systematic name is: (l→4)-3,6- anhydro-α-L-galactopyranosyl- (1→3) -β-D-galactopyran .

Chitosan having a MW of from 500 Da to 350 kDa is a linear polymer of β- (1→4) -linked 2-amino-2-deoxy-D-glucose (D- glucosamine) residues. Polysaccharides containing amino groups, such as D-glucosamine units, constitute preferred species for use herein. Such compounds containing D- glucosamine are particularly preferred considering the convenient formation of the corresponding phosphonates by routinely converting the N-H bonds of the amino group. A specific example of a polysaccharide containing D-glucosamine is chitosan which can be enzymatically hydrolyzed to the corresponding oligosaccharide Suitable arabinogalactan polysaccharides have a MW of from 1000 Da to 350 kDa . Arabinogalactan is composed of D- galactopyranose and L-arabinofuranose residues in the form of a β- (1→3) -galactan main chain with side chains made up of galactose and arabinose units of various lengths. The ratio of D-galactose to L-arabinose can vary e.g. from 5 : 1 to 25 : 1. Arabinogalactan is a water-soluble gum found in concentrations up to 35% in the heartwood of larch.

Xylan polysaccharides for use herein has a MW of from 800 Da to 350 kDa. Xylans consist of a backbone of β-(l→4)-D- xylopyranosyl units. According to the type and amount of substituents, arabinoxylans (varying in the amount of single unit side chains of α-L-arabinofuranose attached to the 0-3 or both the 0-2 and 0-3 of the xylosyl residues) , 4-0- methylglucuronoxylans (with α- (1→2) -linked (4-0- methyl) glucoronosyl substituents) and arabino-glucuronoxylans can be distinguished. The xylosyl residues may additionally be acetylated at the 0-2 or 0-3 position. Xylans are generally present in lignified tissues or in the cell walls of cereals.

Alginic acid polysaccharides herein have a MW of from 800 Da to 350 kDa. The alginate molecule is a linear copolymer of β- D- ( 1→4 ) -linked mannopyranosyluronic acid units and α-L- (1→4) - linked gulopyranosyluronic acid units. These (homo) polymeric units are linked together by segments that have a predominantly alternating copolymer composition.

Arabinan polysaccharides for use herein have a MW of from 400 Da to 350 kDa. Arabinan is a polysaccharide which consists mainly of L-arabinose units. These polysaccharides can be extracted from plant materials such as sugar beet pulp. The structure of arabinans is quite complex. The primary chain consists of α-1,5- linked L-arabinofuranose units which is branched with additional L-arabinofuranose units. This hemicellulose also contains small amounts of other monosaccharide units such as L-rhamnose, D-mannose, D- galactose, D-xylose and D-glucose.

The polysaccharide for use herein is most preferably represented by species of the group of: cellulose; starch; fructan; chitosan; and the derivatives thereof selected from; carboxyl; carboxyalkyl with from 1 to 6 carbon atoms in the alkyl chain; and C2-C8 hydroxyalkyl substituents . The number (a) of phosphonate moieties bound to a polysaccharide of the group of starch, cellulose and chitosan is preferably of from 0.05 to 2 whereas if the polysaccharide is fructan a can preferably vary of from 0.05 to 2.5. In one particular execution, a fructan polysaccharide is used with a being of from 0.5 to 2.

The carbohydrate can also be represented by saccharides which are free of aldehyde and/or keto groups. Such saccharides are also known as non-reducing sugars. The term "free" refers obviously to the carbohydrate as manufactured/obtained in natural state. Well known and preferred species of such non- reducing sugars include sucrose with a being from 1 to 8, trehalose with a being from 1 to 8 and raffinose with a being from 1 to 11.

Monosaccharides having protected anomeric centers, with a being from 1 to 4, are well known in the technical domain. Monosaccharides with protected anomeric centers are usually called glycosides. The monosaccharide per se can be represented by known species such as glucose, fructose, mannose, galactose, xylose and arabinose. Suitable monosaccharide species having protected anomeric centers can optionally contain amino groups such as D-glucosamine . The protecting group of the anomeric center is called the "aglycon" and can be represented by C1-C50 linear, branched, cyclic or aromatic hydrocarbon moieties, optionally substituted by OH, COOH, NR' ₂, OR', SR' or AO-[A-O]_x- moieties wherein A is a C2-C9 linear, branched, cyclic or aromatic hydrocarbon moiety, x is 1-100 and A' is selected from C1-C50, preferably C1-C30, linear, branched, cyclic or aromatic hydrocarbon moieties, optionally substituted by a C1-C12 linear, branched, cyclic, or aromatic group, (which moiety and/or which group can be) optionally substituted by OH, COOH, F, OR' and SR' moieties, wherein R' has the meaning given above. The aglycon is connected to the monosaccharide via an oxygen atom, to thus form an acetal group, or via an S atom or an N atom to thus yield S-glycosides and N-glycosides respectively. Preferred species for use herein include C1-C30 linear alkyl glycosides and benzyl glycosides. Particularly preferred species are represented by C1-C16 linear, branched, cyclic or aromatic glycosides, such as aglycon species selected from methyl, ethyl, octyl, benzyl and dodecyl glycosides .

