EP0856046B1 - Additif de lessive - Google Patents

Additif de lessive Download PDF

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Publication number
EP0856046B1
EP0856046B1 EP96934551A EP96934551A EP0856046B1 EP 0856046 B1 EP0856046 B1 EP 0856046B1 EP 96934551 A EP96934551 A EP 96934551A EP 96934551 A EP96934551 A EP 96934551A EP 0856046 B1 EP0856046 B1 EP 0856046B1
Authority
EP
European Patent Office
Prior art keywords
detergent
surfactant
agglomerate
detergent additive
optical brightener
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.)
Expired - Lifetime
Application number
EP96934551A
Other languages
German (de)
English (en)
Other versions
EP0856046A1 (fr
Inventor
Norbert Schall
Wolfgang Heininger
Rüdiger Hirsch
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.)
Dalli Werke GmbH and Co KG
Original Assignee
Sued Chemie AG
Dalli Werke Waesche und Korperpflege GmbH and Co KG
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 Sued Chemie AG, Dalli Werke Waesche und Korperpflege GmbH and Co KG filed Critical Sued Chemie AG
Publication of EP0856046A1 publication Critical patent/EP0856046A1/fr
Application granted granted Critical
Publication of EP0856046B1 publication Critical patent/EP0856046B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
    • 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
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents

Definitions

  • the invention relates to a detergent additive that at least a swellable layered silicate and other additional components contains.
  • FR-A-2 500 475 describes spray-dried detergent additives the 1 to 20% by weight bentonite and optical brighteners can contain.
  • An aqueous slurry is used made from the various components. Subsequently this slurry is spray dried.
  • DE-A-34 34 854 describes a process for the production a granular, free-flowing detergent component that inorganic carrier substances (especially sodium alumosili Zeolite A type cate) contains surfactants and optical brighteners. Zeolites are not swellable Phyllosilicates.
  • WO 94/05 761 describes a process for the production a detergent with a high bulk density and good solubility, with non-swellable silicates (e.g. zeolites), Surfactants and optical brighteners can be used.
  • non-swellable silicates e.g. zeolites
  • Surfactants and optical brighteners can be used.
  • WO 89/08 695 describes a stabilized particulate Composition for use in detergents, which optical Contains brighteners or enzymes. The particles are through one Bentonite coating protected. Contain separated particles Bleaches, surfactants or builders.
  • DE-A-35 26 405 describes layered silicates with limited Swelling capacity, as well as their use in detergents and cleaning agents, which also contain surfactants and optical brighteners.
  • the layered silicates are synthetic aluminosilicates.
  • Detergents are also known from other references, which Na alumosilicates, such as zeolites, that is not swellable Silicates, as well as optical brighteners and surfactants.
  • An essential step in the development of highly concentrated Detergent with a high bulk density consists of Omission of fillers or so-called adjusting agents, such as Sodium sulfate.
  • DE-C-3 424 987 describes the production of detergent concentrates with high bulk density, which is not sodium sulfate included as a set.
  • a basic powder is passed through Spray drying, which contains the usual detergent ingredients, such as surfactants, carboxymethyl cellulose (CMC), Sodium polyphosphate, zeolite A, water glass, optical brighteners et al contains.
  • the base powder obtained with low bulk density, which is free of sodium sulfate will increase the bulk density sprayed with further nonionic surfactant and with a separately produced granulate with high Bulk weight mixed dry.
  • This product is the optical brighteners on contact, especially oxidation, exposed unprotected by other detergent ingredients.
  • optical brightener either processed in the spray product, or it was subsequently added to the tower product as a powder (Spray product) mixed.
  • the optical brightener through a coating created during production or by the presence of thinning, spatially separating and water-adsorbing adjusting agents, of which likewise bleaches contained in the detergent, such as sodium perborate, but especially sodium percarbonate, separated, so optical Brighteners are oxidized. That used up here Bleaching potential stands for the later bleaching effect the wash liquor is no longer available.
  • the oxidation product of the optical brightener is colored yellow be, causing the detergent on the one hand a yellow tint shows, on the other hand, the yellow oxidation product of the brightener Nouns on the laundry textiles, causing an impairment the aesthetic aspect, especially with whites Laundry performs.
  • the origin preceding the oxidation of the optical brightener of active oxygen in the washing powder is due to a reaction of bleach contained in washing powder, especially when containing percarbonate as a bleach is.
  • TAED tetraacetylethylenediamine
  • the detergent agglomerates of high bulk density generally have poor dispersibility; this can be improved by adding dispersing and disintegrating agents which swell in contact with water and blow up or loosen the agglomerates, which leads to improved solubility and availability of the active components.
  • dispersing and disintegrating agents which swell in contact with water and blow up or loosen the agglomerates, which leads to improved solubility and availability of the active components.
  • the invention had the object of adding a detergent to provide in agglomerate form (granulate form), which at least one swellable layered silicate and an optical one Brightener contains which with good mechanical stability decays well in water and in which the optical brightener is present in a homogeneous distribution and against oxidation by the Oxidizing agent contained in the detergent is protected.
  • the invention relates to a detergent additive in non-spray-dried agglomerate form, which is characterized in that it has at least one swellable layered silicate, which is a natural or synthetic clay mineral, an optical brightener embedded between the layers of layered silicate and contains a surfactant.
  • the surfactant is believed to contribute to the optical Brightener at least partially homogeneous between the layers of the layered silicate because of the X-ray diffraction pattern of the dried product a layer expansion of from about 1.05 to 1.30 nm down to about 1.35 to 1.85 nm becomes.
  • the detergent additive preferably contains in addition to the swellable Layered silicate, the optical brightener and the surfactant an alkali carbonate.
  • the swellable layered silicate is a natural one or synthetic clay mineral.
  • the swellable Clay mineral is preferably montmorillonite, beidellite, saponite or hectorite.
  • Montmorillonite can be in sodium or calcium form or in the form of a calcium montmorillonite ion-exchanged with soda be used. It can also be synthetically made Clay minerals from the above group used become.
  • the layered silicate is preferably in one Amount of 10 to 50% by weight, in particular 30 to 50% by weight used.
  • the swellable layered silicates have the property under intra-crystalline swelling polar agents between the Intercalate silicate lamellae, which occurs at higher concentrations noticeable in an increase in the layer spacing makes.
  • the surfactant is preferably selected from the group consisting of anionic and selected nonionic surfactants, the nonionic Surfactant preferably a mixture of fatty alcohol ethoxylates represents different degrees of ethoxylation.
  • the fatty alcohol ethoxylates have the formula: RO- (EO) y -H, where R is a hydrocarbon radical having 10 to 18, in particular 12 to 18 carbon atoms, EO is an ethylene oxide group and y is a number from 2 to 20, in particular from 3 to 10. Mixtures of fatty alcohol ethoxylates of various degrees of ethoxylation can also be produced in a targeted manner.
  • the nonionic surfactants in which the optical brighteners, especially of the stilbene type, are soluble, promote their transport between the slats of the swellable layered silicate.
  • the optical brighteners are intercalated between the lamellae of the layered silicate and share with other detergents before the reaction protected.
  • the alkali carbonate especially in the form of sodium carbonate is used for several functions:
  • the layered silicate is agglomerated with the surfactant, it is obtained a soft, sticky with increasing content of surfactant Agglomerate that is not free-flowing and not capable of ensiling. Due to the presence of sodium carbonate, the mechanical Improved stability of the agglomerate and its stickiness reduced. There is also sodium carbonate in the detergent for adjusting the alkalinity and as a builder component he wishes.
