EP3820983A1 - Composition d'anti-tartre comprenant un polysaccharide d'acide uronique - Google Patents

Composition d'anti-tartre comprenant un polysaccharide d'acide uronique

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Publication number
EP3820983A1
EP3820983A1 EP19737734.4A EP19737734A EP3820983A1 EP 3820983 A1 EP3820983 A1 EP 3820983A1 EP 19737734 A EP19737734 A EP 19737734A EP 3820983 A1 EP3820983 A1 EP 3820983A1
Authority
EP
European Patent Office
Prior art keywords
pectin
scale
polysaccharide
scaling composition
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19737734.4A
Other languages
German (de)
English (en)
Inventor
Henricus Wilhelmus Carolina Raaijmakers
Jacobus Petrus Maria Bink
Tom Brooijmans
Robbert De Boer
Khalid Mahmud
René Mol
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalli Werke GmbH and Co KG
Koninklijke Cooperatie Cosun UA
Original Assignee
Dalli Werke GmbH and Co KG
Koninklijke Cooperatie Cosun UA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalli Werke GmbH and Co KG, Koninklijke Cooperatie Cosun UA filed Critical Dalli Werke GmbH and Co KG
Publication of EP3820983A1 publication Critical patent/EP3820983A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-compounds

Definitions

  • 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.
  • 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.
  • 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.
  • phosphonates to inhibit scale formation.
  • 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.
  • 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.
  • 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.
  • the present invention provides an anti-scaling composition comprising a combination of the following two distinct components:
  • the uronic acid containing polysaccharide (i) preferably is a pectin or a pectin derived polysaccharide.
  • 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.
  • the ready-to-use product further comprises a surfactant or a bleaching agent.
  • the ready-to-use product of the present invention is a dishwashing detergent product, preferably an automatic dishwashing detergent product.
  • the ready-to-use product of the present invention is a dishwashing detergent product comprising a surfactant.
  • the ready-to-use product of the present invention is an anti-deposition product.
  • the ready-to-use product of the present invention is an antideposition product comprising a bleaching agent.
  • 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.
  • 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).
  • a first aspect of the present invention relates to an anti-scaling composition
  • an anti-scaling composition comprising a combination of the following two distinct components:
  • 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.
  • 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.
  • molecular weight refers to the mass average molecular weight defined by the following formula
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the UV-Vis detector operates at 260, 280 and 310 nm.
  • 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.
  • 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.
  • 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.
  • an anti-scaling composition comprising a combination of the following two distinct components:
  • the uronic acid containing polysaccharide (i) is pectin or a pectin derived polysaccharide, is provided.
  • an anti-scaling composition comprising a combination of the following two distinct components:
  • 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.
  • the pectin rich biomass is sugar beet pulp, which constitutes the production side stream from the sugar beet industry.
  • pectin 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.
  • 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.
  • 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.
  • 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.
  • hydrolysis as used herein refers to partial hydrolysis of the naturally occurring pectin, unless specified otherwise.
  • the uronic acid containing polysaccharide is a pectin derived polysaccharide obtainable through hydrolysis, preferably enzymatic hydrolysis of pectin.
  • 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.
  • an anti-scaling composition in accordance with the invention wherein the pectin derived polysaccharide is a partially hydrolysed naturally occurring pectin.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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%.
  • 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 %.
  • the degree of methylation of the pectin 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%.
  • 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 %.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 %.
  • the uronic acid containing polysaccharide is a pectin derived polysaccharide obtainable through acetylation of pectin.
  • 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.
  • 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.
  • 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.
  • amidation may be introduced through ammonia processing in the case of primary amides.
  • 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%.
  • the percentage of carboxyl groups which have been converted to amide groups is lower than 30%, preferably lower than 20%, preferably lower than 10%.
  • 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 %.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • pectin derived polysaccharide 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;
  • 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.
  • 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.
  • 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.
  • step b) further comprises demethylating the pectin or the pectin derived polysaccharide.
  • step b) comprises demethylating the pectin or the pectin derived polysaccharide, preferably by contacting it with a methyl esterase in an aqueous environment.
  • 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.
  • 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.
  • 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.
  • step b) further comprises acetylating the pectin or the pectin derived polysaccharide.
  • step b) comprises acetylating the pectin or the pectin derived polysaccharide, preferably by contacting it with an acetylating agent, preferably acetic acid anhydride.
  • 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.
  • 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.
  • step c) comprises centrifugation. In embodiments step c) comprises centrifugation until a supernatant and solids are formed and collection of the supernatant.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • step c) comprises a membrane filtration wherein the pectin derived polysaccharide is desalted with a 1 kDa membrane and wherein the retentate is recovered.
  • 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.
  • step c) comprises freeze-drying.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the scale-inhibiting agent (ii) does not comprise EDTA.
