EP1354938A1 - Waschmitteltabletten mit verbessertem Auflöseverhalten - Google Patents

Waschmitteltabletten mit verbessertem Auflöseverhalten Download PDF

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Publication number
EP1354938A1
EP1354938A1 EP03075889A EP03075889A EP1354938A1 EP 1354938 A1 EP1354938 A1 EP 1354938A1 EP 03075889 A EP03075889 A EP 03075889A EP 03075889 A EP03075889 A EP 03075889A EP 1354938 A1 EP1354938 A1 EP 1354938A1
Authority
EP
European Patent Office
Prior art keywords
soap
surfactants
granules
coagel
laundry
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.)
Withdrawn
Application number
EP03075889A
Other languages
English (en)
French (fr)
Inventor
Judith Maria R & D Port Sunlight Bonsall
John George R & D Port Sunlight Chmabers
William John R & D Port Sunlight Wilson
Douglas Wraige
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.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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 Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP03075889A priority Critical patent/EP1354938A1/de
Publication of EP1354938A1 publication Critical patent/EP1354938A1/de
Withdrawn legal-status Critical Current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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
    • 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
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0086—Laundry tablets
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides
    • C11D3/323—Amides; Substituted amides urea or derivatives thereof

Definitions

  • This invention not only enhances the rate of tablet dispersion/dissolution, expressed as T90 and measured by the method disclosed e.g. in the examples of WO 00/22089 , but as a result of this improvement, also reduces the risk of residues and patch damage.
  • Tablets that comprise low solubility soap and anionics in ratios of about 0.1 are disclosed in e.g. US 5 900 399 (examples 1 and 2); in EP 716 144 (examples) tablets are disclosed wherein the ratio between a non specified soap and anionics ranges from about 2.3 to about 0.4, while the ratio between the soap and the total of anionics and non-ionics herein is about 0.1 to 0.2. Still these tablets do not display satisfying dissolution properties. This is due, as we found, to the fact that the soap and anionics are not added in the correct physical form. We found that if first a coagel is made from at least the anionics (but the non-ionics can be present as well) and the low solubilty soap and this coagel is added to the tablets the dissolution properties improved considerably.
  • a coagel is defined here as a thermoreversible gel, which is formed by spontaneous separation of an anisotropic interconnected solid network from an isotropic continuum.
  • One way to make a coagel of these ingredients is to contact a mix of solid carrier material, in particular a mix of zeolite and soda ash with at least part of the free fatty acid constituents of the low solubility soap and the acidic form of anionic surfactants (optionally in the presence of non-ionic surfactants) and then neutralise the acids by an in-situ neutralisation reacting the soda ash which is part of the carrier material with the acids.
  • a mix of solid carrier material in particular a mix of zeolite and soda ash with at least part of the free fatty acid constituents of the low solubility soap and the acidic form of anionic surfactants (optionally in the presence of non-ionic surfactants) and then neutralise the acids by an in-situ neutralisation reacting the soda ash which is part of the carrier material with the acids.
  • an in-situ neutralisation of a mix of at least the anionics and the free fatty acid constituents of the soap using an alkali
  • our invention concerns in the first instance novel laundry tablets comprising granules wherein soap and surfactants are present and wherein the surfactants comprise either one or more anionic surfactants or a mix of one or more anionic and one or more non-ionic surfactants and wherein the soap has a Tk of at least 35°C while the weight ratio of soap to anionic surfactants is at least 0.1, preferably 0.1 to 0.5 and the weight ratio of soap to total surfactants is less than 0.5.
  • the soap can be present as a coagel with the anionics only but also coagels of soap and all surfactants present lead to good results.
  • the laundry tablet so-formed has enhanced dispersion/dissolution properties while maintaining tablet integrity. This integrity can be expressed as Fmax, which is measured by the method disclosed in the examples of WO 00/22089
  • Very convenient soaps are soap derived from one or more fatty acids selected from the group consisting of straight chain fatty acids with 12 to 24 carbon atoms.
  • the "low solubility soap” is defined by its solubility in water expressed as a Kraft temperature, (Tk value, i.e. the minimum solubility temperature for the soap corresponding to the crystal solubility boundary).
  • Tk value i.e. the minimum solubility temperature for the soap corresponding to the crystal solubility boundary
  • the target minimum value for this Tk is 35°C.
  • suitable soaps include those selected from one or more of saturated and unsaturated alkyl carboxylates where the counterion is one of sodium, potassium, calcium or magnesium.
  • the soap or blend must have a Tk value in excess of 35 Celsius.
  • Examples of single soaps include sodium laurate, sodium myristate, sodium palmitate, sodium stearate, sodium behenate, potassium palmitate, potassium stearate and calcium laurate.
  • Examples of blends include blends from 99/1 to 1/99 of sodium soaps of palmitate and myristate, palmitate and stearate, and myristate and stearate.
