EP1165739B1 - Verwendung von optischen aufhellern in reinigungsmitteln - Google Patents

Verwendung von optischen aufhellern in reinigungsmitteln Download PDF

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Publication number
EP1165739B1
EP1165739B1 EP00925127A EP00925127A EP1165739B1 EP 1165739 B1 EP1165739 B1 EP 1165739B1 EP 00925127 A EP00925127 A EP 00925127A EP 00925127 A EP00925127 A EP 00925127A EP 1165739 B1 EP1165739 B1 EP 1165739B1
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EP
European Patent Office
Prior art keywords
water
whitening agent
urea
brightener
pigment
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
EP00925127A
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English (en)
French (fr)
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EP1165739A1 (de
Inventor
Claudio Puebla
Jürgen Kaschig
Rainer Hans Traber
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.)
BASF Schweiz AG
Original Assignee
Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
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Publication of EP1165739A1 publication Critical patent/EP1165739A1/de
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Publication of EP1165739B1 publication Critical patent/EP1165739B1/de
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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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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 present invention relates to the use of a brightener pigment for increasing the degree of whiteness of detergents or cleaners, of compounds thereof, and of individual raw materials comprising
  • urea-formaldehyde resin of which the molar ratio of urea to formaldehyde is preferably from 1:1.3 to 2 moles.
  • the urea-formaldehyde resin is also distinguished by a small particle diameter of from 2 to 10 ⁇ m and a low BET specific surface area of from 15 to 120 m 2 /g.
  • the BET specific surface area of the water-insoluble urea-formaldehyde resins is ascertained according to the B runauer, E mmett and T eller method [cf. J.Am.Chem.Soc. 60 , 309-319 (1938), Chemie-Ing.Techn. 32 , 349-354 (1960) and 35 , 568-589 (1963)] according to DIN 66132.
  • the water-insoluble urea-formaldehyde resins which correspond to component (a), and the preparation of those polymers, are known, for example, from A. Renner: Makromolekulare Chemie 149 , 1-27 (1971).
  • the component (a) compounds are prepared by reacting formaldehyde with urea in aqueous solution in the above-described ratios.
  • the reaction is carried out preferably in two steps.
  • urea is reacted with formaldehyde according to a customary condensation mechanism, resulting in a low-molecular-weight, water-soluble pre-condensate.
  • an acid catalyst can be used in order to accelerate the reaction and for crosslinking, an insoluble, finely divided solid being obtained.
  • the water content of the reaction solution should never be lower than the total weight of the reactants present in the reaction mixture, and should be higher than the total weight of all the other components in the reaction mixture during the precipitation of the insoluble polymer particles.
  • the reaction temperature in the first reaction step is usually in the range from 20 to 100°C.
  • the pH can be adjusted to from 6 to 9 by the addition of a strong, aqueous, inorganic base, such as, for example, sodium hydroxide solution.
  • the preparation of the pre-condensate can be carried out in the presence of a surfactant.
  • the surfactant is used, for example, in amounts of from 0.5 to 5 % by weight, based on the total weight of the urea and formaldehyde. Ionic surfactants cause an increase in the specific surface area of the urea-formaldehyde polymer product, whereas non-ionic surfactants have the opposite effect.
  • the first reaction step is carried out in the presence of a macromolecular water-soluble protective colloid having polyelectrolytic properties.
  • protective colloids include gelatin, tragacanth, agar and polyvinylpyrrolidone, especially methacrylic acid.
  • the amount of protective colloid used can be within a range of, for example, from 0.5 to 5 % by weight, based on the total weight of urea and formaldehyde.
  • polyvinylpyrrolidone nor polymethacrylic acid causes an increase in the specific surface area of the water-insoluble urea-formaldehyde resin.
  • Suitable catalysts include, for example, relatively strong inorganic and/or organic acids, such as, for example, sulfuric acid, sulfurous acid, sulfamic acid, phosphoric acid, hydrochloric acid, chloroacetic acid, maleic acid or maleic anhydride.
  • relatively strong inorganic and/or organic acids such as, for example, sulfuric acid, sulfurous acid, sulfamic acid, phosphoric acid, hydrochloric acid, chloroacetic acid, maleic acid or maleic anhydride.
  • such gel-formation catalysts should have an ionisation constant in excess of 10 -4 .
  • Sulfuric acid and its acidic ammonium or amine salts and also ammonium sulfate, methylamine hydrogen sulfate and ethanolamine hydrogen sulfate, are preferred.
  • the acids are generally used in the form of 1 to 15 % by weight aqueous solutions.
  • As a rough guide from 20 to 100 mmoles of a crosslinking catalyst are used per mole of urea added. This causes a reduction in the pH of the reaction mixture to from 1 to 3.0 in the second reaction step during the formation of the polymer.
