EP0715648B1 - Adjuvant de lavage pour produits de lavage ou de nettoyage - Google Patents

Adjuvant de lavage pour produits de lavage ou de nettoyage Download PDF

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Publication number
EP0715648B1
EP0715648B1 EP94926214A EP94926214A EP0715648B1 EP 0715648 B1 EP0715648 B1 EP 0715648B1 EP 94926214 A EP94926214 A EP 94926214A EP 94926214 A EP94926214 A EP 94926214A EP 0715648 B1 EP0715648 B1 EP 0715648B1
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EP
European Patent Office
Prior art keywords
weight
builder component
crystalline layer
impregnated
builder
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.)
Revoked
Application number
EP94926214A
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German (de)
English (en)
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EP0715648A1 (fr
Inventor
Wolfgang Seiter
Volker Bauer
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
    • 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
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O

Definitions

  • the invention relates to a builder component with a very high bulk density and to detergents or cleaning agents which contain this component.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates are those in which M is sodium and x is 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.
  • ⁇ -sodium disilicate is commercially available under the name SKS 7 (R)
  • ⁇ -sodium disilicate is available under the name SKS 6 (R) (commercial products from Hoechst AG, Federal Republic of Germany).
  • SKS 7 (R) commercial products from Hoechst AG, Federal Republic of Germany.
  • crystalline layered silicates can suffer losses in their washing effectiveness when spraying slurries containing detergents or cleaning agents, they should preferably be incorporated into detergents or cleaning agents by other process methods.
  • the powders are not very suitable for being mixed into modern washing or cleaning agents with high bulk densities of at least 650 g / l. If they are mixed in anyway, segregation occurs in most cases due to the high proportion of fine grains in the crystalline layered silicates.
  • the object was therefore to provide a preparation form for crystalline layered silicates which has high bulk densities and essentially no fine-grained fractions with particle sizes below 0.1 mm and with liquid preparation forms, the ingredients of which are essentially components of conventional detergents and cleaning agents and preferably also in the Spray drying pose problems, is impregnated.
  • the invention accordingly relates to a builder component for use in detergents or cleaning agents, which crystalline phyllosilicates of the general formula NaNsi x O 2x + 1 ⁇ yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, this builder component consisting of crystalline sheet silicates and impregnating agent and the proportion of crystalline sheet silicates in granular form with bulk densities above 650 g / l being at least 60% by weight, based on the impregnated builder component.
  • the crystalline sheet silicates used are preferably those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.
  • the builder component according to the invention consists not only of powdery crystalline sheet silicate, but at least 60% by weight, preferably at least 65% by weight and in particular at least 70% by weight, based in each case on the builder component impregnated according to the invention, of crystalline sheet silicates in granular form.
  • these granular crystalline layered silicates have a high bulk density of above 700 g / l and in particular even between 800 g / l and 900 g / l. They can be produced by granulation, for example by roller compacting, in particular by roller compacting, without further additives.
  • the builders component can also contain conventional powdered layered silicates in part.
  • the content of the powdery crystalline sheet silicates is advantageously not more than 10% by weight, based on the impregnated builder component, including the powdery crystalline sheet silicate.
  • Preferred builder components contain powdery crystalline sheet silicates in amounts of 0.5 to 5% by weight and in particular in amounts of 1 to 3% by weight, the powdery crystalline sheet silicates being used in particular for powdering the surface of the impregnated builder components.
  • ingredients of washing or cleaning agents are used in particular as impregnating agents.
  • Their content, based on the builder component impregnated according to the invention, is preferably 1 to 30% by weight and in particular 5 to 25% by weight.
  • the preferred impregnation agents which are optionally applied to the crystalline layered silicate granules form at elevated temperatures under customary process conditions, include primarily ethoxylated nonionic surfactants, in particular ethoxylated fatty alcohols, mixtures of nonionic and anionic surfactants, paste-like aqueous nonionic and / or anionic surfactants and Foam inhibitors such as silicone oils and paraffin oils.
  • Aqueous surfactant pastes can be of particular interest if the water is subsequently dried away. In the case of aqueous surfactant pastes, the amounts given above for the impregnating agent relate either to the paste if the water is not or not completely dried off, or to the surfactant active substance of the paste if the water is dried off.
  • Suitable impregnating agents are, for example, advantageously ethoxylated, in particular primary, alcohols which are liquid under the process conditions and preferably have 8 to 18 carbon atoms and an average of 1 up to 12 moles of ethylene oxide (E0) per mole of alcohol, in which the alcohol radical may be linear or preferably methyl-branched in the 2-position, or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 E0 per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 E0 or 4 E0, C 9 -C 11 alcohol with 7 E0, C 13 -C 15 alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, C 12 -C 18 alcohols with 3 E0, 5 E0 or 7 E0 and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 E0 and C 12 -C 18 alcohol with 5 E0.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • nonionic surfactants are therefore preferably not processed via a spray drying process, but rather via the impregnated builder components according to the invention.
  • alkyl glycosides of the general formula R0 (G) x can also be used in particular as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4. They are preferably used in the form of an aqueous paste.
