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WO1993011214A1 - Produits de lavage et detergents - Google Patents

Produits de lavage et detergents Download PDF

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Publication number
WO1993011214A1
WO1993011214A1 PCT/EP1992/002702 EP9202702W WO9311214A1 WO 1993011214 A1 WO1993011214 A1 WO 1993011214A1 EP 9202702 W EP9202702 W EP 9202702W WO 9311214 A1 WO9311214 A1 WO 9311214A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkali
polysaccharides
cleaning agents
monomers
monoethylenically unsaturated
Prior art date
Application number
PCT/EP1992/002702
Other languages
German (de)
English (en)
Inventor
Alexander Kud
Wolfgang Trieselt
Paul Diessel
Walter Denzinger
Heinrich Hartmann
Johannes Perner
Volker Schwendemann
Original Assignee
Basf Aktiengesellschaft
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 Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Publication of WO1993011214A1 publication Critical patent/WO1993011214A1/fr

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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3788—Graft polymers
    • 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
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite

Definitions

  • the invention relates to detergents and cleaning agents which contain at least one surfactant and as builder (I) a graft copolymer of monoethylenically unsaturated dicarboxylic acids and monoethylenically unsaturated monocarboxylic acids on mono-, OHgo- or polysaccharides or their derivatives and (II) at least one alkali silicate.
  • (B) monosaccharides, oligosaccharides, polysaccharides, oxidatively, hydrolytically or enzymatically degraded polysaccharides, oxidized hydrolytically or oxidized enzymatically degraded polysaccharides or chemically modified mono-, oligo- and polysaccharides in the weight ratio (A): (B) from 95 to 20): (5 to 80).
  • the graft polymers are used as additives for washing and cleaning agents in amounts of 0.1 to 20% by weight.
  • EP-B-0025551 discloses the use of copolymers of, for example, acrylic acid and maleic acid as an incrustation inhibitor in low-phosphate or phosphate-free detergents.
  • EP-B-0164514 discloses the use of crystalline layered sodium silicates for softening water, which contains calcium and / or magnesium ions and the use of these layered sodium silicates as builders in detergents and cleaners containing surfactants.
  • EP-A-0337219 is a storage-stabilized detergent with increased bleaching action with a content of 2 to
  • the detergent formulations contain polycarboxylates.
  • the crystalline layered silicate preferably corresponds to the ⁇ modification of Na 2 Si 2 O 5 .
  • EP-A-0416366 discloses a dishwashing detergent which contains a crystalline, largely water-insoluble sodium sheet silicate with a SiO 2 / Na 2 O molar ratio of 1.9 to 3.5: 1 in combination with a proton donor.
  • Proton donors include polycarboxylates, e.g. E. Copolymers of acrylic acid and maleic acid with a molecular weight of 70,000 are used.
  • EP-A-0444415 discloses detergents which contain 5 to 50% by weight of at least one surfactant, 0.5 to 60% by weight of an amorphous, low-water sodium disilicate with a water content of 0.3 to 6% by weight. and contain common washing aids.
  • the detergent formulations contain a copolymer of acrylic acid and maleic acid with a molecular weight of approximately 60,000.
  • the copolymers or graft copolymers known from EP-B-0025551 and EP-A-0441197 it is possible to formulate phosphate-reduced or phosphate-free detergents which, in terms of detergency, contain detergents with a phosphate content of approximately 45% by weight .-% correspond.
  • the object of the present invention is to provide detergents and cleaning agents which are reduced in phosphate or free of phosphate and which have an increased detergency compared to the previously known polymer-containing detergent formulations.
  • detergents and cleaning agents which contain at least one surfactant and a builder and, if appropriate, customary additives, if, as builders (I), they contain 0.5 to 15% by weight of graft copolymers which are obtainable by free-radically initiated copolymerization from (A) monomer mixtures
  • (B) monosaccharides, oligosaccharides, polysaccharides, oxidatively, hydrolytically or enzymatically degraded polysaccharides, oxidized hydrolytically or oxidized enzy matically degraded polysaccharides or chemically modified mono-, oligo- and polysaccharides in the weight ratio (A): (B) from (95 to 20): (5 to 80), and
  • (II) contain 10 to 50% by weight of at least one alkali silicate.
  • the washing and cleaning agent builder consists of the above-mentioned graft polymers (I) and alkali silicates (II), the weight ratio (I): (II) being from 1.5: 1 to 1: 100.
  • the graft copolymers (I) and processes for their preparation are described in detail in EP-A-0441197. All graft copolymers mentioned in EP-A-0441197 come into consideration as component (T) of the builder system of the present washing and cleaning agents.
  • graft copolymers which are obtainable by free-radically initiated copolymerization of (a) maleic acid and (b) acrylic acid and / or methacrylic acid in the presence of (B) acid, catalytically or enzymatically degraded starches, which are sold commercially under the name starch saccharification products, and chemically modified degraded starches, e.g. B. hydrogenation products of starch hydrolysates such as sorbitol and mannitol, maltose and especially hydrogenated glycose syrups.
  • the monomers of group (a) are preferably contained in the monomer mixture (A) in an amount of 15 to 60% by weight and the monomers in group (b) preferably in an amount of 40 to 85% by weight.
