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EP1219700A1 - Compositions de nettoyage - Google Patents

Compositions de nettoyage Download PDF

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Publication number
EP1219700A1
EP1219700A1 EP00311743A EP00311743A EP1219700A1 EP 1219700 A1 EP1219700 A1 EP 1219700A1 EP 00311743 A EP00311743 A EP 00311743A EP 00311743 A EP00311743 A EP 00311743A EP 1219700 A1 EP1219700 A1 EP 1219700A1
Authority
EP
European Patent Office
Prior art keywords
tablet
water
particles
weight
contain
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Withdrawn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
EP00311743A
Other languages
German (de)
English (en)
Inventor
Jelles Vincent Unilever Res. Vlaardingen Boskamp
Ian Charles Unilever Res. Vlaardingen Callaghan
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 EP00311743A priority Critical patent/EP1219700A1/fr
Publication of EP1219700A1 publication Critical patent/EP1219700A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • 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
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • 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
    • C11D3/395—Bleaching agents

Definitions

  • This invention relates to cleaning compositions in the form of tablets. These tablets are intended to disintegrate when placed in water and thus are intended to be consumed in a single use.
  • the tablets may be suitable for use in machine dishwashing, the washing of fabrics or other cleaning tasks.
  • Tablets of a cleaning composition are generally made by compressing or compacting a composition in particulate form. Although it is desirable that tablets have adequate strength when dry, yet disperse and dissolve quickly when brought into contact with water, it can be difficult to obtain both properties together. Tablets formed using a low compaction pressure tend to crumble and disintegrate on handling and packing; while more forcefully compacted tablets may be sufficiently cohesive but then fail to disintegrate or disperse to an adequate extent in the wash. Tableting will often be carried out with enough pressure to achieve a compromise between these desirable but antagonistic properties. However, it remains desirable to improve one or other of these properties without detriment to the other so as to improve the overall compromise between them.
  • a tablet contains organic surfactant, this functions as a binder, plasticising the tablet. However, it can also retard disintegration of the tablet by forming a viscous gel when the tablet comes into contact with water. Thus, the presence of surfactant can make it more difficult to achieve both good strength and speed of disintegration: the problem has proved especially acute with tablets formed by compressing powders containing surfactant and built with insoluble detergency builder such as sodium aluminosilicate (zeolite) including the forms of zeolite P described and claimed in EP 384070 (Unilever)
  • zeolite sodium aluminosilicate
  • EP-A-466484 is concerned with detergent tablets compacted from a composition of particles which have a restricted particle size distribution such that at least 90% of the composition falls between upper and lower limits on particle size which differ from each other by not more than 700 micrometers.
  • This document and EP 522766 disclose tablets made from surfactant-containing particles bearing a coating of a material which functions as a binder and also serves as a tablet disintegrant.
  • One material which is used as such a coating is cross-linked polyvinyl pyrrolidone. In examples, this is sprayed on as a solution in acetone giving a thin coating on the particles. An approximate calculation indicates a coating thickness substantially below 50 micrometers.
  • particulate cross-linked polyvinyl pyrrolidone is unexpectedly effective as a tablet disintegrant when mixed into a particulate cleaning composition.
  • a tablet of a compacted particulate cleaning composition containing at least one cleaning ingredient which is an organic surfactant, a water softening agent or a bleach, wherein the tablet or a discrete region of the tablet contains 0.5% up to 10%, by weight of the tablet or region of disintegrant particles which contain cross-linked polyvinyl pyrrolidone.
  • These disintegrant particles preferably do not contain surfactant or bleach.
  • the cross-linked polyvinyl pyrrolidone When the tablet is placed in water the cross-linked polyvinyl pyrrolidone swells, and this causes or assists disintegration of the tablet or region of a tablet.
  • This invention is particularly applicable when the tablets contain both surfactant and detergency builder, as in tablets for fabric washing.
  • the present invention provides a detergent tablet of compacted particulate composition containing organic surfactant, detergency builder and optionally other ingredients, wherein the tablet or a discrete region thereof comprises
  • these disintegrant particles (ii) do not contain surfactant. Possibly they do not contain bleach.
