WO2020011764A1

WO2020011764A1 - Antiscalant composition comprising a uronic acid polysaccharide

Info

Publication number: WO2020011764A1
Application number: PCT/EP2019/068356
Authority: WO
Inventors: Henricus Wilhelmus Carolina Raaijmakers; Jacobus Petrus Maria Bink; Tom Brooijmans; Robbert De Boer; Khalid Mahmud; René Mol
Original assignee: Koninklijke Coöperatie Cosun U.A.; Dalli-Werke Gmbh & Co. Kg; Coöperatie Koninklijke Cosun U.A.
Priority date: 2018-07-09
Filing date: 2019-07-09
Publication date: 2020-01-16
Also published as: EP3820983A1

Abstract

The invention relates to an anti-scaling composition comprising a combination of a uronic acid containing polyasaccharide (i) and a scaling-inhibiting agent(ii). The uronic acid containing polysaccharide (i) has a solubility in water at a temperature of 25 °C ranging between 1 g/L and 700 g/L and a mass average molecular weight M_w ranging between 1 and 500 kDa. The invention also relates to an automatic dishwashing detergent product comprising such an anti-scaling composition and a surfactant. The invention also relates to an anti-deposition product comprising such an anti-scaling composition and a bleaching agent. The invention further relates to a process for preventing scale-formation in water-using and/or water-processing equipment and to the use of a uronic acid containing polysaccharide (i) for improving the scale-inhibiting performance of a scale-inhibiting agent (ii).

Description

Antisealant composition comprising a uronic acid polysaccharide Field of the invention

The invention relates to an anti-scaling composition comprising a uronic acid polysaccharide in combination with a scale-inhibiting agent. The invention further relates to a dishwashing detergent product and to an anti-deposition product comprising such an anti-scaling composition. Furthermore the invention further relates to a process for preventing scale formation in waterusing and/or water-processing equipment. The invention also relates to the use of uronic acid containing polysaccharide for improving the scale-inhibiting performance of a further scale- inhibiting agent.

Background art

Scale formation is a universal problem encountered in almost every machine or process wherein (tap) water is used. The main cause of scale formation is precipitation of either alkaline earth metal carbonates, phosphates or silicates, for example of calcium carbonate and calcium phosphate. The deposition of scale on surfaces may have several disadvantages, such as reducing equipment performance (e.g. heat exchangers), reducing equipment lifetime, clogging, dirty appearance, et cetera.

Scale formation is for example a well-known problem in dishwashers, wherein scale reduces the efficiency of cleaning and results in an undesirable appearance of the tableware, especially for glass objects. Therefore, dishwasher detergents or additives need to employ anti-scaling measures to ensure a longer service life and to achieve better cleaning performance. These antiscaling measures are often applied in the form of specific dishwasher detergent formulations or additives employing compounds which inhibit scale formation, for example by interfering with crystal growth.

The use of phosphonates to inhibit scale formation is known. However most phosphonates exhibit reduced performance at low temperatures and elevated pH. The current trend for machines, such as dishwashers or washing machines, to operate at reduced temperatures in order to improve energy-efficiency highlights the need for improved anti-sealant compositions. Additionally, at harsh conditions (such as high hardness, pH or temperature), phosphonates are known to precipitate as calcium salts or co-precipitate with other salts, thus causing undesirable deposit formation.

Hasson et al. (Ind. Eng. Chem. Res. 50, 12, 7601-7607) describe poly(aspartic acid) as environmentally benign scale inhibitors.

Amjad et al. (“The use of polymers to improve control of calcium carbonate scaling in high stressed cooling water systems”, The Analyst, 13, 1 ,) describe poly(maleic acid) and poly(acrylic acid) as scale inhibitors and their use to increase phosphonate tolerance to calcium. There still exists a need for improved anti-scaling compositions.

It is an object of the present invention to provide an improved anti-scaling composition.

It is another object of the present invention to provide an anti-scaling composition that is efficient in a wide pH range and temperature range and/or has a reduced environmental impact.

It is another object of the present invention to provide an improved anti-scaling composition suitable for automatic dishwashing detergent products and anti-deposition products.

It is another object of the present invention to provide a process for preventing scale formation in water-using and/or water-processing equipment.

Summary of the invention

The present inventors have surprisingly found that combinations of a uronic acid containing polysaccharide and a scale inhibiting agent provide improved scale-inhibiting properties, such as increased Ca-tolerance.

In a first aspect the present invention provides an anti-scaling composition comprising a combination of the following two distinct components:

(i) a uronic acid containing polysaccharide; and

(ii) a scale inhibiting agent.

The uronic acid containing polysaccharide (i) preferably is a pectin or a pectin derived polysaccharide.

In a second aspect the present invention provides a ready-to-use product, such as a dishwashing detergent product, an anti-deposition product, a laundry detergent product, an industrial surface cleaning product or a household surface cleaning product, comprising the anti-scaling composition of the present invention. In preferred embodiments, the ready-to-use product further comprises a surfactant or a bleaching agent. In preferred embodiments the ready-to-use product of the present invention is a dishwashing detergent product, preferably an automatic dishwashing detergent product. In highly preferred embodiments the ready-to-use product of the present invention is a dishwashing detergent product comprising a surfactant. In other preferred embodiments the ready-to-use product of the present invention is an anti-deposition product. In highly preferred embodiments the ready-to-use product of the present invention is an antideposition product comprising a bleaching agent.

In a third aspect the present invention provides a process for preventing scale formation in waterusing and/or water-processing equipment wherein the process comprises the step of adding the anti-scaling composition in accordance with the invention to the water that is used or processed in said equipment.

In a fourth aspect the present invention provides the use of an uronic acid containing polysaccharide (i) for improving the scale-inhibiting performance of a scale-inhibiting agent (ii). Description of embodiments

A first aspect of the present invention relates to an anti-scaling composition comprising a combination of the following two distinct components:

(i) a uronic acid containing polysaccharide; and

(ii) a scale inhibiting agent.

Polysaccharides are polymers composed of one or more types of monosaccharide units joined by glycosidic bonds. Uronic acid containing polysaccharides are polysaccharides wherein the polymer chain comprises uronic acid residues.

Uronic acids are a class of sugar acids with both carbonyl and carboxylic acid functional groups. Uronic acids comprise sugars in which the terminal carbon's hydroxyl group has been oxidized to a carboxylic acid. The names of uronic acids are generally based on their parent sugars, for example, the uronic acid analog of glucose is glucuronic acid. Uronic acids derived from hexoses are known as hexuronic acids and uronic acids derived from pentoses are known as penturonic acids.

The uronic acid containing polysaccharide of the anti-scaling composition according to the present invention has a solubility at a temperature of 25°C ranging between 1 g and 700 g/L and has a mass average molecular weight ranging between 1 and 500 kDa.

“Solubility” is defined as the maximum amount (by weight) of a substance that will dissolve in a unit of volume of water at a certain temperature. The solubility of the uronic acid containing polysaccharide of the present anti-sealant composition in water at a temperature of 25 °C is preferably between 10 and 700 g/L, preferably between 100 and 600 g/L. In embodiments, the solubility of the uronic acid containing polysaccharide is higher than 100 g/L, preferably higher than 200g/L, for example higher than 250 g/L.

Unless specified otherwise,“molecular weight” refers to the mass average molecular weight defined by the following formula

With M, : the molecular weight of a chain

Ni: the number of chains of that molecular weight.

The mass average molecular weight M_w of the uronic acid containing polysaccharide of the present anti-scaling composition is preferably in the range of 1-500 kDa, preferably in the range of 1.2-400 kDa, preferably in the range of 1.5-300 kDa, preferably in the range of 1.7-200 kDa, preferably in the range of 1.85-100 kDa, most preferably in the range of 2-50 kDa. In a preferred embodiment, the molecular weight of the individual uronic acid containing polysaccharides (‘Mi’) in the present anti-scaling composition is between 0.01 and 1000 kDa, more preferably between 0.1 and 750 kDa, even more preferably between 1 and 500 kDa.

As will be appreciated by those skilled in the art, a mixture of uronic acid containing polysaccharides having different chain lengths can be subjected to membrane filtration, such as for example ultrafiltration, resulting in a permeate and a retentate, wherein the filtrate and the retentate comprise fractions of uronic acid containing polysaccharides having different chain lengths. Accordingly, in an embodiment, the molecular weight of the individual uronic acid containing polysaccharides in the present anti-scaling composition is between 10 and 1000 kDa, such as between 10 and 750 kDa or between 10 and 500 kDa. In another embodiment, the molecular weight of the individual uronic acid containing polysaccharides in the present antiscaling composition is between 25 and 1000 kDa, such as between 25 and 750 kDa or between 25 and 500 kDa. In still another embodiment, the molecular weight of the individual uronic acid containing polysaccharides in the present anti-scaling composition is between 0.01 and 40 kDa, such as between 0.1 and 40 kDa or between 1 and 40 kDa. In yet another embodiment, the molecular weight of the individual uronic acid containing polysaccharides in the present antiscaling composition is between 0.01 and 80 kDa, such as between 0.1 and 80 kDa or between 1 and 80 kDa.