  • Examples of blends containing unsaturated alkyl soaps include less than 1:1 blends of sodium oleate and sodium stearate and sodium oleate and sodium palmitate.
  • compositions can also be post dosed to the compositions.
  • Preferred additional components are urea and sodium carbonate.
  • Other components include one or more detergency builders, bleaches, bleach precursors and optionally other detergent ingredients.
  • the soluble surfactants are usually comprised of one or more anionic and nonionic surfactants but can also include amphoteric and cationic surfactants.
  • anionic surfactant is selected from LAS and PAS.
  • nonionic surfactants are selected from alcohol ethoxylates.
  • amphoteric surfactants are typically betaine-type derivatives.
  • Synthetic (i.e. non-soap) anionic surfactants are well known to those skilled in the art.
  • PAS Primary alkyl sulphate having the formula: ROSO 3 - M + in which R is an alkyl or alkenyl chain of 8 to 18 carbon atoms especially 10 to 14 carbon atoms and M + is a solubilising cation, is commercially significant as an anionic surfactant.
  • Suitable nonionic surfactant compounds which may be used include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide.
  • Nonionic surfactant compounds are alkyl (C 8-22 ) phenolethylene oxide condensates, the condensation products of linear or branched aliphatic C 8-20 primary or secondary alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene-diamine.
  • the primary and secondary alcohol ethoxylates especially the C 9-11 and C 12-15 primary and secondary alcohols ethoxylated with an average of from 5 to 20 moles of ethylene oxide per mole of alcohol.
  • the coagel of soluble and insoluble surfactants necessary for the invention can also be made by a process wherein the in-situ neutralisation of the acids is performed by using an alkali reagent of a co-injected mix of anionic surfactants and the free fatty acid constituent of the soap during an NTR processing.
  • the granules that can be applied can be the result of a spray drying process.
  • the neutralisation reaction between acids and soda ash is performed in a high shear solid mixer.
  • tablet components typically include builders, bleaches, bleach precursors, optical brighteners, polymers, electrolytes, fillers, organic disintegrants and clays
  • the insoluble sodium soap (1:1 blend of C16 and C18 fatty acids which are subsequently neutralised during processing) is mixed with the nonionic surfactant to prevent bleeding on storage.
  • No soaps are blended with the anionic surfactant.
  • the ratio of insoluble soap/ nonionic surfactants is ca 1.6/10, and the ratio of insoluble soap/total soluble surfactants is 0.7/10.
  • Process details All powders (except Zeolite A24 layer) added to FS100 batch high shear granulator. Powders premixed. The LAS acid is heated to approx 70°c and added to the powder.
  • Control product - (wgt%) Formulation Control LAS Acid 18.67 NI 7eo 5.93 NI 3eo 3.11 Pristerine 4916 (A fully hardened tallow fatty acid soap) 1.46 Na Acetate 5.93 Light Soda Ash (LSA) 12.64 Sodium carboxymethyl Cellulose (SCMC) 0.88 Zeolite A24 48.76 Zeolite Layer 2.63 Full formulation details (wgt %) Formulation Control Base Powder 46.40 Anti foam granule 1.80 NaPercarbonate 15.00 Tetraacetyl ethylene diamine (TAED) 5.10 Anti redeposition polymer 5.50 NaCarbonate dense 1.40 NaAcetate 24.90
  • the base detergent formulation is given in Table 4. (wgt %) Formulation LAS Acid 18.4 NI 7eo 5.8 NI 3eo 3.0 Na Acetate 5.8 LSA 12.4 SCMC 0.9 Myristic acid 2914 2.8 Zeolite A24 48.2 Zeolite A24 layer 2.6
  • Example 3 this product contains C14 soap, (myristate) blended in with both LAS and nonionics.
  • the ratio of soap/total soluble surfactants 1/10.
  • the base detergent formulation is given in (wgt %) Formulation LAS Acid 16.64 NI 7eo 5.27 NI 3eo 2.73 Myristate 2914 2.55 Na Acetate 5.27 LSA 11.27 SCMC 0.73 Zeolite A24 53.18 Zeolite Layer 2.36
  • Example 4 - this product contains C14 soap, (myristate) blended in with both LAS and nonionics.
  • the soap/total soluble surfactant ratio 2.7/10.
  • the base detergent formulation is given in Table 8. (wgt %) Formulation LAS Acid 14.56 NI 7eo 4.63 NI 3eo 2.37 Myristate 2914 5.60 Na Acetate 4.20 LSA 8.87 SCMC 0.57 Zeolite A24 55.21 Zeolite Layer 3.99
  • the base detergent formulation is given in Table 11.
  • This soap blend falls outside the scope of the requirement that the Tk of the soap being >35°C.
  • the actual Tk of the sodium soap of Priolene 6930 will be ca 15°C.
  • Example 6B The base detergent formulation for Example 6B is given Formulation LAS Acid 14.56 NI 7eo 4.63 NI 3eo 2.37 Priolene 6930 5.60 Na Acetate 4.20 LSA 8.87 SCMC 0.57 Zeolite A24 55.21 Zeolite Layer 3.99
  • Examples 7 and 8 In these examples the control base powder of example 1 is made and the postdose ingredients, are as shown in Table 13 with the Fmax values as given.
  • T90 values are clearly superior when the sodium acetate is replaced by urea, even though the tablet hardness is greater in the urea containing tablet.
  • Example 8 In this example the base powder of Example 2 has been used with the post dose ingredients as shown in Table 14.
  • T90 values are substantially shorter than those of Example 7 where an identical post-dose was used. This confirms that the combination of modified base and urea.soda ash post dose work together to deliver a further improvement in dissolution.
  • Example 9 In this example the base powder of Example 3 has been used with the postdose ingredients as shown in Table 15.
  • Example 10 In this example the base powder of Example 4 has been used with the postdose ingredients as shown in Table 16. The T90 value is less than that of Example 7 where the conventional base is used.