  • This invention also provides, in a second aspect, a method of making a tablet comprising mixing up to 10% of disintegrant particles of size greater than 250 micrometers and other particulate material to form a cleaning composition, and compacting that composition to form a tablet or a region of a tablet.
  • a tablet of the invention may be either homogeneous or heterogeneous.
  • the term “homogeneous” is used to mean a tablet produced by compaction of a single particulate composition, but does not imply that all the particles of that composition will necessarily be of identical composition.
  • the term “heterogeneous” is used to mean a tablet consisting of a plurality of discrete regions, for example layers, inserts or coatings, each of which is a matrix of particles derived by compaction from a particulate composition.
  • each discrete region of the tablet will preferably have a mass of at least 3gm.
  • At least one of the discrete regions contains the said disintegrant particles which incorporate cross-linked polyvinyl pyrrolidone.
  • the benefit of the cross-linked polyvinyl pyrrolidone to promote disintegration will be conferred on the region or regions of the tablet which contain the material. This can, if desired, be utilised to cause the different regions of the tablet to disintegrate at different rates, thereby liberating their constituent materials into a wash liquor at differing rates.
  • Cross-linked polyvinyl pyrrolidone may or may not be included in every region of a heterogenous tablet, even though the regions differ from each other in some other feature of their composition.
  • disintegrant particles which contain cross-linked polyvinyl pyrrolidone may be present at different concentrations in different tablet regions; they may be present in one region and absent from another; or may be present at equal concentration in every region of the tablet. It is possible that one region will contain disintegrant particles which contain cross-linked polyvinyl pyrrolidone while another region will contain some other water-swellable material.
  • 2-vinyl pyrrolidone of formula can be polymerised to a linear polymer containing repeat units. Such linear polymers are water-soluble.
  • Cross-linked polyvinyl pyrrolidone can be a copolymer of vinyl pyrrolidone and a small amount of a cross-linked co-monomer which is able to become incorporated into more than one polymer chain and thereby link two polymer chains. The formation of cross links between polymer chains by use of a monomer with multiple reactive groups is well known in polymer chemistry.
  • Cross-linked polyvinyl pyrrolidone is available commercially from BASF and from ISP corporation.
  • Particles of desired size can be obtained by sieving out particles which are smaller than desired.
  • cross-linked polyvinyl pyrrolidone has that property to a high degree.
  • Disintegrant particles utilised in this invention may consist of cross-linked polyvinyl pyrrolidone alone or as at least 50% by weight of the particles. If a commercial source of cross-linked polyvinyl pyrrolidone is used as supplied, the particles are likely to contain more than 80% by weight of polyvinyl pyrrolidone.
  • disintegrant particles will contain a minority of cross-linked polyvinyl pyrrolidone mixed with a greater quantity of other material acting as a carrier.
  • such a carrier material will be water-insoluble. Preferably it swells to some extent on contact with water, although not as much as the cross-linked polyvinyl pyrrolidone.
  • Possible carrier materials are starches, for example, maize, rice and potato starches, celluloses, for example Arbocel®-B and Arbocel®-BC (beech cellulose), Arbocel®-BE (beech-sulphite cellulose), Arbocel®-B-SCH (cotton cellulose) and Arbocel®-FIC (pine cellulose) from J Rettenmaier and Söhne in Germany and also microcrystalline cellulosic fibres.
  • celluloses for example Arbocel®-B and Arbocel®-BC (beech cellulose), Arbocel®-BE (beech-sulphite cellulose), Arbocel®-B-SCH (cotton cellulose) and Arbocel®-FIC (pine cellulose) from J Rettenmaier and Söhne in Germany and also microcrystalline cellulosic fibres.
  • the disintegrant particles have a majority or minority of cross-linked polyvinyl pyrrolidone it is desirable that the particles have a mean particle size of at least 200, better at least 250 and preferably at least 350 micrometers.
  • the disintegrant particles may have a size distribution such that at least 75% by weight of the particles have a particle size of 200 micrometers or above, and the mean particle size is at least 250 micrometers.