  • 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).
  • ATMP aminotris(methylenephosphonic acid)
  • HMPA hydroxyethylamino bis(methylene phosphonic acid)
  • ETMP ethylenediamine tetra(methylene phosphonic acid)
  • HDTMP hexamethylenediamine-tetra
  • a preferred bisphosphonate is 1-hydroxyethane 1 ,1-diphosphonic acid (HEDP), also known as 1- hydroxyethylidine 1 ,1-diphosphonic acid.
  • HEDP 1-hydroxyethane 1 ,1-diphosphonic acid
  • the scale-inhibiting agent present in the anti-scaling composition comprises HEDP in the acid, neutral or partially neutralized form.
  • 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.
  • 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.
  • PBTC (2-phosphonobutane-1 ,2,4-tricarboxylic acid)
  • 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;
  • the scale-inhibiting agent comprises polyacrylates, polymaleinates or combinations thereof.
  • 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.
  • 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.
  • 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.
  • 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.
  • the anti-scaling composition comprises more uronic acid containing polysaccharide (i) than scale inhibiting agent (ii).
  • 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 .
  • 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.
  • the anti-scaling composition comprises less uronic acid containing polysaccharide (i) than scale inhibiting agent (ii).
  • 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.
  • the anti-scaling composition comprises a similar amount of uronic acid containing polysaccharide (i) and scale inhibiting agent (ii).
  • 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.
  • 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.
  • 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.%.
  • 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.%.
  • the ready-to-use product 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.%.
  • 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.%.
  • 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.
  • the ready-to-use product comprising the anti-scaling composition of the present invention and a surfactant
  • the surfactant is selected from the group consisting of anionic, non-ionic, cationic and amphoteric surfactants, and combinations thereof.
  • 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.
  • 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 and Cz are linear or branched alkyl chains and are chosen independent from each other.
  • the ready-to-use product comprising the anti-scaling composition of the present invention and a bleaching agent
  • the bleaching agent is selected from the group consisting of active chlorine compounds, inorganic peroxygen compounds, organic peracids and combinations thereof.
  • the ready-to-use product comprising the anti-scaling composition of the present invention and a bleaching agent
  • 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.
  • 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.
  • 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.
  • 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.
  • the ready-to-use product comprising the anti-scaling composition of the present invention and a polymer (co- guilder or dispersing agent is provided.
  • 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.
  • 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.
  • 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.
  • the ready-to-use product comprising the anti-scaling composition of the present invention and a corrosion inhibitor is provided.
  • 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.
  • 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.
  • the ready-to-use product comprising the anti-scaling composition of the present invention and an anti-redeposition agent is provided.
  • 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.
  • 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.
  • the ready-to- use product comprising the anti-scaling composition of the present invention and a process aid is provided.
  • ready-to-use products 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.
  • multi-component formulations are multi-layer tablets; multi-chamber pouches; pouches comprising a tablet surrounded by liquid detergent; a liquid comprising granules et cetera.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • a ready-to-use product which is a dishwashing detergent product, comprising the anti-scaling composition of the present invention.
  • a ready- to-use product which is a dishwashing detergent product, comprising the anti-scaling composition of the present invention and a surfactant.
  • the dishwashing detergent product is formulated as a multi-layer tablet or a multi-chamber pouch.
  • the ready-to-use product of the present invention is an anti-deposition product, comprising an anti-scaling composition as described above.
  • a ready-to-use product which is an anti-deposition product, comprising the anti-scaling composition of the present invention.
  • a ready-to-use product which is an anti-deposition product, comprising the antiscaling composition of the present invention and a bleaching agent.
  • the anti-deposition product is formulated as a liquid.
  • 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.
  • 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.
  • 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.
  • 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.
  • the use of a uronic acid containing polysaccharide (i) for improving the scale-inhibiting performance of a scale-inhibiting agent (ii) is provided.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • test materials are:
  • 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.
  • endo-polygalacturonase M2 from Aspergillus niger (endo-PG) enzyme (20,000 U; Megazyme) was added.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • the test equipment for the turbidity measurements comprises
  • the turbidity of the test materials was monitored at predetermined concentration levels of calcium at a predetermined temperature and pH.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 H 2 SO 4 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.
  • 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%.
  • beet pectin derived polysaccharides used were R3, H3 and R8R10. Properties of these beet pectin derived polysaccharides are listed in Table 3.
  • test equipment for the transmission measurements comprised:
  • a comparative experiment was performed in a dishwasher with all-in-one dishwashing detergent formulations.
  • 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.
  • Sokalan PA25CL a polyacrylic homopolymer or poycarboxylate from BASF
  • 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).
  • compositions of both dishwashing detergent formulations are given in Table 6.
  • 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;
  • 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.

