EP0892041A1 - Verwendung von oxidierten Polysacchariden in Waschmittelzusammensetzungen - Google Patents

Verwendung von oxidierten Polysacchariden in Waschmittelzusammensetzungen Download PDF

Info

Publication number: EP0892041A1
Authority: EP; European Patent Office
Prior art keywords: polysaccharide; oxidation; use according; polycarboxy; degree
Prior art date: 1997-07-15
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 Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Withdrawn

Application number

EP97202196A

Other languages

English (en)

French (fr)

Inventor

Cornelis Gerardus Van De Watering

Hermanna Anthonia Angenita Helena Visser

Johannes Wilhelmus Timmermans

Theodoor Maximiliaan Slaghek

Rik Julia Raoul Langerock

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.)

Instituut Voor Agrotechnologisch Onderzoek ATO DLO

Original Assignee

Instituut Voor Agrotechnologisch Onderzoek ATO DLO

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.)

1997-07-15

Filing date

1997-07-15

Publication date

1999-01-20

1997-07-15 Application filed by Instituut Voor Agrotechnologisch Onderzoek ATO DLO filed Critical Instituut Voor Agrotechnologisch Onderzoek ATO DLO

1997-07-15 Priority to EP97202196A priority Critical patent/EP0892041A1/de

1998-07-15 Priority to AU84659/98A priority patent/AU8465998A/en

1998-07-15 Priority to PCT/NL1998/000409 priority patent/WO1999003961A1/en

1998-07-15 Priority to CA002295481A priority patent/CA2295481A1/en

1998-07-15 Priority to EP98935395A priority patent/EP1002036A1/de

1998-07-15 Priority to JP2000503169A priority patent/JP2001510232A/ja

1999-01-20 Publication of EP0892041A1 publication Critical patent/EP0892041A1/de

Status Withdrawn legal-status Critical Current

Links

229920001282 polysaccharide Polymers 0.000 title claims abstract description 25
239000005017 polysaccharide Substances 0.000 title claims abstract description 25
239000003599 detergent Substances 0.000 title claims abstract description 13
239000000203 mixture Substances 0.000 title claims abstract description 13
150000004676 glycans Chemical class 0.000 title claims abstract 16
230000003647 oxidation Effects 0.000 claims abstract description 27
238000007254 oxidation reaction Methods 0.000 claims abstract description 27
125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
239000002689 soil Substances 0.000 claims abstract description 8
239000002270 dispersing agent Substances 0.000 claims abstract description 5
MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 8
239000003054 catalyst Substances 0.000 claims description 4
238000001556 precipitation Methods 0.000 claims description 4
239000010457 zeolite Substances 0.000 claims description 4
229920002774 Maltodextrin Polymers 0.000 claims description 3
229910021536 Zeolite Inorganic materials 0.000 claims description 3
HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
229910001919 chlorite Inorganic materials 0.000 claims description 2
229910052619 chlorite group Inorganic materials 0.000 claims description 2
QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 2
KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 2
239000005913 Maltodextrin Substances 0.000 claims 1
230000003301 hydrolyzing effect Effects 0.000 claims 1
TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 claims 1
229940035034 maltodextrin Drugs 0.000 claims 1
239000002184 metal Substances 0.000 claims 1
125000001483 monosaccharide substituent group Chemical group 0.000 claims 1
238000000926 separation method Methods 0.000 claims 1
239000000126 substance Substances 0.000 claims 1
229920002472 Starch Polymers 0.000 description 13
235000019698 starch Nutrition 0.000 description 13
239000008107 starch Substances 0.000 description 12
150000004804 polysaccharides Chemical class 0.000 description 9
239000000047 product Substances 0.000 description 8
238000000034 method Methods 0.000 description 7
KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 6
LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
229920001503 Glucan Polymers 0.000 description 4
229920000642 polymer Polymers 0.000 description 4
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
229920002245 Dextrose equivalent Polymers 0.000 description 3
229910019142 PO4 Inorganic materials 0.000 description 3
HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
230000000694 effects Effects 0.000 description 3
ZFTFOHBYVDOAMH-XNOIKFDKSA-N (2r,3s,4s,5r)-5-[[(2r,3s,4s,5r)-5-[[(2r,3s,4s,5r)-3,4-dihydroxy-2,5-bis(hydroxymethyl)oxolan-2-yl]oxymethyl]-3,4-dihydroxy-2-(hydroxymethyl)oxolan-2-yl]oxymethyl]-2-(hydroxymethyl)oxolane-2,3,4-triol Chemical class O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@@H]1[C@@H](O)[C@H](O)[C@](CO)(OC[C@@H]2[C@H]([C@H](O)[C@@](O)(CO)O2)O)O1 ZFTFOHBYVDOAMH-XNOIKFDKSA-N 0.000 description 2
VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
229920002670 Fructan Polymers 0.000 description 2
CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
239000005708 Sodium hypochlorite Substances 0.000 description 2
229920002125 Sokalan® Polymers 0.000 description 2
238000006243 chemical reaction Methods 0.000 description 2
238000004519 manufacturing process Methods 0.000 description 2
239000010452 phosphate Substances 0.000 description 2
235000021317 phosphate Nutrition 0.000 description 2
229920000058 polyacrylate Polymers 0.000 description 2
229920001592 potato starch Polymers 0.000 description 2
