WO2001038479A1 - Compositions de detergent - Google Patents

Compositions de detergent Download PDF

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Publication number
WO2001038479A1
WO2001038479A1 PCT/EP2000/011816 EP0011816W WO0138479A1 WO 2001038479 A1 WO2001038479 A1 WO 2001038479A1 EP 0011816 W EP0011816 W EP 0011816W WO 0138479 A1 WO0138479 A1 WO 0138479A1
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WO
WIPO (PCT)
Prior art keywords
weight
particles
sodium tripolyphosphate
detergent
tablet according
Prior art date
Application number
PCT/EP2000/011816
Other languages
English (en)
Inventor
Peter Willem Appel
Erik Christiaan Berden
Jelles Vincent Boskamp
Henning Wagner
Original Assignee
Unilever N.V.
Unilever Plc
Hindustan Lever Ltd
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 N.V., Unilever Plc, Hindustan Lever Ltd filed Critical Unilever N.V.
Priority to CA002389984A priority Critical patent/CA2389984A1/fr
Priority to EP00988761A priority patent/EP1232241B1/fr
Priority to AT00988761T priority patent/ATE264908T1/de
Priority to DE60010117T priority patent/DE60010117T2/de
Priority to AU25088/01A priority patent/AU2508801A/en
Priority to BR0015903-4A priority patent/BR0015903A/pt
Publication of WO2001038479A1 publication Critical patent/WO2001038479A1/fr

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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
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • 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
    • C11D17/0078—Multilayered 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates

