EP2692843A1 - Utilisation d'hydrolysats d'amidon à oxydation C1 - Google Patents

Utilisation d'hydrolysats d'amidon à oxydation C1 Download PDF

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Publication number
EP2692843A1
EP2692843A1 EP12005684.1A EP12005684A EP2692843A1 EP 2692843 A1 EP2692843 A1 EP 2692843A1 EP 12005684 A EP12005684 A EP 12005684A EP 2692843 A1 EP2692843 A1 EP 2692843A1
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EP
European Patent Office
Prior art keywords
starch hydrolysate
detergent composition
oxidised
enzyme
chelating agent
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.)
Ceased
Application number
EP12005684.1A
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German (de)
English (en)
Inventor
designation of the inventor has not yet been filed The
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.)
Tiense Suikerraffinaderij NV
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Tiense Suikerraffinaderij NV
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 Tiense Suikerraffinaderij NV filed Critical Tiense Suikerraffinaderij NV
Priority to EP12005684.1A priority Critical patent/EP2692843A1/fr
Priority to EP13762399.7A priority patent/EP2880145A1/fr
Priority to PCT/EP2013/002252 priority patent/WO2014019680A1/fr
Publication of EP2692843A1 publication Critical patent/EP2692843A1/fr
Ceased legal-status Critical Current

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    • 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
    • C11D3/221—Mono, di- or trisaccharides or derivatives 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
    • C11D3/20—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
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38663—Stabilised liquid enzyme compositions

