EP0703292B1 - Process for decreasing the build up of inorganic incrustations on textiles and detergent composition used in such a process - Google Patents

Process for decreasing the build up of inorganic incrustations on textiles and detergent composition used in such a process Download PDF

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Publication number
EP0703292B1
EP0703292B1 EP95306663A EP95306663A EP0703292B1 EP 0703292 B1 EP0703292 B1 EP 0703292B1 EP 95306663 A EP95306663 A EP 95306663A EP 95306663 A EP95306663 A EP 95306663A EP 0703292 B1 EP0703292 B1 EP 0703292B1
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EP
European Patent Office
Prior art keywords
carbohydrate
builder
detergent
washing
build
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.)
Expired - Lifetime
Application number
EP95306663A
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German (de)
French (fr)
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EP0703292A1 (en
Inventor
Roland Herwig Friedrick Dr. Beck
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.)
Cerestar Holding BV
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Cerestar Holding BV
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Publication date
Application filed by Cerestar Holding BV filed Critical Cerestar Holding BV
Publication of EP0703292A1 publication Critical patent/EP0703292A1/en
Application granted granted Critical
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Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/40—Products in which the composition is not well defined
    • C11D7/44—Vegetable products

Definitions

  • the present invention relates to a process for decreasing the build-up of inorganic incrustations on fabrics caused by water hardness and repeated washing cycles with detergent compositions.
  • the present invention relates to a process for decreasing the build-up of inorganic incrustations wherein a co-builder is added to the washing cycle, and to detergent and/or anti-incrustation compositions containing said co-builder.
  • detergents contain builders in order to support detergent action and to eliminate calcium and magnesium ions (hardness ions), which arise partly from the water and sometimes also from soil and fabrics.
  • a well known builder is sodium tripolyphosphate which has excellent properties in the washing process even at low concentrations. Despite its many advantageous properties however, it causes serious ecological problems, namely eutrophication of stationary or slowly flowing surface waters leading to extreme algal growth which adversely influences marine organisms. As a result, the use of phosphate free detergents is of great importance.
  • zeolites Some substitutes of phosphate builders such as zeolites have been adopted. However, zeolites alone in water softening have poor efficiency. Therefore, good anti-incrustation effects are achieved only in the presence of auxiliary compounds called co-builders.
  • co-builders are synthetic polymers and/or co-polymers of olefinic mono- or dicarboxylic acids such as acrylic and maleic acid and copolymers of said monomers with other allylic or vinylic monomers.
  • a common characteristic of these polymeric materials is their minimal biodegradability which leads to ecological problems.
  • non-polymeric co-builders such as EDTA (ethylenediaminetetraacetic acid sodium salt), NTA (nitrilotriacetic acid sodium salt) and phosphonates. As with the polymeric co-builders these substances too are non-biodegradable.
  • Another object of the present invention is to provide detergent and/or anti-incrustation compositions containing said biodegradable co-builders.
  • EP-A-0618286 there is described a co-builder based upon a non-reducing carbohydrate or a non-reducing carbohydrate derivative.
  • Preferred among the non-reducing carbohydrate derivatives are certain sugar alcohols exemplified by maltitol and, especially, by mannitol. It has now been found however that the carbohydrate or carbohydrate derivative need not be fully non-reducing but that some reducing activity is tolerable and that certain compounds showing such activity are as effective co-builders as the sugar alcohols referred to above.