  • Such a size and size distribution may be obtained as a result of the process by which the particles are made, or it may be achieved by sieving to remove undersized particles.
  • the amount of disintegrant particles containing cross-linked polyvinyl pyrrolidone is preferably from 1 to 8% of the composition, better from 1 to 5%.
  • Compositions which are compacted to form tablets or tablet regions of this invention may contain one or more organic detergent surfactants.
  • these preferably provide from 5 to 50% by weight of the overall tablet composition, more preferably from 8 or 9% by weight of the overall composition up to 40% or 50% by weight.
  • Surfactant may be anionic (soap or non-soap), cationic, zwitterionic, amphoteric, nonionic or a combination of these.
  • Anionic surfactant may be present in an amount from 0.5 to 50% by weight, preferably from 2% or 4% up to 30% or 40% by weight of the tablet composition.
  • organic surfactant is likely to constitute from 0.5 to 8%, more likely from 0.5 to 4.5% of the overall composition and is likely to consist of nonionic surfactant, either alone or in a mixture with anionic surfactant.
  • Synthetic (i.e. non-soap) anionic surfactants are well known to those skilled in the art.
  • alkylbenzene sulphonates particularly sodium linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 15 ; olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
  • 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.
  • such linear alkyl benzene sulphonate or primary alkyl sulphate of the formula above, or a mixture thereof will be the desired anionic surfactant and may provide 75 to 100 wt% of any anionic non-soap surfactant in the composition.
  • the amount of non-soap anionic surfactant lies in a range from 5 to 20 or 25 wt% of the tablet composition.
  • soaps of fatty acids are preferably sodium soaps derived from naturally occurring fatty acids, for example, the fatty acids from coconut oil, beef tallow, sunflower or hardened rapeseed oil.
  • 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 ) phenol-ethylene 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 amount of nonionic surfactant lies in a range from 4 to 40%, better 4 or 5 to 30% by weight of the composition.
  • Many nonionic surfactants are liquids. These may be absorbed onto particles of the composition, prior to compaction into tablets.
  • Amphoteric surfactants which may be used jointly with anionic or nonionic surfactants or both include amphopropionates of the formula: where 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 where 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 SO 3 - (sulfobetaine or hydroxy sultaine).
  • 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 (amidoprop
  • amphoteric surfactant is amine oxide of the formula where R 1 is C 10 to C 20 alkyl or alkenyl R 2 , R 3 and R 4 are each hydrogen or C 1 to C 4 alkyl while n is from 1 to 5.
  • Cationic surfactants may possibly be used. These frequently have a quaternised nitrogen atom in a polar head group and an attached hydrocarbon group of sufficient length to be hydrophobic.
  • a general formula for one category of cationic surfactants is where each R independently denotes an alkyl group or hydroxyalkyl group of 1 to 3 carbon atoms and R h denotes an aromatic, aliphatic or mixed aromatic and aliphatic group of 6 to 24 carbon atoms, preferably an alkyl or alkenyl group of 8 to 22 carbon atoms.
  • the amount of amphoteric surfactant, if any, may possibly be from 3% to 20 or 30% by weight of the tablet or region of a tablet; the amount of cationic surfactant, if any, may possibly be from 1% to 10 or 20% by weight of the tablet or region of a tablet.
  • a composition which is compacted to form tablets or tablet regions may contain a so-called water-softening agent which serves to remove or sequester calcium and/or magnesium ions in the water.
  • a water-softening agent which serves to remove or sequester calcium and/or magnesium ions in the water.
  • a water-softening agent is more usually referred to as a detergency builder.
  • the amount of it is likely to lie in a broad range from 5 better 15 wt% up to 98% of the tablet composition.
  • the amount is likely to be from 15 to 80%, more usually 15 to 60% by weight of the tablet.
  • Water-softening agents may be provided wholly by water soluble materials, or may be provided in large part or even entirely by water-insoluble material with water-softening properties.
  • Alkali metal aluminosilicates are strongly favoured as environmentally acceptable water-insoluble softening agents (detergency builders) for fabric washing.