Definitions

  • the invention relates to a use of a chelating agent containing a starch hydrolysate that has been selectively oxidised at the C1 location in a detergent composition.
  • WO-A-2010/046070 discloses that starch hydrolysates that contain compounds with a degree of polymerisation (DP) of 2 to 4, whereby the said starch hydrolysates have been selectively oxidized at the C1 location of the carbohydrate moieties, can be used as chelating agents.
  • a starch hydrolysate that has been selectively oxidized at the C1 location of the carbohydrate moieties is herein also referred to as a 'C1-oxidised starch hydrolysate'.
  • the said objective is achieved in that the C1-oxidised starch hydrolysate is used as enzyme stabilising agent in a detergent composition.
  • one component of a detergent composition can fulfil at least two functions at the same time in a detergent composition; namely, a function as chelating agent, i.e. a solubilising agent for sparingly soluble metal ions, and a function as stabiliser of enzymes.
  • the present invention can thus advantageously allow a reduction of the amount of enzyme-stabilising agents other than C1-oxidised starch hydrolysates in a detergent composition.
  • the present invention relates to a further use of a chelating agent.
  • chelating agent has its usual meaning of a compound that can form a soluble complex with certain metal ions, thereby preventing the metal ions to form precipitates or scale.
  • chelating agents are normally used for the purpose of forming soluble complexes with calcium ions and/or transition metal ions.
  • the chelating agent of the present invention contains a starch hydrolysate that has been selectively oxidised at the C1 location.
  • starch hydrolysate has the usual meaning of a starch that has been subjected to a hydrolysis treatment in order to reduce the degree of polymerisation (DP) of the carbohydrate moieties in the starch.
  • DP degree of polymerisation
  • Known examples of such treatments are acid hydrolysis and enzymatic hydrolysis.
  • the hydrolysis treatment on the starch is done such that the resulting starch hydrolysate contains at least 5 wt.%, calculated on the total dry matter of the starch hydrolysate, of compounds having a DP of 2, 3, or 4.
  • the starch hydrolysate contains at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or even at least 85 or 90 wt.%, calculated on the total dry matter of the starch hydrolysate, of compounds having a DP of 2, 3, or 4.
  • a starch hydrolysate is used that has been selectively oxidised at the C1 location of the carbohydrate moieties.
  • a selective oxidation is as such known from for example WO-A-2004/099114 . It is preferred that the selective oxidation is done such that at least 75, 80, 85, 90, or 95%, or even essentially all of the available target groups are oxidised.
  • the C1-oxidised starch hydrolysate contains at least 5 wt.% of maltobionic acid; more preferably, the C1-oxidised starch hydrolysate contains at least 10, 15, 20, 25, 30, or even at least 35 or 40 wt.%, calculated on the total dry matter of the C1-oxidised starch hydrolysate, of maltobionic acid.
  • maltobionic acid refers to the compound itself, as well as to salts thereof such as sodium maltobionate.
  • the chelating agent of the invention consists essentially of a starch hydrolysate that has been selectively oxidised at the C1 location.
  • the terms 'essentially', 'consist(ing) essentially of, 'essentially all' and equivalents have, unless noted otherwise, in relation to a composition or a process step the usual meaning that deviations in the composition or process step may occur, but only to such an extent that the essential characteristics and effects of the composition or process step are not materially affected by such deviations.
  • the chelating agent of the present invention is used as a component in a detergent composition.
  • any type of detergent composition is suitable; it should however be a detergent composition that has, besides having one or more surfactants as components in order to generate the basic detergent functionality, at least one enzyme as a component.
  • Typical examples of enzymes are proteases, amylases, lipases, cellulases, and mannases.
  • Such detergent compositions are widely known, a.o. for the cleaning of textiles.
  • the detergent composition may be in the form of for example a powder, a tablet, a gel capsule, or in liquid form; preferably, the detergent composition is in liquid form or in the form of a gel capsule.
  • the chelating agent containing or consisting essentially of a C1-oxidised starch hydrolysate is not only used in its chelating function, but also as enzyme-stabilising agent. It is known that the functionality of enzymes in detergents can reduce over time. It has therefore already in the past been an object of investigation to find ways to stabilise the enzymes.
  • One popular method of stabilising enzymes involves the use of boron-containing compounds such as boric acid or disodiumtetraborate ('borax').
  • 'borax' disodiumtetraborate
  • the use according to the present invention therefore, achieves the objective of finding alternatives to boron-containing compounds.
  • the objective is achieved by using a component which can at the same time exercise a chelating function.
  • a component which can at the same time exercise a chelating function.
  • This combination is surprising because it is known that most of the currently used enzymes in detergent compositions require the presence of calcium ions in order to function and be stable; thus, a chelating agent may not be of such a nature that too many calcium ions are bound by it under the conditions prevailing in a detergent composition - either as such or when in use.
  • the use of the C1-oxidised starch hydrolysate strikes an advantageous balance between chelating properties and enzyme-stabilizing properties. As the person skilled in the art knows, it may be favourable in this respect to consciously add some amount of calcium in ionic form to the detergent composition.
  • the amount of the chelating agent containing the C1-oxidised starch hydrolysate in the detergent composition may vary within wide limits.