A preferred method to determine the molecular weight distribution and the mass average molecular weight as used herein is by size exclusion chromatography (such as HPSEC) preferably coupled to an UV-Vis detector. In embodiments the UV-Vis detector operates at 260, 280 and 310 nm. In embodiments, the molecular weight distribution is determined after a suitable sample preparation, for example by preparing samples having a concentration of about 5-10 mg polysaccharide per liter in 0.2M sodium nitrate, centrifuging the samples for about 10 minutes and analysing the supernatant.

Preferably, the uronic acid containing polysaccharide (i) contains at least 50 % of uronic acid monosaccharide units, based on the total number of monosaccharide units. More preferably, the uronic acid containing polysaccharide (i) contains at least 60 %, at least 70 % or at least 80 % of uronic acid monosaccharide units, based on the total number of monosaccharide units. A preferred method of determining the carbohydrate composition is by hydrolysis according to Seaman et al. ( Saeman , Moore, Mitchell & Millett, (1954) Techniques for the determination of pulp constituents by quantitative paper chromatography. Tappi, 37(8), 336-343) followed by a suitable analysis method, for example ion chomatography HPLC.

Preferred anti-scaling compositions comprise a galacturonic acid containing polysaccharide.

In preferred embodiments the galacturonic acid containing polysaccharide (i) contains at least 50 % of galacturonic acid monosaccharide units, based on the total number of monosaccharide units. More preferably, the galacturonic acid containing polysaccharide (i) contains at least 60 %, at least 70 % or at least 80 % of galacturonic acid monosaccharide based on the total number of monosaccharide units.

Preferred uronic acid containing polysaccharides are pectin or pectin derived polysaccharides. Thus in a preferred embodiment, an anti-scaling composition comprising a combination of the following two distinct components:

(i) a uronic acid containing polysaccharide; and (ii) a scale inhibiting agent,

wherein the uronic acid containing polysaccharide (i) is pectin or a pectin derived polysaccharide, is provided.

In a very preferred embodiment, an anti-scaling composition comprising a combination of the following two distinct components:

(iii) a uronic acid containing polysaccharide; and

(iv) a scale inhibiting agent,

wherein the uronic acid containing polysaccharide has a solubility in water at a temperature of 25 °C ranging between 1 g/L and 700 g/L and a mass average molecular weight M_w ranging between 1 and 500 kDa, and wherein the uronic acid containing polysaccharide (i) is pectin or a pectin derived polysaccharide, is provided.

Materials may accordingly be utilized that, at present, are still mainly considered by-products in various industries. In preferred embodiments of the invention, the pectin rich biomass is sugar beet pulp, which constitutes the production side stream from the sugar beet industry.

The term "pectin" as used herein refers to a class of plant cell-wall heterogeneous polysaccharides that can be extracted by treatment with acids and chelating agents. Typically, 70-80% of pectin is found as a linear chain of o(1-4)-linked D-galacturonic acid monomers. Rhamnogalacturonan I pectins (RG-I) (<30%) are comprised of alternating (1-4)-linked galacturonic acid and (1-2)-linked L-rhamnose, with substantial arabinogalactan branching emanating from the L-rhamnose residue. Other monosaccharides, such as D-fucose, D-xylose, apiose, aceric acid, Kdo, Dha, 2-O-methyl-D-fucose, and 2-O-methyl-D-xylose, are found either in the Rhamnogalacturonan II pectins (RG-II) pectin fraction (<2%), or as minor constituents in the RG-I fraction.

Suitable pectins according to the invention include extracted, isolated and/or purified pectins and derivatives thereof. Preferred pectins are naturally occurring pectins obtainable from plant material, particularly preferably from residual plant material like pomace, fibers, waste, peel, skin, pulp.

Pectins are for example obtainable from the following fruits, vegetables and crops: sugar beet, chicory/chicory root, sunflower, rapeseed/ rapeseed cake, carrot, citrus peel/citrus fruit including lemon, lime, orange, grapefruit; and non-citrus fruit including for example apple, pear, apricot, guave, mango, plum, grapes, peach, quince, papaya, banana, pineapple, passion fruit and coffee berry without being limited to the mentioned. Preferred pectins are obtainable from sugar beet.

In a preferred embodiment, the pectin is naturally occurring pectin from or obtainable from the following fruits, vegetables and crops: sugar beet, chicory/chicory root, sunflower, rapeseed/ rapeseed cake, carrot, citrus peel/citrus fruit including lemon, lime, orange, grapefruit; and noncitrus fruit including for example apple, pear, apricot, guave, mango, plum, grapes, peach, quince, papaya, banana, pineapple, passion fruit and coffee berry without being limited to the mentioned. Preferred naturally occurring pectins are from or obtainable from sugar beet. In a preferred embodiment, the pectin is naturally occurring pectin from sugar beet, chicory/chicory root, sunflower, rapeseed/rapeseed cake, carrot, citrus peel/citrus fruit, preferably sugar beet, or the pectin derived polysaccharide is derived from naturally occurring pectin from sugar beet, chicory/chicory root, sunflower, rapeseed/rapeseed cake, carrot, citrus peel/citrus fruit, preferably sugar beet.

The pectin derived polysaccharide may be a hydrolysed pectin. Hydrolysis can be used to decrease the molecular weight of the pectin. As will be appreciated by those skilled in the art, hydrolysis as used herein refers to partial hydrolysis of the naturally occurring pectin, unless specified otherwise. In preferred embodiments there is thus provided an anti-scaling composition in accordance with the invention wherein the uronic acid containing polysaccharide is a pectin derived polysaccharide obtainable through hydrolysis, preferably enzymatic hydrolysis of pectin. In another preferred embodiment there is provided an anti-scaling composition in accordance with the invention wherein the pectin derived polysaccharide is a pectin derived polysaccharide obtainable through partial hydrolysis, preferably enzymatic hydrolysis, of naturally occurring pectin. In still another preferred embodiment there is provided an anti-scaling composition in accordance with the invention wherein the pectin derived polysaccharide is a partially hydrolysed naturally occurring pectin. In embodiments, the enzymatic hydrolysis employs endo- polygalacturonase, preferably endo-polygalacturonase obtainable from Aspergillus niger, such as the polygalacturonase M2 enzyme from Aspergillus niger.

The pectin derived polysaccharide may be chemically or enzymatically derivatized. In embodiments there is thus provided an anti-scaling composition in accordance with the invention wherein the uronic acid containing polysaccharide is a pectin derived polysaccharide obtainable through chemical or enzymatic derivatization of pectin.

The pectin or pectin derived polysaccharide may be a partially methylated pectin or pectin derived polysaccharide. The methylation may be present naturally or may have been introduced, increased or decreased after obtaining the pectin from a natural source. Decreasing the degree of methylation is referred to as demethylation. In a preferred embodiment there is provided an anti-scaling composition in accordance with the invention wherein the pectin derived polysaccharide is a pectin derived polysaccharide obtainable through partial methylation or demethylation of pectin, preferably of naturally occurring pectin. In still another preferred embodiment there is provided an anti-scaling composition in accordance with the invention wherein the pectin derived polysaccharide is partially methylated or demethylated pectin, preferably partially methylated or demethylated naturally occurring pectin. Methylation or demethylation may also be performed on pectin that has been obtained by partial hydrolysis of pectin, such as partial hydrolysis of naturally occurring pectin. For example, methylation may be introduced or increased through an esterification reaction with methanol or decreased through the use of a methyl esterase or through alkaline saponification. It has been found that improved scale inhibition properties (e.g. Ca-tolerance) of the anti-scaling composition in accordance with the present invention are associated with a low degree of methylation. Thus, in embodiments there is provided an anti-scaling composition in accordance with the invention wherein the uronic acid containing polysaccharide is a pectin or pectin derived polysaccharide wherein the degree of methylation is 0.1-90%, preferably 1-50%, preferably 1-10%. In preferred embodiments, the percentage of carboxyl groups esterified with methanol is lower than 20%, preferably lower than 10%, preferably lower than 1 %, preferably lower than 0.1 %. In very preferred embodiments, the degree of methylation of the pectin, such as the naturally occurring pectin, or the pectin derived polysaccharide, is between 1 and 62%, preferably between 1 and 50%, more preferably between 1 and 40%, still more preferably between 1 and 30%, yet more preferably between 1 and 20%. As used herein, the“degree of methylation” refers to the proportion of methyl esters in the pectin or pectin derived polysaccharide sample in comparison to the total number of uronic acid residues, expressed as %. In embodiments there is provided an anti-scaling composition in accordance with the invention wherein the uronic acid containing polysaccharide is a pectin derived polysaccharide obtainable through enzymatic demethylation of pectin. In embodiments, the enzymatic demethylation employs a methyl esterase, preferably pectin methyl esterase.

The degree of methylation (methyl esterification) of uronic acid containing polysaccharide, preferably pectin or pectin derived polysaccharide, as used herein can be determined by saponification with sodium hydroxide in isopropanol/water mixtures followed by high performance liquid chromatography (HPLC). The degree of methylation is then calculated as moles of methanol per 100 moles of uronic acid residues.