  • Alkali metal (preferably sodium) aluminosilicates may be either crystalline or amorphous or mixtures thereof, having the general formula: 0.8 - 1.5 Na 2 O.Al 2 O 3 . 0.8 - 6 SiO 2 . xH 2 O
  • These materials contain some bound water (indicated as xH 2 O) and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g.
  • the preferred sodium aluminosilicates contain 1.5-3.5 SiO 2 units (in the formula above). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
  • Suitable crystalline sodium aluminosilicate ion-exchange materials 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 newer zeolite P described and claimed in EP 384070 (Unilever) and mixtures thereof.
  • This form of zeolite P is also referred to as "zeolite MAP".
  • zeolite A24 One commercial form of it is denoted "zeolite A24".
  • a water-insoluble water-softener could be a 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 SiO 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 such as those having the general formula NaMSi x O 2x+1. yH 2 O 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 can be used.
  • the category of water-soluble phosphorus-containing inorganic softeners includes the alkali-metal orthophosphates, metaphosphates, pyrophosphates and polyphosphates.
  • Specific examples of inorganic phosphate detergency builders include sodium and potassium tripolyphosphates, orthophosphates and hexametaphosphates.
  • Non-phosphorus water-soluble water-softening agents may be organic or inorganic.
  • Inorganics that may be present include alkali metal (generally sodium) carbonate; while organics include polycarboxylate polymers, such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphonates, monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono- di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates and hydroxyethyliminodiacetates.
  • alkali metal generally sodium
  • organics include polycarboxylate polymers, such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphonates, monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono- di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxy
  • Tablet compositions preferably include polycarboxylate polymers, more especially polyacrylates and acrylic/maleic copolymers which have some function as water-softening agents and also inhibit unwanted deposition onto fabric from the wash liquor.
  • compositions according to the invention may contain a bleach system.
  • This preferably comprises one or more peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with activators to improve bleaching action at low wash temperatures. If any peroxygen compound is present, the amount is likely to lie in a range from 10 to 85% by weight of the composition. If the tablet contains surfactant and detergency builder, the amount of peroxygen compound bleach is unlikely to exceed 25% of the composition.
  • Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate, advantageously employed together with an activator.
  • Bleach activators also referred to as bleach precursors
  • Preferred examples include peracetic acid precursors, for example, tetraacetylethylene diamine (TAED), now in widespread commercial use in conjunction with sodium perborate; and perbenzoic acid precursors.
  • TAED tetraacetylethylene diamine
  • perbenzoic acid precursors perbenzoic acid precursors.
  • the quaternary ammonium and phosphonium bleach activators disclosed in US 4751015 and US 4818426 are also of interest.
  • 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.
  • a bleach system may also include a bleach stabiliser (heavy metal sequestrant) such as ethylenediamine tetramethylene phosphonate and diethylenetriamine pentamethylene phosphonate.
  • a tablet or a region of a tablet may contain water-soluble particles to promote disintegration, in addition to the water-swellable, water-insoluble particles containing cross-linked polyvinyl pyrrolidone as required by this invention.
  • Such soluble particles typically contain at least 40% (of their own weight) of one or more salts selected from
  • these disintegration-promoting particles can also contain other forms of tripolyphosphate or other salts within the balance of their composition.
  • the material in such water-soluble disintegration-promoting particles can function as a detergency builder, (as is the case with sodium tripolyphosphate) then of course it contributes to the total quantity of detergency builder in the tablet composition.
  • the quantity of water-soluble disintegration-promoting particles may be from 3 or 5% up to 30 or 40% by weight of the tablet or region thereof.
  • the quantity may possibly be from 8% up to 25% or 30% or more (especially if this salt also functions as a detergency builder).
  • the amount of such water-soluble disintegration-promoting particles is low, between 2% and 8% of the tablet or region, reliance being placed on particles containing cross-linked polyvinyl pyrrolidone.
  • these water-soluble disintegration-promoting particles contain at least 40% of their own weight, better at least 50%, of a salt which has a solubility in deionised water at 20°C of at least 50 grams per 100 grams of water.
  • These particles may provide salt of such solubility in an amount which is at least 7 wt% or 12 wt% of the composition of the tablet or discrete region thereof.