  • the detergent composition contains at least 0.25 wt% of the chelating agent containing the C1-oxidised starch hydrolysate, as calculated on the total of the detergent composition, including any water present. In this way, the functionality of the C1-oxidised starch hydrolysate can take noticeable effect. More preferably, the detergent composition contains at least 0.50, 0.75, or 1.00 wt.% of the chelating agent containing the C1-oxidised starch hydrolysate.
  • the detergent composition contains at most 6 wt.% of the chelating agent containing the C1-oxidised starch hydrolysate, more preferably at most 5.50, 5.00, 4.50, 4.00, or even at most 3.50 wt.% of the chelating agent containing C1-oxidised starch hydrolysate.
  • the weight ratio between the chelating agent containing the C1-oxidised starch hydrolysate and the sum of the enzymes in the detergent composition varies between 0.25:1 and 4:1, preferably between 0.50:1 and 2:1.
  • the chelating agent consists essentially of the C1-oxidised starch hydrolysate. It is furthermore preferred that the C1-oxidised starch hydrolysate contains compounds having DP of 2, 3, and 4 in amounts as indicated above; more preferably, that the C1-oxidised starch hydrolysate contains maltobionic acid in the amounts as indicated above.
  • the maltobionic acid may be present as such, or in a corresponding ionic form such as for example sodium maltobionate.
  • the present invention furthermore relates to an enzyme-containing detergent composition, containing a starch hydrolysate that has been selectively oxidised at the C1 location, and at most 5 wt.% of further chelating agents and/or enzyme-stabilizing agents, calculated on the detergent composition as a whole. Due to the chelating action of the C1-oxidised starch hydrolysate, the need to use any further chelating agents can be reduced. Similarly, due to the enzyme-stabilising action of the C1-oxidised starch hydrolysate, the need to use any further enzyme-stabilising agents can be reduced.
  • the detergent composition contains at most 4.0, 3.0, 2.0, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or even at most 0.1 wt. % of further chelating agents and/or enzyme-stabilising agents.
  • the detergent composition according to the invention contains essentially no further chelating agents or enzyme-stabilising agents.
  • the amount and preferred embodiments of the C1-oxidised starch hydrolysate in the detergent composition according to the invention are as indicated above for the method of the present invention.
  • the detergent composition according to the invention is in liquid form or in the form of gel capsules.
  • liquid detergent I The effect of a C1-oxidised starch hydrolysate on the stability of enzymes in a liquid detergent composition was evaluated.
  • Two liquid detergent formulations were used, named liquid detergent I and liquid detergent II.
  • liquid detergent I a typical formulation for a concentrated eco-style laundry liquid detergent, is given in Table 1.
  • Table 1 Ingredient Wt.% Demin water 19.30 Chelating agent 1.50 Ethanol 3.33 Sodium n-Octyl Sulphate (Texapon 842) 2.85 Sodium Lauryl Sulphate (Standapol WAQ-LCK) 45.07 Lauryl/Myristyl Glucoside 17.12 Oleic acid (Emersol 622) 3.33 Potassium hydroxide 1.60 Sodium bicarbonate 1.90 Protease (Savinase 16L Ultra) 1.00 Amylase (Stainzyme 12L) 1.00
  • Liquid detergent I was prepared by first heating the water to 40°C; then, all ingredients except the protease and the amylase were added to the aqueous phase and mixed; this was done in the order of their appearance in Table 1. The so-prepared detergent was cooled down to room temperature, after which the enzymes were added. The pH was adjusted to 8.5 with citric acid/sodium hydroxide; this completed the preparation of liquid detergent I.
  • the type of chelating agent added can be found in Table 3 below.
  • liquid detergent II a typical formulation for a regular heavy duty laundry liquid detergent
  • Table 2 Phase Ingredient Wt.% 1 Demin water 45.44 1 Sodium hydroxide 3.23 1 Palm kernel fatty acid (Endenor K1218) 8.54 1 Propylene glycol 4.74 2 Sodium Laureth Sulphate 2EO (Texapon N 70) 13.57 2 Lauryl/Myristyl Glucoside (Glucopon 600 CSUP) 7.59 2 Fatty alcohol 7EO (Dehydol LT 7) 5.69 3 Chelating agent 1.50 3 Citric acid 2.85 3 Ethanol 2.85 4 Protease (Savinase 16L Ultra) 1.00 4 Amylase (Stainzyme 12L) 1.00
  • Liquid detergent II was prepared by first combining the Phase 1 ingredients, followed by heating to 70°C, mixing during 15 minutes, and cooling to 40°C. The Phase 2 ingredients were then added, followed by mixing. Subsequently, the Phase 3 ingredients were mixed in, followed by cooling down to room temperature and the adding of the Phase 4 ingredients (i.e. the enzymes). The pH was adjusted to 8.5 with citric acid/sodium hydroxide; this completed the preparation of liquid detergent II.
  • the C1-oxidised starch hydrolysate as used in Examples 1 and 2 was prepared from a starch hydrolysate having a high maltose content (75 wt.% on total dry matter), according to the method of WO-A-2004/099114 .
  • the starch hydrolysate was essentially fully converted, and it then contained about 85 wt.% (on total dry matter) of C1-oxidised compounds having a DP of 2, 3, or 4, of which the large majority (75 wt.% on total dry matter) was maltobionic acid - as such and/or in the corresponding sodium maltobionate form.
  • the stability of the enzymes was determined by utilising the known test procedure for detergency enzymes as made available by Megazyme as 'Measurement of endo-Protease and ⁇ -Amylase in Biological Washing Powders & Liquids using Azo-Casein and Amylazyme Tablets' - document code BWPL 11/03, a document freely available for download from www.megazyme.com in at least August 2012.
  • Samples of the liquid detergent compositions of the Examples 1 - 2 and the Comparative Experiments A - D were measured at four moments in time: upon preparation, after 14 days, after 1 month, and after 2 months.
  • Examples 1 and 2 clearly show that in Examples 1 and 2 the enzymes are significantly more stable over time as compared to the enzymes in Comparative Examples A - D, which contained chelating agents not according to the invention that were evaluated, namely MGDA (methylglycine diacetate) and EDTA (ethylene diamino tetraacetate).
  • MGDA methylglycine diacetate
  • EDTA ethylene diamino tetraacetate