Sugar alcohols with a being from 1 to 9 are well known and have found widespread commercial application. Preferred species of such sugar alcohols can be represented by sorbitol with a being from 1 to 6, anhydro-sorbitol with a being from 1 to 4, iso-sorbide with a being from 1 to 2, mannitol with a being from 1 to 6, erythritol with a being from 1 to 4, xylitol with a being from 1 to 5, lactitol with a being from 1 to 9 and isomalt with a being from 1 to 9. Particularly preferred species of such sugar alcohols are represented by sorbitol with a being from 1 to 6, iso-sorbide with the index a being from 1 to 2, anhydro-sorbitol with a being from 1 to 4, and mixtures of said sorbitol and said mannitol, with a being from 1 to 6, in ponderal ratios of 5 : 1 to 1 : 5, especially from 2 : 1 to 1 : 2.

In the definition of X, R' , M, A, A' , "aglycon" and V, the C_x- Cy linear or branched hydrocarbon moiety is preferably linear or branched alkane-diyl with a respective chain length. Cyclic hydrocarbon moiety is preferably C3-Cio-cycloalkane-diyl . Aromatic hydrocarbon moiety is preferably C6-Ci2-arene-diyl . When the foregoing hydrocarbon moieties are substituted, it is preferably with linear or branched alkyl of a respective chain length, C3-Cio-cycloalkyl, or Cδ-Ci2-aryl . All these groups can be further substituted with the groups listed with the respective symbols.

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

One or more, preferably one to five sugar phosphonates, are used in the composition of the invention.

One or more, preferably one to ten surface active agents are used in the composition of the invention.

The sugar phosphonates herein can be prepared by means of conventional measures routinely available in the relevant domain. In one approach, the phosphonate moiety compound and a sugar can be combined, in an aqueous medium, by adding stoichiometric proportions of both species, thereby taking into consideration the required degree of substitution. A process for the manufacture of the sugar phosphonates of Claim 1 comprises reacting a phosphonate compound selected from Y-X- N(W) (ZPO₃M₂) and Y-X-PO₃M₂ wherein Y is a substituent the conjugated acid of which has a pKa equal to or smaller than 4, preferably equal to or smaller than 1, with a carbohydrate selected from the group of: polysaccharides having a MW of up to about 350 kDa and with a being from 0.01 to 3, based on the monosaccharide units of the polysaccharide; saccharides, which are substantially free of aldehyde and keto groups, with a being from 1 to 11; sugar alcohols with a being from 1 to 9; and monosaccharides having protected anomeric centers, containing optionally amino groups, with a being from 1 to 4; in aqueous medium, having a pH of 7 or higher, frequently a pH in the range of from 8-14, at a temperature generally above 0⁰C, usually in the range of from 10 ⁰C to 200 ⁰C, preferably 50 ⁰C to 140 ⁰C. Higher reaction temperatures can be used subject to adequate pressure containment e.g. by means of standard pressure vessels. The pH value is measured in the reaction medium at the reaction temperature.

The manufacture of the sugar phosphonates herein is illustrated by the following testing data, Examples I-XII:

I:

8.55g (0.025 mole) of sucrose were mixed with 1Og (0.125 mole) of 50% aqueous sodium hydroxide solution, 25g of water and 0.2g (0.0012 mole) of potassium iodide. To this solution was added under stirring 7.037g (0.025 mole) of 3-chloropropyl imino bis (methylene phosphonic acid) . The mixture was heated under reflux for 10 hours. ³¹P NMR analysis showed that 66% of the propyl imino bis (methylene phosphonic acid) moiety was attached to sucrose and that 28% of the 3-chloropropyl imino bis (methylene phosphonic acid) had been converted to the corresponding hydroxy derivative with about 3% of the azetidinium equivalent of the 3-chloropropyl imino bis (methylene phosphonic acid) .