  • a solubility of at least 50 grams per 100 grams of water at 20°C is an exceptionally high solubility: many salts are classified as water soluble are less soluble than this.
  • solubilities of some other common materials at 20°C are:- Material Water Solubility (g/100g) Sodium chloride 36 Sodium sulphate decahydrate 21.5 Sodium carbonate anhydrous 8.0 Sodium percarbonate anhydrous 12 Sodium perborate anhydrous 3.7 Sodium tripolyphosphate anhydrous 15
  • this highly water soluble salt is incorporated as particles of the salt in a substantially pure form (i.e. each such particle contains over 95% by weight of the salt).
  • the said particles may contain salt of such solubility in a mixture with other material, provided that salt of the specified solubility provides at least 40% by weight of these particles.
  • a preferred salt is sodium acetate in a partially or fully hydrated form.
  • water-soluble particles which promote disintegration are particles containing sodium tripolyphosphate with more than 40% (by weight of the particles) of the anhydrous phase I form.
  • phase II which is the low temperature form
  • phase I which is stable at high temperature.
  • the conversion of phase II to phase I proceeds fairly rapidly on heating above the transition temperature, which is about 420°C, but the reverse action is slow. Consequently phase I sodium tripolyphosphate is metastable at ambient temperature.
  • Particles which contain this phase I form will often contain the phase I form of sodium tripolyphosphate as at least 50% or 55% by weight of the tripolyphosphate in the particles.
  • Suitable material is commercially available. Suppliers include Rhone-Poulenc, France and Albright & Wilson, UK.
  • this sodium tripolyphosphate is partially hydrated.
  • the extent of hydration should be at least 0.5% by weight of the sodium tripolyphosphate in the particles. It may lie in a range from 0.5 to 4%, or it may be higher, e.g. up to 9 or 10% by weight of the sodium tripolyphosphate.
  • water-soluble particles which promote disintegration contain at least 40 wt% sodium tripolyphosphate which has a phase I content of at least 50% by weight of the tripolyphosphate but is also sufficiently hydrated so as to contain at least 0.5% water by weight of the sodium tripolyphosphate.
  • the remainder of the tablet composition used to form the tablet or region thereof may include additional sodium tripolyphosphate.
  • This may be in any form, including sodium tripolyphosphate with a high content of the anhydrous phase II form.
  • composition of the tablet or region of the tablet which incorporates cross-linked polyvinyl pyrrolidone contains not more than 15% possibly not more than 12% or 10% by weight of water-soluble constituents with an above mentioned water-solubility of at least 50 grams per 100 grams of water at 20°C.
  • 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.
  • 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 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 4,4'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 if organic surfactant is present, especially if a 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.
  • a tablet of the invention includes an amount of an alkali metal silicate, particularly sodium ortho-, meta- or disilicate.
  • an alkali metal silicate particularly sodium ortho-, meta- or disilicate.
  • a composition for fabric washing will generally not contain more than 15 wt% silicate.
  • a tablet for machine dishwashing will frequently contain at least 20 wt% silicate.
  • compositions which can optionally be employed in fabric washing detergent tablets of the invention include anti-redeposition agents such as sodium carboxymethylcellulose, straight-chain polyvinyl pyrrolidone which inhibits dye transfer, 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 which inhibits dye transfer, 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.
  • a tablet of this invention or a discrete region of such a tablet, is a matrix of compacted particles.
  • the particulate composition has an average particle size in the range from 200 to 2000 ⁇ m, more preferably from 250 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.
  • This invention may be employed when the tablet or region of a tablet has a wider particle size distribution than the narrow range recommended by EP-A-466484.
  • the particle size distribution of the composition which is compacted is such that 5% by weight of the composition consists of particles smaller than a size which may be referred to as the "lower boundary” and 5% by weight of the composition consists of particles larger than a value referred to as the "upper boundary” the upper boundary may well be more than 700 micrometers greater than the lower boundary.
  • the starting particulate composition may in principle have any bulk density
  • the present invention may be especially relevant to tablets of detergent composition 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 400 g/litre, preferably at least 500 g/litre, and possibly at least 600 g/litre.
