WO1999003961A1 - Use of oxidised polysaccharides in detergent compositions - Google Patents
Use of oxidised polysaccharides in detergent compositions Download PDFInfo
- Publication number
- WO1999003961A1 WO1999003961A1 PCT/NL1998/000409 NL9800409W WO9903961A1 WO 1999003961 A1 WO1999003961 A1 WO 1999003961A1 NL 9800409 W NL9800409 W NL 9800409W WO 9903961 A1 WO9903961 A1 WO 9903961A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polysaccharide
- oxidation
- use according
- polycarboxy
- degree
- Prior art date
Links
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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
-
- 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
- C11D3/223—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin oxidised
Definitions
- the invention relates to the use of polycarboxy polysaccharides in detergent compositions.
- Detergent compositions contain a builder to neutralise the effect of water hardness, dissolution of soil and the like.
- phosphate is an effective builder, its use is undesired for environmental reasons.
- Zeolites have largely replaced phosphates as builder.
- they require the presence of a cobuilder which prevents the redeposition of soil and the precipitation of calcium carbonate, and improves whiteness of the washed laundry.
- Synthetic polymers, such as polyacrylates have found extensive use as cobuilders, but they are poorly biodegradable. Thus there is need for biodegradable and yet effective cobuilder materials for use in textile washing compositions, dish-washing compositions and the like.
- EP- A- 755944 discloses a method for the production of oxidising maltodextrins having a DE (dextrose equivalent) between 2 and 20, especially a DE of 11-14, using oxygen or hydrogen peroxide under alkaline conditions in the absence of a catalyst followed by bleaching. This oxidation results in conversion of the reducing end groups in arabinonic acid groups.
- the product can be used as a cobuilder in detergent compositions wherein it improves whiteness and reduces inorganic incrustation, or as a binder or thickening agent.
- dicarboxylic polysaccharides such as dicarboxy starch and dicarboxy amylodextrins as a calcium sequestering agent has been described in various documents, e.g. Kohn and Tihlarik, Coll. Czech. Chem. Commun. 49 (1984) 2116, EP-A-427349 and NL-A-8802907.
- the polysaccharides to be oxidised according to the invention are primarily starch and starch derivatives such as hydrolysed starch and carboxymethyl starch.
- Other glucans such as cellulose derivatives, 1,3-glucans or 1,6-glucans, galactomannans (e.g. guar) and other vegetal and bacterial gums, can also be used. These have molecular weights of 1600-12,000 (10-75 anhydromonose units), preferably of 2000-10,000 (12-60 amu's), most preferably 2900-7300 (18-40 amu's).
- Other classes of suitable poly-saccharides are fructans (e.g.
- inulin which can be used with molecular weights from about 240 upwards, especially 500-12,000, more preferably 1600-5000 (10-30 amu's), and pentosans, such as xylans (hemicellulose), e.g. from waste carbohydrates, with molecular weights of 1500-12,000, preferably 2000-8000, most preferably 2600- 6600 (20-50 amu's).
- the degree of oxidation is preferably from 0.12 to 0.6, preferably from 0.15 to 0.55, especially form 0.2 to 0.5.
- the oxidised polysaccharides are preferably obtained by treatment of the poly- saccharide (e.g. starch) with a hypochlorite solution at pH 7.5-10, especially at pH 8-9, the hypochlorite being added gradually in order to be able to maintain the pH more or less constant by addition of a base.
- the reaction temperature can be e.g. between 0 and 40 °C, especially at ambient temperature.
- the oxidised product can be isolated by known techniques, including ethanol precipitation and freeze-drying. Such precipitation has the advantage of removing products that have excessive degrees of oxidation.
- C2-C3 oxidation of glucans, mannans, xylans etc. are also suitable, for example oxidation with periodate (cf. WO 95/12619 or Nieuwenhuizen et al, StarchlSt ⁇ rke, 37 (1985) 192-200), followed by chlorite oxidation.
- Other oxidations can also be used, e.g. oxidation with hydrogen peroxide in the presence of acetylated polysaccharides, or oxidation with hydrogen peroxide in the presence of copper and magnesium or other oxidation catalysts.
- Combinations of oxidation processes may also be used.
- a hydrolysis step (acid or enzymatic) may precede or follow the oxidation step.
- the invention also pertains to detergent compositions containing a polycarboxy polysaccharide as described above as a cobuilder, anti-redeposition agent and/or soil dispersant.
- the composition contains 0.5-5 wt.% of the cobuilder prepared according to the invention, and further a detergent (12-25, especially 16-20 wt.%), a zeolite or silicate builder (15-30, especially 20-28 wt.%), a carboxylate such as sodium citrate (3-5 wt.%), a bleaching agent such as sodium perborate (10-20 wt.%), a catalyst such as TAED (3-4 wt.%), and optional further components such as enzymes (about 1-2 %: amylases, proteases), foaming or defoaming agents, odorants and the like.