  • Suitable surfactants which are used instead of or together with the alkyl glycosides are polyhydroxy fatty acid amides of the formula (I), in the R 2 CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands. They are also preferably used in the form of an aqueous paste.
  • Suitable anionic surfactants of the sulfonate type are preferably the known C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates and alkanesulfonates. Esters of ⁇ -sulfofatty acids or the disalts of ⁇ -sulfofatty acids are also suitable.
  • Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol be preserved.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C 10 -C 20 oxo alcohols, and those secondary alcohols of this chain length.
  • the sulfuric acid monoesters of alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 moles of ethylene oxide, are also suitable.
  • anionic surfactants in particular their alkali metal salts such as sodium and / or potassium salts, are used either in the form of an aqueous paste or in a mixture with nonionic surfactants, in particular in a mixture with ethoxylated fatty alcohols. It is also possible to use aqueous pastes which contain both anionic surfactants, in particular alkylbenzenesulfonates and / or alkyl sulfates, and nonionic surfactants, in particular ethoxylated fatty alcohols and / or alkylglycosides.
  • alkyl sulfates are particularly preferred because alkyl sulfates still contain unreacted alcohol from their production, which leads to visible pluming problems when spray drying large amounts of alkyl sulfate. Alkyl sulfates are therefore preferably not over one Spray drying process, but processed via the impregnated builders components according to the invention.
  • the impregnated builder components according to the invention preferably have a bulk density of above 800 g / l and in particular of above 900 g / l, the bulk weight of the impregnated builder component being in any case higher than the bulk weight of the granular crystalline layered silicate starting material used.
  • the impregnation of the granular crystalline layered silicates increases the bulk density compared to the layered silicate starting material.
  • the builders components according to the invention can advantageously be produced by a process using crystalline sheet silicates in granular form with bulk densities above 650 g / l, which are produced by roller compaction and then by grinding and sieving and are then treated with an impregnating agent.
  • the roller-compacted crystalline sheet silicates are used in at least 60% by weight, based on the impregnated builders component.
  • the builders components are then powdered in a preferred embodiment of the invention and in particular powdered with powdery crystalline layered silicates.
  • the invention relates to a washing or cleaning agent which contains the builders components according to the invention.
  • these agents preferably contain the builder components according to the invention in amounts of 10 to 70% by weight and in particular in amounts of 20 to 60% by weight.
  • the detergents or cleaning agents contain further conventional inorganic and / or organic builders, contents of 25 to 50% by weight of the builders components according to the invention are particularly advantageous.
  • the washing or cleaning agents can contain all the usual ingredients such as anionic, nonionic, amphoteric, cationic and / or zwitterionic surfactants, other builders such as zeolite and / or phosphates, phyllosilicates such as bentonites, polycarboxylates such as citrates etc., polymeric polycarboxylates such as salts of homo- or copolymers of acrylic acid, bleaching agents and bleach activators, graying inhibitors such as cellulose ethers or polyvinylpyrrolidone, optical brighteners, dyes and fragrances and enzymes and enzyme stabilizers. Foam inhibitors can also be included.
  • other builders such as zeolite and / or phosphates, phyllosilicates such as bentonites, polycarboxylates such as citrates etc., polymeric polycarboxylates such as salts of homo- or copolymers of acrylic acid, bleaching agents and bleach activators, graying inhibitors such as cellulose
  • the agents can consist of a base granulate or of a multicomponent mixture, whereby multicomponent mixtures can be advantageous.
  • enzyme granules and, for example, bleach activator granules, but also foam inhibitor granules or individual constituents such as sodium carbonate, sodium silicate or polycarboxylate are subsequently mixed in.
  • the individual components can be made by spray drying, granulation, extrusion or other conventional techniques.
  • the agents have a bulk density above 650 g / l, preferably above 700 g / l.
  • detergents or cleaning agents with bulk densities above 800 g / l can also be produced without these agents tending to separate.
  • These agents are also suitable for concentrates with high surfactant contents.
  • a high anionic surfactant content can be achieved by admixing a highly concentrated anionic surfactant compound obtained, for example, by spray drying, spray neutralization or by granulation and simultaneous drying in a fluidized bed, and a high nonionic surfactant content by admixing the builder components with high nonionic surfactant components. Washing or cleaning agents with 15 to 40% by weight, in particular with 18 or 20 to 35% by weight, anionic and nonionic surfactants are preferred.
  • a compacted crystalline layered silicate (SKS6 (R) granulate, product of Hoechst AG, Federal Republic of Germany) had a bulk density of 860 g / l and was mixed with the amounts of an ethoxylated fatty alcohol mixture of 80% by weight specified in Examples 1 to 5 12 -C 18 fatty alcohol with 5 ethylene oxide groups (E0) and 20% by weight C 12 -C 14 fatty alcohol with 3 E0 at 60 ° C.
  • the impregnated builder component was additionally powdered with powdered crystalline layered silicate (SKS6 (R) ). All impregnated builders had a bulk density above 900 g / l.
  • the builder components had no particles below 0.1 mm and no particles above 1.6 mm.
  • Table 1 Bulk weight in g / l of Examples 1-5, V1 for comparison example amounts Bulk density SKS6 (R) granules 860 1 95% by weight of SKS6 (R) granules 5% by weight nonionic surfactant 936 2nd 90% by weight of SKS6 (R) granules 10% by weight nonionic surfactant 987 3rd 85% by weight of SKS6 (R) granules 15% by weight nonionic surfactant 990 4th 80% by weight of SKS6 (R) granules 20% by weight nonionic surfactant 950 5 78% by weight of SKS6 (R) granules 20% by weight nonionic surfactant 930 2% by weight of SKS6 (R) powder V SKS6 (R) powder 490 V1 95% by weight of SKS6 (R) powder 5% by weight nonionic surfactant 457 Grain size distributions (sieve analysis in% by weight) on 1.6 mm 0.8 mm