  • the graft copolymers have K values (determined according to H. Fikentscher) from 8 to 90, preferably 20 to 75.
  • Component (I) of the builders is in the washing and cleaning agents in an amount of 0.5 to 15, preferably 1 to 10% by weight present.
  • Component (II) of the builder system of washing and cleaning agents consists of at least one alkali silicate, which is contained in the respective formulations in an amount of 10 to 50% by weight.
  • the alkali silicates are preferably sodium silicates.
  • Suitable products of this type are, for example, sodium disilicates, which are obtained by drying Water glass solutions are available. This usually results in water-containing sodium disilicates which have water contents of about 15 to 23% by weight. Products of this type are commercially available.
  • component (II) there are also low-water sodium disilicates with water contents, which are preferably produced by partial dewatering of commercially available powdered sodium disilicates with water contents of 15 to 23% by weight.
  • the low-water sodium disilicates obtainable in this way have a water content of less than 15% by weight.
  • the water content of the partially dewatered sodium disilicate is preferably 0.3 to 6% by weight.
  • These products are referred to in EP-A-0444415 as amorphous sodium disilicate.
  • Another group of sodium silicates that can be used as component (II) are crystalline, largely water-insoluble sodium silicates with a molar ratio of SiO 2 / Na 2 O of 5: 1 to 1: 1, preferably 3.5: 1 to 1.9: 1.
  • a crystalline silicate having a weight ratio of SiO 2 to Na 2 O 2: 1 to 2.1: 1, which is under the name Portil ® A commercially and has water contents of 15 to 23, preferably 18 to 20, preferably as Component (II) used.
  • Compounds of component (II) which are preferably used in detergents and cleaning agents are crystalline slide-shaped sodium silicates or crystalline sodium disilicate.
  • the average particle diameter of the alkali silicates used in the washing and cleaning agents is approximately 0.01 to 1000 ⁇ m.
  • Components (I) and (II) can be added to the other constituents of the formulation either individually or as a mixture in the preparation of the washing and cleaning agents.
  • Low-phosphate detergents and cleaning agents should be understood to mean such formulations that are less than
  • composition of detergents and cleaning agents can vary widely. Examples of the composition of washing formulations described in
  • WO-A-90/13581 can be taken.
  • Detergents and cleaning agents usually contain tensides in amounts of 1 to
  • the detergents and cleaning agents can either be in Form of a powder or as a liquid.
  • Detergents can in particular also contain a bleaching agent, for example peroxo compounds, such as sodium percrate, peroxocarboxylic acids or polymers with groups containing peroxo. However, sodium perborate is preferred.
  • the bleaches are; in the case of their use in detergents and cleaning agents: contained in amounts of 2 to 30% by weight.
  • the detergents and cleaning agents may optionally contain other conventional additives, e.g. B. complexing agents, citrates, opacifiers, optical brighteners, enzymes, perfume oils, color transfer inhibitors, graying inhibitors and / or Bieich activators.
  • the graft polymers can also be used together with the silicate in liquid detergent formulations. In this case, aqueous solutions of alkali silicates can also be used.
  • the mixture of components (I) and (II) can also advantageously be used in conventional dishwashing detergents.
  • the amounts to be used essentially correspond to the amounts used as additives for the formulation of textile detergents.
  • the DE values of the starches or their derivatives mean dextrose equivalents. They were determined using the LufrSchoorl method, cf. G. Tegge, Starch and Starch Derivatives, Behr's Verlag, Hambur 1984, page 305.
  • Copolymer A Commercial copolymer of 30% maleic acid and 70% acrylic acid with a K value of 60.
  • Cotton fabric was subjected to a series of 3 washes together with standard dirt fabric. The dirty fabric is renewed after each wash, the test fabric becoming more soiled after each wash. The whiteness of the test fabric after the 3rd wash is used to assess the degree of soiling, the values are secured by repeated repetition and averaging. Percent remission was measured with an Elrepho (Zeiss) filter 8 at 480 nm. Test conditions:
  • Test duration per cycle 30 minutes (with heating up time)
  • the graft copolymer 1 to be used according to the invention in combination with both a crystalline layered silicate and with a crystalline silicate exhibits a significantly higher remission and thus better primary washing action than when the commercially available copolymer A is combined with the same crystalline one Layered silicate or the crystalline silicate.
  • Layered silicate is better than a combination of commercially available copolymer A and the same layered silicate in a phosphate-free detergent formulation.
  • the secondary washing effect was determined using the incrustation.
  • the incrustation-inhibiting effect of a detergent is of great importance. The one with the water hardness and
  • Insoluble salts formed from detergent ingredients can deposit on the tissues and thus encrust them. The result is increased wear on the fabrics and poorer wearing properties of the textiles.
  • Test duration per cycle 30 minutes (with heating up time)
  • the ash content is lower when using the graft polymer 1 than with the copolymer A and thus the incrustation inhibition of the graft polymer 1 is also better.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

