EP1405901B1 - Waschmittel - Google Patents

Waschmittel Download PDF

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Publication number
EP1405901B1
EP1405901B1 EP03077852A EP03077852A EP1405901B1 EP 1405901 B1 EP1405901 B1 EP 1405901B1 EP 03077852 A EP03077852 A EP 03077852A EP 03077852 A EP03077852 A EP 03077852A EP 1405901 B1 EP1405901 B1 EP 1405901B1
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EP
European Patent Office
Prior art keywords
semi
smooth
tablet
polyoxyethylene
solid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP03077852A
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English (en)
French (fr)
Other versions
EP1405901A1 (de
Inventor
Felix Marco Van Der Kooij
Lammert Nauta
Johannes Cornelis Van De Pas
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Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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Publication date
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Priority to EP03077852A priority Critical patent/EP1405901B1/de
Publication of EP1405901A1 publication Critical patent/EP1405901A1/de
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Publication of EP1405901B1 publication Critical patent/EP1405901B1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/008—Polymeric surface-active agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0086—Laundry tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC

Definitions

  • This invention relates to cleaning compositions in the form of tablets for example, for use in fabric washing or machine dishwashing.
  • Detergent compositions in tablet form have advantages over powdered products in that they do not require measuring and are thus easier to handle and dispense into the washload.
  • Tablets of a cleaning composition are generally made by compressing or compacting a quantity of the composition in particulate form.
  • WO 01/42416 describes the production of multi-phase moulded bodies comprising a combination of core moulded bodies and a particulate premix.
  • WO 00/61717 describes a detergent tablet which is characterised in that at least part of its outer surface is semi-solid.
  • WO 00/04129 describes a multi-phase detergent tablet comprising a first phase in the form of a shaped body having at least one mould therein and a second phase in the form of a particulate solid compressed within said mould.
  • a further objective of the present invention is to provide a method to produce a smooth or semi-solid tablet or phase thereof wherein the choice of materials and the manufacturing method allows the low cost production of tablets of good performance and of good consistency and texture.
  • a cleaning tablet which has a plurality of discrete regions with differing compositions, characterised in that at least one first region of the tablet is a smooth or semi-solid region and at least one second region of the tablet is a solid region of compacted particulate material.
  • the invention relates to a cleaning tablet comprising a smooth or semi-solid phase wherein the smooth or semi-solid phase comprises:
  • tablets of the invention are of cylindrical shape wherein the two main surfaces (upper side and bottom side) are substantially flat.
  • tablets of the invention can be single phase tablets, which are predominantly constituted by the semi-solid phase as described above.
  • a preferred embodiment of the invention relates to a multiphase tablet wherein the smooth or semi-solid phase is present and additionally one or more other phases are present.
  • these additional phases can be smooth, semi-solid or solid.
  • Particularly suitable are solid phases composed of compacted particulate solids.
  • the regions of a multi-phase tablet are possibly separate layers within a tablet. However, a discrete region of a tablet could also have other forms for example one or more core(s) or insert(s).
  • the first region is a smooth or semi-solid layer and the second region is a layer of compacted particulate material.
  • the first region is a core or insert of smooth or semi-solid material embedded in the second region which is a layer of compacted particulate material.
  • the weight of this tablet will be from 5 to 100 g, more preferably from 10 to 40 g, most preferably from 15 to 35 g.
  • the tablet is a multi-phase tablet comprising the smooth or semi-solid phase of the invention then preferably the smooth or semi-solid phase is present as a distinctive region having a weight of from 2 to 20 grammes, preferably from 3 to 10 grammes.
  • the other phases together have a weight of 10 to 50 grammes, more preferred 15 to 40 grammes.
  • smooth phase refers to compositions which are on the one hand solid enough to retain their shape at ambient temperature and on the other hand smooth in appearance. Smooth textures are generally of low or no porosity and have - at normal viewing distance - the appearance of a continuous phase for example as opposed to porous and particulate appearance of a compacted particulate material.
  • semi-solid refers to compositions which are on the one hand solid enough to retain their shape at ambient temperature but which are not completely solid. Semi-solid phases generally have a smooth non-porous appearance.