II:

A solution of potassium iodide (4.5 g, 27 mmol) in water (206 g) was heated to 70⁰C. During heating of this solution, inulin (150 g, 0.93 mol, average DP = 25) was added. Then 3-chloro- propyl imino bis (methylenephosphonic acid) (CPIBMPA, 152 g, 0.54 mol) was slowly added in portions over a period of 90 minutes while maintaining the pH at 11.5 by the simultaneous addition of aqueous sodium hydroxide (50%, 218 g, 2,73 mol). The reaction mixture was kept for another 6h at 80⁰C and then cooled to room temperature. The degree of substitution of the inulin phosphonate in the crude reaction mixture was determined using ³¹P, ¹³C and ¹H-NMR as 0.39, which corresponds with a reaction efficiency of 67%.

III:

A solution of CPIBMPA (197 g, 0.70 mol) in water (207 g) was heated to 70⁰C and neutralised with aqueous sodium hydroxide

(177 g, 2.21 mol). Then inulin (150 g, 0.93 mol, average DP = 25) and potassium iodide (5.8 g, 35 mmol) was added. The reaction mixture was heated to 80⁰C and the pH was adjusted to and maintained at 12 using aqueous sodium hydroxide (50%, 280 g, 3.49 mol) . The reaction mixture is heated for another 6-7 h at 80 ⁰C and then cooled to room temperature.

The crude reaction mixture was purified by membrane filtration

(G5 membrane, General Electric, MW cut off = 500 Dalton (Da)) using a diafiltration factor of 4. This gave a purified inulin phosphonate, which was characterised using ³¹P, ¹³C, and ¹H-NMR. The DS of the product was determined as 0.6 which corresponds to a reaction efficiency of 80 %.

IV:

A solution of potassium iodide (21 g, 130 mmol) in water (193 g) was heated to 80⁰C. During heating of this solution inulin (140 g, 0.82 mol, average DP = 25) was added. Then CPIBMPA (367.4 g, 1.26 mol) was slowly added in portions over a period of 120 minutes, while maintaining the pH at 11.5 by the simultaneous addition of aqueous sodium hydroxide (50%, 512 g, 6.4 mol) . The reaction mixture was kept for another 16h at 80⁰C and then cooled to room temperature and the pH was adjusted to 9 using aqueous hydrochloric acid (6N).

773 g of the crude reaction mixture was purified by membrane filtration (G5 membrane, General Electric, MW cut off = 500 Da) using a diafiltration factor of 4. This gave purified inulin phosphonate. The inulin phosphonate was further characterised, using ³¹P, ¹³C, and ¹H-NMR, as having a DS of 1.1 This corresponds to a reaction efficiency of 72 %.

V:

A solution of potassium iodide (17.9 g, 108 mmol) in water (183 g) was heated to 80⁰C in 15 minutes. During heating of this solution sucrose (120 g, 0.35 mol.) was added. Then CPIBMPA (304.3 g, 1.08 mol) was slowly added in portions over a period of 120 minutes, while maintaining the pH at 11.5 by the simultaneous addition of aqueous sodium hydroxide (50%, 440 g, 5.5 mol.) . The reaction mixture was kept for another 16h at 80⁰C, cooled to room temperature and the pH was adjusted to 9 using aqueous hydrochloric acid (6N) . The degree of substitution of the sucrose phosphonate in the crude reaction mixture was determined using ³¹P, ¹³C and ¹H-NMR as 2.1 (per sucrose molecule) which corresponds with a reaction efficiency of 68 %.

VI:

A solution of potassium iodide (20.6 g, 124 mmol) in water (97 g) was heated to 80⁰C. During heating of this solution inulin (70 g, 0.41 mol, average DP = 25) was added. Then CPIBMPA (361 g, 1.24 mol) was slowly added in portions over a period of 120 minutes, while maintaining the pH at 11.5 by the simultaneous addition of aqueous sodium hydroxide (50%, 500 g, 6.25 mol). The reaction mixture was kept for another 16h at 80⁰C and then cooled to room temperature and the pH was adjusted to 9 using aqueous hydrochloric acid (6N). The crude reaction mixture was purified by membrane filtration in the manner described in example III to give a purified inulin phosphonate, which was characterised using ³¹P, ¹³C and ¹H-NMR. The DS amounted to 1.52 which corresponds to a reaction efficiency of 50%.

