EP0857200B1 - Additif de lessive - Google Patents

Additif de lessive Download PDF

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Publication number
EP0857200B1
EP0857200B1 EP96934550A EP96934550A EP0857200B1 EP 0857200 B1 EP0857200 B1 EP 0857200B1 EP 96934550 A EP96934550 A EP 96934550A EP 96934550 A EP96934550 A EP 96934550A EP 0857200 B1 EP0857200 B1 EP 0857200B1
Authority
EP
European Patent Office
Prior art keywords
detergent
agglomerate
detergent additive
optical brightener
additive according
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
EP96934550A
Other languages
German (de)
English (en)
Other versions
EP0857200A1 (fr
Inventor
Wolfgang Heininger
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.)
Sued Chemie AG
Original Assignee
Sued Chemie AG
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 filed Critical Sued Chemie AG
Publication of EP0857200A1 publication Critical patent/EP0857200A1/fr
Application granted granted Critical
Publication of EP0857200B1 publication Critical patent/EP0857200B1/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
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • 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

Definitions

  • the invention relates to a detergent additive, based of swellable layered silicates.
  • 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 for the production made from the various components. Subsequently this slurry is spray dried.
  • DD-220325, 220326, 220327 and 220328 are washing aids known for whiteness enhancement. These contain optical Brightener and non-swellable layered silicates, e.g. the natural mineral magadiite.
  • 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 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 is 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. Is not the optical brightener through a coating created during production or by the presence of thinning, spatially separating and water adsorbing actuators, from the bleaches also contained in the detergent, such as sodium perborate, but especially sodium percarbonate, separated, so optical brighteners can be oxidized. That used up here Bleaching potential stands for the later bleaching effect no longer available in the wash liquor.
  • the oxidation product of the optical brightener can turn yellow be colored, which gives the detergent a yellow tint shows, on the other hand, the yellow oxidation product of the brightener substantively on the washing textiles, what to an impairment of the aesthetic aspect, above all white laundry leads.
  • the formation 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 according to claim 1.
  • the optical brightener Due to the close contact of the optical brightener with the Layered silicate is used during the oxidation processes Storage of the detergent is reliably removed and it will when using the detergent, the "brightener spotting" on the Avoid laundry. It is believed that the optical brightener at least partially between the layers of layered silicate is stored because the discrete Brightener particles in the detergent additive have largely disappeared and the layered silicate particles in the fluorescence microscope appear homogeneously colored by the brightener.
  • the weight ratio is preferably swellable Layered silicate (s): optical brightener about 200-7: 1, in particular 100-10: 1st
  • 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 be used.
  • the layered silicate is preferably in an amount of 90 to 99 wt .-% used.
  • the swellable layered silicates have the property under intra-crystalline swelling polar agents between the Intercalate silicate lamellae, which can be seen at higher concentrations noticeable in an increase in the layer spacing makes.
  • 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.
  • Suitable optical brighteners are, for example
  • the agglomerate particles of the detergent additive are preferably coated with synthetic zeolite or layered sodium silicate (preferably about 3 to 15% by weight), which increases the whiteness of the agglomerate is improved.
  • Further preferred alternatives for concealing the intrinsic color of the agglomerates consist of dyeing with dyes customary in detergents, in particular pigment dyes, for example Unidisperse® blue BE (commercial product from Ciba-Geigy) (preferably about 0.01 to 0.5% by weight), or in the addition of colored active substances (preferably about 0.3 to 5% by weight), for example the photo bleach Tinolux® BB 5 (commercial product from Ciba-Geigy).
  • dyes customary in detergents in particular pigment dyes, for example Unidisperse® blue BE (commercial product from Ciba-Geigy) (preferably about 0.01 to 0.5% by weight), or in the addition of colored active substances (preferably about 0.3 to 5% by weight), for example the photo bleach Tinolux® BB 5 (commercial product from Ciba-Geigy).
  • 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 of the detergent additive described above in Agglomerate form, which is characterized in that the optical brighteners as an aqueous slurry to the (the) Layered silicate (s) exist.
  • the layered silicate (s) can be, for example, in an intensive mixer, e.g. in an Eirich mixer (mixed together). Then the optical brightener (preferably as an aqueous dispersion) sprayed with swirling to the powder component. in this connection an agglomerate forms, which is sieved and added of powdered zeolite superficially to improve the Whiteness is coated.
  • an intensive mixer e.g. in an Eirich mixer (mixed together).
  • the optical brightener preferably as an aqueous dispersion
  • an agglomerate forms, which is sieved and added of powdered zeolite superficially to improve the Whiteness is 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 to 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, builders (polymers), 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, builders (polymers), polymers (co-builders), Graying inhibitors, bleaching agents and bleach activators, Enzymes, foam inhibitors, fragrances and / or Dyes.
  • the powdery layered silicate becomes with intensive swirling the optical brightener or a mixture of different optical brightener as an aqueous dispersion (slurry) added.
  • 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 sieving 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 again Agglomeration fed. Coarse grain that forms is also removed crushed with a roller crusher and again on the screening plant given.
  • 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 with high bulk density is compatible.
  • the agglomerates quickly disintegrate in water. It won't Whitening spotting observed on the laundry.
  • the optical brightener is fully available in the detergent.
  • the agglomerate is mechanically stable. The agglomerate can be subsequently Mix in detergent, which makes up essential parts of the detergent production system not contaminated with optical brighteners become.
  • a detergent additive was produced according to the following recipe: A Bentonite (Laundrosil® DGA, Süd-Chemie AG) 98% by weight B Optical brightener (Tinopal® DMS-X hc) 2% by weight
  • the loss in% was calculated from the brightener content determined before and after the storage test by means of HPLC analysis. The results are shown in Table I. Brighteners use Loss in% after 8 weeks about detergent additive 23% about spray product 55%
  • the decrease in the brightener content due to oxidative degradation is when using the detergent additive according to Example 1 clearly smaller compared to a detergent of the same gross composition, where the brightener is included in the spray product is.
  • a detergent additive was produced according to the following recipe: A Bentonite (Laundrosil® DGA, Süd-Chemie AG) 99% by weight B Optical brightener (Tinopal® -CBS-X) 1% by weight
  • the detergent additive was subjected to a spotting test on pre-lightened cotton fabric as described in Example 1.
  • the evaluation is as follows: In daylight very good Under UV light acceptable.
  • the brighteners are broken down less than in a detergent of the same gross composition, where the brightener is included in the spray product is.