  • a suitable test to check if a composition can be considered as semi-solid can be described as follows.
  • a cylindrical tablet with a diameter of 45 mm and a height of 20 mm is compressed radially between the plates of a material testing machine until the tablet fractures.
  • the testing machine measures the applied force (F), and also the displacement (x) of the plates towards each other as the tablet is compressed.
  • the distance (y) between the plates before force is applied which is the diameter of the tablet, is also known.
  • the tablet cracks and the applied force, needed to maintain the displacement, drops. Measurement is discontinued when the applied force needed to maintain the displacement has dropped by 25% from its maximum value.
  • the displacement at failure (x f ) is measured.
  • a graph of force (F) against displacement (x) will be made.
  • the maximum force is the force at failure (F f ).
  • Semi-solid compositions are characterised by a ratio of F f to E b of less than 1.0, more preferred from 0.1 to 0.9, most preferred from 0.2 to 0.6, while traditional tablets of compacted particulate materials are generally characterised by a ratio of F f to E b of more than 1, more generally more than 1.25 or even more than 1.5 up to say 6.
  • the tablets of the invention comprise a phase which is both smooth and semi-solid.
  • a smooth (non semi-solid) phase may equally be suitable.
  • the smooth or semi-solid phase comprises from 20-80 wt% of non-soap surfactants (based on the total weight of said semi-solid phase), more preferred from 25 to 75 wt%, most preferred 30 to 70 wt%. It has been found that the combination of a separate smooth or semi-solid first region and these high surfactant levels provide very good dispersing and cleaning properties to the tablet.
  • the non-soap surfactants in the first region comprise a combination of anionic surfactants and non-ionic surfactants in a weight ratio of from 5 : 1 to 1 : 5, more preferred 3 : 1 to 1 : 3, more preferred 2 : 1 to 1: 2.
  • Further surfactants for example cationic surfactants may equally be present for example at a level of 0.1 to 10 wt% based on the weight of the smooth or semi-solid part.
  • the smooth or semi-solid region will comprise soap at a level of 2 to 75 wt% based on the weight of the smooth or semi-solid part, preferably from 3 to 70 wt%, more preferred from 5 to 40 wt%.
  • the soap provides good structuring properties to the smooth or semi-solid phase, especially if this phase comprises relatively high levels of surfactants.
  • This structuring leads on the one hand to a desired firm consistency of the semi-solid phase but on the other hand retains the smooth or semi-solid nature of the phase.
  • the soap is capable of reducing the bleeding of the smooth or semi-solid phase.
  • the smooth or semi-solid region of the tablet will also contain 5 to 50 wt% of a material selected from polyalkoxylated carbohydrates, selected from the group of polyoxyethylene-sorbitan mono-fatty esters, polyoxyethylene-sorbitol fatty esters, polyoxyethylene glycerol esters, polyoxyethylene glycerol sorbitan isostearate, polyoxyethylene-hexitan-fatty esters, polyoxyethylene sorbitan, polyoxyethylene-sorbitol, polyoxyethylene glycerol, polyoxyethylene glycerol sorbitan, polypropoxylated sorbitan, and alkyl polyalkoxylated carboxylates, and stabilising surfactants having an average alkyl chain of more than 6 C atoms and having a salting out resistance greater than or equal to 3.0, selected from alkyl polyalkoxylated phosphates, alkyl polyalkoxylated sulphosuccinates, dialkyl diphenyl oxide disulphonates,
  • polyoxyethylene-sorbitan mono-fatty esters for example Tween 20, Tween 40 and Tween 60
  • polyoxyethylene-sorbitol fatty esters for example Atlas G4895, Atlox 1045A
  • polyoxyethylene glycerol esters for example Atlas G7074
  • polyoxyethylene glycerol sorbitan isostearate for example Arlacel 582
  • polyoxyethylene-hexitan-fatty esters for example Arlacel 121
  • polyoxyethylene sorbitan for example obtainable by hydrolysing Tween 20, Tween 40 and Tween 60
  • polyoxyethylene-sorbitol for example Atlas G2320, G2330 and G2401
  • polyoxyethylene-sorbitan mono-fatty esters for example Atlas G4895, Atlox 1045A
  • polyoxyethylene glycerol esters for example Atlas G7074
  • polyoxyethylene glycerol sorbitan isostearate for example Arlacel 582
  • stabilising surfactants having an average alkyl chain of more than 6 C atoms and having a salting out resistance greater than or equal to 3.0 are described in EP 328, 177 and EP 359, 308 .
