EP0903405A2 - Machine dish washing composition - Google Patents

Machine dish washing composition Download PDF

Info

Publication number
EP0903405A2
EP0903405A2 EP98307432A EP98307432A EP0903405A2 EP 0903405 A2 EP0903405 A2 EP 0903405A2 EP 98307432 A EP98307432 A EP 98307432A EP 98307432 A EP98307432 A EP 98307432A EP 0903405 A2 EP0903405 A2 EP 0903405A2
Authority
EP
European Patent Office
Prior art keywords
tablet
dish washing
silicone
machine dish
packaging system
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Withdrawn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
EP98307432A
Other languages
German (de)
French (fr)
Other versions
EP0903405A3 (en
Inventor
Claudio R. c/o Ind. Gessy Lever Ltda Grigolon
Amauri Z. c/o Ind. Gessy Lever Ltda Luna
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
Original Assignee
Unilever PLC
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 filed Critical Unilever PLC
Publication of EP0903405A2 publication Critical patent/EP0903405A2/en
Publication of EP0903405A3 publication Critical patent/EP0903405A3/en
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3742—Nitrogen containing silicones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D75/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes or webs of flexible sheet material, e.g. in folded wrappers
    • B65D75/28—Articles or materials wholly enclosed in composite wrappers, i.e. wrappers formed by associating or interconnecting two or more sheets or blanks
    • B65D75/30—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding
    • B65D75/32—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents
    • B65D75/325—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents one sheet being recessed, and the other being a flat not- rigid sheet, e.g. puncturable or peelable foil
    • B65D75/327—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents one sheet being recessed, and the other being a flat not- rigid sheet, e.g. puncturable or peelable foil and forming several compartments
    • 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
    • C11D17/0091—Dishwashing 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
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • 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
    • C11D3/3942—Inorganic per-compounds

Definitions

  • the present invention relates to a tablet for use in a dish washing machine, a method of preparing the tablet and packaging for the tablet.
  • Detergent tablets for dish-washing machines are liked by consumers as they find them are more convenient to use than alternative products such as powders and the like.
  • Powder flowability is an important factor to consider in the manufacture of a tablet. Powders with a low flowability (less than 50 ml/s) can have two negative aspects namely: they can compact at the press feed line reducing throughput and they do not flow at a rate which is compatible with the pressing cycle and thus do not completely fill the tablet forming mold.
  • Manufacture of tablets can also be difficult due to difficulty in ejecting the tablet from a mold. This difficulty means that the mechanical wear on the tabletting machine is increased and may flaws can occur on the tablet's surface
  • binding and disintegrating agents may contain binding and disintegrating agents.
  • An important property of these such agents is that they are compatible with the active ingredients in the tablet. Frequently an agent can have a dual role e.g., a binding agent also acts as a disintegrating agent.
  • Effervescent systems have been included in a tablets formulation to increase their dissolution rate.
  • Such effervescent systems includes weak acids or acid salts such as citric acid, maleic acid, sodium and hydrogen phosphates, in combination with a basic ingredient that liberates carbon dioxide when interacting with this source of acid. Examples include sodium and potassium carbonate and bicarbonate and sodium sesquicarbonate.
  • the present invention relates to a tablet that dissolves rapidly when added to water and is easy to manufacture accordingly the present invention relates to a machine dish washing tablet comprising a bleaching system, a silicone and less than 10 wt% of surfactant.
  • the invention also relates to a process for preparing machine dish washing tablets comprising the step of adding a silicone emulsion to a formulation that is to be tableted.
  • the invention also relates to a dish washing tablet(1) and a packaging system (2) the packaging system comprising a body (3) shaped to receive a tablet and a cover(4) which keeps the tablet in the body.
  • a dish washing tablet (1) and a packaging system (2) the packaging system comprising a body (3) shaped to receive a tablet and a cover(4) which keeps the tablet in the body.
  • the use of this packaging system to store dish washing tablet is also described.
  • the tablets according to the present invention not only dissolve quickly in the dish washing machine but they are easy to process in that the powder used to manufacture the tablets has good flowability, does not adhere to the punch's surface and the tablets produced are easily ejected from the mold.
  • tablets of the invention can be prepared by conventional presses instead of powerful presses which are commonly used to for making detergent tablets.
  • Conventional presses are those with engines with up to 5hp, a sole compression stage with a working capacity of up to 12t/cm 2 and production rate of 18000 tablets per hour.
  • the cost of these presses is up to 8 times smaller than the double-stage large presses with a high pressing rate normally used to prepare detergent tablets.