  • EP-A-0472042 discloses calcium-sequestering agents based on oxidised carbohydrates, a method for their preparation, and their use as builders or detergents. The document also relates to the sequestering capacity of oxidised glucosidic oligomers. The oxidisation is performed with hypochlorite or periodate, both giving highly oxidised products.
  • JP-A-52059605 (Abstract) describes as a builder component a carboxymethylated hydrolysate of starch, cellulose or hemicellulose, in which the average degree of substitution by carboxymethyl groups for three hydroxyl groups in a structural unit is 1.5 to 3.0. The products contain a high density of carboxymethyl groups.
  • a process for decreasing the build-up of inorganic incrustations on fabrics and on washing machine components during multiple washing cycles with detergent compositions characterised by the addition to the washing cycle of a co-builder based on a carbohydrate or carbohydrate derivative having a DE of 0.5 to 20 inclusive.
  • the carbohydrate or carbohydrate derivative is selected from polydextrose, partially degraded inulin and maltodextrin.
  • a range of carbohydrates or carbohydrate derivatives having a DE of 0.5 to 20 inclusive may be used in the process of the invention eg. polydextrose or partially degraded inulin but preferably the carbohydrate or carbohydrate derivative is a maltodextrin having a DE of 0.5 to 20 inclusive, particularly a DE of 8 to 17 inclusive.
  • DE dextrose equivalent
  • the co-builders based on such carbohydrates and carbohydrate derivatives having a DE of 0.5 to 20 inclusive can be incorporated into the detergent compositions or added as such directly to the washing bath.
  • detergent and/or anti-incrustation compositions containing the hereinbefore defined co-builders. These compositions may also contain other conventional components such as anionic, non-ionic, cationic or amphoteric surfactants, alkali metal salts (e.g. sodium carbonate, sodium silicate), neutral salts (e.g. sodium sulphate), zeolites, bleaching agents, bleaching activators and other minor ingredients.
  • alkali metal salts e.g. sodium carbonate, sodium silicate
  • neutral salts e.g. sodium sulphate
  • zeolites zeolites
  • bleaching agents bleaching activators and other minor ingredients.
  • novel co-builders are used in combination with zeolite-based detergents.
  • co-builders used according to the present invention are particularly efficacious in the presence of inorganic persalts, such as sodium perborate tetrahydrate or monohydrate.
  • the amount of the co-builders used in the process can vary from 1 g/washing cycle to 40 g/washing cycle, and preferably from 2 g/washing cycle to 20 g/washing cycle. This amount is achieved by a range of from 0.5 % to 20 % and preferably by a range of from 1 % to 10 %, expressed as 100 % dry substance of co-builder in the detergent or anti-incrustation compositions.
  • the co-builders used according to the present invention are naturally derived, biodegradable compounds. In combination with detergents they reduce the build up of inorganic incrustations on fabrics and on washing machine components. Such activity is more significant at high temperatures e.g. at 90°C.
  • the co-builder activities of the following compositions were evaluated on a laboratory scale using the so-called "Hampshire" test which measures the Ca ++ sequestering capacity of the composition.
  • the test was carried out as follows: 1 gram of the substance under test is dissolved in 100 ml of demineralised water, the solution filtered and the filtrate made up to 100 ml with demineralised water. 10 ml of a 2 % by weight aqueous solution of sodium carbonate is then added, the pH adjusted to 11 with sodium hydroxide solution (0.1 N or more concentrated for a large pH adjustment) and the temperature regulated at 20°C.
  • the solution is then titrated with a calcium acetate solution (39.59 g/l) at a rate of 1 ml/min until a permanent turbidity becomes apparent.
  • the quantity of Ca ++ in the calcium acetate solution determined by a preliminary titration with EDTA, is 10.03 mg Ca ++ /ml.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

A process for decreasing the build-up of inorganic incrustations on textiles deriving from water hardness and due to repeated washing cycles with detergent compositions comprises the addition to the washing batch of a carbohydrate or carbohydrate derivative having a DE of 0.5 to 20 inclusive as co-builder.