239000002244 precipitate Substances 0.000 description 2
SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
239000007858 starting material Substances 0.000 description 2
239000000725 suspension Substances 0.000 description 2
102000013142 Amylases Human genes 0.000 description 1
108010065511 Amylases Proteins 0.000 description 1
OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
QXKAIJAYHKCRRA-JJYYJPOSSA-N D-arabinonic acid Chemical group OC[C@@H](O)[C@@H](O)[C@H](O)C(O)=O QXKAIJAYHKCRRA-JJYYJPOSSA-N 0.000 description 1
102000004190 Enzymes Human genes 0.000 description 1
108090000790 Enzymes Proteins 0.000 description 1
229920002488 Hemicellulose Polymers 0.000 description 1
229920001202 Inulin Polymers 0.000 description 1
BQSLGJHIAGOZCD-CIUDSAMLSA-N Leu-Ala-Ser Chemical compound CC(C)C[C@H](N)C(=O)N[C@@H](C)C(=O)N[C@@H](CO)C(O)=O BQSLGJHIAGOZCD-CIUDSAMLSA-N 0.000 description 1
FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
229920000881 Modified starch Polymers 0.000 description 1
GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
102000035195 Peptidases Human genes 0.000 description 1
108091005804 Peptidases Proteins 0.000 description 1
239000004365 Protease Substances 0.000 description 1
239000004115 Sodium Silicate Substances 0.000 description 1
DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
239000004141 Sodium laurylsulphate Substances 0.000 description 1
QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 1
239000002253 acid Substances 0.000 description 1
GUBGYTABKSRVRQ-ASMJPISFSA-N alpha-maltose Chemical class O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-ASMJPISFSA-N 0.000 description 1
235000019418 amylase Nutrition 0.000 description 1
229940025131 amylases Drugs 0.000 description 1
239000002518 antifoaming agent Substances 0.000 description 1
QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
239000011230 binding agent Substances 0.000 description 1
238000004061 bleaching Methods 0.000 description 1
239000007844 bleaching agent Substances 0.000 description 1
239000011575 calcium Substances 0.000 description 1
229910052791 calcium Inorganic materials 0.000 description 1
229910000019 calcium carbonate Inorganic materials 0.000 description 1
150000001720 carbohydrates Chemical class 0.000 description 1
235000014633 carbohydrates Nutrition 0.000 description 1
150000007942 carboxylates Chemical class 0.000 description 1
125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
230000003197 catalytic effect Effects 0.000 description 1
239000001913 cellulose Substances 0.000 description 1
229920002678 cellulose Polymers 0.000 description 1
239000003795 chemical substances by application Substances 0.000 description 1
239000000460 chlorine Substances 0.000 description 1
229910052801 chlorine Inorganic materials 0.000 description 1
239000004927 clay Substances 0.000 description 1
238000004140 cleaning Methods 0.000 description 1
229910052802 copper Inorganic materials 0.000 description 1
239000010949 copper Substances 0.000 description 1
238000004851 dishwashing Methods 0.000 description 1
238000004090 dissolution Methods 0.000 description 1
230000007613 environmental effect Effects 0.000 description 1
230000002255 enzymatic effect Effects 0.000 description 1
229940088598 enzyme Drugs 0.000 description 1
238000012869 ethanol precipitation Methods 0.000 description 1
238000005187 foaming Methods 0.000 description 1
239000004088 foaming agent Substances 0.000 description 1
238000009472 formulation Methods 0.000 description 1
239000003205 fragrance Substances 0.000 description 1
238000004108 freeze drying Methods 0.000 description 1
230000007062 hydrolysis Effects 0.000 description 1
238000006460 hydrolysis reaction Methods 0.000 description 1
JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 description 1
229940029339 inulin Drugs 0.000 description 1
-1 inulin) Chemical class 0.000 description 1
102100033718 m7GpppX diphosphatase Human genes 0.000 description 1
101710129383 m7GpppX diphosphatase Proteins 0.000 description 1
239000011777 magnesium Substances 0.000 description 1
229910052749 magnesium Inorganic materials 0.000 description 1
239000000463 material Substances 0.000 description 1
235000019426 modified starch Nutrition 0.000 description 1
229910017604 nitric acid Inorganic materials 0.000 description 1
239000001301 oxygen Substances 0.000 description 1
229910052760 oxygen Inorganic materials 0.000 description 1
NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
239000003352 sequestering agent Substances 0.000 description 1
229910000029 sodium carbonate Inorganic materials 0.000 description 1
239000001509 sodium citrate Substances 0.000 description 1
NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
235000019333 sodium laurylsulphate Nutrition 0.000 description 1
229960001922 sodium perborate Drugs 0.000 description 1
NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
229910052911 sodium silicate Inorganic materials 0.000 description 1
YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
229920001059 synthetic polymer Polymers 0.000 description 1
239000004753 textile Substances 0.000 description 1
239000002562 thickening agent Substances 0.000 description 1
238000005406 washing Methods 0.000 description 1
239000002699 waste material Substances 0.000 description 1
229920001221 xylan Polymers 0.000 description 1
150000004823 xylans Chemical class 0.000 description 1