  • the tablets of the invention comprise a silicone, preferably in the form of an emulsion.
  • the addition of water to the tablet via the emulsion is beneficial because it can prevent the powder from granulating.
  • the granulation of the powder to from granules greater than 10mm is undesirable because it causes difficulties when press feeding press feeding.
  • the silicones used are preferably polymers or copolymers of dimethyl silicone or aminomethoxy functionalised dimethyl silicone. Mixtures of the polymers may also be used.
  • the level of silicone emulsion added to the product is from 0.5 wt% to 10 wt% of the total product, preferably from 1 to 3 wt%.
  • the level of silicone within the silicone emulsion is from 2 wt% to 50 wt% of the total weight of the silicone emulsion, preferably from 5 to 15 wt%.
  • any emulsifier may be used, preferably the emulsifier is a surfactant, most preferred as the emulsifier a nonionic surfactant.
  • silicone emulsions preferentially used in the present invention are those available from Dow Corning under the trademarks Dow Corning 36, 346, and 347; Dow Corning HV-490, Dow Corning 190 and 93; Dow Corning 531 and 536; Dow Corning 8075, 7242, Dow Corning 2-8707 and OSI-SAG 470,
  • the bleaching systems of the invention are preferably oxygen based.
  • the oxygen bleaching agents of the compositions include organic peroxy acids and diacylperoxides.
  • Typical monoperoxy acids useful herein include alkyl peroxy acids and aryl peroxy acids such as:
  • Typical diperoxy acids useful herein include alkyl diperoxy acids and aryl diperoxy acids, such as:
  • a typical diacylperoxide useful herein includes dibenzoylperoxide.
  • Inorganic peroxygen compounds are especially suitable for the present invention.
  • these materials useful in the invention are salts of monopersulfate, perborate monohydrate, perborate tetrahydrate, and percarbonate. sodium perborate and sodium percarbonate are particularly preferred.
  • the organic peroxy acid is present in the composition in an amount such that the level of organic peroxy acid in the wash solution is 1 ppm to 300 ppm AvOx, preferably 2 ppm to 200 ppm AvOx.
  • Typical levels of organic peroxy acid are from 2 wt% to 15 wt% of the total formulation.
  • the oxygen bleaching agent may be incorporated directly into the formulation or may be encapsulated by any number of encapsulation techniques.
  • Suitable peracid precursors for peroxy bleach compounds have been amply described in the literature, including GB Nos. 836,988; 855,735; 907,356; 907;358; 907,950; 1,003,310 and 1,246,339; US-A-3,332,882 and US-A-4,128,494.
  • Typical examples of precursors are polyacylated alkylene diamines, such as N,N,N',N'-tetraacetylethylene diamine (TAED) and N,N,N',N'-tetraacetylmethylene diamine (TAMD); acylated glycolurils, such as tetraacetylglycoluril (TAGU); triacetylcyanurate, sodium sulfophenyl ethyl carbonic acid ester, sodium acetyloxybenene sulfonate (SABS), sodium nonanoyloxy benzene sulfonate (SNOBS) and choline sulfophenyl carbonate.
  • SABS sodium acetyloxybenene sulfonate
  • SNOBS sodium nonanoyloxy benzene sulfonate
  • choline sulfophenyl carbonate choline sulfophenyl carbonate
  • Peroxybenzoic acid precursors are known in the art, e.g., as described in GB-A-836,988. Examples of suitable precursors are phenylbenzoate; phenyl p-nitrobenzoate; o-nitrophenyl benzoate; o-carboxyphenyl benzoate; p-bromophenylbenzoate; sodium or potassium benzoyloxy benzene-sulfonate; and benzoic anhydride.
  • Preferred peroxygen bleach precursors are sodium p-benzoyloxybenzene sulfonate, N,N,N',N'-tetraacetylethylene diamine, sodium nonanoyloxybenzene sulfonate and choline sulfophenyl carbonate.
  • the peroxygen bleach precursors may be present in the composition in an amount from 1 to 20 wt. %, preferably from 1 to 15 wt. %, most preferably from 2 to 10 weight %.
  • a source of hydrogen peroxide is required.
  • the hydrogen peroxide source is preferably a compound that delivers hydrogen peroxide on dissolution.
  • Preferred sources of hydrogen peroxide are sodium perborate, either as mono- or tetrahydrate and sodium percarbonate.
  • the source of hydrogen peroxide, when included in the composition, is present at a level from 1% to 30% by weight, preferably from 2% to 25% by weight, most preferably from 4% to 20% by weight.
  • An effective amount of a bleach catalyst can also be present in the first layer.