- Starch was oxidised generally according to Floor, "Oxidation of maltodextrins and starch with alkaline sodium hypochlorite", Thesis, Chapter 6, Delft (NL), 1989, as follows: 75 g of potato starch was suspended in 250 ml water. The pH was adjusted to 8.5. The appropriate amount of sodium hypochlorite solution (4% or 16% active chlorine) was added at a rate of 10 ml/min for the first half hour and 20 ml/min afterwards for 4 % Cl 2 (2.5 and 5 ml/min, respectively, for 15% CI2) at ambient temperature. The pH was maintained at 8.5 by the addition of 5 M NaOH. After 20 h the pH was adjusted to 9 and 500 ml of ethanol 98% was added.
- the suspension was stored at -4°C for 16 h and then decanted.
- the precipitate was dissolved in 150 ml water and 300 ml of ethanol was added.
- the suspension was again stored at -4°C for 16 h and then decanted.
- the precipitate was dissolved in 150 ml water and the solution was freeze-dried.
- DCS-1 Paselli 6 (molecular weight of native starch reduced by a factor 6), 550 ml 4% Cl 2 , dicarboxy content 9% (carboxyl content 0.36 per anhydromonose unit), MW about 5400;
- DCS-2 Paselli 2, 500 ml 15% Cl 2 , dicarboxy content 19% (carboxyl content 0.48), MW about 3200;
- DCS-3 native potato starch, 390 ml 15% Cl , dicarboxy content 18% (carboxyl content 0.36), MW about 4700;
- DCS-4 native potato starch, 500 ml 15% Cl 2 , dicarboxy content 21% (carboxyl content 0.48), MW about 3600.
- Example 3 Wash tests Two co-builders were tested in a standard heavy duty formulation (HDF: see table 1) during 25 wash cycles using the 60°C cotton washing programme without prewash.
- product R HDF with reference cobuilder Sokalan CP 5 (a commercial polyacrylate cobuilder)
- the washing tests were carried out in commercial drum-type domestic washing machines Miele Novotronic W 918.
- the test of each product was made in alternating machines, in order to avoid effects caused by specific differences of the machines.
- the tests were carried out at a water hardness of 2.86 mmol/1 in a 60°C cotton programme without prewash.
- the total machine load was 4.5 kg.
- the dosage of formulation was 80 g per wash.
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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)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98935395A EP1002036A1 (en) | 1997-07-15 | 1998-07-15 | Use of oxidised polysaccharides in detergent compositions |
CA002295481A CA2295481A1 (en) | 1997-07-15 | 1998-07-15 | Use of oxidised polysaccharides in detergent compositions |
AU84659/98A AU8465998A (en) | 1997-07-15 | 1998-07-15 | Use of oxidised polysaccharides in detergent compositions |
JP2000503169A JP2001510232A (en) | 1997-07-15 | 1998-07-15 | Use of oxidized polysaccharides in detergent compositions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97202196.8 | 1997-07-15 | ||
EP97202196A EP0892041A1 (en) | 1997-07-15 | 1997-07-15 | Use of oxidised polysaccharides in detergent compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999003961A1 true WO1999003961A1 (en) | 1999-01-28 |
Family
ID=8228559
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/NL1998/000409 WO1999003961A1 (en) | 1997-07-15 | 1998-07-15 | Use of oxidised polysaccharides in detergent compositions |
Country Status (5)
Country | Link |
---|---|
EP (2) | EP0892041A1 (en) |
JP (1) | JP2001510232A (en) |
AU (1) | AU8465998A (en) |
CA (1) | CA2295481A1 (en) |
WO (1) | WO1999003961A1 (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7727945B2 (en) | 2005-07-15 | 2010-06-01 | Akzo Nobel N.V. | Modified polysaccharides |
JP2009263641A (en) * | 2008-03-31 | 2009-11-12 | Kao Corp | Method for producing polyuronate |
JP5544107B2 (en) * | 2008-03-31 | 2014-07-09 | 花王株式会社 | Polymer builder |
WO2009122953A1 (en) * | 2008-03-31 | 2009-10-08 | 花王株式会社 | Method for manufacturing polyuronate |
US9376648B2 (en) | 2008-04-07 | 2016-06-28 | The Procter & Gamble Company | Foam manipulation compositions containing fine particles |