  • materials according to the invention, selected from stabilising surfactants having an average alkyl chain of more than 6 C atoms and having a salting out resistance greater than or equal to 3.0 are alkyl polyalkoxylated carboxylates, alkyl polyalkoxylated phosphates, alkyl polyalkoxylated sulphosuccinates, dialkyl diphenyl oxide disulphonates, and alkyl polysaccharides.
  • the level of the material according to the invention selected from polyalkoxylated carbohydrates, selected from the group of polyoxyethylene-sorbitan mono-fatty esters, poloyxyethylene-sorbitol fatty esters, polyoxyethylene glycerol esters, polyoxyethylene glycerol sorbitan isostearate, polyoxyethylene-hexitan-fatty esters, polyoxyethylene sorbitan, polyoxyethylene-sorbitol, polyoxyethylene glycerol, polyoxyethylene glycerol sorbitan, and polypropoxylated sorbitan, and stabilising surfactants having an average alkyl chain of more than 6 C atoms and having a salting out resistance greater than or equal to 3.0, selected from alkyl polyalkoxylated carboxylates, alkyl polyalkoxylated phosphates, alkyl polyalkoxylated sulphosuccinates, dialkyl diphenyl oxide disulphonates, and alkyl polysaccharides, is
  • a test to measure the salting out resistance of a material is decribed in EP 328 177 .
  • 200ml is prepared of a 5% by weight aqueous solution of the material in question.
  • Trisodium nitrolotriacetate (NTA) is added at room temperature (ca 25°C) until phase separation, as observed by the onset of cloudiness, occurs.
  • the smooth or semi-solid region of the tablet may also contain diluent materials for example polyethyleneglycol preferably having a molecular weight of less than 5000 or even less than 1000, dipropyleneglycol, isopropanol or (mono-)propyleneglycol.
  • the level of these diluents is from 5 to 50 wt%, preferably from 5 to 45 wt%, most preferred from 15 to 40 wt% based on the weight of the smooth or semi-solid phase.
  • the smooth or semi-solid phase comprises no or only low levels of water.
  • the level of water is less than 20 wt% based on the weight of the semi-solid phase, preferably less than 15 wt%, more preferred from 5 to 12 wt%.
  • Most preferably the smooth or semi-solid phases are substantially free from water, which means that apart from low levels of moisture (e.g. for neutralisation or as crystal water) no additional added water is present.
  • the total weight of surfactants in the smooth or semi-solid phase is from 2 to 20 grammes, more preferred from 3 to 10 grammes.
  • the tablet may be a multi-phase tablet wherein the phases other than the smooth or semi-solid phase as described above comprise no or only low levels of surfactants.
  • the level of surfactants in the other phases is less than 10 wt%(based on the total weight of said phases), more preferred from 0 to 9 wt%, most preferred from 1 to 8 wt%.
  • the cleaning tablets comprise a first smooth or semi-solid region (as described above) in combination with a second region of the tablet which is a solid region, for example prepared by compression of a particulate composition.
  • the second region may comprise surfactant materials
  • this region preferably comprises ingredients of the tablet other than surfactants.
  • these ingredients are for example builders, bleach system, enzymes etc.
  • the builders in the tablet are predominantly present in the second region.
  • the bleach system is predominantly present in the second region.
  • the enzymes are predominantly present in the second region.
  • the term "predominantly present” refers to a situation wherein at least 90 wt% of an ingredient is present in the second region, more preferred more than 98 wt%, most preferred substantially 100 wt%.
  • each of the regions may be composed of a limited number of discrete regions.
  • the first smooth or semi-solid region may be a single discrete part of the tablet but may also be a limited number (say 1-5) discrete smooth or semi-solid parts.