  • organic catalysts are available such as the sulfonimines as described in US-A-5,041,232; US-A-5,047,163 and US-A-5,463,115.
  • Transition metal bleach catalysts are also useful especially those based on manganese, iron, cobalt, titanium, molybdenum, nickel, chromium, copper, ruthenium, tungsten and mixtures thereof. These include simple water-soluble salts such as those of iron, manganese and cobalt as well as catalysts containing complex ligands.
  • Suitable examples of manganese catalysts containing organic ligands are described in US-A-4,728,455, US-A-5,114,606, US-A-5,153,161, US-A-5,194,416, US-A-5,227,084, US-A-5,244,594, US-A-5,246,612, US-A-5,246,621, US-A-5,256,779, US-A-5,274,147, US-A-5,280,117 and EP-A-544,440, EP-A-544,490, EP-A-549,271 and EP-A-549,272.
  • Preferred examples of these catalysts include Mn IV 2 (u-O) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (PF 6 ) 2 , Mn III 2 (u-O) 1 (u-OAC) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (CIO 4 ) 2 , Mn IV 4 (u-O) 6 (1,4,7-triazacyclononane) 4 (CIO 4 ) 4 , Mn III Mn IV 4 (u-O) 1 (u-OAC) 2 (1,4,7-trimethyl-1,4,7triazacyclononane) 2 (ClO 4 ) 3 , Mn IV (1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH 3 ) 3 (PF 6 ), and mixtures thereof.
  • metal-based bleach catalysts include those disclosed in US-A-4,430,243 and US-A-5,l14,611.
  • Iron and manganese salts of aminocarboxylic acids in general are useful herein including iron and manganese aminocarboxylate salts disclosed for bleaching in the photographic color processing arts.
  • a particularly useful transition metal salt is derived from ethylenediaminedisuccinate and any complex of this ligand with iron or manganese.
  • Another type of bleach catalyst is a water soluble complex of manganese (II), (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
  • Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, mesoerythritol, meso-inositol, lactose and mixtures thereof. Especially preferred is sorbitol.
  • US-A-5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including manganese, cobalt, iron or copper with an non-(macro)-cyclic ligand.
  • transition metals including manganese, cobalt, iron or copper
  • non-(macro)-cyclic ligand include Mn gluconate, Mn(CF 3 SO 3 ) 2 , and binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including [bipy 2 Mn III (u-O) 2 Mn IV bipy 2 ]-(CIO 4 ) 3 .
  • bleach catalysts are described, for example, in EP-A-408,131 (cobalt complexes), EP-A-384,503 and EP-A-306,089 (metallo-porphyrins), US-A-4,728,455 (manganese/multidenate ligand), US-A-4,711,748 (absorbed manganese on aluminosilicate), US-A-4,601,845 (aluminosilicate support with manganese, zinc or magnesium salt), US-A-4,626,373 (manganese/ligand), US-A-4,119,557 (ferric complex), US-A-4,430,243 (Chelants with manganese cations and non-catalytic metal cations), and US-A-4,728,455 (manganese gluconates).
  • WO 96/23860 describe cobalt catalysts of the type [Co n L m X p ] Z Y z , where L is an organic ligand molecule containing more than one heteroatom selected from N, P, O and S; X is a co-ordinating species; n is preferably 1 or 2; m is preferably 1 to 5; p is preferably 0 to 4 and Y is a counterion.
  • L is an organic ligand molecule containing more than one heteroatom selected from N, P, O and S
  • X is a co-ordinating species
  • n is preferably 1 or 2
  • m is preferably 1 to 5
  • p is preferably 0 to 4
  • Y is a counterion.
  • One example of such a catalyst is N,N'-Bis(salicylidene)ethylenediaminecobalt (II).
  • transition-metal containing bleach catalysts can be prepared in the situ by the reaction of a transition-metal salt with suitable chelating agent, for example, a mixture of manganese sulfate and ethylenediaminedisuccinate.
  • suitable chelating agent for example, a mixture of manganese sulfate and ethylenediaminedisuccinate.
  • Highly colored transition metal-containing bleach catalysts may be co-processed with zeolites to reduce the color impact.
  • the bleach catalyst is typically incorporated at a level of 0.0001 to 10% by wt., preferably 0.001 to 5% by weight.
  • compositions of this invention can contain all manner of detergent builders commonly taught for use in machine dishwashing or other cleaning compositions.
  • the builders can include any of the conventional inorganic and organic water-soluble builder salts, or mixtures thereof and comprise 5 to 90% by weight, preferably from 10 to 80% by weight of the cleaning composition.
  • phosphorus-containing inorganic builders when present, include the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates and polyphosphates.
  • specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, pyrophosphates and hexametaphosphates.
  • non-phosphorus-containing inorganic builders when present, include water-soluble alkali metal carbonates, bicarbonates, sesquicarbonates, borates, silicates, including layered silicates such as SKS-6 ex. Hoechst, metasilicates, and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates including layered silicates and zeolites.
  • Organic detergent builders can also be used in the present invention.
  • organic builders include alkali metal citrates, succinates, malonates, fatty acid sulfonates, fatty acid carboxylates, nitrilotriacetates, phytates, phosphonates, alkanehydroxyphosphonates, oxydisuccinates, alkyl and alkenyl disuccinates, oxydiacetates, carboxymethyloxy succinates, ethylenediamine tetraacetates, tartrate monosuccinates, tartrate disuccinates, tartrate monoacetates, tartrate diacetates, oxidized starches, oxidized heteropolymeric polysaccharides, polyhydroxysulfonates, polycarboxylates such as polyacrylates, polymaleates, polyacetates, polyhydroxyacrylates, polyacrylate/polymaleate and polyacrylate/ polymethacrylate copolymers, acrylate/maleate/vinyl alcohol terpolymers, aminopol
  • Alkali metal citrates, nitrilotriacetates, oxydisuccinates, polyphosphonates, acrylate/maleate copolymers and acrylate/maleate/vinyl alcohol terpolymers are especially preferred organic builders.
  • the buffering system may be present in order to deliver a pH of about 6 to about 11 in the wash water.
  • Materials which may be selected for the buffering system include water-soluble alkali metal carbonates, bicarbonates, sesquicarbonates, borates, silicates, layered silicates such as SKS-6 ex Hoechst, metasilicates, phytic acid, citric acid, borate and crystalline and amorphous aluminosilicates and mixtures thereof.
  • Preferred examples include sodium and potassium carbonate, sodium and potassium bicarbonates, borates and silicates, including layered silicates
  • a surfactant may be included in the tablet including anionic, nonionic, cationic, amphoteric, zwitteronic surfactants and mixtures of these surface active agents.
  • anionic, nonionic, cationic, amphoteric, zwitteronic surfactants and mixtures of these surface active agents are well known in the detergent arts and are described at length at "Surface Active Agents and Detergents", Vol. 2 by Schwartz, Perry and Birch, Interscience Publishers, Inc., 1959, herein incorporated by reference.
  • Preferred surfactants are one or a mixture of:
  • Anionic synthetic detergents can be broadly described as surface active compounds with one or more negatively charged functional groups.
  • An important class of anionic compounds are the water-soluble salts, particularly the alkali metal salts, of organic sulfur reaction products having in their molecular structure an alkyl radical containing from about 6 to 24 carbon atoms and a radical selected from the group consisting of sulfonic and sulfuric acid ester radicals.
  • R 1 OSO 3 M where R 1 is a primary alkyl group of 8 to 18 carbon atoms and M is a solubilizing cation.
  • the alkyl group R 1 may have a mixture of chain lengths. It is preferred that at least two thirds of the R 1 alkyl groups have a chain length of 8 to 14 carbon atoms. This will be the case if R 1 is coconut alkyl, for example.
  • the solubilizing cation may be a range of cations which are in general monovalent and confer water solubility. Alkali metal, notably sodium, is especially envisaged. Other possibilities are ammonium and substituted ammonium ions, such as trialkanolammonium or trialkylammonium.
  • R 2 CH (SO 3 M) CO 2 R 3 where R 2 is an alkyl group of 6 to 16 atoms, R 3 is an alkyl group of 1 to 4 carbon atoms and M is a solubilizing cation.
  • the group R 2 may have a mixture of chain lengths. Preferably at least two thirds of these groups have 6 to 12 carbon atoms. This will be the case when the moiety R 2 CH(-)CO 2 (-) is derived from a coconut source, for instance. It is preferred that R 3 is a straight chain alkyl, notably methyl or ethyl.
  • Alkyl Benzene Sulfonates R 4 ArSO 3 M where R 4 is an alkyl group of 8 to 18 carbon atoms, Ar is a benzene ring (C 6 H 4 ) and M is a solubilizing cation.
  • the group R 4 may be a mixture of chain lengths. Straight chains of 11 to 14 carbon atoms are preferred.
  • Paraffin sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms, in the alkyl moiety. These surfactants are commercially available as Hostapur SAS from Hoechst Celanese.
  • Olefin sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms.
  • U.S. Patent No. 3,332,880 contains a description of suitable olefin sulfonates.