  • a composition which is compacted into a tablet or tablet region may contain particles which have been prepared by spray-drying or granulation and which contain a mixture of ingredients. Such particles may contain organic detergent surfactant and some or all of the water-softening agent (detergency builder) which is also present in a detergent tablet.
  • 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.
  • disintegrant particles containing cross-linked polyvinyl pyrrolidone as required by this invention are mixed with the remainder of the particulate composition prior to compaction.
  • This remainder of the particulate composition preferably includes particles which have been prepared by spray-drying or granulation and which contain organic detergent surfactant mixed with detergency builder and possibly other ingredients.
  • other particulate constituents notably including any optional water-soluble particles to promote disintegration, may also be mixed into the particulate composition.
  • compositions intended for compaction to tablets for machine dishwashing, or bleaching or water-softening may be prepared by mixing all of the particulate ingredients together including the electrolyte-impregnated swellable material required by this invention.
  • Detergent compositions for fabric washing may also be made in this way. However it is likely that such compositions will begin with an initial step of preparing a base powder containing surfactant especially ionic surfactant and at least some detergency builder. Preparation of such a base powder may be carried out by spray-drying or by a granulation process.
  • the base powder is them desirably mixed with other ingredients including water-soluble salts to promote disintegration, other constituents of the overall composition such as bleach and bleach activator and the disintegrant particles containing cross-linked polyvinyl pyrrolidone.
  • Liquid constituents of the overall composition such as perfume or nonionic detergent may be sprayed on to the resulting mixture before it is compacted into tablets.
  • the present invention may especially be embodied as a tablet for fabric washing.
  • a tablet will generally contain, overall, from 5 to 50% by weight of surfactant and from 5 to 80% by weight of detergency builder which is a water softening agent.
  • Peroxygen bleach may be present and if so is likely to be in an amount not exceeding 25% by weight of the total composition.
  • a region which contains water-swellable material in accordance with this invention may also contain surfactant in an amount which is from 5 to 50% by weight of that region and detergency builder in an amount which is from 5 to 80% by weight of that region.
  • the invention may be embodied as tablets whose principal or sole function is that of removing water hardness.
  • the water-softening agents especially water-insoluble aluminosilicate, may provide from 50 to 98% of the tablet composition.
  • a water-soluble supplementary builder may well be included, for instance in an amount from 2% to 30wt% of the composition, or may be considered unnecessary and not used.
  • Water-softening tablets embodying this invention may include some surfactant.
  • the invention may be embodied as tablets for machine dishwashing.
  • Such tablets typically contain a high proportion of water soluble salts, such as 50 to 95% by weight, at least some of which, exemplified by sodium tripolyphosphate, sodium citrate and sodium silicate, have water-softening properties.
  • Both water-softening and machine dishwashing tablets may include nonionic surfactant which can act as a lubricant during tablet manufacture and as a low foaming detergent during use.
  • the amount may be small, e.g. from 0.2 or 0.5% by weight of the composition up to 3% or 5% by weight.
  • Tablets for use as a bleaching additive will typically contain a high proportion of peroxygen bleach, such as 25 to 85% by weight of the composition. This may be mixed with other soluble salt as a diluent.
  • the composition of such a tablet may well include a bleach activator such as tetraacetylethylene diamine (TAED). A likely amount would lie in the range from 1 to 20% by weight of the composition.
  • TAED tetraacetylethylene diamine
  • Tableting entails compaction of a particulate composition.
  • a variety of tableting machinery is known, and can be used. Generally it will function by stamping a quantity of the particulate composition which is confined in a die.
  • Tableting may be carried out at ambient temperature or at a temperature above ambient which may allow adequate strength to be achieved with less applied pressure during compaction.
  • the particulate composition is preferably supplied to the tableting machinery at an elevated temperature. This will of course supply heat to the tableting machinery, but the machinery may be heated in some other way also. If any heat is supplied, it is envisaged that this will be supplied conventionally, such as by passing the particulate composition through an oven, rather than by any application of microwave energy.
  • 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.