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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)

Claims (12)

  1. Additif pour agents de lavage sous la forme d'un agglomérat, caractérisé en ce qu'il contient au moins un silicate en feuillets capable de gonflement, contenant un minéral argileux naturel ou capable de gonflement, et au moins un azurant optique en contact l'un avec l'autre, l'azurant optique étant inclus au moins partiellement entre les couches du silicate en feuillet.
  2. Additif pour agents de lavage selon la revendication 1, caractérisé en ce que le rapport en poids entre le(s) silicate(s) en feuillets capable(s) de gonflement et le ou les azurants optiques est de 200 - 7 : 1, de préférence environ 100 -10: 1.
  3. Additif pour agents 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.
  4. Additif pour agents de lavage selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l'azurant optique est un dérivé de stilbène.
  5. Additif pour agents de lavage selon l'une quelconque des revendications 1 à 4, caractérisé en ce que les particules d'agglomérat sont enrobées de zéolithe de synthèse ou de silicate de sodium en feuillets.
  6. Additif pour agents de lavage selon l'une quelconque des revendications 1 à 4, caractérisé en ce que les particules d'agglomérat sont colorées avec un colorant, de préférence un pigment.
  7. Additif pour agents de lavage selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'il contient, outre le silicate en feuillet capable de gonflement et l'azurant optique, une substance active, de préférence un agent photo-blanchissant.
  8. Additif pour agents de lavage selon l'une quelconque des revendications 1 à 7, caractérisé en ce que l'agglomérat présente une densité en vrac supérieure à 700 g/litre environ.
  9. Procédé de fabrication d'un additif pour agents de lavage sous la forme d'un agglomérat selon l'une quelconque des revendications 1 à 8, caractérisé en ce que le ou les azurants optiques sont ajoutés au(x) silicate(s) en feuillets sous la forme d'une bouillie aqueuse.
  10. Procédé selon la revendication 9, 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 % du poids.
  11. Procédé selon la revendication 9 ou 10, caractérisé en ce que l'agglomérat obtenu (a) est enrobé avec 3 à 15 % en poids d'une zéolithe de synthèse ou d'un silicate en feuillets, (b) teinté avec environ 0,01 à 0,5 % en poids d'un colorant, notamment d'un pigment, ou (c) traité avec environ 0,3 à 5 % en poids d'une substance active colorée, de préférence un agent photo-blanchissant.
  12. Agent de lavage contenant un additif pour agents de lavage selon l'une quelconque des revendications 1 à 8 ou fabriqué selon l'une des revendications 9 à 11, en supplément des composants habituels du détergent.
EP96934550A 1995-10-12 1996-10-05 Additif de lessive Expired - Lifetime EP0857200B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19538029 1995-10-12
DE19538029A DE19538029A1 (de) 1995-10-12 1995-10-12 Waschmittelzusatz
PCT/EP1996/004336 WO1997013830A1 (fr) 1995-10-12 1996-10-05 Additif de lessive