  • reaction temperatures in the second, resin-forming reaction step usually reach from 20 to 100°C. Large differences in temperature in the reaction mixture should be avoided during the addition of the catalyst. It is therefore desirable to heat the aqueous catalyst solution to the temperature of the reaction mixture before it is added to that mixture. Generally, a white gel is obtained after only from 15 to 30 seconds.
  • the crosslinking reaction is usually finished after a reaction time of from 30 minutes to 3 hours.
  • the insoluble polymer is obtained in the form of a white gel and can be comminuted mechanically, treated with an approximately equal amount of water, adjusted with alkali or ammonium hydroxide to a pH of from 6 to 9, and then isolated from the aqueous phase, for example by filtration, centrifugation or concentration by evaporation.
  • the drying can be carried out e.g. by spray-drying or convection-drying.
  • the gel obtained is then worked up in customary manner, for example by allowing the reaction to proceed to completion, neutralising, where appropriate adding one or more of the fluorescent whitening agents mentioned hereinbelow in cases where the addition of the fluorescent whitening agent is not undertaken until after gelation, and then filtering, washing, drying and, if desired, grinding to obtain a suitable particle size.
  • the fluorescent whitening agent of the present invention corresponds to formula (15).
  • the fluorescent whitening agent corresponding to component (b) used in accordance with the invention is employed preferably in amounts of from 0.001 to 1.0 % by weight, especially from 0.01 to 0.5 % by weight, and more especially from 0.01 to 0.5 % by weight, based on the total amount of urea-formaldehyde resin.
  • the fluorescent whitening agent can be added to the urea-formaldehyde resin in the form of individual compounds or in the form of mixtures of several individual compounds.
  • the brightener pigment used in accordance with the invention comprising components (a) and (b) can, in principle, be used for whitening detergents or cleansers on its own or together with other pigments.
  • Other pigments that can be used include, e.g., talc, titanium dioxide, aluminium oxide, aluminium hydroxide, zinc oxide, chalk, zeolite or clays, e.g. kaolin.
  • the brightener pigment used in accordance with the invention is usually prepared by adding the water-soluble fluorescent whitening agent before, during or after gelation.
  • the procedure comprises dispersing the urea-formaldehyde resin in hot water with a vigorous stirring action.
  • the pH is adjusted to ⁇ 10 using an aqueous alkali metal hydroxide solution and the water-soluble fluorescent whitening agent is added thereto.
  • the batch is further stirred for some time, cooled, and the pH is adjusted to ⁇ 3 using a strong acid, especially sulfuric acid.
  • a viscous suspension is obtained which is further processed by customary methods, such as filtration, drying and, if desired, grinding.
  • the brightener pigment is subjected to a surface treatment.
  • an emulsion of long-chain alcohols, of paraffin waxes, or of hydrogenated natural or synthetic resins, and especially a dodecanol emulsion is added to the viscous urea-formaldehyde resin/whitening agent suspension.
  • the batch is stirred for a further 10 to 15 minutes at elevated temperature. After cooling, the batch is filtered, dried and ground in customary manner, yielding a surface-treated formaldehyde resin/whitening agent suspension.
  • Dazzlingly white organic brightener pigments are obtained which have a very low content of free formaldehyde (typically less than 0.1 % DIN 58187) in which the fluorescent whitening agent has been incorporated or adsorbed.
  • Such products are solid, colloidal particles having an average diameter of from 0.1 to 0.2 ⁇ m, which are agglomerated to form pigment particles having an average diameter of from 3 to 20 ⁇ m.
  • the fluoresecently brightened pigments prepared in that manner are excellently suitable for improving the degree of whiteness (improvement in appearance) of commercially available detergents and cleansers, of compounds thereof, and of individual raw materials.
  • the brightener pigment used in accordance with the invention is usually incorporated into the detergents or cleansers by first suspending the brightener pigment in water, with stirring, and then adding the detergent or cleanser in question to the resulting suspension with the further addition of water. A creamy slurry is obtained, which is then dried and sieved to yield a detergent or cleanser having a particle size of approximately from > 0.3 to 1 mm.
  • the fluorescently brightened detergent or cleanser, compounds thereof and individual raw materials are prepared by simply dusting with the brightener pigment in powder form.
  • the brightener pigment in powder form.
  • compositions that can be treated in accordance with the invention with the brightener pigment comprising components (a) and (b) are detergents or cleansers in the form of powder or granules.
  • Such formulations may be particulate detergents composed of one or more granular components in which at least one granular component is acted upon by the brightener pigment.
  • the detergent may comprise further ingredients, e.g. surfactants, inorganic and organic builder substances, bleaching agents, substances that have a positive effect on the ability to wash out oil and grease, greying inhibitors, if desired substances that improve the solubility and the rate of dissolution of the individual granular components and/or of the entire formulations, fabric-softening substances, colorants and perfumes, and also alkaline and/or neutral salts in the form of their sodium and/or potassium salts.