  • each of these smooth or semi-solid parts are at least 1 gramme, also preferably each of these smooth or semi-solid parts is substantially of the same composition. If reference is made to the composition or weight of the first region it is understood that this concerns the , total weight and composition of these smooth or semi-solid parts.
  • the solid second region may be composed of a limited number (say 1-5) of solid parts e.g. separate layers in the tablet.
  • each of these parts has a weight of at least 10 grammes, also preferably each of the solid parts is substantially of the same composition. If reference is made to the composition or weight of the second region it is understood that this concerns the total weight and composition of these solid parts.
  • the cleaning tablets of the invention may optionally comprise further regions, for example the tablet may be partly or wholly coated.
  • Cleaning tablets according to the invention are preferably manufactured by firstly preparing a smooth or semi-solid part.
  • the preparation of the smooth or semi-solid phase may include the heating of the ingredients followed by cooling.
  • the preparation of the smooth or semi-solid phase may involve extrusion.
  • Extrusion processes for washing articles are known, for example WO 01/02532 describes the extrusion of washing articles with a pressure of less than 1 000 kN/m 2 (10 bar).
  • extrusion processes for preparing the smooth or semi-solid parts for use in tablets of the invention will involve the forming of an extrudable mass which is then subsequently extruded from an extrusion device and optionally then partioned into parts of the desired size and weight.
  • the semi-solid parts may then be hardened.
  • the extrudable mass preferably has an initial elevated temperature for example from 60 to 120 °C, more preferred from 70 to 90 °C.
  • the extrudable mass is during the production of the smooth or semi-solid mass cooled e.g. to a final temperature of 20 °C. If extrusion is used this low temperature may for example be the temperature at the extrusion die for example from 10 to 40 °C, preferably from 15 to 25 °C, most preferred at ambient temperature (20 °C).
  • the conditions for extrusion are carefully controlled.
  • semi-solid parts which on the one hand contain relatively high levels of soap and non-soap surfactants and on the other hand have the right textural properties (i.e not too soft and of semi-solid character) can advantageously be produced by an extrusion process wherein no high-shear conditions are applied, in particular under cooling.
  • the extrusion takes place under low-shear conditions in the extrusion device.
  • Suitable extrusion devices for this purpose are for example free from extrusion screws.
  • the feeding of the extrudable mass to a elongated chamber e.g a pipe provided with cooling means but not provided with stirring or shearing devices.
  • the particulate composition is compressed at a force of 0.1 to 100 kN/cm 2 .
  • a tablet of this invention may be intended for use in machine dishwashing.
  • Such a tablet is likely to contain surfactant in a low concentration such as 0.5 to 2 wt% based on the whole tablet, although higher concentrations ranging up to 10 wt% may be used.
  • Such will typically contain salts, such as over 60 wt%, often over 85 wt% of the tablet.
  • Water soluble salts typically used in machine dishwashing compositions are phosphates (including condensed phosphates) carbonates and silicates, generally as alkali metal salts.
  • Water soluble alkali metal salts selected from phosphates, carbonates and silicates may provide 60 wt% or more of a dishwashing composition.
  • a tablet of this invention will be intended for fabric washing.
  • the tablet will be likely to contain at least 2 wt%, probably at least 5 wt%, up to 40 or 50 wt% non-soap surfactant based on the whole tablet, and from 5 to 80 wt% detergency builder, based on the whole tablet.
  • compositions which are used in tablets of the invention will contain one or more 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.
  • 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.
  • Linear alkyl benzene sulphonate of the formula where R is linear alkyl of 8 to 15 carbon atoms and M + is a solubilising cation, especially sodium, is also a commercially significant 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 wt% of the tablet composition.
  • Soaps for use in accordance to the invention 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.
  • soaps are selected from C 10 to C 20 soaps for example from C 16 to C 18 or C 12 soaps.
  • 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 whole tablet.
  • nonionic surfactants are liquids. These may be absorbed onto particles of the composition.
  • the surfactant may be wholly nonionic, in an amount below 5 wt% of the whole tablet although it is known to include some anionic surfactant and to use up to 10 wt% surfactant in total.
  • a composition which is used in tablets of the invention will usually contain from 5 to 80%, more usually 15 to 60% by weight of detergency builder. This 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. Water-insoluble detergency builder may be present as 5 to 80 wt%, better 5 to 60 wt% of the composition.