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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)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Claims (10)

  1. Composant adjuvant pour utilisation dans les produits de lavage ou de nettoyage, qui contient des silicates stratifiés cristallins de la formule générale NaMSixO2X+1·yH2O, dans laquelle M représente le sodium ou l'hydrogène, x correspond à un nombre de 1,9 à 4 et y est un nombre de 0 à 20, caractérisé en ce que ledit composant adjuvant est constitué de silicates stratifiés cristallins et d'un agent d'imprégnation, la proportion de silicates stratifiés cristallins sous forme granulaire, avec une densité en vrac supérieure à 650 g/l, étant d'au moins 60 % en poids par rapport au composant adjuvant imprégné.
  2. Composant selon la revendication 1, caractérisé en ce que la proportion du ou des agents d'imprégnation est de 1 à 30 % en poids, de préférence, de 5 à 25 % en poids, dans chaque cas par rapport au composant adjuvant imprégné.
  3. Composant selon la revendication 1 ou 2, caractérisé en ce que le silicate stratifié cristallin présente, sous forme granulaire, une densité en vrac supérieure à 700 g/l, de préférence comprise entre 800 et 900 g/l.
  4. Composant selon une des revendications 1 à 3, caractérisé en ce que l'agent d'imprégnation est sélectionné parmi le groupe des tensioactifs non ioniques éthoxylés, des mélanges de surfactifs non ioniques et anioniques, des tensioactifs non ioniques et/ou anioniques aqueux pâteux, l'eau étant éventuellement éliminée postérieurement par séchage, ainsi que des huiles de silicone et de paraffine.
  5. Composant selon une des revendications 1 à 4, caractérisé en ce qu'il présente une densité en vrac supérieure à 800 g/l, de préférence supérieure à 900 g/l, la densité en vrac du composant adjuvant imprégné étant supérieure à celle de la matière de départ - silicate stratifié cristallin granulaire.
  6. Composant selon une des revendications 1 à 5, caractérisé en ce qu'il contient des silicates stratifiés cristallins pulvérulents en proportions de 0,5 à 5 % en poids, de préférence en quantités de 1 à 3 % en poids, dans chaque cas par rapport au composant adjuvant imprégné, y compris le silicate stratifié cristallin pulvérulent.
  7. Procédé de fabrication d'un composant adjuvant pour utilisation dans des produits de lavage ou de nettoyage, qui contient des silicates stratifiés cristallins de la formule générale NaMSixO2X+1·yH2O, dans laquelle M représente le sodium ou l'hydrogène, x correspond à un nombre de 1,9 à 4 et y est un nombre de 0 à 20, les silicates stratifiés cristallins étant mis en oeuvre sous forme granulaire avec une densité en vrac supérieure à 650 g/l, caractérisé en ce que le silicate stratifié cristallin est fabriqué par compactage par rouleaux et est ensuite traité par un agent d'imprégnation, les silicates stratifiés cristallins compactés étant mis en oeuvre en proportion d'au moins 60 % en poids par rapport au composant adjuvant imprégné.
  8. Procédé selon la revendication 7, caractérisé en ce que le composant adjuvant imprégné est finalement traité par des silicates stratifiés cristallins pulvérulents.
  9. Produit de lavage ou de nettoyage contenant un composant adjuvant conforme à une des revendications 1 à 6.
  10. Produit selon la revendication 9, caractérisé en ce qu'il contient le composant adjuvant en proportions de 10 à 70 % en poids, de préférence, de 20 à 60 % en poids et, en particulier, de 25 à 50 % en poids, ainsi que, le cas échéant, d'autres adjuvants inorganiques et/ou organiques usuels.
EP94926214A 1993-08-28 1994-08-20 Adjuvant de lavage pour produits de lavage ou de nettoyage Revoked EP0715648B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4329064 1993-08-28
DE4329064A DE4329064A1 (de) 1993-08-28 1993-08-28 Gerüststoffkomponente für Wasch- oder Reinigungsmittel
PCT/EP1994/002773 WO1995006705A1 (fr) 1993-08-28 1994-08-20 Adjuvant de lavage pour produits de lavage ou de nettoyage