  • Organic phosphate based anionic surfactants include organic phosphate esters such as complex mono- or diester phosphates of hydroxyl- terminated alkoxide condensates, or salts thereof. Included in the organic phosphate esters are phosphate ester derivatives of polyoxyalkylated alkylaryl phosphate esters, of ethoxylated linear alcohols and ethoxylates of phenol. Also included are nonionic alkoxylates having a sodium alkylenecarboxylate moiety linked to a terminal hydroxyl group of the nonionic through an ether bond. Counterions to the salts of all the foregoing may be those of alkali metal, alkaline earth metal, ammonium, alkanolammonium and alkylammonium types.
  • Particularly preferred anionic surfactants are the fatty acid ester sulfonates with formula: R 2 CH(SO 3 M)CO 2 R 3 where the moiety R 2 CH(-)CO 2 (-) is derived from a coconut source and R 3 is either methyl or ethyl; primary alkyl sulfates with the formula: R 1 OSO 3 M wherein R 1 is a primary alkyl group of 10 to 18 carbon atoms and M is a sodium cation; and paraffin sulfonates, preferably with 12 to 16 carbon atoms to the alkyl moiety.
  • Nonionic surfactants can be broadly defined as surface active compounds with one or more uncharged hydrophilic substituents.
  • a major class of nonionic surfactants are those compounds produced by the condensation of alkylene oxide groups with an organic hydrophobic material which may be aliphatic or alkyl aromatic in nature.
  • the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Illustrative, but not limiting examples, of various suitable nonionic surfactant types are:
  • polyoxyalkene condensates of aliphatic carboxylic acids whether linear- or branched-chain and unsaturated or saturated, especially ethoxylated and/or propoxylated aliphatic acids containing from about 8 to about 18 carbon atoms in the aliphatic chain and incorporating from about 2 to about 50 ethylene oxide and/or propylene oxide units.
  • Suitable carboxylic acids include "coconut” fatty acids (derived from coconut oil) which contain an average of about 12 carbon atoms, "tallow” fatty acids (derived from tallow-class fats) which contain an average of about 18 carbon atoms, palmitic acid, myristic acid, stearic acid and lauric acid,
  • polyoxyalkene condensates of aliphatic alcohols whether linear- or branched-chain and unsaturated or saturated, especially ethoxylated and/or propoxylated aliphatic alcohols containing from about 6 to about 24 carbon atoms and incorporating from about 2 to about 50 ethylene oxide and/or propylene oxide units.
  • Suitable alcohols include "coconut” fatty alcohol, "tallow” fatty alcohol, lauryl alcohol, myristyl alcohol and oleyl alcohol.
  • Ethoxylated fatty alcohols may be used alone or in admixture with anionic surfactants, especially the preferred surfactants above.
  • the average chain lengths of the alkyl group R 5 in the general formula: R 5 O(CH 2 CH 2 O) n H is from 6 to 20 carbon atoms.
  • the group R 5 may have chain lengths in a range from 9 to 18 carbon atoms.
  • the average value of n should be at least 2.
  • the numbers of ethylene oxide residues may be a statistical distribution around the average value. However, as is known, the distribution can be affected by the manufacturing process or altered by fractionation after ethoxylation.
  • Particularly preferred ethoxylated fatty alcohols have a group R 5 which has 9 to 18 carbon atoms while n is from 2 to 8.
  • nonionic surfactants having a formula: wherein R 6 is a linear alkyl hydrocarbon radical having an average of 6 to 18 carbon atoms, R 7 and R 8 are each linear alkyl hydrocarbons of about 1 to about 4 carbon atoms, x is an integer of from 1 to 6, y is an integer of from 4 to 20 and z is an integer from 4 to 25.
  • One preferred nonionic surfactant of the above formula is Poly-Tergent SLF-18 7 a registered trademark of the Olin Corporation, New Haven, Conn. having a composition of the above formula where R 6 is a C 6 -C 10 linear alkyl mixture, R 7 and R 8 are methyl, x averages 3, y averages 12 and z averages 16.
  • R 9 is a linear, aliphatic hydrocarbon radical having from about 4 to about 18 carbon atoms including mixtures thereof; and R 10 is a linear, aliphatic hydrocarbon radical having from about 2 to about 26 carbon atoms including mixtures thereof; j is an integer having a value of from 1 to about 3; k is an integer having a value from 5 to about 30; and z is an integer having a value of from 1 to about 3. Most preferred are compositons in which j is 1, k is from about 10 to about 20 and l is 1. These surfactants are described in WO 94/22800. Other preferred nonionic surfactants are linear fatty alcohol alkoxylates with a capped terminal group, as described in U.S. 4,340,766 to BASF. Particularly preferred is Plurafac LF403 ex. BASF.