The pectin or pectin derived polysaccharide may be a partially acetylated pectin or pectin derived polysaccharide. The acetylation may be present naturally or may have been introduced, increased or decreased after obtaining the pectin from a natural source. Decreasing the degree of acetylation is referred to as deacetylation. In a preferred embodiment there is provided an antiscaling composition in accordance with the invention wherein the pectin derived polysaccharide is a pectin derived polysaccharide obtainable through partial acetylation or deacetylation of pectin, preferably of naturally occurring pectin. In still another preferred embodiment there is provided an anti-scaling composition in accordance with the invention wherein the pectin derived polysaccharide is partially acetylated or deacetylated pectin, preferably partially acetylated or deacetylated naturally occurring pectin. Acetylation or deacetylation may also be performed on pectin that has been obtained by partial hydrolysis of pectin, such as partial hydrolysis of naturally occurring pectin. For example, acetylation may be introduced or increased through an esterification reaction with acetic acid anhydride, or decreased through the use of an acetyl esterase or through alkaline saponification. Thus, in embodiments there is provided an antiscaling composition in accordance with the invention wherein the uronic acid containing polysaccharide is a pectin or pectin derived polysaccharide that is partially acetylated. As used herein, the“degree of acetylation” refers to the proportion of acetyl esters in the pectin or pectin derived polysaccharide sample in comparison to the total number of uronic acid residues, expressed as %. In embodiments there is provided an anti-scaling composition in accordance with the invention wherein the uronic acid containing polysaccharide is a pectin derived polysaccharide obtainable through acetylation of pectin. In embodiments, the acetylation employs a chemical acetylating agent, such as acetic acid anhydride.

The degree of acetylation of uronic acid containing polysaccharide, preferably pectin or pectin derived polysaccharide, as used herein can be determined by saponification with sodium hydroxide in isopropanol/water mixtures followed by high performance liquid chromatography (HPLC). The degree of acetylation is then calculated as moles of acetic acid per 100 moles of uronic acid residues.

The uronic acid containing polysaccharide may be a partially amidated pectin or pectin derived polysaccharide. The amidation may have been introduced after obtaining the pectin from a natural source. In a preferred embodiment there is provided an anti-scaling composition in accordance with the invention wherein the pectin derived polysaccharide is a pectin derived polysaccharide obtainable through partial amidation of pectin, preferably of naturally occurring pectin. In still another preferred embodiment there is provided an anti-scaling composition in accordance with the invention wherein the pectin derived polysaccharide is partially amidated pectin, preferably partially amidated naturally occurring pectin. Amidation may also be performed on pectin that has been obtained by partial hydrolysis of pectin, such as partial hydrolysis of naturally occurring pectin. For example, amidation may be introduced through ammonia processing in the case of primary amides. Thus, in embodiments there is provided an anti-scaling composition in accordance with the invention wherein the uronic acid containing polysaccharide is a pectin or pectin derived polysaccharide wherein the degree of amidation is 0.1-90%, preferably 1-50%, preferably 1-10%. In preferred embodiments, the percentage of carboxyl groups which have been converted to amide groups is lower than 30%, preferably lower than 20%, preferably lower than 10%. As used herein, the“degree of amidation” refers to the proportion of amide in the pectin or pectin derived polysaccharide sample in comparison to the total number of uronic acid residues, expressed as %.

Accordingly, in a preferred embodiment, the pectin derived polysaccharide is a partially hydrolysed pectin, preferably a partially hydrolysed naturally occurring pectin, a partially methylated or demethylated pectin, preferably a partially methylated or demethylated naturally occurring pectin, a partially acetylated or deacetylated pectin, preferably a partially acetylated or deacetylated naturally occurring pectin, or a partially amidated pectin, preferably a partially amidated naturally occurring pectin. In another preferred embodiment, the pectin derived polysaccharide is a partially hydrolysed pectin, preferably a partially hydrolysed naturally occurring pectin, a partially methylated or demethylated pectin, preferably a partially methylated or demethylated naturally occurring pectin, a partially acetylated or deacetylated pectin, preferably a partially acetylated or deacetylated naturally occurring pectin, a partially amidated pectin, preferably a partially amidated naturally occurring pectin, or combinations thereof. In still another preferred embodiment, the pectin derived polysaccharide is a pectin derived polysaccharide obtainable through partial hydrolysis of pectin, preferably of naturally occurring pectin, obtainable through partial methylation or demethylation of pectin, preferably of naturally occurring pectin, obtainable through partial acetylation or deacetylation of pectin, preferably of naturally occurring pectin, or obtainable through partial amidation of pectin, preferably of naturally occurring pectin. In yet another preferred embodiment, the pectin derived polysaccharide is a pectin derived polysaccharide obtainable through partial hydrolysis of pectin, preferably of naturally occurring pectin, obtainable through partial methylation or demethylation of pectin, preferably of naturally occurring pectin, obtainable through partial acetylation or deacetylation of pectin, preferably of naturally occurring pectin, obtainable through partial amidation of pectin, preferably of naturally occurring pectin, or combinations thereof.

In a very preferred embodiment, the pectin derived polysaccharide is a partially hydrolysed pectin, preferably a partially hydrolysed naturally occurring pectin, a partially methylated or demethylated pectin, preferably a partially methylated or demethylated naturally occurring pectin, or combinations thereof. In another very preferred embodiment, the pectin derived polysaccharide is a pectin derived polysaccharide obtainable through partial hydrolysis of pectin, preferably of naturally occurring pectin, obtainable through partial methylation or demethylation of pectin, preferably of naturally occurring pectin, or combinations thereof.

In embodiments, the pectin or pectin derived polysaccharide has a degree of methylation of 0.1- 90% and a degree of amidation of 0.1-90%, more preferably a degree of methylation of 0.1-50% and a degree of amidation of 0.1-50%, more preferably a degree of methylation of 0.1-10% and a degree of amidation of 0.1-10%.

A preferred method to determine the degree of acetylation and methylation is by incubating the uronic acid containing polysaccharide, preferably a pectin or pectin derived polysaccharide, in a basic solution, preferably a sodium hydroxide solution, centrifuging the resulting mixture and analysing the supernatant by a suitable analysis method. In embodiments the analysis of the supernatant is done by liquid chromatography (such as HPLC), preferably coupled to a UV detector, optionally employing an acetic acid/methanol dilution series.

The uronic acid containing polysaccharide may be a desalted pectin or pectin derived polysaccharide. Thus, in embodiments there is provided an anti-scaling composition in accordance with the invention wherein the uronic acid containing polysaccharide is a pectin or pectin derived polysaccharide obtainable by desalting a pectin or pectin derived polysaccharide, preferably by filtration such as ultrafiltration.

In embodiments there is provided an anti-scaling composition in accordance with the invention wherein the uronic acid containing polysaccharide is a pectin derived polysaccharide obtainable by a method comprising the steps of:

a) providing a naturally occuring pectin, preferably a beet pulp pectin, more preferably a sugar beet pectin; b) hydrolyzing the pectin, preferably by contacting the pectin with an endo-polygalacturonase in an aqueous environment, to obtain pectin derived polysaccharide;

c) recovering the pectin derived polysaccharide.

In preferred embodiments, there is provided an anti-scaling composition in accordance with the invention wherein the uronic acid containing polysaccharide is a pectin derived polysaccharide obtainable by the method described herein, wherein step b) comprises contacting the pectin with an endo-polygalacturonase in an aqueous environment at a pH of 1-7, preferably 3-6, preferably 4.5-6, preferably 5-6.

In preferred embodiments, step b) comprises contacting the pectin with an endo- polygalacturonase for at least 1 hour, preferably at least 2 hours, preferably at least 4 hours.

In preferred embodiments, step b) comprises contacting the pectin with an endo- polygalacturonase at a temperature of 25-70°C, preferably 30-60°C, preferably 35-55°C.

In preferred embodiments, step b) further comprises demethylating the pectin or the pectin derived polysaccharide. In embodiments, step b) comprises demethylating the pectin or the pectin derived polysaccharide, preferably by contacting it with a methyl esterase in an aqueous environment.

In preferred embodiments, step b) further comprises demethylating the pectin or the pectin derived polysaccharide by contacting it with a methyl esterase in an aqueous environment at a pH of 1-7, preferably 3-6, preferably 4.5-6, preferably 5-6.

In preferred embodiments, step b) further comprises demethylating the pectin or the pectin derived polysaccharide by contacting it with a methyl esterase for at least 2 hours, preferably at least 4 hours.

In preferred embodiments, step b) further comprises demethylating the pectin or the pectin derived polysaccharide by contacting it with a methyl esterase at a temperature of 25-70 °C, preferably 30-60 °C, preferably 35-55 °C.

In preferred embodiments, step b) further comprises acetylating the pectin or the pectin derived polysaccharide. In embodiments, step b) comprises acetylating the pectin or the pectin derived polysaccharide, preferably by contacting it with an acetylating agent, preferably acetic acid anhydride.