  • the alkali carbonate is preferably used in amounts of about 10 to 40% by weight, in particular about 12 to 30% by weight If the layered silicate is agglomerated with the surfactant, it is obtained a soft, sticky with increasing content of surfactant Agglomerate that is not free-flowing and not capable of ensiling.
  • the alkali carbonate is preferably used in amounts of about 10 to 40% by weight, in particular about 12 to 30% by weight used.
  • the optical brightener is preferably a stilbene derivative But it can also benzoxazole, coumarin and pyrazoline derivatives be used. These products generally have an anionic dye residue, which is why it was surprising that they are between the negatively charged layers of the swellable Layered silicate can be stored.
  • the agglomerate particles are the detergent additive, preferably with synthetic zeolite envelops, resulting in the flowability of the agglomerate particles is improved.
  • the coating with zeolite continues to improve the degree of whiteness of the agglomerate.
  • the agglomerate preferably has a bulk density of more than about 700 g / liter and is due to this high bulk density Compatible with highly concentrated, high density detergents.
  • the invention further relates to a method for the production the detergent additive described above in agglomerate form, which is characterized in that (a) the optical brightener as an aqueous slurry at the same time with the surfactant (s) to the layered silicate (s) or (b) at least part of the optical brightener (s) previously dissolved in the surfactant (s) and the solution to the Layer silicates (s) are added.
  • the swellable layered silicate is preferably mixed before Add the optical brightener / surfactant with the alkali carbonate.
  • the powder components can, for example, in an intensive mixer, e.g. mixed together in an Eirich mixer. Subsequently, the optical brighteners (preferably as an aqueous dispersion) and that Surfactant sprayed through to the powder component. This forms an agglomerate, which is lower Mixing speed with which zeolite is powdered. The resulting Agglomerate is sieved and by adding more Zeolite (especially Zeolite P) in powder form on the surface to reduce stickiness and improve Whiteness coated.
  • an intensive mixer e.g. mixed together in an Eirich mixer.
  • the optical brighteners preferably as an aqueous dispersion
  • Surfactant sprayed through to the powder component.
  • the resulting Agglomerate is sieved and by adding more Zeolite (especially Zeolite P) in powder form on the surface to reduce stickiness and improve Whiteness coated.
  • the agglomerate obtained is readily dispersible in water.
  • the optical brightener is protected from oxidation and after the dissolution of the agglomerate in the wash liquor is fully available. Due to the presence of the layer silicate swellable in water there is no "brightener spotting".
  • the agglomerate can be manufactured in brightener-free production facilities Detergents are added subsequently, so that the systems not be contaminated with brighteners.
  • the invention further relates to a detergent containing the detergent additive described above in addition to usual Detergent components such as anionic and nonionic Surfactants, framework substances (builders), polymers (co-builders), Graying inhibitors, bleaching agents and bleach activators, Enzymes, foam inhibitors, fragrances and / or dyes.
  • Detergent components such as anionic and nonionic Surfactants, framework substances (builders), polymers (co-builders), Graying inhibitors, bleaching agents and bleach activators, Enzymes, foam inhibitors, fragrances and / or dyes.
  • the powdered layered silicate and the powdered sodium carbonate are premixed intensively. Under intense The surfactant or a Solution of the surfactant added. At the same time, the optical Brightener or a mixture of different optical brighteners added as an aqueous dispersion (slurry). Alternatively, you can a solution of the optical brightener in a surfactant solution be given to the powder mixture.
  • the mixture agglomerates at a water content of approximately 20 to 30 wt .-%, based on the total mixture.
  • a suitable dryer preferably in a Fluid bed dryer to a residual water content of about 2 to 15% by weight, preferably dried from about 5 to 10% by weight becomes.
  • the agglomerate obtained is broken up with a screening machine a particle size of about 0.2 to 2.5 mm, preferably of 0.5 to 1.7 mm, sieved. The fraction ⁇ 0.2 mm becomes the again Agglomeration fed. Coarse grain that forms is also removed crushed with a roller crusher and again on the screening plant given.
  • the optical is first Brightener dissolved in powder form in the surfactant.
  • the weight ratio between surfactant and optical brightener can be 15: 2 to 4:10, preferably 10: 3 to 10: 8.
  • the solution or Dispersion of the optical brightener in the surfactant becomes more intense Whirling is added to the powder, at the same time further portions of the optical brightener in aqueous dispersion be added.
  • the sieved agglomerate is placed in a drum mixer (for Example in a drum mixer from Telschig) or one Given granulation plate. Then about 3 to 15 wt .-%, preferably about 5 to 10% by weight synthetic zeolite in fine-grained form added.
  • the average particle size of this Powder should preferably be ⁇ 20 ⁇ m, in particular approximately 3 to 10 ⁇ m.
  • the detergent additive produced by the process described also has the following advantages:
  • the bulk density is greater than 700 g / liter, so that it with Detergent of high bulk density is compatible.
  • the agglomerates quickly disintegrate in water. It won't Whitening spotting observed on the laundry.
  • the active components Surfactant and optical brightener are full in the detergent available. Due to the presence of layered silicate and alkali carbonate the agglomerate is mechanically stable. The agglomerate can be added to the detergent afterwards, whereby essential parts of the detergent production plant not be contaminated with optical brighteners.
  • Optical brightener A Teopal® DMS, slurry in water with 36% active ingredient
  • Optical brightener B (Tinopal® CBS, slurry in water with 30% solids content) 5.88% by weight
  • the brightener is degraded A and B significantly lower, and there is no annoying Yellow color of the detergent due to oxidation products.
  • Example 1 As an alternative to Example 1, components A and B in mixed in an Eirich mixer. A solution of 134 g was obtained Tinopal® DMS-X h.c. (Powder form) in 438 g of component C (Surfactant), which is added to the mixture during the mixing process is given from components A and B. Then was component E added as a slurry. It also became a Obtained yellow tinted agglomerate, which is processed as in Example 1 has been.
  • component C Sudfactant
  • the stabilization of brightener A occurs regardless of whether as a slurry in water (example 1) or in non-ionic Surfactant (Example 2) incorporated into the detergent additive has been.
  • Optical brightener A Teinopal® DMS, slurry in water with 36% active ingredient) 7.0% by weight
  • Optical brightener B (Tinopal® CBS, slurry in water with 30% solids content) 1.8% by weight
  • Example 1 As in Example 1, 840 g were in an Eirich intensive mixer of component A and 424 g of component B for about one minute premixed. Then a mixture of components E (140 g) and F (36 g) added. Then 180 g of the component C and 180 g of component D (premixed) added.
  • the agglomerate obtained was to a grain size of 0.2 mm sieved to 2.0 mm.
  • the sieved agglomerate was then again with 5 % By weight of zeolite P, and mixed in a granulating plate, the agglomerate on the surface with zeolite powder was coated, thereby obtaining a white agglomerate has been.
  • the detergent remains white.