  • R 11 is a C 6 -C 24 linear or branched alkyl hydrocarbon radical and q is a number from 2 to 50; more preferably R 11 is a C 8 -C 18 linear alkyl mixture and q is a number from 2 to 15.
  • polyoxyethylene or polyoxypropylene condensates of alkyl phenols whether linear- or branched-chain and unsaturated or saturated, containing from about 6 to 12 carbon atoms and incorporating from about 2 to about 25 moles of ethylene oxide and/or propylene oxide.
  • the preferred polyoxyethylene derivatives are of sorbitan monolaurate, sorbitan trilaurate, sorbitan monopalmitate, sorbitan tripalmitate, sorbitan monostearate, sorbitan monoisostearate, sorbitan tripalmitate, sorbital tristearate, sorbitan monooleate, and sorbitan trioleate.
  • the polyoxyethylene chains may contain between about 4 and 30 ethylene oxide units, preferably about 10 to 20.
  • the sorbitan ester derivatives contain 1, 2 or 3 polyoxyethylene chains dependent upon whether they are mono-, di- or tri-acid esters.
  • polyoxyethylene-polyoxypropylene block copolymers having formula: HO(CH 2 CH 2 O) a (CH(CH 3 ) CH 2 O) b (CH 2 CH 2 O) c H or HO(CH(CH 3 )CH 2 O) d (CH 2 CH 2 O) e (CH(CH 3 )CH 2 O) f H wherein a, b, c, d, e and f are integers from 1 to 350 reflecting the respective polyethylene oxide and polypropylene oxide blocks of said polymer.
  • the polyoxyethylene component of the block polymer constitutes at least about 10% of the block polymer.
  • the material preferably has a molecular weight of between about 1,000 and 15,000, more preferably from about 1,500 to about 6,000. These materials are well-known in the art. They are available under the trademark "Pluronic” and "Pluronic R", a product of BASF Corporation.
  • Amine oxides having formula: R 12 R 13 R 14 N O wherein R 12 , R 13 and R 14 are saturated aliphatic radicals or substituted saturated aliphatic radicals.
  • Preferable amine oxides are those wherein R 12 is an alkyl chain of about 10 to about 20 carbon atoms and R 13 and R 14 are methyl or ethyl groups or both R 12 and R 13 are alkyl chains of about 6 to about 14 carbon atoms and R 14 is a methyl or ethyl group.
  • Amphoteric synthetic detergents can be broadly described as derivatives of aliphatic tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contain from about 8 to about 18 carbons and one contains an anionic water-solubilizing group, i.e., carboxy, sulpho, sulphato, phosphato or phosphono.
  • an anionic water-solubilizing group i.e., carboxy, sulpho, sulphato, phosphato or phosphono.
  • Examples of compounds falling within this definition are sodium 3-dodecylamino propionate and sodium 2-dodecylamino propane sulfonate.
  • Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium and sulphonium compounds in which the aliphatic radical may be straight chained or branched, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water-solubilizing group, e.g., carboxy, sulpho, sulphato, phosphato or phosphono. These compounds are frequently referred to as betaines. Besides alkyl betaines, alkyl amino and alkyl amido betaines are encompassed within this invention.
  • R 15 is a monovalent organic radical (e.g., a monovalent saturated aliphatic, unsaturated aliphatic or aromatic radical such as alkyl, hydroxyalkyl, alkenyl, hydroxyalkenyl, aryl, alkylaryl, hydroxyalkylaryl, arylalkyl, alkenylaryl, arylalkenyl, etc.) containing from about 6 to about 30 (preferably from about 8 to 18 and more preferably from about 9 to about 13) carbon atoms; R 16 is a divalent hydrocarbon radical containing from 2 to about 4 carbon atoms such as ethylene, propylene or butylene (most preferably the unit (R 16 O) n represents repeating units of ethylene oxide, propylene oxide and/or random or block combinations thereof); n is a number having an average value of from 0 to about 12; Z 1 represents a moiety derived from a monovalent organic radical (e.g., a monovalent saturated aliphatic, unsaturated alipha
  • Examples of commercially available materials from Henkel Techandit GmbH Aktien of Dusseldorf, Germany include APG 7 300, 325 and 350 with R 15 being C 9 -C 11 , n is 0 and p is 1.3, 1.6 and 1.8-2.2 respectively; APG 7 500 and 550 with R 15 is C 12 -C 13 , n is 0 and p is 1.3 and 1.8-2.2, respectively; and APG 7 600 with R 15 being C 12 -C 14 , n is 0 and p is 1.3.