In preferred embodiments, step b) further comprises acetylating the pectin or the pectin derived polysaccharide by contacting it with an acetylating agent in an aqueous environment at a pH of 7-12, preferably 7.5-9, preferably 7.5-8.5.

In highly preferred embodiments, there is provided an anti-scaling composition in accordance with the invention wherein the uronic acid containing polysaccharide is a pectin derived polysaccharide obtainable by the method described herein, wherein step b) comprises demethylating and acetylating the pectin or the pectin derived polysaccharide.

In preferred embodiments, step c) comprises centrifugation. In embodiments step c) comprises centrifugation until a supernatant and solids are formed and collection of the supernatant.

In preferred embodiments, step c) comprises a membrane filtration step wherein the pectin derived polysaccharide is separated into high and low molecular weight fractions, preferably with a 5-25 kDa membrane, a 6-20 kDa membrane, a 8-12 kDa membrane or a 9.5-10.5 kDa membrane. In preferred embodiments step c) comprises a membrane filtration wherein the pectin derived polysaccharide is separated into high and low molecular weight fractions with a 10 kDa membrane. In very preferred embodiments, step c) comprises a membrane filtration wherein the pectin derived polysaccharide is separated into high and low molecular weight fractions with a 25 kDa membrane. In embodiments, step c) comprises a membrane filtration wherein the pectin derived polysaccharide is separated into high and low molecular weight fractions as described herein, and wherein the low molecular weight fraction is recovered. In embodiments, step c) comprises a membrane filtration wherein the pectin derived polysaccharide is separated into high and low molecular weight fractions as described herein, and wherein the high molecular weight fraction is recovered.

In preferred embodiments, step c) comprises a membrane filtration, such as ultrafiltration, wherein the pectin derived polysaccharide is desalted, preferably with a 0.5-1.5 kDa membrane, a 0.8-1.2 kDa membrane or a 0.95-1.05 kDa membrane and wherein the retentate is recovered. In preferred embodiments step c) comprises a membrane filtration wherein the pectin derived polysaccharide is desalted with a 1 kDa membrane and wherein the retentate is recovered.

In preferred embodiments, step c) comprises a membrane filtration wherein the pectin derived polysaccharide is separated into high and low molecular weight fractions and a membrane filtration wherein the pectin derived polysaccharide is desalted.

In preferred embodiments, step c) comprises freeze-drying.

In preferred embodiments, step c) comprises centrifugation until a supernatant and solids are formed and filtration of the supernatant. In other preferred embodiments, step c) comprises centrifugation until a supernatant and solids are formed and freeze-drying of the supernatant. In other preferred embodiments, step c) comprises filtration and freeze-drying of the filtrate. In most preferred embodiments, step c) comprises centrifugation until a supernatant and solids are formed, filtration of the supernatant and freeze-drying of the filtrate.

The scale-inhibiting agent present in the anti-scaling composition may comprise any scale- inhibiting agents known in the art. Preferred scale-inhibiting agents are selected from the group consisting of phosphonates, dicarboxylic acids, tricarboxylic acids and polycarboxylates, either in acid, neutral or partially neutralized form. As will be appreciated by those skilled in the art, the term‘agent’ in‘scale-inhibiting agent’ means that more than one agent can be used as long as the mixture results in scale inhibition. Accordingly, preferred scale-inhibiting agents are selected from the group consisting of phosphonates, dicarboxylic acids, tricarboxylic acids, polycarboxylates, either in acid, neutral or partially neutralized form, and combinations thereof. In a very preferred embodiment, the scale-inhibiting agent (ii) is selected from the group consisting of phosphonates, dicarboxylic acids, tricarboxylic acids, polycarboxylates, polyacrylic homopolymers, polyacrylic/maleic copolymers, and polyacrylic/sulfonic copolymers, either in acid, neutral or partially neutralized form. In another very preferred embodiment, the scale- inhibiting agent (ii) is selected from the group consisting of phosphonates, dicarboxylic acids, tricarboxylic acids, polycarboxylates, polyacrylic homopolymers, polyacrylic/maleic copolymers, polyacrylic/sulfonic copolymers, either in acid, neutral or partially neutralized form, and combinations thereof. In a very preferred embodiment, the scale-inhibiting agent (ii) does not comprise EDTA. In another very preferred embodiment, the anti-scaling composition according to the invention does not comprise EDTA.

Preferred phosphonates comprise aminopolyphosphonates or bisphosphonates.

Preferred aminopolyphosphonates comprise aminotris(methylenephosphonic acid) (ATMP), hydroxyethylamino bis(methylene phosphonic acid) (HEMPA), ethylenediamine tetra(methylene phosphonic acid) (EDTMP), hexamethylenediamine-tetra(methylene phosphonic) acid (HDTMP), polyamino polyether methylene phosphonic acid (PAPEMP), bis(hexamethylene triamine penta(methylenephosphonic acid)) (BHMTMP), DTPMP (diethylenetriamine penta(methylene phosphonic acid) (DTPMP), lysine tetra(methylene phosphonates) (LTMP).

A preferred bisphosphonate is 1-hydroxyethane 1 ,1-diphosphonic acid (HEDP), also known as 1- hydroxyethylidine 1 ,1-diphosphonic acid. In embodiments the scale-inhibiting agent present in the anti-scaling composition comprises HEDP in the acid, neutral or partially neutralized form. In preferred embodiments the scale-inhibiting agent comprises HEDP in a neutral or partially neutralized form, more preferably the scale-inhibiting agent comprises HEDP as an alkali metal salt. In preferred embodiments the scale-inhibiting agent comprises the sodium salt of HEDP, the potassium salt of HEDP or combinations thereof.

Preferred dicarboxylic acid comprises oxalic acid, adipic acid, glutamic acid, succinic acid, either in acid, neutral or partially neutralized form.

Preferred tricarboxylic acids comprise (2-phosphonobutane-1 ,2,4-tricarboxylic acid) (PBTC) and citric acid, either in acid, neutral or partially neutralized form.

Preferred polycarboxylates comprise carboxy methyl inulin (CMI); carboxy methyl cellulose (CMC); polycarboxy succinic acid (PESA); polyaspartic acid (PASA); polyacrylic acid (pAA); acrylic acid / maleic acid copolymer (pAA/MA); acrylic acid / methacrylic acid copolymer (pAA/MAA); acrylic acid / propene copolymer (pAA/propene); acrylic acid / 1 -butene copolymer (pMA/1-butene); acrylic acid / styrene copolymer; acrylic acid / 2-acrylamido-2-methylpropane sulphonic acid copolymer (pAA/AMPS); acrylic acid / maleic acid / methyl metacrylic acid / 2- acrylamido-2-methylpropane sulphonic acid copolymer (pAA/MA/MMA/AMPS); acrylic acid / sulphonated styrene copolymer; maleic acid / sulphonated styrene copolymer; acrylic acid / styrene / 2-acrylamido-2-methylpropane sulphonic acid copolymer; acrylic acid / methallyl sulphonic acid copolymer; maleic acid / methallyl sulphonic acid copolymer and acrylic acid / olefin / 2-acrylamido-2-methylpropane sulphonic acid copolymer.

In embodiments the scale-inhibiting agent comprises polyacrylates, polymaleinates or combinations thereof.

A particularly preferred embodiments, the scale-inhibiting agent present in the anti-scaling composition comprises aminopolycarboxylates, preferably a compound selected from the group of: L-glutamic acid N,N-diacetic acid (GLDA), methylglycinediacetic acid (MGDA), iminodisuccinic acid IDS, ethylenediamine-N,N'-disuccinic acid (EDDS) and combinations thereof.

It has been found that the uronic acid containing polysaccharide (i), preferably pectin or pectin derived polysaccharide, is particularly suitable for improving the scale-inhibiting performance of a scale-inhibiting agent (ii). Thus, in embodiments there is provided an anti-scaling composition in accordance with the invention wherein the scale-inhibiting agent has a low calcium tolerance, for example a scale-inhibiting agent which may be characterized by a calcium tolerance which is 200% of the calcium tolerance of HEDP when tested under identical conditions or lower, preferably 100% of the calcium tolerance of HEDP when tested under identical conditions or lower, preferably 50% of the calcium tolerance of HEDP when tested under identical conditions or lower.

Preferably, the uronic acid containing polysaccharide (i), preferably pectin or pectin derived polysaccharide, and the scale inhibiting agent (ii) are present in a ratio (wt/wt) within the range of 1/100 to 100/1.

In embodiments, the anti-scaling composition comprises more uronic acid containing polysaccharide (i) than scale inhibiting agent (ii). Thus, in embodiments the ratio (wt/wt) of uronic acid containing polysaccharide (i) to scale inhibiting agent (ii) is within the range of 80/1 to 2/1 , preferably 60/1 to 10/1 , preferably 50/1 to 25/1 , preferably 45/1 to 35/1 , most preferably 40/1 . In other embodiments the ratio (wt/wt) of uronic acid containing polysaccharide (i) to scale inhibiting agent (ii) is within the range of 1/1 to 40/1 , preferably 10/1 to 30/1 , preferably 15/1 to 25/1 , most preferably 20/1.