Produits de lavage et détergents renfermant au moins un agent tensioactif et, éventuellement, des additifs habituels, ainsi qu'une combinaison d'adjuvants (I) et (II). On utilise, comme adjuvant (I), des copolymères greffés obtenus par copolymérisation, amorcée par des radicaux, de mélanges monomères comprenant a) des acides dicarboxyliques en C4 à C8 monoéthyléniquement insaturés, ou leurs sels alcalins et/ou d'ammonium, b) des acides carboxyliques en C3 à C10 monoéthyléniquement insaturés, ou leurs sels alcalins et/ou d'ammonium et, éventuellement, d'autres monomères, en présence de monosaccharides, oligosaccharides, polysaccharides, de polysaccharides décomposés par oxydation, hydrolytiquement ou enzymatiquement, de polysaccharides décomposés, oxydés par hydrolyse ou enzymatiquement ou des mono-, oligo- et polysaccharides modifiés chimiquement, et, comme adjuvant (II), au moins un silicate alcalin. L'invention concerne également l'utilisation des mélanges formés des copolymères greffés (I) et des silicates alcalins (II) précités, dans les proportions en poids (I) à (II) comprises entre 1,5:1 et 1:100, comme adjuvants dans les produits de lavage et détergents contenant des agents tensioactifs.
PCT/EP1992/002702 1991-12-03 1992-11-24 Produits de lavage et detergents WO1993011214A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4139826.2 1991-12-03
DE19914139826 DE4139826A1 (de) 1991-12-03 1991-12-03 Wasch- und reinigungsmittel

Publications (1)

Publication Number Publication Date
WO1993011214A1 true WO1993011214A1 (fr) 1993-06-10

Family

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Application Number Title Priority Date Filing Date
PCT/EP1992/002702 WO1993011214A1 (fr) 1991-12-03 1992-11-24 Produits de lavage et detergents

Country Status (2)

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DE (1) DE4139826A1 (fr)
WO (1) WO1993011214A1 (fr)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995033813A1 (fr) * 1994-06-02 1995-12-14 Unilever N.V. Composition detergente amelioree
WO1996014267A1 (fr) * 1994-11-02 1996-05-17 Henkel Kommanditgesellschaft Auf Aktien Synthese directe de disilicates cristallins a partir d'une solution de silicate de sodium
EP0725131A1 (fr) * 1995-02-01 1996-08-07 BASF Aktiengesellschaft Utilisation de produits naturels greffés hydrosolubles comme additifs pour compositions détergentes pour lave-vaisselles
WO1996037530A1 (fr) * 1995-05-24 1996-11-28 Degussa Aktiengesellschaft Copolymeres greffes a base de monosaccharides, oligosaccharides et polysaccharides, leur procede de preparation et leur utilisation
EP0669958B1 (fr) * 1992-11-20 1998-02-04 BASF Aktiengesellschaft Melanges de polymerisats d'acides dicarboxyliques monoethyleniquement insatures et de polymerisats d'acides monocarboxyliques ethyleniquement insatures et/ou d'acides polyaminocarboxyliques et utilisation
GB2322137A (en) * 1997-02-14 1998-08-19 Unilever Plc Detergent composition with soil release agents
US8636918B2 (en) 2011-08-05 2014-01-28 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of controlling hard water scale
US8674021B2 (en) 2006-07-21 2014-03-18 Akzo Nobel N.V. Sulfonated graft copolymers
US8679366B2 (en) 2011-08-05 2014-03-25 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of controlling hard water scale
US8841246B2 (en) 2011-08-05 2014-09-23 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
US8853144B2 (en) 2011-08-05 2014-10-07 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage
US8945314B2 (en) 2012-07-30 2015-02-03 Ecolab Usa Inc. Biodegradable stability binding agent for a solid detergent
US9051406B2 (en) 2011-11-04 2015-06-09 Akzo Nobel Chemicals International B.V. Graft dendrite copolymers, and methods for producing the same
US9109068B2 (en) 2005-07-21 2015-08-18 Akzo Nobel N.V. Hybrid copolymer compositions
US9365805B2 (en) 2014-05-15 2016-06-14 Ecolab Usa Inc. Bio-based pot and pan pre-soak
US9988526B2 (en) 2011-11-04 2018-06-05 Akzo Nobel Chemicals International B.V. Hybrid dendrite copolymers, compositions thereof and methods for producing the same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10047481A1 (de) * 2000-09-26 2002-04-25 Henkel Kgaa Wasch- und Reinigungsmittel