VII:

A solution of potassium iodide (16.6 g, 0.1 mol) in water (154 g) was heated to 80⁰C. During heating of this solution sorbitol (106 g, 0.58 mol) was added. Then CPIBMPA (281 g, 1.00 mol) was slowly added in portions over a period of 120 minutes, while maintaining the pH at 11.5 by the simultaneous addition of aqueous sodium hydroxide (50%, 408 g, 5.1 mol). The reaction mixture was kept for another 16h at 80⁰C and then cooled to room temperature and the pH was adjusted to 9 using aqueous hydrochloric acid (6N) . The DS of the sorbitol phosphonate was determined using ³¹P, ¹³C and ¹H-NMR as 1.1 which corresponds to a reaction efficiency of 64%. VI I I :

A solution of potassium iodide (8.8g; 53 mmol.) was heated to 80 °C. During the heating of this solution, maltodextrin (64.2g; 0.35 mol; Passelli Excel™, DE = 2.6) was added. Then CPIBMPA (155.2g; 0.534 mol.) was slowly added in portions over a period of 120 minutes, while maintaining the pH at 11.5 by the simultaneous addition of aqueous sodium hydroxide (50 %; 216g; 2.7 mol.) . The reaction mixture was kept for another 16 hours at 80 ⁰C and then cooled to room temperature and the pH was adjusted to 9 using aqueous hydrochloric acid (6 N) . The DS of the crude reaction mixture was determined using ³¹P, ¹³C and ¹H-NMR as 0.8, which corresponds to a reaction efficiency of 53%.

IX:

A solution of 3-chloropropylphosphonic acid (3-CPPA 111 g, 0.70 mol) in water (207 g) is heated to 70⁰C and neutralised with 50% aqueous sodium hydroxide (115 g) . Then inulin (150 g, 0.93 mol, average DP = 25) and potassium iodide (6 g, 36 mmol) is added. The reaction mixture is heated to 80⁰C and the pH adjusted to and maintained at 12 using aqueous sodium hydroxide. The reaction mixture is heated for another 6-7 h at 80 ⁰C and then cooled to room temperature and the pH is adjusted to 9 using aqueous hydrochloric acid (6N) . The crude reaction mixture is purified by membrane filtration (G5 membrane, General Electric, MW cut off = 500 Dalton (Da) ) using a diafiltration factor of 6. The DS of the purified 3- phosphono propyl inulin phosphonate is determined using ³¹P, ¹³C, and ¹H-NMR as 0.55, which corresponds to a reaction efficiency of 73%. X :

A solution of potassium iodide (20 g, 120 mmol) in water (100 g) is heated to 80⁰C. During heating of this solution inulin (70 g, 0.41 mol, average DP = 25) is added. Then 3-CPPA (200 g, 1.27 mol) is slowly added in portions over a period of 2 h, while maintaining the pH at 11.5 by the simultaneous addition of 50% aqueous sodium hydroxide. The reaction mixture is kept for another 16h at 80⁰C and then cooled to room temperature and the pH is adjusted to 9 using aqueous hydrochloric acid

(6N) . The crude reaction mixture is purified by membrane filtration in the manner described in Example IX to give a purified 3-phosphonopropyl inulin, which is characterised using ³¹P, ¹³C and ¹H-NMR. The DS amounts to 1.6 which corresponds to a reaction efficiency of 52%.

XI:

A solution of potassium iodide (18 g, 108 mmol) in water (200 g) is heated to 80⁰C in 15 minutes. During heating of this solution sucrose (120 g, 0.35 mol) is added. Then 3-CPPA (174 g, 1.1 mol) is slowly added in portions over a period of 2 h, while maintaining the pH at 12 by the simultaneous addition of aqueous sodium hydroxide. The reaction mixture is kept for another 16h at 80⁰C, cooled to room temperature and the pH is adjusted to 9 using aqueous hydrochloric acid (6N) . The degree of substitution of the 3-phosphono propyl sucrose in the crude reaction mixture is determined using ³¹P, ¹³C and ¹H-NMR as 2.2

(per sucrose molecule) which corresponds to a reaction efficiency of 70 %.

XII:

A solution of potassium iodide (16.6 g, 0.1 mol) in water (154 g) is heated to 80⁰C. During heating of this solution sorbitol (106 g, 0.58 mol) is added. Then CPPA (158 g, 1.00 mol) is slowly added in portions over a period of 2h, while maintaining the pH at 12 by the simultaneous addition of aqueous sodium hydroxide. The reaction mixture is kept for another 16h at 80⁰C and then cooled to room temperature and the pH is adjusted to 9 using aqueous hydrochloric acid (6N) . The DS of the 3-phosphonopropyl sorbitol is determined using ³¹P, ¹³C and ¹H-NMR as 1.0, which corresponds to a reaction efficiency of 58%.

In more detail, the essential phosphonate compound herein can be neutralized, depending upon the degree of alkalinity/acidity required by means of conventional agents including alkali hydroxides, earth alkali hydroxides, ammonia and/or amines. Beneficial amines can be represented by alkyl, dialkyl and tri alkyl amines having e.g. from 1 to 20 carbon atoms in the alkyl group, said groups being in straight and/or branched configuration. Alkanol amines such as ethanol amines, di- and tri-ethanol amines can constitute one preferred class of neutralizing agents. Cyclic alkyl amines, such as cyclohexyl amine and morpholine, polyamines such as 1,2- ethylene diamine, polyethylene imine and polyalkoxy mono- and poly-amines can also be used.