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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)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)

Claims (13)

  1. Additif pour agent de lavage sous forme d'agglomérat non pulvérisé à sec, caractérisé en ce qu'il contient au moins un silicate en feuillets capable de gonflement composé d'un minéral argileux naturel ou synthétique, un azurant optique inclus entre les feuillets du silicate en feuillets et un tensioactif inclus entre les feuillets du silicate en feuillets, et en ce qu'il présente une densité en vrac supérieure à 700 g/l.
  2. Additif pour agent de lavage selon la revendication 1, caractérisé en ce qu'il contient, outre le silicate en feuillets capable de gonflement, l'azurant optique et le tensioactif, un carbonate alcalin.
  3. Additif pour agent de lavage selon la revendication 1, caractérisé en ce qu'il contient :
    a) environ 5 à 60 % du poids de silicate(s) en feuillets capable(s) de gonflement,
    b) environ 5 à 35 % du poids de tensioactif(s),
    c) environ 5 à 60 % du poids de carbonate(s) alcalin(s),
    d) environ 1 à 20 % du poids d'azurant(s) optique(s).
  4. Additif pour agent de lavage selon la revendication 1, caractérisé en ce que le minéral argileux capable de gonflement est de la montmorillonite, de la beidellite, de la saponite ou de l'hectorite.
  5. Additif pour agent de lavage selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le tensioactif est choisi dans le groupe des tensioactifs anioniques et non ioniques.
  6. Additif pour agent de lavage selon la revendication 5, caractérisé en ce que le tensioactif non ionique se compose d'un mélange d'éthoxylates d'alcools gras à différents degrés d'éthoxylation.
  7. Additif pour agent de lavage selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'azurant optique est un dérivé de stilbène.
  8. Additif pour agent de lavage selon l'une quelconque des revendications 1 à 6, caractérisé en ce que les particules d'agglomérat sont enrobées de zéolithe de synthèse, de préférence de Zéolithe P.
  9. Procédé de production d'un additif pour agent de lavage sous forme d'agglomérat selon l'une quelconque des revendications 1 à 8, caractérisé en ce que (a) l'on ajoute le(s) azurant(s) optique(s) sous forme de suspension aqueuse au(x) silicate(s) en feuillets en même temps que le(s) tensioactif(s), ou (b) on dissout au préalable une partie au moins du (des) azurant(s) optique(s) dans le(s) tensioactif(s) avant d'ajouter la solution au(x) silicate(s) en feuillets.
  10. Procédé selon la revendication 9, caractérisé en ce que le silicate en feuillets capable de gonflement est mélangé au carbonate alcalin avant l'ajout de l'azurant optique et du tensioactif.
  11. Procédé selon la revendication 9 ou 10, caractérisé en ce que l'on forme un agglomérat ayant une taille de particules de 0,2 à 2,5 mm environ et contenant un taux résiduel d'eau de 2 à 15 % en poids.
  12. Procédé selon l'une quelconque des revendications 9 à 11, caractérisé en ce que l'agglomérat obtenu est enrobé de 3 à 15 % en poids d'une zéolithe de synthèse, de préférence de la Zéolithe P.
  13. Agent de lavage contenant un additif pour agent de lavage selon l'une quelconque des revendications 1 à 8 ou fabriqué selon l'une des revendications 9 à 12, en complément des composants habituels de l'agent de lavage.
EP96934551A 1995-10-12 1996-10-05 Additif de lessive Expired - Lifetime EP0856046B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19538028 1995-10-12
DE19538028A DE19538028A1 (de) 1995-10-12 1995-10-12 Waschmittelzusatz
PCT/EP1996/004337 WO1997013831A1 (fr) 1995-10-12 1996-10-05 Additif de lessive