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1937575A1 (de) * 1968-11-02 1971-02-11 Benckiser Gmbh Joh A Verfahren zur Verhinderung von steinbildenden Ablagerungen in waessrigen Systemen
EP0337219A2 (fr) * 1988-04-15 1989-10-18 Hoechst Aktiengesellschaft Composition détergente à stockage stable avec un effet de blanchiment renforcé
EP0441197A2 (fr) * 1990-02-03 1991-08-14 BASF Aktiengesellschaft Copolymère greffé à base de monosaccharides, oligosaccharides, polysaccharides et de polysaccharides modifiées, procédé de fabrication de celle-ci et son utilisation
EP0465287A1 (fr) * 1990-07-02 1992-01-08 Rhone-Poulenc Chimie Composition détergente contenant un polysaccharide greffé biodégradable

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1937575A1 (de) * 1968-11-02 1971-02-11 Benckiser Gmbh Joh A Verfahren zur Verhinderung von steinbildenden Ablagerungen in waessrigen Systemen
EP0337219A2 (fr) * 1988-04-15 1989-10-18 Hoechst Aktiengesellschaft Composition détergente à stockage stable avec un effet de blanchiment renforcé
EP0441197A2 (fr) * 1990-02-03 1991-08-14 BASF Aktiengesellschaft Copolymère greffé à base de monosaccharides, oligosaccharides, polysaccharides et de polysaccharides modifiées, procédé de fabrication de celle-ci et son utilisation
EP0465287A1 (fr) * 1990-07-02 1992-01-08 Rhone-Poulenc Chimie Composition détergente contenant un polysaccharide greffé biodégradable

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0669958B1 (fr) * 1992-11-20 1998-02-04 BASF Aktiengesellschaft Melanges de polymerisats d'acides dicarboxyliques monoethyleniquement insatures et de polymerisats d'acides monocarboxyliques ethyleniquement insatures et/ou d'acides polyaminocarboxyliques et utilisation
WO1995033813A1 (fr) * 1994-06-02 1995-12-14 Unilever N.V. Composition detergente amelioree
WO1995033814A1 (fr) * 1994-06-02 1995-12-14 Unilever N.V. Composition detergente amelioree
WO1996014267A1 (fr) * 1994-11-02 1996-05-17 Henkel Kommanditgesellschaft Auf Aktien Synthese directe de disilicates cristallins a partir d'une solution de silicate de sodium
EP0725131A1 (fr) * 1995-02-01 1996-08-07 BASF Aktiengesellschaft Utilisation de produits naturels greffés hydrosolubles comme additifs pour compositions détergentes pour lave-vaisselles
WO1996037530A1 (fr) * 1995-05-24 1996-11-28 Degussa Aktiengesellschaft Copolymeres greffes a base de monosaccharides, oligosaccharides et polysaccharides, leur procede de preparation et leur utilisation
GB2322137A (en) * 1997-02-14 1998-08-19 Unilever Plc Detergent composition with soil release agents
US9321873B2 (en) 2005-07-21 2016-04-26 Akzo Nobel N.V. Hybrid copolymer compositions for personal care applications
US9109068B2 (en) 2005-07-21 2015-08-18 Akzo Nobel N.V. Hybrid copolymer compositions
US8674021B2 (en) 2006-07-21 2014-03-18 Akzo Nobel N.V. Sulfonated graft copolymers
US8841246B2 (en) 2011-08-05 2014-09-23 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
US8853144B2 (en) 2011-08-05 2014-10-07 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage
US8679366B2 (en) 2011-08-05 2014-03-25 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of controlling hard water scale
US9309489B2 (en) 2011-08-05 2016-04-12 Ecolab Usa Inc Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
US8636918B2 (en) 2011-08-05 2014-01-28 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of controlling hard water scale
US9051406B2 (en) 2011-11-04 2015-06-09 Akzo Nobel Chemicals International B.V. Graft dendrite copolymers, and methods for producing the same
US9988526B2 (en) 2011-11-04 2018-06-05 Akzo Nobel Chemicals International B.V. Hybrid dendrite copolymers, compositions thereof and methods for producing the same
US8945314B2 (en) 2012-07-30 2015-02-03 Ecolab Usa Inc. Biodegradable stability binding agent for a solid detergent
US9365805B2 (en) 2014-05-15 2016-06-14 Ecolab Usa Inc. Bio-based pot and pan pre-soak
US10053652B2 (en) 2014-05-15 2018-08-21 Ecolab Usa Inc. Bio-based pot and pan pre-soak

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