  • 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 for fabric washing preferably lies in a range from 1040 or 1050gm/litre preferably at least 1100gm/litre up to 1400gm/litre.
  • the tablet density may well lie in a range up to no more than 1350 or even 1250gm/litre.
  • the overall density of a tablet of some other cleaning composition such as a tablet for machine dishwashing or as a bleaching additive, may range up to 1700gm/litre and will often lie in a range from 1300 to 1550gm/litre.
  • the accompanying drawing is a cross-sectional view which illustrates a piece of apparatus used in conjunction with a materials testing machine.
  • the apparatus consists of a cylinder (10) with internal diameter 25mm and a length of 20mm. This cylinder is perforated by a ring of holes (12) adjacent one end. There are 36 of these holes, of 1mm diameter, with centres 2.5mm from the end of the cylinder.
  • This end of the cylinder is glued to the base of a glass container (14) of internal diameter 73mm.
  • a plunger (18) of the Instron machine is moved into the upper set of the cylinder, over this powder bed.
  • the plunger is applied to the top of the powder bed (16) with a force of 1 Newton.
  • a strongly swelling material if tested, by itself, has ability to absorb at least twice its own volume of water and has a development of expansion force which exceeds 1.5 Newton/second.
  • the significant parameter in the third column of the above table is the maximum slope of a graph of expansion force against time.
  • Measurement of water-absorption can be recorded with the same apparatus.
  • the plunger is again applied to the top of a bed of the dry powder, and pressed against it with a force of 1 Newton. 50ml of water is poured in as before.
  • the Instron machine is programmed to allow expansion of the bed of powder, while maintaining a force on it of 1 Newton. Displacement of the plunger is recorded.
  • a detergent base powder was made by a neutralisation and granulation process as described in WO-A-98/11193.
  • the composition of the base powder is shown below: Ingredient Parts by Weight Sodium linear alkylbenzene sulphonate 10.40 Nonionic surfactant (C 13-15 branched fatty alcohol 7EO) 3.12 Soap 0.55 Zeolite A24 (Zeolite MAP available from Crosfields) 20.20 Sodium acetate trihydrate 2.70 Sodium carbonate (light soda ash) 2.90 Linear sodium carboxymethyl cellulose (SCMC) 0.42 Moisture and impurities 3.70 TOTAL 44.00
  • This base powder was sieved to obtain particles between 500 and 1000 ⁇ m.
  • the sodium acetate trihydrate and the cross-linked polyvinyl pyrrolidone are both disintegration-promoting particles.
  • the former is highly water-soluble. The latter swells on contact with water.
  • compositions were compacted on a single punch tableting machine, to produce cylindrical tablets with diameter 44mm, weight approximately 40 gm and substantially equal tablet strength.
  • the speed of disintegration of the tablets was tested by means of a procedure in which a tablet was placed on a metal grid with holes of 1cm by 1cm and immersed in 1 litre of water at either 10°C or 20°C. If any residue remained after a standard time of 60 seconds, this was recovered and dried enabling the percentage disintegration in 60 seconds to be calculated.
  • composition A As comparative example A' another, less effective polymer was used in composition A, in place of polyvinyl pyrrolidone. As comparative examples C' and D' a cellulosic disintegrant was used in place of cross-linked polyvinyl pyrrolidone in compositions C and D.
  • cross-linked polyvinyl pyrrolidone was effective as a tablet disintegrant, even when sodium acetate was absent.
  • Tablets for use in fabric washing were made, starting with granulated base powder of the following composition, made by mixing under high shear followed by densification under reduced shear in accordance with the procedure described in WO-A-98/11193.