Publications (2)

Publication Number Publication Date
EP0857200A1 EP0857200A1 (fr) 1998-08-12
EP0857200B1 true EP0857200B1 (fr) 2002-03-20

Family

ID=7774675

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96934550A Expired - Lifetime EP0857200B1 (fr) 1995-10-12 1996-10-05 Additif de lessive

Country Status (8)

Country Link
US (1) US6541440B2 (fr)
EP (1) EP0857200B1 (fr)
JP (1) JP3453388B2 (fr)
AT (1) ATE214726T1 (fr)
DE (2) DE19538029A1 (fr)
ES (1) ES2174110T3 (fr)
RU (1) RU2175002C2 (fr)
WO (1) WO1997013830A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0905317B1 (fr) * 1997-09-16 2009-12-23 Basf Se Procédé d'azurage optique de papier
NZ331438A (en) * 1997-09-16 2000-01-28 Ciba Sc Holding Ag A method of increasing the whiteness of paper by using a formulation containing a swellale layered silicate and an optical brightener 4,4-bis-(triazinylamino)-stilbene-2,2-disulphonic acid
US6790814B1 (en) * 1999-12-03 2004-09-14 Procter & Gamble Company Delivery system having encapsulated porous carrier loaded with additives, particularly detergent additives such as perfumes
EP1392925A1 (fr) * 2001-05-29 2004-03-03 Ciba SC Holding AG Composition de blanchiment fluorescent du papier
KR100430332B1 (ko) * 2001-06-22 2004-05-04 주식회사 대하맨텍 형광증백제 함유 유무기 복합체 및 그 제조방법
DE60302883T2 (de) * 2002-04-19 2006-08-17 Dow Corning S.A. Schaumregulierungsmittel
JP4115827B2 (ja) * 2002-12-26 2008-07-09 ライオン株式会社 洗剤組成物
DE10334045A1 (de) * 2003-07-25 2005-02-10 Clariant Gmbh Additive für Wasch- und Reinigungsmittel
JP5744744B2 (ja) 2008-11-20 2015-07-08 ユニリーバー・ナームローゼ・ベンノートシヤープ 個人向け洗浄用組成物
EA021087B1 (ru) 2009-08-17 2015-04-30 Юнилевер Нв Формованная твердая очищающая композиция
CN102822095A (zh) * 2009-09-24 2012-12-12 荷兰联合利华有限公司 微粒荧光增白剂及其制备方法
US8476216B2 (en) * 2010-05-28 2013-07-02 Milliken & Company Colored speckles having delayed release properties
US8470760B2 (en) 2010-05-28 2013-06-25 Milliken 7 Company Colored speckles for use in granular detergents