Definitions

  • This invention relates to detergent compositions in the form of tablets for cleaning, and in particular tablets for fabric washing and tablets for machine dish washing. It is known to make such tablets by compressing or compacting a quantity of detergent composition in particulate form.
  • tablets should have adequate mechanical strength when dry, before use, yet disintegrate and disperse/dissolve quickly when added to wash water. It has not proved simple to achieve both properties simultaneously. As more pressure is used when a tablet is compacted, so the tablet density and strength rise, but the speed of disintegration/dissolution when the tablet comes into contact with wash water goes down.
  • these tablets will contain base powder particles which incorporate organic detergent-active surfactant together with some tripolyphosphate detergency builder, separate particles containing sodium tripolyphosphate which is rich in the Phase I form and also partially hydrated, and thirdly particles of other ingredients.
  • a substantial proportion of the other ingredients is constituted by peroxygen bleach which may be sodium perborate tetrahydrate .
  • Such tablets have been marketed commercially. For use one or two tablets are placed in a net bag, closed with a drawstring. The bag containing these tablets is placed in the washing machine, with fabrics to be washed.
  • the tablets exemplified in this co-pending application contain a considerable amount of sodium disilicate as a detergency builder, as well as a peroxygen bleach, sodium perborate, and sodium carbonate.
  • sodium disilicate as a detergency builder
  • peroxygen bleach sodium perborate
  • sodium carbonate sodium carbonate
  • This separation of ingredients can be accomplished by isolating most, if not all, of the fully hydrated salts, in a region of the tablet which may be a layer, core or insert, while the sodium tripolyphosphate which is rich in the Phase I form is in another region of the tablet.
  • a detergent tablet of compressed particulate composition comprising a detergent-active compound, a detergency builder, particles which contain sodium tripolyphosphate with a content of the Phase I form which is more than 40% by weight of the sodium tripolyphosphate in the said particles, at least one salt which is fully hydrated, and optionally other detergent ingredients, where the tablet comprises a plurality of discrete regions, characterised in that in one or more of the discrete regions containing said particles which contain sodium tripolyphosphate there is less than 10% by weight of that region of fully hydrated salts, and there is at least one discrete region containing at least 10% by weight of that region of fully hydrated salts.
  • all of the discrete regions containing said particles which contain sodium tripolyphosphate will contain less than 10% by weight of that region of fully hydrated salts. However, this may not be the case, particularly if there is a very small discrete region containing said particles which contain sodium tripolyphosphate, or the discrete regions contain a minor amount of sodium tripolyphosphate, for example less than 5% by weight.
  • the region containing at least 10% by weight of fully hydrated salts may also contain a disintegrant system which does not comprise said particles which contain said sodium tripolyphosphate .
  • the sodium tripolyphosphate in the said particles has a content of the Phase I form which is at least 50% by weight of the sodium tripolyphosphate in the said particles. It is also preferred that the amount of water of hydration in the sodium tripolyphosphate particles lies in a range from 0.5% to 5% by weight of the sodium tripolyphosphate in those particles.
  • Sodium Tripolyphosphate with High Phase I Content sodium tripolyphosphate can be converted to the phase I form by heating to above the transition temperature at which phase II anhydrous sodium polyphosphate is transformed into the phase I form.
  • a process for the manufacture of particles containing a high proportion of the phase I form of sodium tripolyphosphate by spray drying below 420°C is given in US-A-4536377.
  • the sodium tripolyphosphate is preferably partially hydrated, but the phase I anhydrous form should also be present.
  • the sodium tripolyphosphate in the particles may incorporate from 0.5% up to, at least, 5% (by weight of the sodium tripolyphosphate in these particles) of water of hydration.
  • the extent of hydration is desirably from 1% to 4%, 5% or 7% by weight.
  • the sodium tripolyphosphate in these particles is preferably hydrated by a process which leads to a homogeneous distribution of the water of hydration within the tripolyphosphate.
  • the particles preferably consist solely of sodium tripolyphosphate with a high content of the phase I form. However, it may be preferred that only at least 80% or 90% by weight of the particles is sodium tripolyphosphate. It is possible that only at least 50% by weight of the particles are sodium tripolyphosphate .
  • the particles preferably contain sodium tripolyphosphate in a porous form so as to have high surface area.
  • a blowing agent that is a compound such as ammonium carbonate which decomposes to yield a gas during the course of the spray drying. This gives the dried material a porous structure, with higher surface area than hollow beads of tripolyphosphate obtained without blowing agent.
  • the bulk density of the sodium tripolyphosphate particles is preferably 0.75 kg/m 3 or less, more preferably from 0.52 to 0.72 kg/m 3
  • the particles which contain or consist of sodium tripolyphosphate may have a small mean particle size, such as not over 300 ⁇ m, better not over 250 ⁇ m. Small particle size can if necessary be achieved by grinding.
  • Rhodiaphos HPA 3.5 is a grade of sodium tripolyphosphate from Rhone-Poulenc which has been found to be particularly suitable. It consists of porous particles of small particle size (mean size below 250 ⁇ m) with 70% phase I and prehydrated with 3.5% water of hydration.
  • the said particles containing sodium tripolyphosphate with more than 40% of phase I material provide sodium tripolyphosphate, including the phase I tripolyphosphate, in a quantity which is from 20% up to 45% or 50%, or even 60% by weight of the whole tablet.
  • a quantity of at least 30% has been found useful in some tablets. The amount of these particles in any one region of the tablet may be higher then these limits, in order to provide a suitable level of particles in the whole tablet.
  • the remainder of the tablet composition may include additional sodium tripolyphosphate not in the form discussed above, such as anhydrous sodium tripolyphosphate with a high content of the phase II form, hydrated sodium tripolyphosphate or some combination of the two.
  • the total quantity of sodium tripolyphosphate, in all forms, present in the tablet composition of a laundry tablet will generally lie in a range up to 70% by weight of the tablet. This may also be the case for a machine dish wash tablet, although a range of up to 60% by weight of the tablet is preferred for this type of tablet. Therefore it will be appreciated that the overall quantity of sodium tripolyphosphate may be provided at least partially by other material in addition to the said particles.
  • These salts are those which are in their maximum thermodynamically stable hydration state at ambient temperature. This maximum hydration state may be the highest possible for the salt, or may be lower than the highest possible for the salt, but where the higher hydration states are thermodynamically unstable at ambient temperature.
  • These fully hydrated salts include perborates, citrates, acetates, sulphates, carbonates and thiosulphates .
  • Perborates may exist in a range of hydration states, and have at least one hydrogen peroxide present instead of, or in addition to, water of hydration.
  • sodium perborate exists in a monohydrated or tetrahydrated form both of which are suitable for use in detergent formulations. Therefore it can be seen that sodium perborate tetrahydrate is a fully hydrated salt.
  • Perborates are used as bleaches in detergent tablets (see below) .
  • Carbonates naturally display a range of hydration states.
  • sodium carbonate may be anhydrous, or may have one, seven or ten water molecules present as water of hydration.
  • Both potassium and magnesium carbonates also have a variety of hydration states. Thus, as long as some of the carbonate present is in its maximum thermodynamically stable hydration state, the salt will be fully hydrated.
  • Carbonates in particular sodium and potassium carbonates
  • Sulphates can have different hydration states.
  • Sodium sulphate may be anhydrous, heptahydrated or decahydrated, whilst magnesium sulphate may be anhydrous or heptahydrated. Sulphates may be included in detergent tablets as fillers. Sodium thiosulphate may be anhydrous or pentahydrated.
  • Sodium acetate may exist in a range of hydration states from 0 (anhydrous) to 3 (trihydrate) .
  • Sodium acetate trihydrate may be present as a disintegration aid (see below) .
  • Sodium citrate has two hydration states, 2 (dihydrate) and 5 (pentahydrate) .