In embodiments, the anti-scaling composition comprises less uronic acid containing polysaccharide (i) than scale inhibiting agent (ii). Thus, in embodiments the ratio (wt/wt) of uronic acid containing polysaccharide (i) to scale inhibiting agent (ii) is within the range of 1/10 to 1/1.1 , preferably 1/10 to 1/2, preferably 1/10 to 1/3.

In embodiments, the anti-scaling composition comprises a similar amount of uronic acid containing polysaccharide (i) and scale inhibiting agent (ii). Thus, in embodiments the ratio (wt/wt) of uronic acid containing polysaccharide (i) to scale inhibiting agent (ii) is within the range of 1/10 to 50/1 , preferably 1/10 to 40/1 , preferably 1/10 to 30/1 , preferably 1/10 to 20/1 , preferably 1/10 to 10/1 , preferably 1/5 to 5/1 , most preferably 1/1.

According to a second aspect of the invention, a ready-to-use product, such as a dishwashing detergent product, an anti-deposition product, a laundry detergent product, an industrial surface cleaning product or a household surface cleaning product, comprising the anti-scaling composition of the present invention is provided.

In embodiments, the ready-to-use product comprises the uronic acid containing polysaccharide (i) , preferably pectin or pectin derived polysaccharide, in an amount within the range of 0.1-60 wt.%, preferably 0.25-25 wt.%, preferably 0.5-10 wt.%. In embodiments the ready-to-use product is provided wherein the uronic acid containing polysaccharide (i) is present in an amount within the range of 0.5-5 wt.%. In embodiments the ready-to-use product is provided wherein the uronic acid containing polysaccharide (i) is present in an amount within the range of 2.5-7.5 wt.%. In embodiments the ready-to-use product is provided wherein the uronic acid containing polysaccharide (i) is present in an amount within the range of 5-10 wt.%.

In embodiments, the ready-to-use product comprises the scale-inhibiting agent (ii) in an amount within the range of 0.1-90 wt.%, preferably 0.2-70 wt.%, preferably 0.2-50 wt.%. In embodiments the ready-to-use product is provided wherein the scale-inhibiting agent (ii) is present in an amount within the range of 30-70 wt.%, preferably 40-60 wt.%, preferably 45-55 wt.%. In embodiments the ready-to-use product is provided wherein the scale-inhibiting agent (ii) is present in an amount within the range of 0.2-10 wt.%, preferably 0.3-8 wt.%, preferably 0.4-6 wt.%. In embodiments the ready-to-use product is provided wherein the scale-inhibiting agent (ii) is present in an amount within the range of 0.5-7 wt.%, preferably 1-6 wt.%, preferably 2-6 wt.%. In embodiments the ready-to-use product is provided wherein the scale-inhibiting agent (ii) is present in an amount within the range of 8-22 wt.%, preferably 10-20 wt.%, preferably 12-18 wt.%. In embodiments the ready-to-use product is provided wherein the scale-inhibiting agent (ii) is present in an amount within the range of 15-50 wt.%, preferably 20-40 wt.%, preferably 25-35 wt.%.

In preferred embodiments the ready-to-use product comprises the uronic acid containing polysaccharide (i) in an amount within the range of 0.1-60 wt.%, preferably 0.25-25 wt.%, preferably 0.5-10 wt.% and the scale-inhibiting agent (ii) in an amount within the range of 0.1-90 wt.%, preferably 0.2-70 wt.%, preferably 0.2-50 wt.%.

In embodiments the ready-to-use product comprising the anti-scaling composition of the present invention and a further ingredient, such as an ingredient selected from the group consisting of surfactants, bleaching agents, bleach activators, bleach catalysts, dyes, polymers, corrosion inhibitors, complexing agents, anti-redeposition agents, perfumes, process aids, enzymes, and combinations thereof is provided.

In embodiments the ready-to-use product comprising the anti-scaling composition of the present invention and a surfactant is provided. In embodiments the surfactant is selected from the group consisting of anionic, non-ionic, cationic and amphoteric surfactants, and combinations thereof. In preferred embodiments the surfactant is selected from the group formed by sulfate esters; sulfonate esters; phosphate esters; carboxylates; ethoxylates; fatty acid esters of polyhydroxy compounds; amine oxides; sulfoxides; phosphine oxides; quaternary ammonium salts and combinations thereof, preferably ethoxylates. In preferred embodiments the ready-to-use product comprising the anti-scaling composition of the present invention and a surfactant is provided wherein the surfactant is according to the following formula :

Cx - O - [- CH₂ - CH₂ - 0-]_y - CH₂ - CH(OH) - C_z ,

wherein

the average of x ranges between 6 and 13,

the average of y ranges between 12 and 41 ;

and the average of z ranges between 6 to 12,

and wherein Cx and Cz are linear or branched alkyl chains and are chosen independent from each other.

In embodiments the ready-to-use product comprising the anti-scaling composition of the present invention and a bleaching agent is provided. In embodiments, the bleaching agent is selected from the group consisting of active chlorine compounds, inorganic peroxygen compounds, organic peracids and combinations thereof. In preferred embodiments the ready-to-use product comprising the anti-scaling composition of the present invention and a bleaching agent is provided wherein the bleaching agent is selected from the group consisting of sodium percarbonate, sodium perborate monohydrate, sodium perborate tetrahydrate, hydrogen peroxide, hydrogen peroxide based compounds, persulphates, sodium hypochlorite, peracetic acid, peroxynonanoic acid, PAP (e-phthalimido peroxy hexanoic acid), sodium dichloroisocyanurate and combinations thereof. In more preferred embodiments the bleaching agent is selected from the group consisting of sodium percarbonate, sodium perborate, hydrogen peroxide, peracetic acid, peroxynonanoic acid, persulphates, PAP (e-phthalimido peroxy hexanoic acid) and combinations thereof.

In embodiments the ready-to-use product comprising the anti-scaling composition of the present invention and a compound selected from the group consisting of bleaching activators and bleach catalysts is provided.

Dyes are used to colour the ready-to-use product, parts of the product or provide speckles in the product to render it more attractive to the consumer. In embodiments the ready-to-use product comprising the anti-scaling composition of the present invention and a dye is provided.

Polymers may function as a (co-)builder or dispersing agent. In embodiments the ready-to-use product comprising the anti-scaling composition of the present invention and a polymer (co- guilder or dispersing agent is provided. In embodiments the polymer (co-)builder or dispersing agent is selected from the group consisting of homo-, co-, or terpolymers of or based on oleic monomers, acrylic acid, methacrylic acid or maleic acid or salts thereof. In embodiments the ready-to-use product comprising the anti-scaling composition of the present invention; a polymer (co-)builder or dispersing agent, optionally selected from the group consisting of homo-, co-, or terpolymers of or based on oleic monomers, acrylic acid, methacrylic acid or maleic acid or salts thereof; and a monomer is provided. In embodiments the monomer is selected from the group consisting of oleic monomers, acrylic acid, methacrylic acid or maleic acid or salts thereof. Corrosion inhibitors can be added, for example to reduce or inhibit glass corrosion or metal corrosion. In embodiments the ready-to-use product comprising the anti-scaling composition of the present invention and a corrosion inhibitor is provided. In embodiments the ready-to-use product comprising the anti-scaling composition of the present invention and a corrosion inhibitor selected from the group consisting of triazole-based compounds; polymers with an affinity to attach to glass surfaces; strong oxidizers such as permanganate; silver-protectors such as cysteine; silicates; organic and inorganic metal salts; metal salts of biopolymers and combinations thereof is provided.

Complexing agents can be added to capture trace metal ions. Complexing agents can also be used as co-builder or builder. In embodiments the ready-to-use product comprising the antiscaling composition of the present invention and a complexing agent is provided.

Anti-redeposition agents prevent the soil form redepositioning on the substrate. In embodiments the ready-to-use product comprising the anti-scaling composition of the present invention and an anti-redeposition agent is provided. In embodiments the ready-to-use product comprising the antiscaling composition of the present invention and an anti-redeposition agent selected from the group consisting of carboxymethyl cellulose, polyester-PEG co-polymer, polyvinyl pyrrolidone based polymers and combinations thereof is provided.

Perfume can be added to improve the sensorial properties of the ready-to-use product or of the target surface after cleaning, such as the load of a dishwashing machine. Also perfumes that have a deodorizing effect can be applied. In embodiments the ready-to-use product comprising the anti-scaling composition of the present invention and a perfume is provided. The perfume can for example be added to the ready-to-use product as a liquid, paste or as a co-granulate.

Process aids can be added for example to optimize compressibility, friability, toughness, elasticity, disintegration speed, hygroscopicity, density, free flowing properties, stickiness, viscosity, rheology of a detergent composition in a certain physical shape. In embodiments the ready-to- use product comprising the anti-scaling composition of the present invention and a process aid is provided.