DE102008053607A1 (en) | 2008-10-20 | 2010-04-22 | Südzucker AG Mannheim/Ochsenfurt | Solubilizing agent for metal ions |
FR2961394B1 (en) * | 2010-06-21 | 2012-06-01 | Oreal | COSMETIC COMPOSITION COMPRISING AT LEAST ONE NON-CATIONIC OXIDE POLYSACCHARIDE AND OIL, OF POLAR PREFERENCE |
US9695253B2 (en) * | 2014-03-11 | 2017-07-04 | E I Du Pont De Nemours And Company | Oxidized poly alpha-1,3-glucan |
EP3797146A1 (en) * | 2018-05-23 | 2021-03-31 | Dow Global Technologies, LLC | Anhydrous autodish formulation |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL8802907A (en) * | 1988-11-25 | 1990-06-18 | Avebe Coop Verkoop Prod | Di:carbox poly-saccharide(s) prodn. - by oxidn. of di:aldehyde polysaccharide(s) using alkali(ne earth) chlorite(s) |
EP0427349A2 (en) * | 1989-11-10 | 1991-05-15 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Method for the preparation of polydicarboxysaccharides |
EP0472042A1 (en) * | 1990-08-13 | 1992-02-26 | NOVAMONT S.p.A. | Calcium-sequestering agents based on oxidised carbohydrates and their use as builders for detergents |
WO1993008251A1 (en) * | 1991-10-23 | 1993-04-29 | Henkel Kommanditgesellschaft Auf Aktien | Washing and cleaning agents with selected builder systems |
EP0542496A1 (en) * | 1991-11-14 | 1993-05-19 | The Procter & Gamble Company | C6/C2-C3 Oxidized starch as detergent ingredient |
EP0548399A1 (en) * | 1991-12-23 | 1993-06-30 | Cerestar Holding B.V. | Process for the production of oxyacids from carbohydrates |
WO1995012619A1 (en) * | 1993-11-04 | 1995-05-11 | Instituut Voor Agrotechnologisch Onderzoek (Ato-Dlo) | Method for the oxidation of carbohydrates |
EP0755944A2 (en) * | 1995-07-11 | 1997-01-29 | Cerestar Holding Bv | Polyhydroxycarboxylic acid composition derived from maltodextrins by oxidation with an oxygen containing oxidant |
-
1997
- 1997-07-15 EP EP97202196A patent/EP0892041A1/en not_active Withdrawn
-
1998
- 1998-07-15 AU AU84659/98A patent/AU8465998A/en not_active Abandoned
- 1998-07-15 EP EP98935395A patent/EP1002036A1/en not_active Withdrawn
- 1998-07-15 CA CA002295481A patent/CA2295481A1/en not_active Abandoned
- 1998-07-15 WO PCT/NL1998/000409 patent/WO1999003961A1/en not_active Application Discontinuation
- 1998-07-15 JP JP2000503169A patent/JP2001510232A/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL8802907A (en) * | 1988-11-25 | 1990-06-18 | Avebe Coop Verkoop Prod | Di:carbox poly-saccharide(s) prodn. - by oxidn. of di:aldehyde polysaccharide(s) using alkali(ne earth) chlorite(s) |
EP0427349A2 (en) * | 1989-11-10 | 1991-05-15 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Method for the preparation of polydicarboxysaccharides |
EP0472042A1 (en) * | 1990-08-13 | 1992-02-26 | NOVAMONT S.p.A. | Calcium-sequestering agents based on oxidised carbohydrates and their use as builders for detergents |
WO1993008251A1 (en) * | 1991-10-23 | 1993-04-29 | Henkel Kommanditgesellschaft Auf Aktien | Washing and cleaning agents with selected builder systems |
EP0542496A1 (en) * | 1991-11-14 | 1993-05-19 | The Procter & Gamble Company | C6/C2-C3 Oxidized starch as detergent ingredient |
EP0548399A1 (en) * | 1991-12-23 | 1993-06-30 | Cerestar Holding B.V. | Process for the production of oxyacids from carbohydrates |
WO1995012619A1 (en) * | 1993-11-04 | 1995-05-11 | Instituut Voor Agrotechnologisch Onderzoek (Ato-Dlo) | Method for the oxidation of carbohydrates |
EP0755944A2 (en) * | 1995-07-11 | 1997-01-29 | Cerestar Holding Bv | Polyhydroxycarboxylic acid composition derived from maltodextrins by oxidation with an oxygen containing oxidant |
Also Published As
Publication number | Publication date |
---|---|
EP0892041A1 (en) | 1999-01-20 |
CA2295481A1 (en) | 1999-01-28 |
JP2001510232A (en) | 2001-07-31 |
EP1002036A1 (en) | 2000-05-24 |
AU8465998A (en) | 1999-02-10 |
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