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 Tihlárik, 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, and 1,3-glucans or 1,6-glucans can also be used.
Another class of suitable polysaccharides are fructans (e.g. inulin), which can be used with molecular weights from about 240 upwards, especially 500-12,000, most preferably 1600-5000, and pentosans, such as xylans (hemicellulose), e.g. from waste carbohydrates.
the degree of oxidation is preferably from 0.12 to 0.6, preferably from 0.2 to 0.55.
the oxidised polysaccharides are preferably obtained by treatment of the polysaccharide (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 or C3-C4 oxidation in fructans
oxidation with periodate cf. WO 95/12619 or Nieuwenhuizen et al, Starch/Stärke , 37 (1985) 192-200
chlorite oxidation 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), 198.., as follows: 75 g of 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% Cl 2 ) at ambient temperature. The pH was maintained at 8.5 by the addition of 5 M NaOH.

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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)

EP97202196A 1997-07-15 1997-07-15 Verwendung von oxidierten Polysacchariden in Waschmittelzusammensetzungen Withdrawn EP0892041A1 (de)

Priority Applications (6)

Application Number	Priority Date	Filing Date	Title
EP97202196A EP0892041A1 (de)	1997-07-15	1997-07-15	Verwendung von oxidierten Polysacchariden in Waschmittelzusammensetzungen
AU84659/98A AU8465998A (en)	1997-07-15	1998-07-15	Use of oxidised polysaccharides in detergent compositions
PCT/NL1998/000409 WO1999003961A1 (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
EP98935395A EP1002036A1 (de)	1997-07-15	1998-07-15	Verwendung von oxidierten polysacchariden in waschmittelzusammensetzungen
JP2000503169A JP2001510232A (ja)	1997-07-15	1998-07-15	洗剤組成物における酸化された多糖の使用