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Abstract

L'invention concerne une composition anti-tartre comprenant une association d'un polysaccharide contenant de l'acide uronique (i) et d'un agent anti-tartre (ii). Le polysaccharide contenant de l'acide uronique (i) a une solubilité dans l'eau à une température de 25°C comprise entre 1 g/l et 700 g/l et une masse moléculaire moyenne en masse Mw comprise entre 1 et 500 kDa. L'invention concerne également un produit détergent pour lave-vaisselle automatique comprenant une telle composition anti-tartre et un tensioactif. L'invention concerne également un produit anti-déposition comprenant une telle composition anti-tartre et un agent de blanchiment. L'invention concerne en outre un procédé permettant d'empêcher la formation de tartre dans un appareil utilisant de l'eau et/ou de traitement d'eau et l'utilisation d'un polysaccharide contenant de l'acide uronique (i) pour l'amélioration des performances d'inhibition de la formation de tartre d'un agent anti-tartre (ii).
EP19737734.4A 2018-07-09 2019-07-09 Composition d'anti-tartre comprenant un polysaccharide d'acide uronique Pending EP3820983A1 (fr)

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PCT/EP2019/068356 WO2020011764A1 (fr) 2018-07-09 2019-07-09 Composition d'anti-tartre comprenant un polysaccharide d'acide uronique

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CN113122854A (zh) * 2021-03-12 2021-07-16 河北爱节能源科技有限公司 一种翅片管的防垢试剂
CN113292170A (zh) * 2021-06-09 2021-08-24 西安瑞杰实业股份有限公司 一种底滤法高炉矿渣处理系统抗板结药剂、制备方法及其应用
US20230279313A1 (en) * 2022-03-01 2023-09-07 Kurita Water Industries Ltd. Cleaning agent, cleaning method of water treatment apparatus, and cleaning method of silica-based scale

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DE4134914A1 (de) * 1991-10-23 1993-04-29 Henkel Kgaa Wasch- und reinigungsmittel mit ausgewaehlten builder-systemen
EP0542496B1 (fr) * 1991-11-14 1998-05-20 The Procter & Gamble Company Amidon oxydé à C6/C2-C3 utilisé comme ingrédient pour détergent
ATE140594T1 (de) * 1991-11-14 1996-08-15 Gist Brocades Nv Verfahren zur herstelllung von säften aus früchten und gemüse
DE4228786A1 (de) * 1992-08-29 1994-03-03 Henkel Kgaa Geschirrspülmittel mit ausgewähltem Builder-System
US5929051A (en) * 1998-05-13 1999-07-27 Carrington Laboratories, Inc. Aloe pectins
EP2261262A4 (fr) * 2008-03-31 2013-07-10 Kao Corp Procédé de fabrication de polyuronate

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