  • the pentahydrate state is not thermodynamically stable at temperatures between 20°C and 60°C, and therefore sodium citrate dihydrate is a fully hydrated salt.
  • Sodium citrate also functions as a disintegration aid (see below) .
  • the fully hydrated salts have a solubility at 20°C of at least 50 gms per 100 gms of water.
  • the discrete regions may be in the form of layers, and a tablet with two layers is one preferred embodiment of the present invention.
  • One layer of this two-layer tablet contains granules of sodium tripolyphosphate rich in Phase I form and also partially hydrated, whilst the other layer contains fully hydrated salts and/or persalts and optionally another disintegrant.
  • Each layer of such a tablet is preferably substantially homogeneous, that is to say, is the compaction product of a single particulate composition, although that particulate composition may have been prepared by mixing a number of components and all its particles will not necessarily be identical.
  • such a two-layer tablet is made on a tableting press by part filling the die with the composition of the first layer, pressing this layer, and then adding the composition of the second layer before pressing the tablet for a second time. It is preferred that the two layers of this tablet are not equal in size - a weight ratio range of 10:90 to 40:60 is preferable, and a ratio range of 20:80 to 30:70 is more preferred, with a ratio of 25:75 being most preferred.
  • a discrete region typically has a minimum weight of 5g.
  • the layer or layers containing the particles of sodium tripolyphosphate make up at least 50 wt% of the tablet, and that the layer (or layers) which contain the fully hydrated salts and/or persalts make up at least 15% by weight of the whole tablet.
  • An alternative preferred embodiment of the invention is a tablet which has a pair of opposite faces spaced apart from each other and joined by a peripheral surface of the tablet, wherein the tablet is subdivided into at least two regions which are each visible at a said face.
  • One such tablet is one having a central core passing through the whole tablet.
  • One particular method of manufacturing such tablets is described in our co pending application, GB 9901688.3.
  • Other forms of discrete regions are known for detergent tablets and are included in the present invention, and include cores which do not pass all the way through the tablet and a central region completely enclosed by an outer region.
  • detergent-active compounds are suitably present in an amount of from 2% or 5% up to 50 wt%, more preferably from 5% or 8% up to 40 wt% of the whole tablet. These will most usually be anionic and nonionic surfactants and mixtures of the two. Amphoteric (including zwitterionic) and less commonly cationic detergents can also be used.
  • anionic surfactants are well known to those skilled in the art.
  • the anionic surfactant may comprise, wholly or predominantly, linear alkyl benzene sulphonate of the formula
  • R is linear alkyl of 8 to 15 carbon atoms and M + is a solubilising cation, especially sodium.
  • ROS0 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 also commercially significant as an anionic surfactant and may be used in this invention.
  • such linear alkyl benzene sulphonate or primary alkyl sulphate of the formula above, or a mixture thereof will be the desired non-soap anionic surfactant and may provide 75 to 100 wt% of any anionic non-soap surfactant in the composition.
  • non-soap anionic surfactants examples include olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
  • One or more soaps of fatty acids may also be included in addition to non-soap anionic surfactant.
  • Examples are sodium soaps derived from the fatty acids from coconut oil, beef tallow, sunflower or hardened rapeseed oil.
  • Nonionic surfactant compounds 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 a - 22 ) phenol-ethylene oxide condensates, the condensation products of linear or branched aliphatic C 8 - 2 o 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 Cg-n and C i2 -i 5 primary and secondary alcohols ethoxylated with an average of from 3 to 20 moles of ethylene oxide per mole of alcohol.
  • Amphoteric surfactants which may be used jointly with anionic or nonionic surfactants or both include amphopropionates of the formula:
  • RCO is a acyl group of 8 to 18 carbon atoms, especially coconut acyl.
  • amphoteric surfactants also includes amine oxides and also zwitterionic surfactants, notably betaines of the general formula
  • R 4 is an aliphatic hydrocarbon chain which contains 7 to 17 carbon atoms
  • R 2 and R 3 are independently hydrogen, alkyl of 1 to 4 carbon atoms or hydroxyalkyl of 1 to 4 carbon atoms such as CH 2 OH
  • Y is CH 2 or of the form CONHCH 2 CH 2 CH 2 (amidopropyl betaine);
  • Z is either a COO " (carboxybetaine) , or of the form CHOHCH 2 S0 3 - (sulfobetaine or hydroxy sultaine) .
  • amphoteric surfactant is amine oxide of the formula
  • Ri is Cio to C 20 alkyl or alkenyl
  • R 2 , R 3 and R 4 are each hydrogen or Ci to C 4 alkyl while n is from 1 to 5.
  • detergent-active compounds are preferably present in an amount of 5 wt% of the total composition or less.
  • the detergent-active compound is a low to non foaming nonionic surfactant, which may be an alkoxylated nonionic surface-active agent wherein the alkoxy moieties are selected from the group consisting of ethylene oxide, propylene oxide and mixtures thereof.
  • This nonionic surfactant is used to improve the detergency without excessive foaming, however, an excessive proportion of nonionic surfactant should be avoided.
  • the level of nonionic surfactant is at least 0.1% by weight, more preferably at least 0.5% by weight.
  • suitable nonionic surfactants for use in machine dish washing tablets of the invention are the low- to non-foaming ethoxylated straight-chain alcohols.
  • Preferred nonionic surfactants are Plurafac LF series ex BASF, the Synperonic series ex Id; Lutensol® LF series, ex BASF Company and the Triton ® DF series, ex Rohm & Haas Company.
  • anionic surfactant may be used but may require the additional presence of an antifoam to suppress foaming. If an anionic surfactant is used it is advantageously present at levels of 2 wt% or below.
  • the detergent tablets of the invention contain one or more detergency builders, in addition to the sodium tripolyphosphate builder of the invention. These builders may be either water-soluble or water-insoluble, and a mixture of the two is also included within the scope of the present invention.
  • Alkali metal aluminosilicates are strongly favoured as environmentally acceptable water-insoluble builders for fabric washing.
  • Alkali metal (preferably sodium) aluminosilicates may be either crystalline or amorphous or mixtures thereof, having the general formula:
  • Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1429143 (Procter & Gamble) .
  • the preferred sodium aluminosilicates of this type are the well known commercially available zeolites A and X, the zeolite P described and claimed in EP 384070 (Unilever) which is also referred to as zeolite MAP and mixtures thereof.
  • Zeolite MAP is available from Crosfields under their designation Zeolite A24.
  • water-insoluble detergency builder could be a crystalline layered sodium silicate as described in US 4664839.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated as "SKS-6").
  • NaSKS-6 has the delta-Na 2 Si0 5 morphology form of layered silicate. It can be prepared by methods such as described in DE-A-3,417,649 and DE-A-3, 742, 043.
  • Other such layered silicates, which can be used have the general formula NaMSi x 0 2x+ ⁇ . yH 2 0 wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0.
  • Crystalline layered silicate may be used in the form of granules which also contain citric acid.
  • Water-soluble builders may be used in the form of granules which also contain citric acid.
  • Suitable organic builders include the carboxylate or polycarboxylate builders containing from one to four carboxy groups, particularly selected from monomeric polycarboxylates or their acid forms, homo or copolymeric polycarboxylic acids or there salts in which the polycarboxylate comprises at least two carboxylic radicals selected from each other by not more than two carbon atoms.
  • Preferred carboxylates include the polycarboxylate materials described in US-A-2, 264, 103, including the water- soluble alkali metal salts of mellitic acid and citric acid (citrate) , gluconic acid, dipicolinic acid, oxydisuccinic acid and alkenyl succinates, glycerol mono- di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates and hydroxyethyliminodiacetates .
  • polycarboxylate polymers and copolymers such as are described in US-A-3, 308, 067 are also be suitable for use with the invention.
  • the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, especially citric acid or its salt, particularly sodium citrate.
  • Further soluble detergency builder salts which can be used with the present invention are poly-valent inorganic and poly-valent organic builders, or mixtures thereof.