The treatment compositions can be used, in a conventional manner, for application in relation to all kind of surfaces. The like applications can be represented by: textile laundry; textile and industrial textile treatments, such as softening, bleaching and finishing; hard surface treatment; dishwasher use; glass and other applications well known in the domain of the technology.

The treatment compositions comprise, as a major constituent a binary active system, expressed in relation to the sum (100 %) of the actives in said binary system, from 99.9% to 40% of a surface active agent and from 0.1% to 60% of a selected amino alkylene phosphonic acid. The treatment, preferably and particularly, cleaning compositions of this invention frequently contain surfactant ingredients in the range of from 2 to 50 %, more preferably of from 3 to 40 %. The sugar phosphonate ingredient herein can be used, in the actual treatment compositions, in sub additive levels in the range of from 0.001 to 4 %, preferably from 0.01 to 2 %. The phosphonate exhibits, within the context of the actual treatment composition, conventional phosphonate functionalities such as chelant, sequestrant, threshold scale inhibition, dispersant and oxygen bleach analogous properties, but, in addition, can provide, in part due to structural particularities of the essential phosphonate ingredient, additional synergistic functionalities in relation to e.g. optional ingredients, such as aesthetics e.g. perfumes, optical brighteners, dyes, and catalytic enhancers for enzymes, and also to provide improved storage stability to e.g. bactericides thus allow a reformulation of the composition without adversely affecting performance objectives. The essential phosphonate constituent, very importantly, can greatly facilitate the environmental and regulatory acceptability of the treatment compositions herein.

The treatment compositions can also comprise conventional additives and optional components which are used in art established levels and for their known functionalities. The surface active agents herein can be represented by conventional species selected from e.g. cationic, anionic, non-ionic, ampholytic and zwitterionic surfactants and mixtures thereof. The cleaning compositions can also comprise conventional additives and optional components which are used in art established levels and for their known functionalities. The surface active agents herein can be represented by conventional species selected from e.g. cationic, anionic, non-ionic, ampholytic and zwitterionic surfactants and mixtures thereof. Typical examples of the like conventional detergent components are recited. Useful surfactants include Cii-20 alkyl benzene sulfonates, Cio-20 alkyl sulfates, C12-20 alkyl alkoxy sulfates containing e.g. 1-6 ethoxy groups and Cio-20 soaps. Suitable non-ionic surfactants can also be represented by amine oxides having the formula R,R',R''N→O wherein R, R' and R'' can be alkyl having from 10 to 18 carbon atoms. Cationic surfactants include quaternary ammonium surfactants such as Cε-iβ N-alkyl or alkenyl ammonium surfactants .

Treatment compositions for the above-mentioned purposes are well known and have found commercial application for a long time. The ingredients of such compositions are eminently well known, including quantitative and qualitative parameters. We wish to exemplify, in a summary manner, some of the matrixes of treatment compositions to which the essential phosphonate ingredient can be added. Solid machine dishwashing composition containing a surfactant selected from cationic, anionic, non- ionic ampholytic and zwitterionic species and mixtures thereof in a level of from 2 to 40 %, a builder broadly in a level of from 5 to 60 %. Suitable builder species include water-soluble salts of polyphosphates, silicates, carbonates, polycarboxylates e.g. citrates, and sulfates and mixtures thereof and also water-insoluble species such as zeolite type builders. The dishwashing composition can also include a peroxybleach and an activator therefore such as TAED (tetra acetyl ethylene diamine) . Conventional additives and optional components including enzymes, proteases and/or lipases and/or amylases, suds regulators, suds suppressors, perfumes, optical brighteners, and possibly coating agents for selected individual ingredients. Such additives and optional ingredients are generally used for their established functionality in art established levels.

The various types of treatment compositions are well known and have found widespread commercial application. Specific examples of individual treatment compositions are recited below.

Heavy Duty Liquid Laundry Detergent .

Parts by weight.

Cio-22 fatty acids 10

Nonionic surfactant 10

Anionic surfactant 15

Potassium hydroxide (50%) 3

1, 2-Propanediol 5

Sodium citrate 5

Ethanol 5

Enzymes 0.2-2

Phosphonate 1-3

Minors and water balance to 100

Laundry Detergent Powder

Parts by weight.