Applications Claiming Priority (1)

Application Number	Priority Date	Filing Date	Title
EP97202196A EP0892041A1 (de)	1997-07-15	1997-07-15	Verwendung von oxidierten Polysacchariden in Waschmittelzusammensetzungen

Publications (1)

Publication Number	Publication Date
EP0892041A1 true EP0892041A1 (de)	1999-01-20

Family

ID=8228559

Family Applications (2)

Application Number	Title	Priority Date	Filing Date
EP97202196A Withdrawn EP0892041A1 (de)	1997-07-15	1997-07-15	Verwendung von oxidierten Polysacchariden in Waschmittelzusammensetzungen
EP98935395A Withdrawn EP1002036A1 (de)	1997-07-15	1998-07-15	Verwendung von oxidierten polysacchariden in waschmittelzusammensetzungen

Family Applications After (1)

Application Number	Title	Priority Date	Filing Date
EP98935395A Withdrawn EP1002036A1 (de)	1997-07-15	1998-07-15	Verwendung von oxidierten polysacchariden in waschmittelzusammensetzungen

Country Status (5)

Country	Link
EP (2)	EP0892041A1 (de)
JP (1)	JP2001510232A (de)
AU (1)	AU8465998A (de)
CA (1)	CA2295481A1 (de)
WO (1)	WO1999003961A1 (de)

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DE102008053607A1 (de) *	2008-10-20	2010-04-22	Südzucker AG Mannheim/Ochsenfurt	Solubilisierungsmittel für Metallionen
US7727945B2 (en)	2005-07-15	2010-06-01	Akzo Nobel N.V.	Modified polysaccharides
FR2961394A1 (fr) *	2010-06-21	2011-12-23	Oreal	Composition cosmetique comprenant au moins un polysaccharide oxyde non cationique et une huile, de preference polaire
US9376648B2 (en)	2008-04-07	2016-06-28	The Procter & Gamble Company	Foam manipulation compositions containing fine particles
EP3820983A1 (de) *	2018-07-09	2021-05-19	Coöperatie Koninklijke Cosun U.A.	Antischuppenmittel mit uronsäure-polysaccharid

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WO2009122953A1 (ja) *	2008-03-31	2009-10-08	花王株式会社	ポリウロン酸塩の製造方法
JP2009263641A (ja) *	2008-03-31	2009-11-12	Kao Corp	ポリウロン酸塩の製造方法
JP5544107B2 (ja) *	2008-03-31	2014-07-09	花王株式会社	高分子ビルダー
EP3116914B8 (de) *	2014-03-11	2021-04-21	E. I. du Pont de Nemours and Company	Oxidierter poly-alpha-1,3-glucan als waschmittelbuilder
CN112020550A (zh) *	2018-05-23	2020-12-01	陶氏环球技术有限责任公司	无水自动餐具配制物

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1997
- 1997-07-15 EP EP97202196A patent/EP0892041A1/de not_active Withdrawn
1998
- 1998-07-15 WO PCT/NL1998/000409 patent/WO1999003961A1/en not_active Ceased
- 1998-07-15 JP JP2000503169A patent/JP2001510232A/ja active Pending
- 1998-07-15 AU AU84659/98A patent/AU8465998A/en not_active Abandoned
- 1998-07-15 EP EP98935395A patent/EP1002036A1/de not_active Withdrawn
- 1998-07-15 CA CA002295481A patent/CA2295481A1/en not_active Abandoned