  • suitable water-soluble, inorganic alkaline detergency builder salts include the alkali metal (generally sodium) carbonates (see above) , bicarbonates, borates, phosphates, and polyphosphates, phosphono carboxylates.
  • Specific examples of such salts include the sodium and potassium tetraborates, carbonates, bicarbonates, orthophosphates and hexametaphosphates .
  • detergency builders include organic alkaline compounds such as water-soluble amino polyacetates, e.g. nitrilotriacetates and N- (2-hydroxyethyl) nitrilodiacetates; and water-soluble salts of phytic acid, e.g. sodium and potassium phytates.
  • organic alkaline compounds such as water-soluble amino polyacetates, e.g. nitrilotriacetates and N- (2-hydroxyethyl) nitrilodiacetates
  • water-soluble salts of phytic acid e.g. sodium and potassium phytates.
  • the total amount of builders in the composition including the particles containing sodium tripolyphosphate (having a water of hydration in an amount from 1% to 5% by weight and wherein at least 50% by weight of the sodium tripolyphosphate within the particles is of a phase I form) for fabric laundry tablets is from 30 to 70% by weight, whereas for machine dish washing tablets is from 40 to about 80% by weight.
  • Bleach material may preferably be incorporated in composition for use in processes according to the present invention. These materials may be incorporated in solid form or in the form of encapsulates and less preferably in dissolved form.
  • the bleach material may be a chlorine- or bromine-releasing agent or a peroxygen compound.
  • Peroxygen based bleach materials are however preferred for use in detergent tablets of the invention.
  • Inorganic peroxygen bleaches are however preferred for use in detergent tablets of the invention.
  • Inorganic peroxygen-generating compounds are most preferably used as the bleaching material of the present invention, and salts (especially sodium salts) of perborate monohydrate and tetrahydrate and percarbonate have been mentioned above, and of these, sodium perborate tetrahydrate is a fully hydrated salt.
  • Organic peroxy acids can be used as the bleach material.
  • the peroxyacids suitable for use in the present invention are solid and, preferably, substantially water-insoluble compounds.
  • substantially water-insoluble is meant herein a water-solubility of less than about 1% by weight at ambient temperature.
  • peroxyacids containing at least about 7 carbon atoms are sufficiently insoluble in water for use herein.
  • Monoperoxy acids useful herein include alkyl peroxy acids and aryl peroxyacids such as peroxybenzoic acid and ring-substituted peroxybenzoic acids (e.g. peroxy-alpha- naphthoic acid) ; aliphatic and substituted aliphatic monoperoxy acids (e.g. peroxylauric acid and peroxystearic acid) ; and phthaloyl amido peroxy caproic acid (PAP) .
  • alkyl peroxy acids and aryl peroxyacids such as peroxybenzoic acid and ring-substituted peroxybenzoic acids (e.g. peroxy-alpha- naphthoic acid) ; aliphatic and substituted aliphatic monoperoxy acids (e.g. peroxylauric acid and peroxystearic acid) ; and phthaloyl amido peroxy caproic acid (PAP) .
  • PAP phthaloyl amido peroxy caproic
  • diperoxy acids useful herein include alkyl diperoxy acids and aryldiperoxy acids, such as 1, 12-di-peroxy- dodecanedioic acid (DPDA) ; 1, 9-diperoxyazelaic acid, diperoxybrassylic acid, diperoxysebacic acid and diperoxy- isophthalic acid; and 2-decyldiperoxybutane-l, 4-dioic acid.
  • DPDA 1, 12-di-peroxy- dodecanedioic acid
  • 1, 9-diperoxyazelaic acid diperoxybrassylic acid, diperoxysebacic acid and diperoxy- isophthalic acid
  • 2-decyldiperoxybutane-l, 4-dioic acid 2-decyldiperoxybutane-l, 4-dioic acid.
  • suitable reactive chlorine- or bromine-oxidizing materials are heterocyclic N-bromo and N-chloro imides such as trichloroisocyanuric, tribromoisocyanuric, dibromoisocyanuric and dichloroisocyanuric acids, and salts thereof with water-solubilising cations such as potassium and sodium.
  • Hydantoin compounds such as 1, 3-dichloro-5, 5- dimethyl-hydantion are also quite suitable.
  • Particulate, water-soluble anhydrous inorganic salts are likewise suitable for use herein such as lithium, sodium or calcium hypochlorite and hypobromite.
  • Chlorinated trisodium phosphate and chloroisocyanurates are also suitable bleaching materials.
  • Encapsulation techniques are known for both peroxygen and chlorine bleaches, e.g. as described in US-A-4, 126, 573, US- A-4,327,151, US-A-3, 983, 254, US-A-4, 279, 764, US-A-3, 036, 013 and EP-A-0,436,971 and EP-A-0, 510, 761.
  • encapsulation techniques are particularly useful when using halogen based bleaching systems.
  • compositions of the invention may comprise from about 0.5% to about 3% AvCl (available Chlorine) .
  • AvCl available Chlorine
  • peroxygen bleaching agents a suitable range are also from 0.5% to 3% AvOx (available Oxygen).
  • the amount of bleach material in the wash liquor is at least 12.5 x 10 _4 % and at most 0.03% AvOx by weight of the liquor.
  • Detergent tablets of the present invention which contain an inorganic peroxygen bleaching material such as sodium percarbonate or sodium perborate preferably also contain a bleach activator.
  • Bleach activators have been widely disclosed in the art. Preferred examples include peracetic acid precursors, for example tetraacetylethylene diamine (TAED) , and perbenzoic acid precursors.
  • TAED tetraacetylethylene diamine
  • the quaternary ammonium and phosphonium bleach activators disclosed in US 4751015 and US 4818426 (Lever Brothers Company) are also of interest.
  • Another type of bleach activator which may be used, but which is not a bleach precursor is a transition metal catalyst as disclosed in EP-A-458397, EP-A-458398 and EP-A-549272.
  • the bleach activator is present in a different region of the tablet to the bleach, and in particular alkali metal percarbonate/perborate monohydrate (if present) .
  • the bleach activator may be present in the region containing the particles of sodium tripolyphosphate which is rich in Phase I form, especially if the tablet has only two discrete regions, e.g. layers.
  • bleach activator is usually present in an amount from 1 to 10% by weight of the tablet, possibly less in the case of a transition metal catalyst which may be used as 0.1% or more by weight of the tablet.
  • a detergent tablet of the invention may also include a heavy metal chelating agent, which may also act as a bleach stabiliser. Such components will also chelate non-heavy metals to a limited extent, and similarly builders such as tripolyphosphate will chelate heavy metals to a limited extent.
  • Preferred chelating agents include organic phosphonates, amino carboxylates, polyfunctionally-substituted compounds, and mixtures thereof.
  • Particularly preferred chelating agents are organic phosphonates such as ethylenediamine tetramethylene phosphonate; _-hydroxy-2 phenyl ethyl diphosphonate; methylene diphosphonate; ethylene diphosphonate; hydroxy 1, 1-hexylidene; vinylidene 1,1 diphosphonate; 1,2 dihydroxyethane 1,1 diphosphonate; and hydroxy-ethylene 1,1 diphosphonate.
  • Most preferred is hydroxy-ethylene 1,1 diphosphonate; 2 phosphono-1, 2, 4 butanetricarboxylic acid or salts there of.
  • EDDS ethylenediamine disuccinate
  • the level of chelating agent is from 0.5 to 3 wt% of the total composition.
  • the region of the tablet which does not include the sodium tripolyphosphate rich in Phase I form may contain a further disintegrant system. This is particularly preferred in discrete regions which contain more than 5% detergent active compounds, which is generally the case for laundry detergent tablets.
  • the further disintegrant system helps such regions to disperse quickly, which counters the binding effect of the detergent active compound.
  • the fully hydrated salt may in fact be a disintegrant itself, or be part of a disintegrant system.
  • Suitable disintegrants may preferably be present in the region as at least 15 or 20% by weight of the region, possibly at least 25% up to 50 or 60%.
  • Suitable disintegrants may be grouped into the following classes: swelling (physical) disintegrants; effervescent disintegrants; and materials of high solubility.
  • Swelling disintegrants include organic materials such as starches, for example, corn/ maize, rice and potato starches and starch derivatives, such as Pri ojelTM, carboxymethyl starch and ExplotabTM, sodium starch glycolate; celluloses, for example, Arbocel®-B and Arbocel®-BC (beech cellulose) , Arbocel®-BE (beech-sulphite cellulose), Arbocel ® -B-SCH (cotton cellulose), Arbocel®-FIC (pine cellulose) as well as further Arbocel® types
  • organic materials such as starches, for example, corn/ maize, rice and potato starches and starch derivatives, such as Pri ojelTM, carboxymethyl starch and ExplotabTM, sodium starch glycolate
  • celluloses for example, Arbocel®-B and Arbocel®-BC (beech cellulose) , Arbocel®-BE (beech-sulphite cellulose), Arbocel
  • Inorganic swelling disintegrants include bentonite clay. Effervescent disintegrants