Zeolite builder 25

Nonionic surfactant 10

Anionic surfactant 10

Calcium carbonate 10

Sodium meta silicate 3

Sodium percarbonate 15

TAED 3

Optical brightener 0.2

Polyvinyl pyrrolidone 1

Carboxymethyl cellulose 2 Acrylic copolymer 2 Enzymes 0.2-2 Perfumes 0.2-0.4 Phosphonates 0.1-2 Sodium sulphate balance to 100

Fabric softener.

Parts by weight.

Phosphoric acid 1 Distearyl dimethyl ammonium chloride 10-20

Stearyl amine ethoxylate 1-3

Magnesium chloride (10%) 3

Perfume; dye 0.5

Phosphonate 0.1-2 Water balance to 100

Automatic dishwashing powder.

Parts by weight.

Sodium tripolyphosphate 40

Nonionic surfactant (low foaming) 3-10

Sodium carbonate 10

Sodium metasilicate 3

Sodium percarbonate 15

TAED 5

Acrylic copolymer 2

Zinc sulphate 0.1-2

Enzymes 0.2-2

Phosphonate 0.1-2

Sodium sulphate balance to 100

Hard surface cleaner (Industrial)

Parts by weight.

Sodium hydroxide (50%) 40

Low foaming non-ionic surfactant 5-20 Sodium carbonate 2-5

Phosphonate o.1-3

Water balance to 100

Multi-surface Kitchen Cleaner

Parts by weight.

Low-foaming non-ionic surfactant 5-10

Phosphoric acid (85 %) 70-40

Isopropanol 2-5

Phosphonate 0.01-1

Water balance to 100

Bottle Washing Composition

Parts by weight

Low-foaming non-ionic surfactant 1-5

Sodium hydroxide (50%) 25-50

Sodium gluconate 1-2

Phosphonate 0.1-1

Water balance to 100

In a further aspect of the invention, there is provided the use of a composition as described above for the treatment of surfaces, in particular for textile laundry, textile and industrial textile treatment, such as softening, bleaching and finishing, hard surface treatment specifically cleaning, household and industrial dishwashing applications.

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

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

Examples

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

Clay Dispersion.

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

A one liter 0.15%w/w solution of the selected phosphonate is prepared in tap water. The solution pH is brought to 11.5 by addition of a 50% sodium hydroxide aqueous solution. Kaolin

(Ig) is added and the liquid is agitated, at ambient temperature, until a homogeneous suspension is obtained. The suspension is then introduced in an Imhoff cone. Gradually a 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 aspect and colour 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 which does not contain a phosphonate.

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

This test is used to measure and compare the calcium tolerance of phosphonate compounds. The calcium tolerance is an indirect (qualifying) parameter for using selected phosphonate compounds in the presence of major levels of water hardness e.g. calcium and magnesium.

A solution of the tested product is prepared in 1200ml of water so as to correspond to a 15ppm active acid solution in 1320ml. The solution is heated to 60⁰C and its pH adjusted to 10 by addition of 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. Calcium concentration in the tested solution is gradually increased by increments of 200ppm calcium based on the tested solution. After each calcium addition the pH is adjusted to 10 by addition of a 50% sodium hydroxide solution and turbidity is measured 10 minutes after the calcium addition. A total of 6 calcium solution additions are done .

(*) FTU = Formazin Turbidity Units.

Stain Removal

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

A typical base detergent formulation is prepared by mixing together 12 g of C13-C15 oxo alcohol ethoxylated with 8 moles of ethylene oxide, 10 g of Cs-Cis coco fatty acid, 6 g of triethanolamine, 4 g of 1,2 propanediol, 15 g of C10-C13 linear alkylbenzene sulfonate sodium salt, 3 g of ethanol and 50 g water. The first four ingredients are added in the indicated order and heated at 50⁰C until a uniform liquid is obtained before adding the other ingredients.

The stain removal testing is conducted at 40⁰C in a tergotometer using one litre city water per wash to which are added 5g of the base detergent formulation and lOOppm as active acid of the tested phosphonate. Soil coupons are added to the liquid which is agitated at lOOrpm during 30 minutes. After the washing cycle, the swatches are rinsed with city water and dried in the oven for 20 minutes at 40° C. The whiteness of the swatches is measured with the Elrepho 2000, made by Datacolor of Dietlikon, Switzerland. The equipment is standardized, in a conventional manner, with black and white standards prior to the measurement of the washed swatches. The Rz chromatic value is recorded for each swatch before and after the wash cycle. The percentage stain removal for a specific stain and formulation is calculated as follows:

(Rz_w - Rz₁)

% stain x 100 removal (100 - Rz₁)

with Rz_w = the Rz value for the washed swatch Rz₁ = the Rz value for the unwashed swatch.

Calcium carbonate scale inhibition procedure

These methods are used to compare the relative ability of selected phosphonates to inhibit calcium carbonate scale formation in e.g. laundry applications.