  • 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: 0.8 - 1.5 Na 2 O.Al 2 O 3 . 0.8 - 6 SiO 2 . xH 2 O
  • xH 2 -O Some bound water
  • xH 2 -O some bound water
  • 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 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 novel zeolite P described and claimed in EP 384070 (Unilever) and mixtures thereof.
  • a water-insoluble detergency builder 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").
  • KSKS-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 .
  • 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.
  • Water-soluble phosphorous-containing inorganic detergency builders include the alkali-metal orthophosphates, metaphosphates, pyrophosphates and polyphosphates.
  • Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, orthophosphates and hexametaphosphates.
  • Non-phosphorous water-soluble builders may be organic or inorganic.
  • Inorganic builders that may be present include alkali metal (generally sodium) carbonate; while organic builders 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
  • organic builders 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, dip
  • At least one region (preferably the second region) of a fabric washing tablet preferably include polycarboxylate polymers, more especially polyacrylates and acrylic/maleic copolymers which can function as builders and also inhibit unwanted deposition onto fabric from the wash liquor.
  • Tablets according to the invention may contain a bleach system in at least one region of a tablet, preferably in the second region.
  • 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 25% by weight 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 bleach is present and is a water-soluble inorganic peroxygen bleach, the amount may well be from 10% to 25% by weight of the composition.
  • the detergent tablets of the invention may also contain (preferably in the second region) 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 DSM N.V. (formerly known as Gist-Brocades N.V.), Delft, Holland, and Alcalase (Trade Mark), and Savinase (Trade Mark), as supplied by Novozymes A/S (formerly known as 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 detergent tablets of the invention may also contain (preferably in the second region) a fluorescer (optical brightener), for example, Tinopal (Trade Mark) DMS or Tinopal CBS available from Ciba Speciality Chemicals AG (formerly known as Ciba-Geigy AG), Basel, Switzerland.
  • a fluorescer optical brightener
  • Tinopal DMS is disodium 4,4'bis-(2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene disulphonate
  • Tinopal CBS is disodium 2,2'-bis-(phenylstyryl) disulphonate.
  • An antifoam material is advantageously included (preferably in the second region), 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, absorbed 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 detergent 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.
  • the presence of such alkali metal silicates at levels, for example, of 0.1 to 10 wt%, may be advantageous in providing protection against the corrosion of metal parts in washing machines, besides providing some measure of building and giving processing benefits in manufacture of the particulate material which is compacted into tablets.
  • a tablet for fabric washing will generally not contain more than 15 wt% silicate.
  • a tablet for machine dishwashing will often contain more than 20 wt% silicate.
  • the silicate is present in the second region of the tablet.
  • ingredients which can optionally be employed in a region of a fabric washing detergent of the invention tablet 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.
  • dispersing aids are water-swellable polymers (e.g. SCMC) highly soluble materials (e.g. sodium citrate, potassium carbonate or sodium acetate) or sodium tripolyphospate with preferably at least 40% of the anhydrous phase I form.
  • SCMC water-swellable polymers
  • highly soluble materials e.g. sodium citrate, potassium carbonate or sodium acetate
  • sodium tripolyphospate preferably at least 40% of the anhydrous phase I form.
  • the second region of a detergent tablet of this invention is a preferably 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.
  • 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 400 g/litre, preferably at least 500 g/litre, and perhaps at least 600 g/litre.
  • Tableting machinery able to carry out the manufacture of tablets of the invention is known, for example suitable tablet presses are available from Fette and from Korch.
  • 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.
  • 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 preferably lies in a range from 1040 or 1050gm/litre up to 1600gm/litre.
  • Soap fatty acid (ex Uniqema), diluent dipropylene glycol (ex Vopak) and ethoxylated materials were added to the mixture in the amounts as indicated in the table.
  • the mixture was kept at a temperature around 80°C until the fatty acid had dissolved and then further neutralised with a 50% NaOH solution to a pH of 11.
  • the mixture was pumped into a sequence of 2 stainless steel tubes by a Maag Sinox P7 pump or a piston pump, type SIBa HK 05016SST4000M000 ex Prominent, Vleuten (NL). Both tubes were double jacketed.