  • Effervescent disintegrants include weak acids or acid salts, for example, citric acid (preferred) , malic acid or tartaric acid, in combination with alkali metal carbonate 5 or bicarbonate; these may suitably be used in an amount of from 1 to 25 wt%, preferably from 5 to 15 wt%. Further examples of acid and carbonate sources and other effervescent systems may be found in Pharmaceutical Dosage Forms: Tablets, Volume 1, 1989, pages 287-291 (Marcel 10 Dekker Inc, ISBN 0-8247-8044-2).
  • Highly water soluble materials which are one of the two possibilities are compounds, especially salts, with a 15 solubility at 20°C of at least 50 gms per 100 gms of water.
  • a solubility of at least 50 grams per 100 grams of water at 20°C is an exceptionally high solubility: many materials which are classified as water soluble are less soluble than 20 this.
  • Potassium acetate >200 Particularly preferred materials are sodium acetate trihydrate and sodium citrate dihydrate.
  • the tablets may provide for the sequential release of components of the tablet into the wash liquor.
  • a tablet may be able to deliver detergent actives first, and fabric softeners later.
  • disintegrants falling into the above categories particularly swelling disintegrants, are known for use in pharmaceutical tablets.
  • Silica material for Machine Dish Washing Tablet Dish washing tablets may preferably contain silica material.
  • Suitable forms of silica include amorphous silica, such as precipitated silica, pyrogenic silica and silica gels, such as hydrogels, xerogels and aerogels, or the pure crystal forms quartz, tridymite or crystobalite, but the amorphous forms of silica are preferred.
  • Suitable silicas may readily be obtained commercially. They are sold, for example under the Registered Trade Name Gasil 200 (ex Crosfield, UK) .
  • the silica is in the product in such a form that it can dissolve when added to the wash liquor. Therefore, addition of silica by way of the addition of anti-foam particles of silica and silicone oil is not preferred.
  • the particle size of the silica material of the present invention may be of importance, especially as it is believed that any silica material that remains undissolved during the washing process, may deposit on the glass at a later stage. Therefore, it is preferred that silica material are used that have a particle size (as determined with a Malvern Laser, i.e. "aggregated" particles size) of 5 at most 40 ⁇ m, more preferably at most 30 ⁇ m, most preferably at most 20 ⁇ m provides better results in the wash.
  • the particle size of the silica material is at least l ⁇ m, more preferably at least 2 ⁇ m, 10 most preferably at least 5 ⁇ m.
  • the primary particle size of the silica is in general less than about 30nm, in particular less than about 25nm.
  • elementary particles size are less than
  • the silica material is present in the wash liquor at a level of at least 2.5xl0 ⁇ 4 %, more preferably at least 12.5xl0 "4 %, most preferably at least 2.5xl0 "3 % by weight of the wash liquor and preferably at most lxl0 _1 %,
  • the level of dissolved silica material in the wash liquor is at least 80 ppm, more preferably at least 30 100 ppm, most preferably at least 120 ppm and preferably at most 1,000 ppm.
  • the lower level of dissolved silica material depends on the pH value, i.e. thus at pH 6.5, the level is preferably at least 100 ppm; at pH 7.0 preferably at least 110 ppm; at pH 7.5 preferably at least 120 ppm; at pH 9.5 preferably at least 200 ppm; at pH 10 preferably at least 300 ppm; at pH 10.5 preferably at least 400ppm.
  • the silica material is present in the cleaning composition at a level of at least 0.1%, more preferably at least 0.5%, most preferably at least 1% by weight of the cleaning composition and preferably at most 10%, more preferably at most 8%, most preferably at most 5% by weight of the cleaning composition.
  • the composition of the invention optionally comprises alkali metal silicates.
  • the alkali metal silicate has some detergency builder properties, and particularly for machine dish washing may provide pH adjusting capability and protection against corrosion of metals and against attack on dishware, including fine china and glassware benefits.
  • the presence of such alkali metal silicates in detergent tablets may be advantageous in providing protection against the corrosion of metal parts in washing machines, and also in aiding the detergency builder and in adjusting the alkalinity of the wash liquor.
  • silicates are present in machine dish washing tablets, they are preferably included at a level of from 1% to 30%, preferably from 2% to 20%, more preferably from 3% to 10%, based on the weight of the composition.
  • preferred amounts of silicate are between 1 and 6 % by weight, which may be achieved through the base powder or by post dosing.
  • M alkali metal
  • alkali metal silicate is typically from 1 to 3.5, preferably from 1.6 to 3, more preferably from 2 to 2.8.
  • the alkali metal silicate is hydrous, having from 15% to 25% water, more preferably, from 17% to 20%.
  • the highly alkali metasilicates can in general be employed, although the less alkaline hydrous alkali metal silicates having a Si0 2 :M 2 0 ratio of from 2.0 to 2.4 are, as noted, greatly preferred.
  • Anhydrous forms of the alkali metal silicates with a Si0 2 :M 2 0 ratio of 2.0 or more are also less preferred because they tend to be significantly less soluble than the hydrous alkali metal silicates having the same ratio.
  • a particularly preferred alkali metal silicate is a granular hydrous sodium silicate having a Si0 2 :Na 2 0 ratio of from 2.0 to 2.4 available from Ak30 PQ Corporation, especially preferred is Britesil H20 and Britesil H24. Most preferred is a granular hydrous sodium silicate having a Si0 2 :Na 2 0 ratio of 2.0. While typical forms, i.e. powder and granular, of hydrous silicate particles are suitable, preferred silicate particles having a mean particle size between 300 and 900 microns and less than 40% smaller than 150 microns and less than 5% larger than 1700 microns.
  • compositions of the present invention having a pH of 9 or less preferably will be substantially free of alkali metal silicate. 5
  • a water soluble polymeric polycarboxylic compound may be present in the composition, and is advantageously present in a dish wash composition. They inhibit unwanted 10 deposition from the wash liquor onto the material being washed, either laundry or dish ware, and also onto machine parts .
  • these compounds are homo- or co-polymers of 15 polycarboxylic compounds, especially co-polymeric compounds in which the acid monomer comprises two or more carboxyl groups separated by not more than two carbon atoms. Salts of these materials can also be used.
  • Particularly preferred polymeric polycarboxylates are copolymers derived from monomers of acrylic acid and maleic acid.
  • the average molecular weight of these polymers in the acid form preferably ranges from 4,000 to 70,000.
  • polymeric polycarboxylic compounds suitable for use in the composition of the invention are homo- polymeric polycarboxylic acid compounds with acrylic acid as the monomeric unit.
  • the average weight of such homopolymers in the acid form preferably ranges from 1,000 to
  • this polymeric material is present at a level of at least 0.1%, more preferably at levels from 1 wt% to 7 wt% of the total composition.
  • Tablets of this invention may include an organic water-soluble polymer, serving as a binder when the particles are compacted into tablets.
  • This polymer may be a polycarboxylate included as a supplementary builder, as mentioned earlier. It may be applied as a coating to some or all of the constituent particles prior to compaction.
  • such polymers can function to enhance tablet disintegration at the time of use, as well as acting as a binder to enhance tablet strength prior to use.
  • such a binder material should melt at a temperature of at least 35°C, better at 40°C or above, which is above ambient temperatures in many temperate countries.
  • the melting temperature is somewhat above 40°C, so as to be above the ambient temperature.
  • the melting temperature of the binder material should be below 80°C.
  • Preferred binder materials are synthetic organic polymers of appropriate melting temperature, especially polyethylene glycol.
  • Polyethylene glycol of average molecular weight 1500 (PEG 1500) melts at 45°C and has proved suitable.
  • the binder may suitably be applied to the particles by spraying, e.g. so as a solution or dispersion. It may be applied to particles which contain organic surfactant.
  • the binder may be provided in a powder form, and be dispersed into the composition to be tableted. If used, the binder is preferably used in an amount within the range from 0.1 to 10% by weight of the tablet composition, more preferably the amount is at least 1% or even at least 3% by weight of the tablets. Preferably the amount is not over 8% or even 6% by weight unless the binder serves some other additional function.
  • the detergent tablets of the invention may also contain one of the detergency enzymes well known in the art for their ability to degrade and aid in the removal of various soils and stains.