In embodiments ready-to-use products are provided comprising the anti-scaling composition of the present invention and an enzyme, preferably an enzyme selected from the group of proteases, amylases, lipases, cellulases, mannanase, peroxidase, oxidase, xylanase, pullulanase, glucanase, pectinase, cutinase, hemicellulases, glucoamylases, phospholipases, esterases, keratanases, reductases, phenoloxidase, lipoxygenases, ligninases, tannases, pentosanases, malanases, arabinosidases, hyalurodindase, chondroitinase, laccase or mixtures thereof. The enzymes can for example be used as a granulate and/or liquid in commonly used amounts.

The ready-to-use product according to the present invention can be formulated in various forms, for example as a compacted body, such as a tablet; powder; paste; liquid; gel; granulate; compacted granulate; et cetera.. The formulation comprising the ready-to-use product of the present invention may comprise two or more distinct components, wherein said components may even have different physical phases. Examples of multi-component formulations are multi-layer tablets; multi-chamber pouches; pouches comprising a tablet surrounded by liquid detergent; a liquid comprising granules et cetera.

In preferred embodiments, the ready-to-use product according to the present invention is formulated as a multi-layer tablet comprising two or more, such as two, three or four layers, wherein each layer may independently comprise a compacted powder or granulate. In preferred embodiments, the detergent composition according to the present invention is formulated as a multi-chamber pouch comprising two or more, such as two, three or four chambers, wherein each chamber may independently comprise a tablet, powder, paste, liquid, gel, granulate or compacted granulate. In embodiments the formulation comprising the detergent composition of the present invention comprises a granulate with a particle size of an average particle size of between 0.6mm and 1.3mm, preferably between 0.7mm and 1.2mm, more preferably between 0.8mm and 1.2, most preferably between 0.9mm and 1.2mm. In preferred embodiments, the ready-to-use product according to the present invention is formulated as a liquid.

The formulation comprising the ready-to-use product of the present invention may be formulated as a multi-component formulation wherein a unit-dose of the ready-to-use product comprises the uronic acid containing polysaccharide (i) and the scale-inhibiting agent (ii) physically separated from each other. For example, a multi-chambered pouch comprising a first chamber and a second chamber, wherein the first chamber comprises the uronic acid containing polysaccharide (i) and the second chamber comprises the scale-inhibiting agent (ii).

In preferred embodiments the ready-to-use product of the present invention is a dishwashing detergent product, preferably an automatic dishwashing detergent product, comprising an antiscaling composition as described above. Thus, in preferred embodiments there is provided a ready-to-use product, which is a dishwashing detergent product, comprising the anti-scaling composition of the present invention. In highly preferred embodiments there is provided a ready- to-use product, which is a dishwashing detergent product, comprising the anti-scaling composition of the present invention and a surfactant. In preferred embodiments the dishwashing detergent product is formulated as a multi-layer tablet or a multi-chamber pouch.

In preferred embodiments the ready-to-use product of the present invention is an anti-deposition product, comprising an anti-scaling composition as described above. Thus, in preferred embodiments there is provided a ready-to-use product, which is an anti-deposition product, comprising the anti-scaling composition of the present invention. In highly preferred embodiments there is provided a ready-to-use product, which is an anti-deposition product, comprising the antiscaling composition of the present invention and a bleaching agent. In preferred embodiments the anti-deposition product is formulated as a liquid.

According to a third aspect of the present invention a process for preventing scale formation in water-using and/or water-processing equipment comprising the step of adding the anti-scaling composition of the present invention to the water that is used or processed in said equipment. The process is in particular suitable for water-using and/or water-processing equipment using water at temperatures within the range of 15-95 °C, for example in the range of 30-75 °C, more preferably in the range of 30-50 °C. Thus, in preferred embodiments of the invention a process for preventing scale formation in water-using and/or water-processing equipment comprising the step of adding the anti-scaling composition of the present invention to the water that is used or processed in said equipment is provided, wherein the equipment uses and/or processes water at temperatures within the range of 15-95 °C, preferably 30-75 °C, more preferably in the range of 30-50 °C.

In embodiments, the process described herein is provided wherein the water-using and/or waterprocessing equipment is selected from the group consisting of dishwashers, laundry machines, cooling water treatment, boilers, heating elements, piping systems, swimming pools, steam generators, heat exchangers and combinations thereof. In preferred embodiments the process described herein is provided wherein the water-using and/or water-processing equipment is selected from the group consisting of dishwashers and laundry machines, preferably dishwashers.

According to a fourth aspect of the present invention the use of a uronic acid containing polysaccharide (i) for improving the scale-inhibiting performance of a scale-inhibiting agent (ii) is provided. In preferred embodiments, the scale-inhibiting performance of the scale-inhibiting agent is improved within the temperature range of 15-95 °C, preferably in the range of 30-75 °C, more preferably in the range of 30-50 °C.

In embodiments the use of a uronic acid containing polysaccharide (i) as defined herein for improving the scale-inhibiting performance of a scale-inhibiting agent as defined herein in waterusing and/or water-processing equipment is provided. In preferred embodiments, the use of a uronic acid containing polysaccharide (i) as defined herein for improving the scale-inhibiting performance of a scale-inhibiting agent as defined herein in water-using and/or water-processing equipment operating at temperatures within the range of 15-95 °C, preferably in the range of 30- 75 °C, more preferably in the range of 30-50 °C, is provided.

In embodiments the use of the anti-scaling composition of the present invention for preventing scale formation in water-using and/or water-processing equipment is provided. In preferred embodiments, the use of the anti-scaling composition of the present invention for preventing scale formation in water-using and/or water-processing equipment operating at temperatures within the range of 15-95 °C, preferably in the range of 30-75 °C, more preferably in the range of 30-50 °C, is provided.

For a proper understanding of this document and its claims, it is to be understood that the verb ‘to comprise’ and its conjugations are used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded. In addition, reference to an element by the indefinite article‘a’ or‘an’ does not exclude the possibility that more than one of the element is present, unless the context clearly requires that there be one and only one of the elements. The indefinite article‘a’ or‘an’ thus usually means‘at least one’.

Figures

Figure 1 : turbidity measurements (in FNU) at pH 10 and at a temperature of 60 °C for Example 1.

Figure 2: molecular weight distribution of beet pectin derived polysaccharide SBP15 used in Example 1.

Figure 3: results of the turbidity measurements of samples with 10 mg/L of the phosphonate scale- inhibiting agent HEDP and different concentrations of beet pectin derived polysaccharide SBP15 at 45 °C and pH = 9 (Example 3).

Figure 4: results of the turbidity measurements of samples with 10 mg/L of the phosphonate scale- inhibiting agent HEDP and different concentrations of beet pectin derived polysaccharide R3-2 at 45 °C and pH = 9 (Example 3).

Figure 5: results of the turbidity measurements of samples with 10 mg/L of the phosphonate scale- inhibiting agent HEDP and different concentrations of beet pectin derived polysaccharide R3-2a at 45 °C and pH = 9 (Example 3).

Figure 6: results of the turbidity measurements of samples with 10 mg/L of the phosphonate scale- inhibiting agent HEDP and different concentrations of beet pectin derived polysaccharide R3-2b at 45 °C and pH = 9 (Example 3).

Figure 7: results of the turbidity measurements of samples with 10 mg/L of the phosphonate scale- inhibiting agent HEDP and different concentrations of beet pectin derived polysaccharide R3-2c at 45 °C and pH = 9 (Example 3).

Figure 8: results of the turbidity measurements of samples with 10 mg/L of the phosphonate scale- inhibiting agent HEDP and different concentrations of beet pectin derived polysaccharide R8R10 at 45 °C and pH = 9 (Example 3).

Figure 9: comparison of the turbidity measurements of samples with 10 mg/L of the phosphonate scale-inhibiting agent HEDP and 5 mg/L of different beet pectin derived polysaccharides at 45 °C and pH = 9 (Example 3).

Figure 10: comparison of the turbidity measurements of samples with 10 mg/L of the phosphonate scale-inhibiting agent HEDP and 10 mg/L of different beet pectin derived polysaccharides at 45 °C and pH = 9 (Example 3).

Figure 1 1 : comparison of the turbidity measurements of samples with 10 mg/L of the phosphonate scale-inhibiting agent HEDP and 20 mg/L of different beet pectin derived polysaccharides at 45 °C and pH = 9 (Example 3). Examples

Example 1

The calcium tolerance of a uronic acid containing polysaccharide, the calcium tolerance of a scale-inhibiting agent known in the art and the calcium tolerance of a uronic acid containing polysaccharide in combination with a scale-inhibiting agent were determined and compared. Calcium tolerance of a chemical compound is defined as the ability of the chemical compound to remain soluble in the presence of calcium ions. Calcium tolerance of a chemical compound thus corresponds with the ability of a chemical to resist to complexation with calcium. When the concentration of a tested chemical compound exceeds the solubility limit, the solution becomes turbid which is detected as a steep decrease in light transmittance in the turbidity measurements. Calcium tolerance is assessed by measuring the turbidity (in NTU) of a liquid at varying calcium concentrations.