The following solutions are prepared: - pH buffer: A 10 % solution of NH₄Cl in deionized water is adjusted to pH 9.5 with 25 % NH₄OH aqueous solution.

- pH buffer: A 10% solution of NH₄Cl in deionized water is adjusted to pH 10.0 with 25 % NH₄OH aqueous solution. - Inhibitor mother solution 1 : An "as is" 1 % solution of each inhibitor is prepared. These solutions contain 10,000 ppm inhibitor "as is".

- Inhibitor mother solution 2: An "as is" 10% solution of each inhibitor is prepared. These solutions contain 100,000 ppm of inhibitor "as is".

Inhibitor testing solution 1 : Weigh accurately Ig of inhibitor mother solution 1 into a 100ml glass bottle and adjust to lOOg with deionized water. These solutions contain lOOppm of inhibitor "as is". Inhibitor testing solution 2 : Weigh accurately Ig of inhibitor mother solution 2 into a 100ml glass bottle and adjust to lOOg with deionized water. These solutions contain lOOppm of inhibitor "as is".

- 2N sodium hydroxide solution.

The test is carried out as follows:

In a 250 ml glass bottle are placed 75g of 38° French hardness degrees water; appropriate levels of the inhibitor mother or testing solutions corresponding to 0, 5, 10, 20, 50, 200, 500, 1000, 2500 and 5000ppm of "as is" inhibitor and 5ml of the pH 9.5 buffer solution are added. The pH of the mixture is adjusted to 10, 11 or 12 by addition of 2N sodium hydroxide and appropriate amount of deionized water is added to adjust the total liquid weight to lOOg solution.

The bottle is immediately capped and placed in a shaker controlled at 60 ⁰C for 20 hours. After 20 hours the bottles are removed from the shaker and about 50 ml of the hot solution are filtered using a syringe fitted with a 0.45 micron filter. This filtrate is diluted with 80ml of deionized water and stabilized with ImI of the pH 10 buffer solution. Calcium in solution is titrated using a 0.01M EDTA solution and a calcium selective electrode combined with a calomel electrode .

Performance of the inhibitor is calculated as follows:

V₁ - Vo

Scale inhibition V₂ - Vo

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

V₂ is the volume of the EDTA solution needed for 100 % inhibition and is determined by titrating a solution containing 10ml of the inhibitor mother solution 2 diluted with deionized water to 100 g total weight. Vi is the volume of EDTA solution needed for the test sample .

The testing results were as follows. Inulin phosphonate samples used:

35% active acid; DS =0.52; termed IPO.52; 48.3% active acid; DS =1.1; termed IPl.1; 50.9% active acid; DS =1.52; termed IPl.52.

% Stain Removal

Tea Oil Clay Wine stains Stains stains stains

Blank (5 g/1 25.36 42.03 53.08 48 31 HDL)

Blank + 100 ppm 32.19 43.67 52.66 55 79 DTPMPA

Blank + 100 ppm 32.92 44.12 54.10 53 67 IPO.52

Blank + 100 ppm 32.52 43.66 52.81 52 24

2. Calcium carbonate scale inhibition

2.1. pH 10

Scale Inhibition

2.2. pH 11

Scale inhibition

2.3. pH 12

% Scale inhibition

Dosage (ppm) IPO .52 IPl.1 IPl.52

0 0 0 0

5 0.8 3.0 6.1

10 2.0 4.1 5.8

3. Calcium Tolerance

4. Clay Dispersion

Dispersant Time in Minutes % Dispersion

5 15 30 60 120

Blank BP* 20 21 .5 17.5 15 13 0

IPO.54 BP 0.3 0 .65 1 1.25 1.5 88.5

IPl.1 BP 0 0 0 0 0 100 IPl.52 BP 0 0 0 0 0 100 means bottom phase in ml .

Claims

1. A surface-treatment composition comprising a surface- active agent, and optionally further components and additives, characterized in that the treatment composition comprises, a binary active system, expressed in relation to the sum (100 %) of the actives of the components (a) and (b) in said binary system:

(a) of from 99.9 to 40 % by weight of a surface-active agent; and

(b) of from 0.1 to 60 % by weight of a sugar phosphonate

having the formula

T-(B)_a

wherein T is a carbohydrate selected from the group of:

polysaccharides having a molecular weight of up to about 350 kDa, selected from the group of: cellulose; starch; fructan; galactomannan; arabinan; agar; chitosan; arabinogalactan; xylan; alginic acid and derivatives thereof selected from carboxyl; carboxyalkyl with from 1 to 6 carbon atoms in the alkyl chain; C2-C8 linear or branched hydroxylalkyl substituents; with a being from 0.01 to 3 expressed on the basis of the monosaccharide unit in the polysaccharide;

saccharides, which are free of aldehyde and keto groups, with a being from 1 to 11; sugar alcohols with a being from 1 to 9; and

monosaccharides having protected anomeric centers with a being from 1 to 4 ;