Description

  • The present invention relates to a process for decreasing the build-up of inorganic incrustations on fabrics caused by water hardness and repeated washing cycles with detergent compositions.
  • More particularly, the present invention relates to a process for decreasing the build-up of inorganic incrustations wherein a co-builder is added to the washing cycle, and to detergent and/or anti-incrustation compositions containing said co-builder.
  • It is well known that detergents contain builders in order to support detergent action and to eliminate calcium and magnesium ions (hardness ions), which arise partly from the water and sometimes also from soil and fabrics.
  • In case of multiple washing cycles the washing performance is significantly reduced because of the build up of inorganic incrustations on fabrics and on washing machine components. Such build up of inorganic incrustations on fabrics decreases the flexibility of fibres and consequently shortens the fabric life, in addition to greying the tissue.
  • A well known builder is sodium tripolyphosphate which has excellent properties in the washing process even at low concentrations. Despite its many advantageous properties however, it causes serious ecological problems, namely eutrophication of stationary or slowly flowing surface waters leading to extreme algal growth which adversely influences marine organisms. As a result, the use of phosphate free detergents is of great importance.
  • Some substitutes of phosphate builders such as zeolites have been adopted. However, zeolites alone in water softening have poor efficiency. Therefore, good anti-incrustation effects are achieved only in the presence of auxiliary compounds called co-builders.
  • The most widely used co-builders are synthetic polymers and/or co-polymers of olefinic mono- or dicarboxylic acids such as acrylic and maleic acid and copolymers of said monomers with other allylic or vinylic monomers. A common characteristic of these polymeric materials is their minimal biodegradability which leads to ecological problems.
  • There are known other non-polymeric co-builders, such as EDTA (ethylenediaminetetraacetic acid sodium salt), NTA (nitrilotriacetic acid sodium salt) and phosphonates. As with the polymeric co-builders these substances too are non-biodegradable.
  • It is therefore an object of the present invention to provide a process for decreasing the build-up of inorganic incrustations on fabrics and on washing machine components by using co-builders which are very efficient in reducing incrustation build up during washing cycles and which are cheap and biodegradable.
  • Another object of the present invention is to provide detergent and/or anti-incrustation compositions containing said biodegradable co-builders.
  • It has now surprisingly been found that certain carbohydrates show a high efficiency in reducing incrustation build up when combined with detergents, particularly with zeolite-based detergents.
  • In EP-A-0618286 there is described a co-builder based upon a non-reducing carbohydrate or a non-reducing carbohydrate derivative. Preferred among the non-reducing carbohydrate derivatives are certain sugar alcohols exemplified by maltitol and, especially, by mannitol. It has now been found however that the carbohydrate or carbohydrate derivative need not be fully non-reducing but that some reducing activity is tolerable and that certain compounds showing such activity are as effective co-builders as the sugar alcohols referred to above.
  • EP-A-0472042 discloses calcium-sequestering agents based on oxidised carbohydrates, a method for their preparation, and their use as builders or detergents. The document also relates to the sequestering capacity of oxidised glucosidic oligomers. The oxidisation is performed with hypochlorite or periodate, both giving highly oxidised products. JP-A-52059605 (Abstract) describes as a builder component a carboxymethylated hydrolysate of starch, cellulose or hemicellulose, in which the average degree of substitution by carboxymethyl groups for three hydroxyl groups in a structural unit is 1.5 to 3.0. The products contain a high density of carboxymethyl groups.
  • In accordance with one aspect of the present invention therefore there is provided a process for decreasing the build-up of inorganic incrustations on fabrics and on washing machine components during multiple washing cycles with detergent compositions characterised by the addition to the washing cycle of a co-builder based on a carbohydrate or carbohydrate derivative having a DE of 0.5 to 20 inclusive. The carbohydrate or carbohydrate derivative is selected from polydextrose, partially degraded inulin and maltodextrin.
  • A range of carbohydrates or carbohydrate derivatives having a DE of 0.5 to 20 inclusive may be used in the process of the invention eg. polydextrose or partially degraded inulin but preferably the carbohydrate or carbohydrate derivative is a maltodextrin having a DE of 0.5 to 20 inclusive, particularly a DE of 8 to 17 inclusive.
  • "DE" or dextrose equivalent is a measure of the reducing activity of a carbohydrate measured by comparison with dextrose which has a DE of 100.
  • The co-builders based on such carbohydrates and carbohydrate derivatives having a DE of 0.5 to 20 inclusive can be incorporated into the detergent compositions or added as such directly to the washing bath.
  • In accordance with another aspect of the present invention, there are provided detergent and/or anti-incrustation compositions containing the hereinbefore defined co-builders. These compositions may also contain other conventional components such as anionic, non-ionic, cationic or amphoteric surfactants, alkali metal salts (e.g. sodium carbonate, sodium silicate), neutral salts (e.g. sodium sulphate), zeolites, bleaching agents, bleaching activators and other minor ingredients.
  • In accordance with one preferred embodiment of the present invention the novel co-builders are used in combination with zeolite-based detergents.
  • The co-builders used according to the present invention are particularly efficacious in the presence of inorganic persalts, such as sodium perborate tetrahydrate or monohydrate.
  • The amount of the co-builders used in the process can vary from 1 g/washing cycle to 40 g/washing cycle, and preferably from 2 g/washing cycle to 20 g/washing cycle. This amount is achieved by a range of from 0.5 % to 20 % and preferably by a range of from 1 % to 10 %, expressed as 100 % dry substance of co-builder in the detergent or anti-incrustation compositions.
  • The co-builders used according to the present invention are naturally derived, biodegradable compounds. In combination with detergents they reduce the build up of inorganic incrustations on fabrics and on washing machine components. Such activity is more significant at high temperatures e.g. at 90°C.
  • The present invention is disclosed in still further detail in the following Example, which is supplied for purely illustrative and not limiting purposes.
    • Example
  • The co-builder activities of the following compositions were evaluated on a laboratory scale using the so-called "Hampshire" test which measures the Ca++ sequestering capacity of the composition. The test was carried out as follows:
    1 gram of the substance under test is dissolved in 100 ml of demineralised water, the solution filtered and the filtrate made up to 100 ml with demineralised water. 10 ml of a 2 % by weight aqueous solution of sodium carbonate is then added, the pH adjusted to 11 with sodium hydroxide solution (0.1 N or more concentrated for a large pH adjustment) and the temperature regulated at 20°C. The solution is then titrated with a calcium acetate solution (39.59 g/l) at a rate of 1 ml/min until a permanent turbidity becomes apparent. The quantity of Ca++ in the calcium acetate solution, determined by a preliminary titration with EDTA, is 10.03 mg Ca++/ml.
  • The results of the determinations in mg Ca++/g of test substance were as follows :
    Substance Solution with borax (2g/50 ml) Solution without borax
    Maltodextrin (DE = 12) 40.7 9.7
    Mannitol (comparitive) 46.9 7.9
    Maltitol (comparitive) 47.8 9.2