The test materials are

- HEDP (Dequest 2010) active 59.4 %; and

Uronic acid containing polysaccharide: pectin derived polysaccharide (SBP15) active 95 %. The beet pectin derived polysaccharide (SBP15) was produced as follows: A Terlet kettle was filled with 10-12 L demineralised water and the temperature was raised to 40°C. Sugar beet pectin was obtained from Royal Cosun. The sugar beet pectin was obtained by acid extraction of beet pulp at pH 1 and 80 °C for 3 hours followed by separation into a solid and a liquid fraction and isolating the pectins from the liquid fraction by alcohol precipitation. About 625 g of the pectin was slowly added while stirring. The mixture was left stirring until no more lumps were present. The pH was adjusted to 5.5 with 8M sodium hydroxide solution. When the temperature and pH were constant, endo-polygalacturonase M2 from Aspergillus niger (endo-PG) enzyme (20,000 U; Megazyme) was added. During the reaction the pH was checked regularly and if necessary adjusted with concentrated sulphuric acid. The reaction was performed for 6 hours while stirring. The reaction was stopped by heating the mixture at 95° C for 10 minutes (inactivation of the enzyme). Enzymatic removal of the methyl esters was done at a pH of 5.2. Pectin methyl esterase (266 U, Novoshape, Novozymes) was added and the incubation was performed at 40 °C. The pH was adjusted with 2 M NaOH. When the pH was constant the reaction was stopped by heating the mixture at 95°C for 15 minutes. After cooling the hydrolysed and demethylated pectin mixture was centrifuged (10 minutes at 9,000 c g) in order to remove the insoluble material. The clear supernatant was collected and freeze dried to yield the beet pectin derived polysaccharide (SBP15).

The sugar composition of the beet pectin derived polysaccharide (SBP15) is shown in the following table and was determined on the hydrolyzed and demethylated pectin as follows: Freeze dried samples were hydrolysed in sulphuric acid to their monomeric moieties according to Seaman et al. ( Saeman , Moore, Mitchell & Millett, (1954) Techniques for the determination of pulp constituents by quantitative paper chromatography. Tappi, 37(8), 336-343). The material was hydrolysed for 1 h in 72% (w/w) H2SO4 at 30 °C and subsequently water was added till 1 M H2SO4 was obtained. The mixture was incubated for 3 h at 100 °C. After hydrolysis the samples were cooled on ice and hereafter briefly centrifuged. The supernatants were diluted and to one ml_ diluted sample 2.5 pl_ 0.1 % (w/v) bromophenol blue in ethanol wad added. The pH was adjusted with barium carbonate till a clear blue colour was obtained. The remaining solution was filtrated using a 0.45 pm PFTE filter. An ICS-3000 Ion Chromatography HPLC system equipped with a Dionex CarboPac PA-1 column (2 * 250 mm) in combination with a Dionex CarboPac PA- 1 guard column (2 * 25 mm) and a pulsed electrochemical detector in pulsed amperometric detection mode was used (ThermoFisher Scientific, Breda, The Netherlands). A flow rate of 0.25 ml_ min^-1 was used, and the column was equilibrated with H2O. Elution was performed as follows: 0-40 min, H2O; 40-55 min, 0-40% 1 M sodium acetate in 100 mM NaOH; 55-60 min, 1 M sodium acetate in 100 mM NaOH; 60-65 min, 150 mM NaOH; 75-90 min, H2O. Detection of the monosaccharides was possible after post column addition of 0.5 M sodium hydroxide (0.15 mL min^-1). Elution was performed at 20 °C. The concentration of monosaccharides in solution was determined from calibration curves, using deoxygalactose as internal standard. Fucose, rhamnose, galactose, glucose, xylose, mannose, glucosamine, N-acetyl glucosamine, galactosamin, N-acetyl galactosamine, ribose, galacturonic acid and glucuronic acid were the monosaccharides used. Unless otherwise indicated, the method to determine the sugar composition described in this example is used to determine the sugar composition of any uronic acid containing polysaccharide in the present invention.

Sugar beet composition of the beet pectin derived polysaccharide (SBP15):

The molecular weight distribution of the beet pectin derived polysaccharide (SBP15) was determined using high pressure size exclusion chromatography and is shown (together with pullulan standards) in Figures 2a and 2b. The molecular weigth distribution was determined as follows: Samples having a concentration of about 5-10 mg mL ¹ were prepared by dissolving pectin in 0.2 M sodium nitrate. The solutions were centrifuged for 10 min. After centrifugation, the supernatant was transferred to HPLC vials and kept for analysis at 4 °C. For calibration ten pullulan standards with concentration of 10 mg ml_ ¹ were prepared in sodium nitrate solution (0.2 M). Their size ranged from 342 Da to 800 kDa. Samples were analysed using a Dionex UltiMate 3000 HPLC system (ThermoFisher Scientific, Breda, The Netherlands) equipped with three columns connected in series: TosoH Bioscience TSK-GEL AW4000, TosoH Bioscience TSK-GEL AW3000 and TosoH Bioscience TSK-GEL AW2500 (all 6 * 150 mm). The columns were preceded with a guard column (TosoH Bioscience TSK AW-L (4.6 * 35 mm)). The columns were conditioned at 55 °C. Sodium nitrate (0.2 M) was used as eluent at a flow rate of 0.6 mL min ¹ and the injection volume was 10 pL. An UV-VIS detector operating at 260, 280 and 310 nm was used together with a refractive index detector. Unless otherwise indicated, the method to determine the molecular weight distribution described in this example is used to determine the molecular weight distribution of any uronic acid containing polysaccharide in the present invention.

The test equipment for the turbidity measurements comprises

a stirrer (RW 20, Janke and Kunkel),

a 2000 mL water jacket beaker,

- a thermostatic water bath,

a pH meter; and

a turbiditymeter (LPT 4 Dr. Lange).

The turbidity of the test materials was monitored at predetermined concentration levels of calcium at a predetermined temperature and pH. The concentration of calcium is increased step-by-step by adding a volume of a calcium chloride stock solution. The temperature is controlled by the thermostatic water bath. After each addition of calcium chloride stock solution, the pH is adjusted by adding NaOH (0.1 M) to reach the predetermined pH. The turbidity is measured 10 minutes after each calcium chloride dosage.

The results of the turbidity measurements (in NTU) at pH 10 and at a temperature of 60 °C are given in Table 1 and Figure 1.

Table 1

From Table 1 and Figure 1 can be concluded that beet pectin has a high calcium tolerance at pH 10 and at a temperature of 60 °C. The calcium tolerance of HEDP is low at pH 10 and at a temperature of 60 °C. A combination of beet pectin and HEPD results in a positive effect of the calcium tolerance compared to HEDP.

Example 2

An example of a 20 g dishwasher tablet in accordance with the invention may be prepared by mixing the following ingredients listed in Table 2 and compressing the resulting mixture into a tablet.

Table 2

Example 3

Calcium tolerance tests were performed with HEDP as scale-inhibiting agent and with different beet pectin derived polysaccharides according to the invention by turbidity monitoring.

The test set-up used a constant temperature water bath, a pH meter, and a Dr Lange turbidity meter 2100QS for measuring turbidity (expressed in FNU) of the samples. Calcium chloride solution was added to glass bottles containing deionized/distilled water. To these calcium solutions were added varying amounts of beet pectin derived polysaccharide stock solutions. The bottles were capped and equilibrated at 45 °C for 30 minutes. Subsequently, HEDP stock solution was added to obtain a solution with calcium (250, 500, or 750 mg/L as Ca), 10 mg/L HEDP and different concentrations of beet pectin derived polysaccharides (5, 10 or 20 mg/L). The pH levels of these solutions were adjusted to pH 9.0 with dilute NaOH and/or HCI solution and the temperature was maintained at 45 °C. The total volume of the final solution was 100 ml_ in each case. At a known time (typically 45 minutes after obtaining the final solution) the turbidity was determined.

The beet pectin derived polysaccharides tested have different mass average molecular weights, different molecular weight ranges of the individual chains, and different degrees of methylation (see Table 3). The beet pectin derived polysaccharides were prepared via hydrolysis and demethylation analogous to SBP15 in Example 1.

The degree of methylation (methyl esterification) of the beet pectin derived polysaccharides was determined after saponification with 0.4 M sodium hydroxide in isopropanol/water (50/50 v/v) by using Hitachi Chromaster high performance liquid chromatography (HPLC) equipped with Aminex HPX 87H column (Bio-Rad, USA). The elution took place at 40 °C with 0.01 N H₂SO₄ at a flow rate of 0.6 mL/min. The degree of methylation was calculated as moles of methanol per 100 moles of uronic acid residues.

R3, R3-2, R3-2a, R3-2b and R3-2c are the retentate obtained after ultrafiltration with a 25 kDa membrane. R8R10 is the permeate of this ultrafiltration step which has subsequently been subjected to ultrafiltration with a 1 kDa membrane.

Table 3

The results of the turbidity measurements of samples with 10 mg/L of the phosphonate scale- inhibiting agent HEDP and different concentrations of beet pectin derived polysaccharides SBP15, R3-2, R3-2a, R3-2b, R3-2c and R8R10 are shown in Figures 3, 4, 5, 6, 7 and 8, respectively. In these figures, the turbidity measurements of 10 mg/L of HEDP without beet pectin derived polysaccharide are included as a reference.