  • surfactants e.g. surfactants, inorganic and organic builder substances, bleaching agents, substances that have a positive effect on the ability to wash out oil and grease, greying inhibitors, if desired substances that improve the solubility and the rate of dissolution of the individual granular components and/or of the entire formulations, fabric-softening substances, colorants and perfumes, and also alkaline and/or neutral salts in the form of their sodium and/or potassium salts.
  • washing-active or cleaning-active shaped forms for example detergent tablets, stain-removing salt tablets or water-softening tablets, can be provided in accordance with the invention.
  • the washing-active or cleaning-active shaped forms are especially cylindrical shapes or tablets that can be used as detergents, or bleaching agents (stain-removing salts), but can also be used as pretreatment agents, for example as water softeners or bleaching agents.
  • a distinction is drawn between homogeneous (homogeneously distributed ingredients) and heterogeneous (heterogenously distributed ingredients) shaped forms, which have as a special feature a disintegrator, such as, for example, starch, a starch derivative, cellulose or a cellulose derivative, which brings about the disintegration of the washing-active or cleaning-active shaped form. It is possible, in particular, for the degree of whiteness of such a disintegrator to be excellently improved by the brightener pigments used in accordance with the invention.
  • the so-treated detergent is distinguished by a very high degree of whiteness, which is substantially higher than that achieved by the discrete addition of organic white pigment and fluorescent whitening agent.
  • a further advantage of the detergent or cleanser treated in such a manner is that, during the actual washing operation, the brightener pigment or the fluorescent whitening agent does not contact and is not absorbed by the goods being washed.
  • urea-formaldehyde condensation polymer e.g. Pergopack® M2
  • Pergopack® M2 urea-formaldehyde condensation polymer
  • the suspension prepared in Step a. is adjusted to a pH of 2.5 using 1N sulfuric acid and heated to 60°C. Since the solution becomes very viscous, vigorous stirring is necessary.
  • a dodecanol suspension is then prepared by taking 500 ml of water, heating the water to 90°C, and adding 1 g of dodecane-1,2-diol with stirring and while cooling to 60°C.
  • the dodecanol suspension is added at 60°C, with vigorous stirring, to the prepared whitening agent suspension. The solution slowly becomes very liquid.
  • the filter cake is dried at 60°C and finely ground.
  • Degree of whiteness of the filtered product approximately 233 points (degree of whiteness according to Ganz) and 163 points (CIE).
  • urea-formaldehyde condensation polymer e.g. Pergopack® M2
  • Pergopack® M2 urea-formaldehyde condensation polymer
  • the pH is then adjusted to 7 using 0.07 kg of 2N sulfuric acid, and subsequently 4.0 kg of sodium chloride are introduced and the batch is stirred for a further 30 minutes at from 65 to 70°C.
  • 8.0 g of the fluorescent whitening agent of formula are then added.
  • 100.0 g of a commercially available urea-formaldehyde condensation polymer e.g. Pergopack® M2
  • a pH of 10 is established using 0.12 kg of 1N sodium hydroxide solution.
  • a further 400 ml of demineralised water that has previously been adjusted to pH 10.4 by the addition of 1N sodium hydroxide solution and subsequently heated to 60°C is then added.
  • the suspension is stirred for a further 20 minutes at from 65 to 70°C and then the pH is adjusted to 7 by the addition of 2N sulfuric acid.
  • Step a The resulting emulsion is then added to the suspension prepared in Step a., which has been heated to 60°C, and the dispersion is stirred for 10 minutes at 60°C and then allowed to cool to a temperature of ⁇ 40°C.
  • the batch is filtered and the filter cake is dried at 60°C and finely ground.
  • (A) is suspended in approximately 20 ml of deionised water, with stirring, using a pestle.
  • (B) is gradually added and stirred in.
  • a creamy slurry is formed to which a further 30 to 40 ml of deionised water is added in portions.
  • the resulting smooth slurry is transferred to a shallow porcelain dish and dried for approximately 14 hours in a vacuum cabinet at 60°C and from 425 to 475 mbar.
  • the mass After drying, the mass is cooled to room temperature and sieved.
  • the first sieve has a mesh size of from 0.315 to 0.8 mm, and the second a mesh size of ⁇ 0.315 mm. Powder having a particle size of ⁇ 0.315 mm is discarded.
  • the detergent formulation having the desired particle size (0.315 to 0.8 mm) is filled into brown glass bottles.
  • At least 5.5 g of the prepared detergent formulation are conditioned overnight (at least 20 hours) in a controlled environment chamber.
  • the conditions are 25°C and 65 % relative humidity.
  • a tablet is formed by compression and the degree of whiteness according to Ganz is determined.
  • Washing is carried out under the following conditions: dosage 30 g of detergent per kg of fabric liquor 5:1 (5 ml of tap water per g of fabric) washing temperature 30°C number of wash cycles 3 fabric 10 g of bleached cotton (Co-Renforcé) drying ironing