  • esters of glucose are contemplated especially, it is envisaged that corresponding materials based on other reducing sugars, such as galactose and mannose are also suitable.
  • nonionic surfactants are polyoxyethylene and polyoxypropylene condensates of linear aliphatic alcohols.
  • the preferred range of surfactant is from 0.5 to 30 % by wt., more preferably from 0.5 to 15% by wt of the composition.
  • compositions herein may also optionally contain one or more transition metal chelating agents.
  • Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraamine-hexaacetates, diethylenetriaminepentaacetates, ethylenediamine disuccinate, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates), nitrilotris (methylenephosphonates) and diethylenetriaminepentakis (methylenephosphonates). Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See US-A-3,812,044.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
  • these chelating agents will generally comprise from 0.1% to 10% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from 0.1% to 5.0% by weight of such composition.
  • Enzymes capable of facilitating the removal of soils from a substrate may also be present in an amount of up to 10% by wt., preferably 1 to 5 wt. %.
  • Such enzymes include proteases (e.g., Alcalase7, Savinase7 and Esperase7 from Novo Industries A/S and Purafect OxP7, ex. Genencor), amylases (e.g., Termamyl7 and Duramyl7 from Novo Industries and Purafect OxAm7, ex. Genencor).
  • Suitable binding and disintegrating agents for use in tablets are described in the literature (see, for example, "Pharmaceutical Dosage Forms : Volume 1", 1989, Marcel Dekker Inc., ISBN 0-8246-804402). Both natural and synthetic polymeric materials are suitable.
  • starch such as corn, rice and potato starch and starch derivatives such as U-Sperse MTM and U-SperseTM provided by National Starch PrimojelTM, carboxymethyl starch and sodium glycolate such as ExplotabTM, pre-gelatinized corn starches such as NationalTM 1551 and Starch TM 1500; cellulose and cellulose derivatives including carboxymethyl cellulose such as CourloseTM and NymcelTM, reticulated sodium carboxymethyl cellulose, such as Ac-Di-SolTM provided by FMC Corporation, microcystalline cellulose fibres such as HanflocTM, microcrystalline cellulose such as LatticeTM NT provided by FMC Corporation and AvicelTM PH provided by FMC Corporation, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose and hydroxyprorylmethyl cellulose.
  • starch such as corn, rice and potato starch and starch derivatives such as U-Sperse MTM and U-SperseTM provided by National Starch PrimojelTM, carboxymethyl star
  • binding/disintegrating agents are polyvinylpolypyrrolidone products such as PlasdoneTM, PVPTM K-30 and PVPTM K-60 all provided by International Specialty Products; polyvinylpolypyrrolidine products, a crosslinked product of N-vinyl-2-pyrrolidone such as PolyplasdoneTM XL provided by International Specialty Products; polymethacrylates, polyvinyl alcohol and polyethylene glycols. Gums such as acacia, tragacanth, guar, locust bean gum and pectin, gelatin, sucrose and alginates are also suitable as binding/disintegrating agents.
  • Suitable inorganic materials include magnesium-aluminium silicate such as VeegumTM HV provided by R.T. Vanderbilt Co.Inc., bentonite and montmorillonite such as GelwhiteTM provided by Southern Clay Products.
  • Other suitable binding agents include monoglycerids such as ImwitorTM 191 provided by Huls America Inc., glyceril sterates such as ImwitorTM 900 provided by Huls America Inc., and palmoil glycerides such as ImwitorTM 940 provided by Huls America Inc..
  • the most preferred binding/disintegrating agents are microcrystalline cellulose and polyethylene glycols. The most preferred polyethylene glycols have a molecular weight of about 2000 to about 15000.
  • lubricant agents for aiding the tablet's processing, such as stearates, waxes, hydrogenated vegetable oils and polyethylene glycols and charges such as sugars, sodium sulphate and sodium chloride.
  • the tablet may be in the form of a layered product.
  • the level of components may vary in each layer. In some instances it may be desirable to have no or low levels of bleaching ingredient with bleach sensitive ingredients such as perfume in one layer and the bleaching ingredient in a separate layer.
  • the tablets of the invention completely dissolve in 6 litres of water(4oFH) at 65°C within 14 minutes.
  • the total solid material within the tablet is preferably in the range from 0.005 to 1.0mm. in order to maximize the dissolution rate and increase the tablet's resistance.
  • the addition order of the components of within the formulation can alter the appearance of the tablet.
  • a tablet in the context of the present invention can be defined as any particulate material compacted to form a solid material, the tablet comprising at least one thousand particulates.