A comparison of the turbidity measurements of samples with 10 mg/L of the phosphonate scale- inhibiting agent HEDP and 5 mg/L of the different beet pectin derived polysaccharides is shown in Figure 9. Again, the turbidity measurements of 10 mg/L of HEDP without the 5 mg/L beet pectin derived polysaccharide are included as a reference.

Similar comparisons for samples with 10 mg/L of the phosphonate scale-inhibiting agent HEDP and 10 or 20 mg/L of the different beet pectin derived polysaccharides are provided in Figures 10 and 1 1 , respectively.

It can be concluded from the figures that the pectin derived polysaccharides according to the invention increase the calcium tolerance of phosphonate scale-inhibiting agent HEDP. The effect is more pronounced at lower degrees of methylation. Naturally occurring sugar beet pectin typically has a degree of methylation of about 62%.

Example 4:

Calcium tolerance tests were performed with different scale-inhibiting agents and with different beet pectin derived polysaccharides according to the invention by transmission monitoring.

The scale-inhibiting agents used are listed in Table 4.

Table 4: scale-inhibiting agents

The beet pectin derived polysaccharides used were R3, H3 and R8R10. Properties of these beet pectin derived polysaccharides are listed in Table 3.

The test equipment for the transmission measurements comprised:

a) a stirrer (RW 20, Janke and Kunkel);

b) a 2000 mL water jacket beaker; c) a thermostatic water bath;

d) a pH meter; and

e) a Photometer (Metrohm 662) at 560 nm. The transmission of the test materials was monitored at predetermined concentration levels of calcium at a temperature of 60 °C and pH = 9. The concentration of calcium was increased step- by-step by adding a volume of a calcium chloride stock solution. The temperature was controlled by the thermostatic water bath. The pH was adjusted by adding NaOH (0.1 M). The transmission of the sample was measured 10 minutes after each calcium chloride dosage. The results of the transmission measurements (in %) at pH 9 and at a temperature of 60 °C are presented in Table 5.

Table 5: Transmission (%) at 60°C / pH = 9 after addition x mg/L Ca

It was concluded from Table 5 that the pectin derived polysaccharides according to the invention increase the calcium tolerance of the different scale-inhibiting agents tested.

Example 5: Build-up performance test of automatic dishwashing detergent

A comparative experiment was performed in a dishwasher with all-in-one dishwashing detergent formulations. In a first test (I), all-in-one composition MX-41 comprising 6 wt% of the scale- inhibiting agent Sokalan PA25CL (a polyacrylic homopolymer or poycarboxylate from BASF) was used. In a similar test (II), all-in-one composition MX-41 wherein the Sokalan PA25CL was replaced by 6 wt% sugar beet pectin SBP15 was used (see Table 3 for characteristics).

The compositions of both dishwashing detergent formulations are given in Table 6.

Table 6

A build-up performance test was performed in accordance with the method as used by German StiWa using the following conditions:

a) Miele GSL2 dishwashing machine (robot type);

b) Washing performed in the presence of 50 g of ballast soil (comprising ketchup, mustard, gravy, potato starch, egg yolk, margarine, milk 1.5%, benzoic acid and tap water); c) glass and stainless steel as test materials;

d) evaluation after 30 washes at 21 °GH and 65°C; e) a score of 8 means no deposition at all, a score of 1 means complete deposition with scale.

Results of the build-up performance test are indicated in Table 7. Table 7

It was concluded that the all-in-one composition wherein scale-inhibiting agent Sokalan PA25CL was replaced by a sugar beet pectin derived compound according to the invention showed at least comparable performance.

It was further concluded that the bio-based and biodegradable beet pectin derived polysaccharides according to the invention can be used to replace oil-based/synthetic and non- or hardly biodegradable polycarboxylates without compromising performance.

Claims

1. Anti-scaling composition comprising a combination of the following two distinct components (i) a uronic acid containing polysaccharide; and

(ii) a scale-inhibiting agent;

wherein the uronic acid containing polysaccharide has a solubility in water at a temperature of 25 °C ranging between 1 g/L and 700 g/L and a mass average molecular weight M_w ranging between 1 and 500 kDa, and

wherein the uronic acid containing polysaccharide (i) is pectin or a pectin derived polysaccharide.

2. Anti-scaling composition according to claim 1 , wherein the degree of methylation of the pectin or the pectin derived polysaccharide is between 1 and 62%, preferably between 1 and 50%, more preferably between 1 and 40%, still more preferably between 1 and 30%, yet more preferably between 1 and 20%.

3. Anti-scaling composition according to claim 1 or 2, wherein the pectin is naturally occurring pectin from sugar beet, chicory/chicory root, sunflower, rapeseed/rapeseed cake, carrot, citrus peel/citrus fruit, preferably sugar beet, or wherein the pectin derived polysaccharide is derived from naturally occurring pectin from sugar beet, chicory/chicory root, sunflower, rapeseed/rapeseed cake, carrot, citrus peel/citrus fruit, preferably sugar beet.

4. Anti-scaling composition according to any one of claims 1 to 3, wherein the pectin derived polysaccharide is a partially hydrolysed pectin, preferably a partially hydrolysed naturally occurring pectin, a partially methylated or demethylated pectin, preferably a partially methylated or demethylated naturally occurring pectin, a partially acetylated or deacetylated pectin, preferably a partially acetylated or deacetylated naturally occurring pectin, a partially amidated pectin, preferably a partially amidated naturally occurring pectin, or combinations thereof.

5. Anti-scaling composition according to claim 4, wherein the pectin derived polysaccharide is a partially hydrolysed pectin, preferably a partially hydrolysed naturally occurring pectin, a partially methylated or demethylated pectin, preferably a partially methylated or demethylated naturally occurring pectin, or combinations thereof.

6. Anti-scaling composition according to any one of claims 1 to 5, wherein the pectin or the pectin derived polysaccharide (i) and the scale inhibiting agent (ii) are present in a ratio (wt/wt) within the range of 1/100 to 100/1.

7. Anti-scaling composition according to any one of claims 1 to 6, wherein the pectin or the pectin derived polysaccharide (i) is characterized by a solubility in water at a temperature of 25°C of at least 100 g/L.

8. Anti-scaling composition according to any one of claims 1 to 7, wherein the pectin or the pectin derived polysaccharide (i) is characterized by a mass average molecular weight of 1- 100 kDa.

9. Anti-scaling composition according to any one of claims 1 to 8, wherein the scale-inhibiting agent (ii) is selected from the group consisting of phosphonates, dicarboxylic acids, tricarboxylic acids, polycarboxylates, polyacrylic homopolymers, polyacrylic/maleic copolymers, polyacrylic/sulfonic copolymers, either in acid, neutral or partially neutralized form, and combinations thereof.

10. Automatic dishwashing detergent product comprising an anti-scaling composition as defined in any one of claims 1 to 9 and a surfactant.

11. Automatic dishwashing detergent product according to claim 10, comprising the pectin or the pectin derived polysaccharide (i) in an amount within the range of 0.1- 60 wt.% and/or the scale-inhibiting agent (ii) in an amount within the range of 0.1- 90 wt.%.

12. Automatic dishwashing detergent product according to claim 10 or 11 wherein the surfactant is selected from the group consisting of sulfate esters; sulfonate esters; phosphate esters; carboxylates; ethoxylates; fatty acid esters of polyhydroxy compounds; amine oxides; sulfoxides; phosphine oxides; quaternary ammonium salts and combinations thereof, preferably ethoxylates.

13. Anti-deposition product comprising a bleaching agent in combination with an anti-scaling composition as defined in any one of claims 1-9.

14. Anti-deposition product according to claim 13, comprising the pectin or the pectin derived polysaccharide (i) in an amount within the range of 0.1- 60 wt.% and/or the scale-inhibiting agent (ii) in an amount within the range of 0.1- 90 wt.%.

15. Anti-deposition product according to claim 13 or 14, wherein the bleaching agent comprises an oxygen based bleaching agent, preferably an oxygen based bleaching agent selected from the group consisting of sodium percarbonate, sodium perborate, hydrogen peroxide, peracetic acid, peroxynonanoic acid, persulphates, PAP (e-phthalimido peroxy hexanoic acid) and combinations thereof.

16. Process for preventing scale-formation in water-using and/or water-processing equipment, comprising the step of adding to the water that is used or processed in said equipment an anti-scaling composition as defined in any one of claims 1-9.

17. Use of a uronic acid containing polysaccharide (i) as defined in any one of claims 1-9 for improving the scale-inhibiting performance of a scale-inhibiting agent (ii) as defined in any one of claims 1-9, preferably for improving the scale-inhibiting performance within the temperature range of 15-95 °C, more preferably in the range of 30-75 °C, even more preferably in the range 30-50 °C.

18. Use of an anti-scaling composition as defined in any one of claims 1-9, for preventing scale- formation in water-using and/or water-processing equipment, preferably for preventing scale- formation in water-using and/or water-processing equipment operating at temperatures within the range of 15-95 °C, preferably in the range of 30-75 °C, more preferably in the range 30-50 °C.