Publications (2)

Publication Number Publication Date
EP0715648A1 EP0715648A1 (fr) 1996-06-12
EP0715648B1 true EP0715648B1 (fr) 1997-03-26

Family

ID=6496300

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94926214A Revoked EP0715648B1 (fr) 1993-08-28 1994-08-20 Adjuvant de lavage pour produits de lavage ou de nettoyage

Country Status (6)

Country Link
EP (1) EP0715648B1 (fr)
JP (1) JPH09501963A (fr)
AT (1) ATE150786T1 (fr)
DE (2) DE4329064A1 (fr)
ES (1) ES2100085T3 (fr)
WO (1) WO1995006705A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19542570A1 (de) * 1995-11-15 1997-05-22 Henkel Kgaa Verfahren zur Herstellung von granularen Wasch- oder Reinigungsmitteln oder Komponenten hierfür
DE19726287A1 (de) * 1997-06-20 1998-12-24 Henkel Ecolab Gmbh & Co Ohg Verfahren zum Waschen von Wäsche, insbesondere von Berufsbekleidung
DE19728588A1 (de) * 1997-07-04 1999-01-07 Henkel Kgaa Schweres Waschmittelgranulat mit hoher Löslichkeit und verbessertem Fettauswaschvermögen
DE19756696A1 (de) 1997-12-19 1999-07-01 Clariant Gmbh Schichtsilikathaltige Wasch- und Reinigungsmittelkomponente
GB2339203A (en) * 1998-07-08 2000-01-19 Procter & Gamble A method of dipensing
GB2339194A (en) * 1998-07-08 2000-01-19 Procter & Gamble Layered crystalline silicate as detergent builder component

Family Cites Families (6)

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Publication number Priority date Publication date Assignee Title
US4276326A (en) * 1976-02-26 1981-06-30 Colgate-Palmolive Company Free flowing builder beads and detergents
US4203851A (en) * 1978-06-16 1980-05-20 Colgate-Palmolive Company Fabric softening compositions and methods for manufacture thereof
JPS5712118A (en) * 1980-06-23 1982-01-22 Mitsubishi Heavy Ind Ltd Fitting structure between rotary disc of high speed rotary member and shaft
JPS6225290U (fr) * 1985-07-31 1987-02-16
DE3936405A1 (de) * 1989-11-02 1991-05-08 Henkel Kgaa Koerniges, nichtionische tenside enthaltendes additiv fuer wasch- und reinigungsmittel mit verbessertem einspuelverhalten
US5108646A (en) * 1990-10-26 1992-04-28 The Procter & Gamble Company Process for agglomerating aluminosilicate or layered silicate detergent builders

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"SKS-6 Detergent Builder of the Future", herausgegeben im Mai 1993 vom Hoechst AG *
S.Ö.F.W. 116. Jg. - Nr. 20 (1990) Seiten 805-808 *

Also Published As

Publication number Publication date
DE4329064A1 (de) 1995-03-02
EP0715648A1 (fr) 1996-06-12
ES2100085T3 (es) 1997-06-01
JPH09501963A (ja) 1997-02-25
WO1995006705A1 (fr) 1995-03-09
ATE150786T1 (de) 1997-04-15
DE59402250D1 (de) 1997-04-30

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