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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)
EP12005684.1A 2012-08-03 2012-08-03 Utilisation d'hydrolysats d'amidon à oxydation C1 Ceased EP2692843A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP12005684.1A EP2692843A1 (fr) 2012-08-03 2012-08-03 Utilisation d'hydrolysats d'amidon à oxydation C1
EP13762399.7A EP2880145A1 (fr) 2012-08-03 2013-07-30 Utilisation d'hydrolysats d'amidon oxydés en c1
PCT/EP2013/002252 WO2014019680A1 (fr) 2012-08-03 2013-07-30 Utilisation d'hydrolysats d'amidon oxydés en c1

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP12005684.1A EP2692843A1 (fr) 2012-08-03 2012-08-03 Utilisation d'hydrolysats d'amidon à oxydation C1

Publications (1)

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EP2692843A1 true EP2692843A1 (fr) 2014-02-05

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EP12005684.1A Ceased EP2692843A1 (fr) 2012-08-03 2012-08-03 Utilisation d'hydrolysats d'amidon à oxydation C1
EP13762399.7A Withdrawn EP2880145A1 (fr) 2012-08-03 2013-07-30 Utilisation d'hydrolysats d'amidon oxydés en c1

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EP13762399.7A Withdrawn EP2880145A1 (fr) 2012-08-03 2013-07-30 Utilisation d'hydrolysats d'amidon oxydés en c1

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WO (1) WO2014019680A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2794938T3 (es) 2013-11-11 2020-11-19 Ecolab Usa Inc Detergente enzimático, de múltiples usos y métodos de estabilización de una solución de uso
EP3068857B1 (fr) 2013-11-11 2019-06-19 Ecolab USA Inc. Détergent de lavage fortement alcalin offrant un meilleur contrôle du tartre et une meilleure dispersion des salissures
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
BE1027322B1 (fr) * 2019-05-29 2021-01-12 Realco Composition nettoyante et dégraissante pour le traitement de surfaces dures

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69229301T2 (de) * 1991-04-22 1999-12-09 Roquette Freres Zeolitharmes oder zeolithfreies Waschmittel
US6187055B1 (en) * 1996-01-03 2001-02-13 Henkel Kommanditgesellschaft Auf Aktien Washing agents with specific oxidized oligosaccharides
WO2001096519A1 (fr) * 2000-06-15 2001-12-20 Unilever N.V. Composition detergente liquide
DE10112136A1 (de) * 2001-03-14 2002-10-02 Henkel Kgaa Verhinderung von Textilschäden beim Waschen
WO2004099114A1 (fr) 2003-05-05 2004-11-18 Südzucker Aktiengesellschaft Mannheim/Ochsenfurt Procede d'oxydation selective d'un hydrate de carbone au moyen de catalyseurs a base d'or supportes
WO2010046070A1 (fr) 2008-10-20 2010-04-29 Südzucker Aktiengesellschaft Mannheim/Ochsenfurt Agent de solubilisation pour ions de métal

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69229301T2 (de) * 1991-04-22 1999-12-09 Roquette Freres Zeolitharmes oder zeolithfreies Waschmittel
US6187055B1 (en) * 1996-01-03 2001-02-13 Henkel Kommanditgesellschaft Auf Aktien Washing agents with specific oxidized oligosaccharides
WO2001096519A1 (fr) * 2000-06-15 2001-12-20 Unilever N.V. Composition detergente liquide
DE10112136A1 (de) * 2001-03-14 2002-10-02 Henkel Kgaa Verhinderung von Textilschäden beim Waschen
WO2004099114A1 (fr) 2003-05-05 2004-11-18 Südzucker Aktiengesellschaft Mannheim/Ochsenfurt Procede d'oxydation selective d'un hydrate de carbone au moyen de catalyseurs a base d'or supportes
WO2010046070A1 (fr) 2008-10-20 2010-04-29 Südzucker Aktiengesellschaft Mannheim/Ochsenfurt Agent de solubilisation pour ions de métal

Also Published As

Publication number Publication date
EP2880145A1 (fr) 2015-06-10
WO2014019680A1 (fr) 2014-02-06

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