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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)
EP03075889A 2002-04-18 2003-03-27 Waschmitteltabletten mit verbessertem Auflöseverhalten Withdrawn EP1354938A1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP03075889A EP1354938A1 (de) 2002-04-18 2003-03-27 Waschmitteltabletten mit verbessertem Auflöseverhalten

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP02252764 2002-04-18
EP02252764 2002-04-18
EP03075889A EP1354938A1 (de) 2002-04-18 2003-03-27 Waschmitteltabletten mit verbessertem Auflöseverhalten

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1903100A1 (de) * 2006-09-19 2008-03-26 Unilever N.V. Waschmitteltablette
CN101165151B (zh) * 2007-09-29 2010-05-19 上海特地旺农业科技有限公司 一种天然、温和的清洁剂
WO2010105816A1 (en) * 2009-03-17 2010-09-23 Bbt Bergedorfer Biotechnik Gmbh Cleaning agent containing carbamide and/or at least a derivative thereof
WO2018141104A1 (en) * 2017-02-06 2018-08-09 The Procter & Gamble Company Laundry detergent sheet comprising lines of frangibility

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1004596A (en) * 1962-03-07 1965-09-15 Procter & Gamble Detergent tablet
EP0716144A2 (de) * 1994-11-14 1996-06-12 Unilever Plc Reinigungsmittel in Tablettenform mit einer wasserlöslichen Umhüllung
US5900399A (en) * 1994-02-10 1999-05-04 Henkel Kommanditgesellschaft Auf Aktien Tablet containing builders
US6083893A (en) * 1994-05-16 2000-07-04 The Proctor And Gamble Co. Shaped semi-solid or solid dishwashing detergent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1004596A (en) * 1962-03-07 1965-09-15 Procter & Gamble Detergent tablet
US5900399A (en) * 1994-02-10 1999-05-04 Henkel Kommanditgesellschaft Auf Aktien Tablet containing builders
US6083893A (en) * 1994-05-16 2000-07-04 The Proctor And Gamble Co. Shaped semi-solid or solid dishwashing detergent
EP0716144A2 (de) * 1994-11-14 1996-06-12 Unilever Plc Reinigungsmittel in Tablettenform mit einer wasserlöslichen Umhüllung

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1903100A1 (de) * 2006-09-19 2008-03-26 Unilever N.V. Waschmitteltablette
CN101165151B (zh) * 2007-09-29 2010-05-19 上海特地旺农业科技有限公司 一种天然、温和的清洁剂
WO2010105816A1 (en) * 2009-03-17 2010-09-23 Bbt Bergedorfer Biotechnik Gmbh Cleaning agent containing carbamide and/or at least a derivative thereof
US8252122B2 (en) 2009-03-17 2012-08-28 Bbt Bergedorfer Biotechnik Gmbh Use of an agent that contains carbamide and/or at least a derivative thereof as a cleaning agent
WO2018141104A1 (en) * 2017-02-06 2018-08-09 The Procter & Gamble Company Laundry detergent sheet comprising lines of frangibility

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