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US7727945B2 (en)	2005-07-15	2010-06-01	Akzo Nobel N.V.	Modified polysaccharides
US8039428B2 (en)	2005-07-15	2011-10-18	Akzo Nobel, N.V.	Modified polysaccharides
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US8729008B2 (en)	2008-10-20	2014-05-20	Suedzucker Aktiengesellschaft Mannheim/Ochsenfurt	Starch hydrolyzate solubilizer for metal ions
FR2961394A1 (fr) *	2010-06-21	2011-12-23	Oreal	Composition cosmetique comprenant au moins un polysaccharide oxyde non cationique et une huile, de preference polaire
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EP3820983A1 (de) *	2018-07-09	2021-05-19	Coöperatie Koninklijke Cosun U.A.	Antischuppenmittel mit uronsäure-polysaccharid

Also Published As

Publication number	Publication date
WO1999003961A1 (en)	1999-01-28
EP1002036A1 (de)	2000-05-24
CA2295481A1 (en)	1999-01-28
JP2001510232A (ja)	2001-07-31
AU8465998A (en)	1999-02-10

Legal Events

Date	Code	Title	Description
1998-12-04	PUAI	Public reference made under article 153(3) epc to a published international application that has entered the european phase	Free format text: ORIGINAL CODE: 0009012
1999-01-20	AK	Designated contracting states	Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE
1999-01-20	AX	Request for extension of the european patent	Free format text: AL;LT;LV;RO;SI
1999-09-29	AKX	Designation fees paid
2000-03-31	STAA	Information on the status of an ep patent application or granted ep patent	Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN
2000-05-17	18D	Application deemed to be withdrawn	Effective date: 19990721
2000-06-21	REG	Reference to a national code	Ref country code: DE Ref legal event code: 8566

Publication	Publication Date	Title
AU639193B2 (en)	1993-07-15	Calcium-sequestering agents based on oxidised carbohydrates and their use as builders for detergents
WO1996038484A1 (en)	1996-12-05	Oxidized polymeric carbohydrate ethers for use as sequestering agent, and methods for the preparation thereof
US5959101A (en)	1999-09-28	Production of polysaccharide-based polycarboxylates
CA2029542C (en)	2001-04-24	Method for the preparation of polydicarboxysaccharides, and substitutes for phosphates in detergents, based on the polydicarboxysaccharides
EP0892041A1 (de)	1999-01-20	Verwendung von oxidierten Polysacchariden in Waschmittelzusammensetzungen
JPH04356513A (ja)	1992-12-10	単糖類、少糖類、多糖類及びそれらの誘導体のグラフト共重合体、その製造方法及び該共重合体から成る洗浄剤及び清浄剤添加物
EP0526494A1 (de)	1993-02-10	Verfahren zur herstellung von polycarboxylierten polysacchariden welche calcium-binden und phosphatsubstituierten in detergentien auf basis von diesen polycarboxylierten verbindungen
Besemer et al.	1994	Dicarboxy‐Starch by Sodium Hypochlorite/Bromide Oxidation and Its Calcium Binding Properties
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JP5544107B2 (ja)	2014-07-09	高分子ビルダー
NL1004738C2 (nl)	1998-06-11	Fructaan-polycarbonzuur.
CN1212708A (zh)	1999-03-31	氧化淀粉的方法
US6020295A (en)	2000-02-01	Detergent builders/activators derived from the oxidation and acylation of polysaccharides
US4100342A (en)	1978-07-11	Process of producing dextrin carboxylates
EP3880881B1 (de)	2025-02-26	Verfahren zur behandlung von stoffen
US5763381A (en)	1998-06-09	Starched-based adjuncts for detergents
JPH06279504A (ja)	1994-10-04	金属イオン封鎖性オリゴマー化合物の製造方法及びそのオリゴマー化合物を含む洗浄剤組成物
WO2002070574A2 (en)	2002-09-12	Soil release polymers and laundry detergent compositions containing them
Besemer et al.	1996	Calcium sequestering agents based on carbohydrates
NL8802907A (nl)	1990-06-18	Werkwijze voor het vervaardigen van dicarboxypolysacchariden.
MXPA97008497A (en)	1998-01-01	Adjuvants / activators for deterge
Beck	2001	Detergent co-builders
ZA200305614B (en)	2004-07-21	Soil release polymers and laundry detergent compositions containing them.