  • Suitable enzymes include the various proteases, cellulases, lipases, amylases, and mixtures thereof, which are designed to remove a variety of soils and stains from fabrics and dishes.
  • suitable proteases are Maxatase (Trade Mark), as supplied by Gist-Brocades N.V., Delft, Holland, and Alcalase (Trade Mark) , and Savinase (Trade Mark) , as supplied by Novo Industri A/S, Copenhagen, Denmark.
  • Detergency enzymes are commonly employed in the form of granules or marumes, optionally with a protective coating, in amount of from about 0.1% to about 3.0% by weight of the composition; and these granules or marumes present no problems with respect to compaction to form a tablet.
  • the laundry detergent tablets of the invention may also contain a fluorescer (optical brightener) , for example, Tinopal (Trade Mark) DMS or Tinopal CBS available from Ciba-Geigy AG, Basel, Switzerland.
  • Tinopal DMS is disodium , 4 'bis- (2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene disulphonate
  • Tinopal CBS is disodium 2,2'- bis- (phenyl-styryl) disulphonate.
  • An antifoam material is advantageously included, especially if the detergent tablet is primarily intended for use in front-loading drum-type automatic washing machines.
  • Suitable antifoam materials are usually in granular form, such as those described in EP 266863A (Unilever) .
  • Such antifoam granules typically comprise a mixture of silicone oil, petroleum jelly, hydrophobic silica and alkyl phosphate as antifoam active material, sorbed onto a porous absorbed water-soluble carbonate-based inorganic carrier material.
  • Antifoam granules may be present in an amount up to 5% by weight of the composition.
  • ingredients which can optionally be employed in the laundry detergent tablet of the invention include anti- redeposition agents such as sodium carboxymethylcellulose, straight-chain polyvinyl pyrrolidone and the cellulose ethers such as methyl cellulose and ethyl hydroxyethyl cellulose, fabric-softening agents; heavy metal sequestrants such as EDTA; perfumes; and colorants or coloured speckles.
  • anti- redeposition agents such as sodium carboxymethylcellulose, straight-chain polyvinyl pyrrolidone and the cellulose ethers such as methyl cellulose and ethyl hydroxyethyl cellulose, fabric-softening agents
  • heavy metal sequestrants such as EDTA
  • perfumes and colorants or coloured speckles.
  • Anti-tarnishing agents such as benzotriazole and those described in EP 723 577 (Unilever) may be included in dish washing detergent tablets of the present invention.
  • Optional ingredients in dish washing detergents tablets are, for example, buffering agents, reducing agents, e.g., borates, alkali metal hydroxide and the well-known enzyme stabilisers such as the polyalcohols, e.g. glycerol and borax; anti-scaling agents; crystal-growth inhibitors, threshold agents; thickening agents; perfumes and dyestuffs and the like.
  • Reducing agents may e.g. be used to prevent the appearance of an enzyme-deactivating concentration of oxidant bleach compound.
  • Suitable agents include reducing sulphur-oxy acids and salts thereof.
  • Most preferred for reasons of availability, low cost, and high performance are the alkali metal and ammonium salts of sulphuroxy acids including ammonium sulphite ((NH 4 ) 2 S0 3 ), sodium sulphite (Na 2 S0 3 ) , sodium bisulphite (NaHS0 3 ) , sodium metabisulphite (Na 2 S 2 0 3 ) , potassium metabisulphite (K 2 S 2 U5) , lithium hydrosulphite (Li 2 S 2 0 4 ) , etc., sodium sulphite being particularly preferred.
  • Another useful reducing agent is ascorbic acid.
  • the amount of reducing agents to be used may vary from case to case depending on the type of bleach and the form it is in, but normally a range of about 0.01% to about 1.0% by weight, preferably from about 0.02% to about 0.5% by weight, will be sufficient.
  • the discrete regions of a detergent tablet of this invention are each a matrix of compacted particles.
  • the particulate composition has an average particle size in the range from 200 ⁇ m to 2000 ⁇ m, more preferably from 250 ⁇ m to 1400 ⁇ m. Fine particles, smaller than 180 ⁇ m or 200 ⁇ m may be eliminated by sieving before tableting, if desired, although we have observed that this is not always essential.
  • the starting particulate composition may in principle have any bulk density
  • the present invention is especially relevant to tablets made by compacting powders of relatively high bulk density, because of their greater tendency to exhibit disintegration and dispersion problems.
  • Such tablets have the advantage that, as compared with a tablet derived from a low bulk density powder, a given dose of composition can be presented as a smaller tablet.
  • the starting particulate composition may suitably have a bulk density of at least 400g/litre, preferably at least 500g/litre, and advantageously at least 700g/litre.
  • Granular detergent compositions of high bulk density prepared by granulation and densification in a high-speed mixer/granulator, as described and claimed in EP 340013A (Unilever), EP 352135A (Unilever), and EP 425277A (Unilever) , or by the continuous granulation/densification processes described and claimed in EP 367339A (Unilever) and EP 390251A (Unilever) , are inherently suitable for use in the present invention.
  • a spray-dried base powder may also be used, and this can results in a powder to be tableted having a bulk density of 600 to 700 g/litre.
  • Porosity The step of compacting the particles reduces the porosity of the composition. Porosity is conveniently expressed as the percentage of volume which is air.
  • the air content of a tablet or region of a tablet can be calculated from the volume and weight of the tablet or region, provided the air-free density of the solid content is known.
  • the latter can be measured by compressing a sample of the material under vacuum with a very high applied force, then measuring the weight and volume of the resulting solid.
  • the percentage air content of a tablet or region of a tablet varies inversely with the pressure applied to compact the composition while the strength of the tablet or region varies with the pressure applied to bring about compaction.
  • the greater the compaction pressure the stronger the tablet or region becomes but the smaller the air volume within.
  • the invention may be applied when compacting particulate detergent composition to give tablets with a wide range of porosities. Specifically included among possible porosities is a porosity of up to 38% air volume, e.g. from 10 or 15 better 25% up to 35% air by volume in the tablet.
  • Tablet Size and Density 5 The size of a tablet will suitably range from 10 to 160 grams, preferably from 15 to 60 g, depending on the conditions of intended use, and whether it represents a dose for an average load in a fabric washing or dishwashing machine or a fractional part of such a dose.
  • 10 to 160 grams preferably from 15 to 60 g, depending on the conditions of intended use, and whether it represents a dose for an average load in a fabric washing or dishwashing machine or a fractional part of such a dose.
  • a machine dish wash tablet is preferably from 15 to 30 g.
  • the tablets may be of any shape. However for ease of packaging they are preferably blocks of substantially uniform cross-section, such as cylinders or cuboids.
  • the overall density of a tablet preferably lies in a range from
  • the tablet density may well lie in a range up to 1350 to 1400gm/litre for a laundry tablet and in a range from 1300 to 1600gm/litre for a machine dish wash tablet.
  • 25 42g cylindrical detergent tablets having the following formulations were prepared on a rotating table tableting machine from Fette .
  • Two tablets of the invention were made with two layers, the thicker of which contained the Rhodiaphos HPA 3.5, the other sodium percarbonate and a
  • the strength of the tablets, in their dry state, as made on the press, was determined as the force, expressed in Newtons, needed to break the tablet, as measured using an Instron type universal testing instrument to apply compressive force on a diameter (i.e. perpendicular to the axis of a cylindrical tablet) .
  • the rate of disintegration of the detergent tablet was assessed by means of the "still water grid test": the tablet is placed on a 10 x 9 cm metal grid with a mesh size of 1.2 x 1.2 cm and placed into a beaker containing 1 litre of still water at 20°C.
  • the disintegration time was the time taken for 10% residue to be left on the grid. The test was repeated 3 times. The results are shown in the tablet below:
  • 25g cuboid machine dish wash detergent tablets having the following formulations were prepared on a rotating table tableting machine from Fette.
  • Two tablets of the invention were made with two layers, the thicker of which contained the Rhodiaphos HPA 3.5 and optionally a minor proportion of sodium perborate tetrahydrate, the other the major proportion (or all) of this salt.
  • the thicker layer was 75% of the tablet, the thinner layer 25%.
  • a comparative tablet was made having a single layer, but having the same composition as the respective two-layer tablets .
  • the tablets had the formulations below:

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  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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Abstract

On décrit une pastille de détergent à régions multiples formée d'une composition particulaire comprimée comprenant un composé actif de détergent, un adjuvant de détergence, des particules contenant du tripolyphosphate de sodium avec une teneur en forme de Phase I qui représente plus de 40 % en poids du tripolyphosphate de sodium desdites particules, au moins un sel qui est entièrement hydraté et facultativement d'autres ingrédients de détergent. Dans cette pastille, au moins une des régions contenant les particules qui renferment du tripolyphosphate de sodium représente moins de 10 % en poids de ladite région formée de sels entièrement hydratés et au moins une région contient au moins 10 % en poids de ladite région contenant des sels entièrement hydratés.
PCT/EP2000/011816 1999-11-26 2000-11-24 Compositions de detergent WO2001038479A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CA002389984A CA2389984A1 (fr) 1999-11-26 2000-11-24 Compositions de detergent
EP00988761A EP1232241B1 (fr) 1999-11-26 2000-11-24 Compositions detergentes
AT00988761T ATE264908T1 (de) 1999-11-26 2000-11-24 Waschmittelzusammensetzungen
DE60010117T DE60010117T2 (de) 1999-11-26 2000-11-24 Waschmittelzusammensetzungen
AU25088/01A AU2508801A (en) 1999-11-26 2000-11-24 Detergent compositions
BR0015903-4A BR0015903A (pt) 1999-11-26 2000-11-24 Tablete detergente de composição particulada comprimida