Publications (2)

Publication Number Publication Date
EP0856046A1 EP0856046A1 (fr) 1998-08-05
EP0856046B1 true EP0856046B1 (fr) 2003-03-19

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP96934551A Expired - Lifetime EP0856046B1 (fr) 1995-10-12 1996-10-05 Additif de lessive

Country Status (5)

Country Link
EP (1) EP0856046B1 (fr)
AT (1) ATE234912T1 (fr)
DE (2) DE19538028A1 (fr)
ES (1) ES2193265T3 (fr)
WO (1) WO1997013831A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE246722T1 (de) * 1997-09-17 2003-08-15 Ciba Sc Holding Ag Antimikrobieller waschmittelzusatz
EP0903401B1 (fr) * 1997-09-17 2003-08-06 Ciba SC Holding AG Additif antimicrobien pour détergents
GB2339203A (en) * 1998-07-08 2000-01-19 Procter & Gamble A method of dipensing

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4427410A (en) * 1974-09-06 1984-01-24 Colgate-Palmolive Company Fabric softening composition containing molecular sieve zeolite
GB1572815A (en) * 1977-05-06 1980-08-06 Procter & Gamble Process for making detergent compositions
DE2856087A1 (de) * 1978-12-23 1980-07-10 Henkel Kgaa Verfahren zur herstellung weisser, optische aufheller und kationenaustauschfaehige alumosilikate enthaltender, pulverfoermiger waschmittel
EP0056723B1 (fr) * 1981-01-21 1984-12-05 Unilever Plc Compositions détergentes
AU549000B2 (en) * 1981-02-26 1986-01-09 Colgate-Palmolive Pty. Ltd. Base beads for detergent compositions
DE3248022A1 (de) * 1982-12-24 1984-06-28 Henkel KGaA, 4000 Düsseldorf Spruehgetrocknetes mehrkomponenten-waschmittel
DD220328A1 (de) * 1983-09-05 1985-03-27 Bitterfeld Chemie Waschhilfsmittel zur weissgradverstaerkung
DE3434854A1 (de) * 1984-09-22 1986-04-03 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung einer koernigen, freifliessenden waschmittelkomponente
DE3526405A1 (de) * 1985-07-24 1987-02-05 Henkel Kgaa Schichtsilikate mit beschraenktem quellvermoegen, verfahren zu ihrer herstellung und ihre verwendung in wasch- und reinigungsmitteln
DE3717227A1 (de) * 1987-05-21 1988-12-01 Henkel Kgaa Phosphatfreies waschmittel mit reduzierter inkrustierungstendenz
DE3737071A1 (de) * 1987-10-31 1989-05-11 Henkel Kgaa Verwendung von aminethern als netzmittel fuer textilien
WO1989008695A1 (fr) * 1988-03-14 1989-09-21 Novo-Nordisk A/S Composition particulaire stabilisee
DE4009618A1 (de) * 1990-03-26 1991-10-02 Henkel Kgaa Spruehgetrocknetes, avivierend wirkendes waschmitteladditiv
WO1992017404A1 (fr) * 1991-03-26 1992-10-15 Henkel Kommanditgesellschaft Auf Aktien Percarbonate de sodium stabilise
TR27586A (tr) * 1992-09-01 1995-06-13 Procter & Gamble Yüksek yogunlukla zerre deterjanin yapilmasi icin islem ve islem ile yapilan bilesimler.

Also Published As

Publication number Publication date
ATE234912T1 (de) 2003-04-15
DE59610244D1 (de) 2003-04-24
DE19538028A1 (de) 1997-04-17
WO1997013831A1 (fr) 1997-04-17
EP0856046A1 (fr) 1998-08-05
ES2193265T3 (es) 2003-11-01

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