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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)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (7)

  1. Verwendung eines Aufhellerpigments zur Erhöhung des Weissgrades von Wasch- oder Reinigungsmitteln, deren Vorprodukten (Compounds), sowie einzelnen Rohprodukten, enthaltend
    (a) ein wasserunlösliches Hamstoff-Formaldehydharz und
    (b) einen wasserlöslichen optischen Aufheller der Formel (15),
    Figure 00150001
    wobei die Verwendung eine Nachbehandlung des aus den Komponenten (a) und (b) hergestellten Pigmentes umfasst, in der das Pigment mit einer Emulsion aus langkettigen Alkoholen, Parafinwachsen oder hydrogenierten natürlichen oder synthetischen Harzen versehen wird.
  2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, dass die Emulsion aus langkettigen Alkoholen besteht.
  3. Verwendung nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass als Wasch- oder Reinigungsmittel Mittel in Pulver- oder Granulatform oder wasch- oder reinigungsaktive Formkörper verwendet werden.
  4. Verwendung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Vorprodukte (Compounds) sowie einzelne Rohprodukte von Wasch- oder Reinigungsmitteln verwendet werden.
  5. Verfahren zur Herstellung eines Aufhellerpigments, enthaltend
    (a) ein wasserunlösliches Hamstoff-Formaldehydharz und
    (b) einen wasserlöslichen optischen Aufheller der Formel (15),
    durch Zusatz von (a) und (b) und anschliessende Behandlung der Hamstoff-Formaldehyd-Aufhellersuspension mit einer Emulsion aus langkettigen Alkoholen, Parafinwachsen oder hydrogenierten natürlichen oder synthetischen Harzen.
  6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass man die anschliessende Oberflächenbehandlung mit einer Dodecanol-Emulsion durchführt.
  7. Wasch- oder Reinigungsmittel mit erhöhtem Weissgrad enthaltend ein Aufhellerpigment, das
    (a) ein wasserunlösliches Hamstoff-Formaldehydharz und
    (b) einen wasserlöslichen optischen Aufheller der Formel (15) enthält,
    wobei man das aus den Komponenten (a) und (b) hergestellte Aufhellerpigment mit einer Emulsion aus langkettigen Alkoholen, Parafinwachsen oder hydrogenierten natürlichen oder synthetischen Harzen nachbehandelt.
EP00925127A 1999-03-29 2000-03-21 Verwendung von optischen aufhellern in reinigungsmitteln Expired - Lifetime EP1165739B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH58999 1999-03-29
CH58999 1999-03-29
PCT/EP2000/002459 WO2000058432A1 (en) 1999-03-29 2000-03-21 The use of a brightener pigment in detergents or cleansers