B is a phosphonate moiety selected from the group of:

(i) -X-PO₃M₂; and

(ii) -X-N(W) (ZPO₃M₂) ;

wherein X, for each (i) and (ii) , is selected from C₂-C₅O and, in addition Ci for (i) , linear, branched, cyclic or aromatic hydrocarbon moiety, optionally substituted by a Ci-Ci₂ linear, branched, cyclic, or aromatic group, (which moiety and/or which group can be) optionally substituted by OH, COOH, F, OR' , SO₃H and SR' moieties, wherein R' is a Ci-Ci₂ linear, branched, cyclic or aromatic hydrocarbon moiety; and [A-O]_x-A wherein A is a C₂-Cg linear, branched, cyclic or aromatic hydrocarbon moiety and x is an integer from 1 to 200; provided that when the carbohydrate moiety is starch, X is C₃-C₅O with the additional proviso that when X is substituted by OH, the latter moiety can be attached to any carbon atom other than the second carbon atom starting from T;

Z is a Ci-Cε alkylene chain;

M is selected from H, Ci-C₂O linear, branched, cyclic or aromatic hydrocarbon moieties and from alkali, earth alkali and ammonium ions and from protonated amines;

W is selected from H, ZPO₃M₂ and [V-N(K)J_nK, wherein V is selected: a C₂-C₅O linear, branched, cyclic or aromatic hydrocarbon moiety, optionally substituted by Ci-Ci₂ linear, branched, cyclic or aromatic groups, (which moieties and/or groups are) optionally substituted by OH, COOH, F, OR', SO₃H or SR' moieties wherein R' is a C1-C12 linear, branched, cyclic or the carbohydrate is a polysaccharide aromatic hydrocarbon moiety; and from [A-O]_x-A wherein A is a C₂-C₉ linear, branched, cyclic or aromatic hydrocarbon moiety and x is an integer from 1 to 200; and

K is ZPO₃M₂ or H and n is an integer from 0 to 200.

2. The composition in accordance with Claim 1 wherein the carbohydrate is a polysaccharide selected from cellulose, starch and chitosan with the index a being from 0.05 to 2.

3. The composition in accordance with Claim 1 or 2 wherein the carbohydrate is inulin β-2,1 fructan with the index a being from 0.05 to 2.

4. The composition in accordance with Claim 1 wherein the carbohydrate is selected from sorbitol with the index a being from 1 to 6, anhydro-sorbitol with a being from 1 to 4, iso-sorbide with the index a being from 1 to 2, mannitol with the index a being from 1 to 6, erythritol with the index a being from 1 to 4, xylitol with the index a being from 1 to 5, lactitol with the index a being from 1 to 9, isomalt with the index a being from 1 to 9 and mixtures of said sorbitol and said mannitol in ponderal ratios (sorbitol/mannitol) of from 5 : 1 to 1 : 5.

5. The composition in accordance with Claim 1 wherein the carbohydrate is represented by a non-reducing sucrose with the index a being from 1 to 8.

6. The composition in accordance with any one of Claims 1 to 5, wherein the surface-active agent is selected from cationic, anionic, non-ionic, ampholytic and zwitterionic surfactants and mixtures thereof.

7. The composition according to Claim 6, where the surface active agent comprises a compound selected from Cn-20 alkyl benzene sulfonates, Cio-20 alkyl sulfates, C12-20 alkyl alkoxy sulfates containing e.g. 1-6 ethoxy groups and Cio-20 soaps, amine oxides having the formula R, R', R'', N->0 wherein R, R' and R' ' are alkyl having from 10 to 18 carbon atoms, and Cε-iβ N-alkyl or alkenyl ammonium compounds.

8. The composition in accordance with any one of Claims 1 to 7 wherein the surface-active agent represents from 2 to

50 % by weight (based on the total composition) .

9. The composition in accordance with any one of Claims 1 to 8 wherein the surface-active agent represents from 3 to 40 % by weight (based on the total composition) and the sugar phosphonate represents from 0.001 to 4 % by weight (based on the total composition) .

10. The use of a composition according to any one of Claims 1 to 9 for surface treatment.

11. The use according to Claim 10 in textile laundry, textile and industrial textile treatment, hard surface treatment, house- and industrial dishwashing applications.

12. A method for treating a surface comprising the step of applying a composition according to any one of Claims 1 to 9.