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4196103A (en) * 1971-06-18 1980-04-01 Colgate-Palmolive Company Colored detergents
DE2263940C2 (de) * 1972-12-29 1982-04-08 Henkel KGaA, 4000 Düsseldorf Zur Anwendung mit Textilwaschmitteln geeignete Aufheller-Tablette
AT335031B (de) * 1974-01-17 1977-02-25 Degussa Optische aufheller enthaltende gemische und verfahren zu deren herstellung
GB1572815A (en) * 1977-05-06 1980-08-06 Procter & Gamble Process for making detergent compositions
US4196104A (en) * 1977-09-26 1980-04-01 The Procter & Gamble Company Process for producing antistatic, fabric-softening detergent composition
DE2856087A1 (de) * 1978-12-23 1980-07-10 Henkel Kgaa Verfahren zur herstellung weisser, optische aufheller und kationenaustauschfaehige alumosilikate enthaltender, pulverfoermiger waschmittel
US4395342A (en) * 1980-06-06 1983-07-26 The Procter & Gamble Company Granular fabric softening composition
AU549000B2 (en) * 1981-02-26 1986-01-09 Colgate-Palmolive Pty. Ltd. Base beads for detergent compositions
US4399049A (en) 1981-04-08 1983-08-16 The Procter & Gamble Company Detergent additive compositions
US4421657A (en) * 1982-04-08 1983-12-20 Colgate-Palmolive Company Heavy duty laundry softening detergent composition and method for manufacture thereof
US4488972A (en) * 1982-04-08 1984-12-18 Colgate-Palmolive Company Bentonite agglomerates
US4536316A (en) * 1983-06-01 1985-08-20 Colgate-Palmolive Co. Fabric softening composition containing surface modified clay
GB8321683D0 (en) * 1983-08-11 1983-09-14 Procter & Gamble Detergent with fabric softener
DD220325A1 (de) * 1983-09-05 1985-03-27 Bitterfeld Chemie Waschhilfsmittel
DD220328A1 (de) * 1983-09-05 1985-03-27 Bitterfeld Chemie Waschhilfsmittel zur weissgradverstaerkung
DD220326A1 (de) * 1983-09-05 1985-03-27 Bitterfeld Chemie Weissgradverstaerker
DD220327A1 (de) * 1983-09-05 1985-03-27 Bitterfeld Chemie Weisstoener enthaltendes gemisch
GB8502032D0 (en) * 1985-01-28 1985-02-27 Unilever Plc Detergent powder
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
WO1989008695A1 (fr) * 1988-03-14 1989-09-21 Novo-Nordisk A/S Composition particulaire stabilisee
US5318714A (en) 1988-03-14 1994-06-07 Novo Nordisk A/S Stabilized particulate composition
US5030377A (en) * 1988-11-11 1991-07-09 Kao Corporation Detergent compositions containing starch debranching enzymes
DE4009618A1 (de) 1990-03-26 1991-10-02 Henkel Kgaa Spruehgetrocknetes, avivierend wirkendes waschmitteladditiv
US5691294A (en) * 1993-03-30 1997-11-25 The Procter & Gamble Company Flow aids for detergent powders comprising sodium aluminosilicate and hydrophobic silica
GB9323250D0 (en) 1993-11-11 1994-01-05 Unilever Plc Process for the production of a detergent composition
CN1044718C (zh) * 1993-11-19 1999-08-18 普罗格特-甘布尔公司 含氧化胺和磺酸盐表面活性剂的洗涤剂组合物
US5478502A (en) * 1994-02-28 1995-12-26 The Procter & Gamble Company Granular detergent composition containing hydrotropes and optimum levels of anoionic surfactants for improved solubility in cold temperature laundering solutions

Also Published As

Publication number Publication date
EP0857200A1 (fr) 1998-08-12
DE59608930D1 (de) 2002-04-25
US20020039986A1 (en) 2002-04-04
JP3453388B2 (ja) 2003-10-06
JPH11513430A (ja) 1999-11-16
ATE214726T1 (de) 2002-04-15
DE19538029A1 (de) 1997-04-17
US6541440B2 (en) 2003-04-01
WO1997013830A1 (fr) 1997-04-17
ES2174110T3 (es) 2002-11-01
RU2175002C2 (ru) 2001-10-20

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