Publications (2)

Publication Number Publication Date
EP1165739A1 EP1165739A1 (de) 2002-01-02
EP1165739B1 true EP1165739B1 (de) 2005-06-08

Family

ID=4190504

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00925127A Expired - Lifetime EP1165739B1 (de) 1999-03-29 2000-03-21 Verwendung von optischen aufhellern in reinigungsmitteln

Country Status (8)

Country Link
EP (1) EP1165739B1 (de)
CN (1) CN1263837C (de)
AT (1) ATE297458T1 (de)
AU (1) AU4396100A (de)
DE (1) DE60020685T2 (de)
ES (1) ES2242615T3 (de)
IL (1) IL144881A0 (de)
WO (1) WO2000058432A1 (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU6606201A (en) * 2000-06-19 2002-01-02 Albemarle Corporation Fluorescent brightener pigment compositions
BRPI0416687A (pt) * 2003-11-18 2007-01-30 Ciba Sc Holding Ag pigmentos branqueadores fluorescentes
GB0329129D0 (en) * 2003-12-16 2004-01-21 Unilever Plc Laundry composition
WO2005090545A1 (en) * 2004-03-12 2005-09-29 Ciba Specialty Chemicals Holding Inc. Process for the preparation of brightener pigments
EP1746151A1 (de) * 2005-07-20 2007-01-24 Unilever N.V. Wasch- und Reinigungsmitteltabletten
WO2022199897A1 (de) * 2021-03-23 2022-09-29 Henkel Ag & Co. Kgaa Waschmitteltablette

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2213161A (en) * 1987-12-30 1989-08-09 Procter & Gamble Vividly colored laundry or cleaning products
DE4140830A1 (de) * 1990-12-14 1992-06-17 Ciba Geigy Ag Einschlussverbindungen
GB9718081D0 (en) * 1997-08-28 1997-10-29 Ciba Geigy Ag Fluorescent whitening agent

Also Published As

Publication number Publication date
CN1263837C (zh) 2006-07-12
IL144881A0 (en) 2002-06-30
WO2000058432A1 (en) 2000-10-05
DE60020685D1 (de) 2005-07-14
ATE297458T1 (de) 2005-06-15
DE60020685T2 (de) 2006-03-16
AU4396100A (en) 2000-10-16
EP1165739A1 (de) 2002-01-02
CN1345366A (zh) 2002-04-17
ES2242615T3 (es) 2005-11-16

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