  • the first tube was 2.5m long and had an inner diameter of 73mm.
  • the second tube was 1.5m long and had an inner diameter of 45mm.
  • the tubes were connected by a 10cm long pipe.
  • the extrusion was performed via die-head (with inner diameters of resp 24 and 32 mm), which was attached to the second tube.
  • the mixture was pumped into the tubes at a temperature of 85°C at a throughput of 4 kg/hr.
  • the first tube was cooled using a water bath at 40°C.
  • the second tube was cooled using a 50:50 weight mixture of ethylene glycol and water.
  • the coolant temperature was -15°C.
  • the material coming out of the second tube had a temperature of about 20 C and was collected and divided into bars of around 0.5m.
  • the dissolution of the slices was determined by immersing a piece into 500 ml tap water at 20 C, stirring at 200 rpm and measuring the remaining weight of the slices at 3 or 5 minute intervals. t80 (the time by which 80% of the mass of the test piece has dissolved) was determined.
  • Formulations (all levels are dosed on top of the anionic/nonionic mixture) and t80 in minutes.
  • Adjunct (%) DPG (%) C12 soap(%) t80 (min)
  • A (comp) 0 0 25 >35 B 50 (Tween 40) 0 25 25 C 25 (Tween 40) 25 25 18 D 25 (Atlas G2330) 25 25 27
  • Tween 40 is polyoxyethylene sorbitan monopalmitate and Atlas G2330 is ethoxylated sorbitol.
  • a detergent powder was made of the following composition by pregranulating the granule ingredients, followed by post-dosing the rest of the ingredients Ingredient Parts by weight Granules Na-las 1.1 Nonionic 7EO 0.5 C12 soap 0.1 NaAc.3aq 0.3 Zeolite A24 2.4 Light soda ash 0.4 Moisture/minors 0.4 Post-dose EAG (17% silicone) 3.0 Fluorescer (15%) 2.2 STP 62.4 Na-disilicate (80%) 3.8 TAED (83%) 4.3 Percarbonate 16.9 Dequest 2047 1.9 Minors/ enzymes/colour to 100
  • the tablets were made in 2 different ways:
  • the selected co-surfactants were: Trade name/ description Chemical description Supplier Used in example Empicol CBC Alkyl Ether Carboxylate, C12E4C Huntsmann A1 Empicol CBL Alkyl Ether Carboxylate, C10-16E13C Huntsmann A2 Daclor 70-3-23-AL Alkyl Ether Sulphate, C12-13E3S Daclor B1 Glucapon 600 CSUP Alkyl PolyGlucoside, C10-16 Cognis B2 C12-14 APG Alkyl PolyGlucoside, C12-14G1.7 Cognis B3
  • the co-surfactants used in examples A1, A2, B1, B2 and B3 were freeze dried until water activities Aw ⁇ 0.5 before incorporation into the mixture.
  • the hardness of the Gels were quantified using Stevens LFRA Texture Analyser by measuring the resistance of a rod (diameter 12.7mm) pushed into the gel at a penetration speed of 1 mm/s at room temperature.
  • the dissolution rate was measured by measuring the time of dissolution of ⁇ 5 grams of smooth part in 1 liter of demineralised water under stirring at 200 rpm at 20C, the time was taken after 80% of the weight of the smooth sample was dissolved (T80).