Claims (10)

  1. A process for decreasing the build up of inorganic incrustations on fabrics and on washing machine components during multiple washing cycles characterized by the addition to the washing cycle of a co-builder based on a carbohydrate or carbohydrate derivative having a DE of 0.5 to 20 inclusive, wherein the carbohydrate or carbohydrate derivative is selected from polydextrose, partially degraded inulin and maltodextrin.
  2. The process according to Claim 1, characterized in that the carbohydrate or carbohydrate derivative is a maltodextrin.
  3. The process according to Claim 2 characterized in that the maltodextrin has a DE of 8 to 17 inclusive.
  4. The process according to Claim 1, characterized in that the co-builder as such is added directly to the washing bath.
  5. The process according to Claim 4, characterized in that the co-builder is added in amount ranging from 1 g/washing cycle to 40 g/washing cycle, preferably from 2 g/washing cycle to 20 g/washing cycle.
  6. The process according to Claim 1, characterized in that the co-builder is incorporated in the detergent composition.
  7. Detergent and/or anti-incrustation composition containing a co-builder based on a carbohydrate or carbohydrate derivative having a DE of 0.5 to 20, wherein the carbohydrate or carbohydrate derivative is selected from polydextrose, partially degraded inulin and maltodextrin.
  8. Detergent and/or anti-incrustation composition according to Claim 7, characterized in that it contains a zeolite.
  9. Detergent and/or anti-incrustation composition according to Claim 7, characterized in that it contains the co-builder in an amount ranging from 0.5 % to 20 %, preferably from 1 % to 10 %, expressed as 100 % dry substance of the detergent or anti-incrustation composition.
  10. Detergent and/or anti-incrustation composition according to Claim 7, characterized in that it contains an inorganic persalt.
EP95306663A 1994-09-22 1995-09-21 Process for decreasing the build up of inorganic incrustations on textiles and detergent composition used in such a process Expired - Lifetime EP0703292B1 (en)