Applications Claiming Priority (2)

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GB9928078.6 1999-11-26
GBGB9928078.6A GB9928078D0 (en) 1999-11-26 1999-11-26 Detergent compositions

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Cited By (5)

* Cited by examiner, † Cited by third party
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EP3181672A1 (fr) * 2015-12-17 2017-06-21 The Procter and Gamble Company Composition de detergent de lave-vaisselle automatique
EP3181671A1 (fr) * 2015-12-17 2017-06-21 The Procter and Gamble Company Composition de detergent de lave-vaisselle automatique
EP3181679A1 (fr) * 2015-12-17 2017-06-21 The Procter and Gamble Company Procédé de fabrication d'un produit pour laver la vaisselle automatiquement
US10421927B2 (en) 2015-12-17 2019-09-24 The Procter & Gamble Company Automatic dishwashing detergent composition comprising benzotriazole and nonionic surfactant mixture
US10683471B2 (en) 2015-12-17 2020-06-16 The Procter & Gamble Company Automatic dishwashing detergent composition

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AU2002227936A1 (en) * 2000-11-21 2002-06-03 Unilever Plc Detergent compositions
EP1335968B1 (fr) * 2000-11-24 2009-08-05 Unilever N.V. Compositions de nettoyage
FR2842426B1 (fr) * 2002-07-19 2005-03-18 Philippe Guichard Composition nettoyante, detergente, desinfectante et decontaminante, a large spectre d'utilisation
AU2005280915B2 (en) * 2004-09-06 2010-10-07 Furukawa Techno Material Co., Ltd. Surfactant-Based Composition
CN107177429A (zh) * 2016-03-11 2017-09-19 华北制药秦皇岛有限公司 一种便于携带、使用方便的洗衣片及其制备工艺
EP3931293A1 (fr) 2019-02-28 2022-01-05 Ecolab USA Inc. Additifs de dureté et détergents en bloc contenant des additifs de dureté pour améliorer le durcissement des bords
WO2021161059A1 (fr) * 2020-02-14 2021-08-19 Wash To Go, Unipessoal, Lda Composition détergente sous forme de pastille effervescente
BR112023026713A2 (pt) 2021-06-24 2024-03-12 Unilever Ip Holdings B V Composição de limpeza em dose unitária

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WO1998055590A1 (fr) * 1997-06-06 1998-12-10 Unilever Plc Compositions detergentes
EP0922756A1 (fr) * 1997-12-02 1999-06-16 The Procter & Gamble Company Composition détergente
EP0957159A1 (fr) * 1998-05-14 1999-11-17 Chimiotechnic Tablette détergente et procédé de fabrication

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GB2324495A (en) * 1997-04-22 1998-10-28 Procter & Gamble Multi-layer detergent tablet

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WO1998055590A1 (fr) * 1997-06-06 1998-12-10 Unilever Plc Compositions detergentes
EP0922756A1 (fr) * 1997-12-02 1999-06-16 The Procter & Gamble Company Composition détergente
EP0957159A1 (fr) * 1998-05-14 1999-11-17 Chimiotechnic Tablette détergente et procédé de fabrication

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3181672A1 (fr) * 2015-12-17 2017-06-21 The Procter and Gamble Company Composition de detergent de lave-vaisselle automatique
EP3181671A1 (fr) * 2015-12-17 2017-06-21 The Procter and Gamble Company Composition de detergent de lave-vaisselle automatique
EP3181679A1 (fr) * 2015-12-17 2017-06-21 The Procter and Gamble Company Procédé de fabrication d'un produit pour laver la vaisselle automatiquement
WO2017105827A1 (fr) * 2015-12-17 2017-06-22 The Procter & Gamble Company Composition de détergent pour lave-vaisselle automatique
WO2017105856A1 (fr) * 2015-12-17 2017-06-22 The Procter & Gamble Company Procédé de fabrication d'un produit pour lave-vaisselle
WO2017105857A1 (fr) * 2015-12-17 2017-06-22 The Procter & Gamble Company Composition de détergent pour lave-vaisselle
US10421927B2 (en) 2015-12-17 2019-09-24 The Procter & Gamble Company Automatic dishwashing detergent composition comprising benzotriazole and nonionic surfactant mixture
US10683471B2 (en) 2015-12-17 2020-06-16 The Procter & Gamble Company Automatic dishwashing detergent composition
US10808207B2 (en) 2015-12-17 2020-10-20 The Procter & Gamble Company Automatic dishwashing detergent composition

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DE60010117T2 (de) 2004-08-26
DE60013889T2 (de) 2005-01-27
DE60010117D1 (de) 2004-05-27
WO2001038478A1 (fr) 2001-05-31
CA2389984A1 (fr) 2001-05-31
ES2215782T3 (es) 2004-10-16
EP1232240B1 (fr) 2004-09-15
AU2002301A (en) 2001-06-04
ATE276351T1 (de) 2004-10-15
DE60013889D1 (de) 2004-10-21
CN1399672A (zh) 2003-02-26
BR0015903A (pt) 2002-07-16
EP1232241B1 (fr) 2004-04-21
ES2225276T3 (es) 2005-03-16
EP1232240A1 (fr) 2002-08-21
GB9928078D0 (en) 2000-01-26
BR0015904A (pt) 2002-07-16
TR200401112T4 (tr) 2004-06-21
EP1232241A1 (fr) 2002-08-21
CA2389975A1 (fr) 2001-05-31
ATE264908T1 (de) 2004-05-15
AU2508801A (en) 2001-06-04

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