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Molecular Biology (AREA)
  • Detergent Compositions (AREA)
  • Woven Fabrics (AREA)

Claims (8)

  1. Reinigungstablette, umfassend eine glatte oder halbfeste Phase, wobei die glatte oder halbfeste Phase:
    (a) 10 bis 90 Gew.-% nicht seifenartige oberflächenaktive Mittel und
    (b) 2 bis 75 Gew.-% Seife und
    (c) 5 bis 50 Gew.-% eines Materials, ausgewählt aus polyalkoxylierten Kohlenhydraten, ausgewählt aus der Gruppe von Polyoxyethylensorbitanmonofettsäureestern, Polyoxyethylensorbitolfettsäureestern, Polyoxyethylenglycerolestern, Polyoxyethylenglycerolsorbitanisostearat, Polyoxyethylenhexitanfettsäureestern, Polyoxyethylensorbitan, Polyoxyethylensorbitol, Polyoxyethylenglycerol, Polyoxyethylenglycerolsorbitan und polypropoxyliertem Sorbitan, und stabilisierenden oberflächenaktiven Mitteln mit einer durchschnittlichen Alkylkette von mehr als 6 C-Atomen und mit einer Aussalzbeständigkeit von mehr als oder gleich 3,0, ausgewählt aus alkylpolyalkoxylierten Carboxylaten, alkylpolyalkoxylierten Phosphaten, alkylpolyalkoxylierten Sulfosuccinaten, Dialkyldiphenyloxiddisulfonaten und Alkylpolysacchariden; und
    (d) 0 bis 20 Gew.-% Wasser umfaßt.
  2. Reinigungstablette nach Anspruch 1, wobei die Tablette eine mehrphasige Tablette ist und die glatte oder halbfeste Phase 2 bis 20 Gramm wiegt.
  3. Reinigungstablette nach Anspruch 1, umfassend 3 bis 70 Gew.-% Seife, basierend auf dem Gewicht der glatten oder halbfesten Phase.
  4. Reinigungstablette nach Anspruch 1, wobei das Material ein polyethoxyliertes Sorbitan oder ein Ester davon ist.
  5. Reinigungstablette nach einem der Ansprüche 1 bis 4, wobei der Gehalt des Materials 10 bis 45 Gew.-%, basierend auf dem Gewicht der glatten oder halbfesten Phase, beträgt.
  6. Reinigungstablette nach Anspruch 1, wobei das Material ein Alkylpolysaccharid ist.
  7. Reinigungstablette nach einem oder mehreren der vorhergehenden Ansprüche, umfassend 5 bis 50 Gew.-% Verdünnungsmittel, basierend auf dem Gewicht der glatten oder halbfesten Phase.
  8. Reinigungstablette nach Anspruch 7, wobei das Verdünnungsmittel Dipropylenglycol oder Monopropylenglycol ist.
EP03077852A 2002-10-01 2003-09-11 Waschmittel Expired - Lifetime EP1405901B1 (de)

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Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1669438B1 (de) 2004-12-08 2007-10-17 Unilever N.V. Wasch- und Reinigungsmitteltablette
EP1676904B1 (de) 2005-01-04 2009-05-06 Unilever N.V. Wasch- und Reinigungsmittelformkörper
DE602006002151D1 (de) 2005-03-23 2008-09-25 Unilever Nv Körperförmige Wasch- oder Reinigungsmittelzusammensetzungen
EP1705240A1 (de) 2005-03-23 2006-09-27 Unilever N.V. Wasch- oder Reinigungsmitteltabletten
GB0506850D0 (en) * 2005-04-05 2005-05-11 Unilever Plc Dispensing device
EP1746151A1 (de) 2005-07-20 2007-01-24 Unilever N.V. Wasch- und Reinigungsmitteltabletten
EP1746152A1 (de) 2005-07-20 2007-01-24 Unilever N.V. Wasch- oder Reinigungsmittel
DE602006007142D1 (de) * 2006-09-19 2009-07-16 Unilever Nv Waschmitteltablette
DE102010051226A1 (de) 2010-11-12 2012-05-31 Dental Care Innovation Gmbh Ausspültablete mit abrasiven Bestandteilen
WO2018144771A2 (en) 2017-02-02 2018-08-09 Water Pik, Inc. Tablet including abrasive for dental cleaning

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2147674C (en) * 1994-05-16 1999-03-30 David Robert Zint Shaped semi-solid or solid dishwashing detergent
HUP0004038A3 (en) * 1997-10-22 2001-11-28 Unilever Nv Detergent compositions in tablet form and process for producing thereof
EP1043390A1 (de) * 1999-04-09 2000-10-11 The Procter & Gamble Company Wasch- und Reinigungsmittel in Tablettenform

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ATE364680T1 (de) 2007-07-15
DE60314348D1 (de) 2007-07-26
ES2287408T3 (es) 2007-12-16
DE60314348T2 (de) 2008-02-21

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