  • Ingredient Parts by Weight Sodium linear alkylbenzene sulphonate 8.51 C 13-15 fatty alcohol 7EO 2.44 C 13-15 fatty alcohol 3EO 1.31 Soap 0.66 Maximum aluminium zeolite P 19.06 Sodium acetate trihydrate 2.41 Sodium carbonate (light soda ash) 2.82 Linear sodium carboxymethyl cellulose (SCMC) 0.38 Moisture and impurities 3.41 TOTAL 41.0

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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP00311743A 2000-12-28 2000-12-28 Compositions de nettoyage Withdrawn EP1219700A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004046292A1 (fr) * 2002-11-15 2004-06-03 Unilever N.V. Detergent ayant une composition amelioree
WO2011151191A1 (fr) * 2010-06-02 2011-12-08 Henkel Ag & Co. Kgaa Produits à vaisselle compactés
WO2011151192A1 (fr) * 2010-06-02 2011-12-08 Henkel Ag & Co. Kgaa Produits à vaisselle compactés
CN103525569A (zh) * 2013-10-24 2014-01-22 上虞力姿生物科技有限公司 汽车玻璃清洁泡腾片
WO2023202935A1 (fr) * 2022-04-20 2023-10-26 Unilever Ip Holdings B.V. Composition de pastille

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3104371A1 (de) * 1981-02-07 1982-11-11 Henkel KGaA, 4000 Düsseldorf "reinigungsmitteltablette"
US4642197A (en) * 1984-05-14 1987-02-10 Henkel Kommanditgesellschaft Auf Aktien Process for the production of a washing additive in tablet form
EP0522766A2 (fr) * 1991-07-01 1993-01-13 Unilever Plc Compositions détergentes sous forme de tablettes
US5360567A (en) * 1990-07-13 1994-11-01 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions
WO1999020730A1 (fr) * 1997-10-22 1999-04-29 Unilever Plc Compositions detergentes en pastilles
WO1999036493A1 (fr) * 1998-01-13 1999-07-22 The Procter & Gamble Company Granule detergent presentant une aptitude amelioree a la dissolution
WO2000043488A1 (fr) * 1999-01-23 2000-07-27 The Procter & Gamble Company Comprime detergent
EP1036839A2 (fr) * 1999-03-17 2000-09-20 Basf Aktiengesellschaft Tablettes et particules détergentes contenant de la polyvinylpyrrolidone réticulée et son utilisation
EP1074608A1 (fr) * 1999-08-02 2001-02-07 Robert McBride Ltd Pastilles détergentes

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3104371A1 (de) * 1981-02-07 1982-11-11 Henkel KGaA, 4000 Düsseldorf "reinigungsmitteltablette"
US4642197A (en) * 1984-05-14 1987-02-10 Henkel Kommanditgesellschaft Auf Aktien Process for the production of a washing additive in tablet form
US5360567A (en) * 1990-07-13 1994-11-01 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions
EP0522766A2 (fr) * 1991-07-01 1993-01-13 Unilever Plc Compositions détergentes sous forme de tablettes
WO1999020730A1 (fr) * 1997-10-22 1999-04-29 Unilever Plc Compositions detergentes en pastilles
WO1999036493A1 (fr) * 1998-01-13 1999-07-22 The Procter & Gamble Company Granule detergent presentant une aptitude amelioree a la dissolution
WO2000043488A1 (fr) * 1999-01-23 2000-07-27 The Procter & Gamble Company Comprime detergent
EP1036839A2 (fr) * 1999-03-17 2000-09-20 Basf Aktiengesellschaft Tablettes et particules détergentes contenant de la polyvinylpyrrolidone réticulée et son utilisation
EP1074608A1 (fr) * 1999-08-02 2001-02-07 Robert McBride Ltd Pastilles détergentes

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004046292A1 (fr) * 2002-11-15 2004-06-03 Unilever N.V. Detergent ayant une composition amelioree
CN100393863C (zh) * 2002-11-15 2008-06-11 荷兰联合利华有限公司 改进的洗涤剂组合物
WO2011151191A1 (fr) * 2010-06-02 2011-12-08 Henkel Ag & Co. Kgaa Produits à vaisselle compactés
WO2011151192A1 (fr) * 2010-06-02 2011-12-08 Henkel Ag & Co. Kgaa Produits à vaisselle compactés
CN103525569A (zh) * 2013-10-24 2014-01-22 上虞力姿生物科技有限公司 汽车玻璃清洁泡腾片
WO2023202935A1 (fr) * 2022-04-20 2023-10-26 Unilever Ip Holdings B.V. Composition de pastille

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