Applications Claiming Priority (2)

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GB9419091A GB9419091D0 (en) 1994-09-22 1994-09-22 Process for decreasing the build up of inorganic incrustations on textiles and detergent composition used in such process
GB9419091 1994-09-22

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EP0703292A1 EP0703292A1 (en) 1996-03-27
EP0703292B1 true EP0703292B1 (en) 2001-04-18

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EP (1) EP0703292B1 (en)
JP (1) JPH08176593A (en)
AT (1) ATE200692T1 (en)
CA (1) CA2158714A1 (en)
DE (1) DE69520720T2 (en)
ES (1) ES2155500T3 (en)
FI (1) FI113664B (en)
GB (1) GB9419091D0 (en)
MX (1) MX9504068A (en)

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US7417019B2 (en) 2000-07-14 2008-08-26 Henkel Kommanditgesellschaft Auf Aktien Hollow body with a compartment, containing a portion of a washing, cleaning or rinsing agent
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IT1249883B (en) * 1990-08-13 1995-03-30 Ferruzzi Ricerca & Tec CALCIUM SEQUESTRING AGENTS BASED ON OXIDIZED CARBOHYDRATES AND THEIR USE AS BUILDER FOR DETERGENTS
EP0618286A1 (en) * 1993-03-30 1994-10-05 AUSIMONT S.p.A. Process for decreasing the build up of inorganic incrustations on textiles and detergent composition used in such process

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7087570B2 (en) 1999-12-24 2006-08-08 Cognis Deutschland Gmbh & Co. Kg Detergent tablets
US6881359B2 (en) 2000-01-26 2005-04-19 Cognis Deutschland Gmbh & Co. Kg Processes for the preparation of low dust, limited particle size distribution, surfactant granules
US7098178B2 (en) 2000-03-16 2006-08-29 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Silicic acid ester mixtures
US6936581B2 (en) 2000-04-19 2005-08-30 Cognis Deutschland Gmbh & Co. Kg Processes for preparing anhydrous detergent granules
US7417019B2 (en) 2000-07-14 2008-08-26 Henkel Kommanditgesellschaft Auf Aktien Hollow body with a compartment, containing a portion of a washing, cleaning or rinsing agent
US6897193B2 (en) 2001-12-22 2005-05-24 Cognis Deutschland Gmbh & Co., Kg Hydroxy mixed ethers and polymers in the form of solid preparations as a starting compound for laundry detergents, dishwashing detergents and cleaning compositions
US7557145B2 (en) 2003-06-17 2009-07-07 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Inhibition of the asexual reproduction of fungi by eugenol and/or derivatives thereof
US7910647B2 (en) 2003-12-13 2011-03-22 Henkel Ag & Co. Kgaa Adhesion inhibition of microorganisms by non-ionic surfactants

Also Published As

Publication number Publication date
EP0703292A1 (en) 1996-03-27
CA2158714A1 (en) 1996-03-23
GB9419091D0 (en) 1994-11-09
ATE200692T1 (en) 2001-05-15
FI954506A (en) 1996-03-23
MX9504068A (en) 1997-02-28
DE69520720T2 (en) 2001-08-02
FI113664B (en) 2004-05-31
DE69520720D1 (en) 2001-05-23
ES2155500T3 (en) 2001-05-16
FI954506A0 (en) 1995-09-22
JPH08176593A (en) 1996-07-09

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