  • the tablet has a diameter of 0.5 cm.
  • the packaging system of the present invention comprises a body (3) shaped to receive a tablet and a cover(4) which keeps the tablet in the body.
  • a cover which keeps the tablet in the body.
  • the cover covering the tablet is metallic.
  • the packaging system avoids the physical contact of a user with the detergent tablet when placing the tablet in the dish washing machine.
  • Another important aspect of the present invention is the combined use of the detergent material of the present invention with a packaging of the type here illustrated in figure 1 and 2, as examples.
  • a detergent tablet according to the present invention (Example 1) was prepared as follows.
  • a dissolution test was performed in actual use conditions by placing a tablet in a plastic basket within a dish-washing machine Enxuta brand - Futura model, acquired in 1996. The selected cycle was set to a complete wash and the time taken for the tablet to completely dissolve was measured.
  • the obtained values are average values of 3 washes for each product.
  • the table given below demonstrates the tablet according to the invention dissolves completely within 14 minutes, while the comparative examples take longer than 14 minutes to completely dissolve.
  • Examples A to E are commercially available tablets.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

A machine dish washing tablet (1) comprising a bleaching system, a silicone and less than 10 wt% of surfactant. A process is claimed for making this tablet (1) and a packaging system (2) is claimed for its storage and delivery. <IMAGE>

Description

The present invention relates to a tablet for use in a dish washing machine, a method of preparing the tablet and packaging for the tablet.
Background of the Invention
Detergent tablets for dish-washing machines are liked by consumers as they find them are more convenient to use than alternative products such as powders and the like.
However detergent tablets frequently exhibit poor dissolution rates in the washing water of the machine, this poor dissolution can make it necessary for the consumer to operate consecutive rinses which is time consuming.
Another problem that is faced is based on the fact that the detergent tablets for dish-washing machines contain formulations which are aggressive to the users' skin.
Tablets for machine dishwashing are described in EP-A-224,128, EP-A-224,135 EP-A-224,136, WO-91/15568, and EP-A-26,470. All the prior art primarily deals with traditional high pH formulations and suggests routes to improving the performance of tablets which basically rely on modifying the solubility profiles of the tablets.
Powder flowability is an important factor to consider in the manufacture of a tablet. Powders with a low flowability (less than 50 ml/s) can have two negative aspects namely: they can compact at the press feed line reducing throughput and they do not flow at a rate which is compatible with the pressing cycle and thus do not completely fill the tablet forming mold.
Another important factor to consider in the manufacture of a tablet is the powder's adherence to a punch's surface If the surface of the punch retains any residual material, it can mark the next tablets to be produced, thus spoiling the smooth finish of the tablet.
Manufacture of tablets can also be difficult due to difficulty in ejecting the tablet from a mold. This difficulty means that the mechanical wear on the tabletting machine is increased and may flaws can occur on the tablet's surface
To achieve tablets that are easy to process and quick to dissolve detergent tablets may contain binding and disintegrating agents.. An important property of these such agents is that they are compatible with the active ingredients in the tablet. Frequently an agent can have a dual role e.g., a binding agent also acts as a disintegrating agent.
Effervescent systems have been included in a tablets formulation to increase their dissolution rate. Such effervescent systems includes weak acids or acid salts such as citric acid, maleic acid, sodium and hydrogen phosphates, in combination with a basic ingredient that liberates carbon dioxide when interacting with this source of acid. Examples include sodium and potassium carbonate and bicarbonate and sodium sesquicarbonate.
Description of the Invention
The present invention relates to a tablet that dissolves rapidly when added to water and is easy to manufacture accordingly the present invention relates to a machine dish washing tablet comprising a bleaching system, a silicone and less than 10 wt% of surfactant.
The invention also relates to a process for preparing machine dish washing tablets comprising the step of adding a silicone emulsion to a formulation that is to be tableted.
The invention also relates to a dish washing tablet(1) and a packaging system (2) the packaging system comprising a body (3) shaped to receive a tablet and a cover(4) which keeps the tablet in the body. The use of this packaging system to store dish washing tablet is also described.
Detailed description of the Invention
The tablets according to the present invention not only dissolve quickly in the dish washing machine but they are easy to process in that the powder used to manufacture the tablets has good flowability, does not adhere to the punch's surface and the tablets produced are easily ejected from the mold.
Additionally the tablets of the invention can be prepared by conventional presses instead of powerful presses which are commonly used to for making detergent tablets.
Conventional presses are those with engines with up to 5hp, a sole compression stage with a working capacity of up to 12t/cm2 and production rate of 18000 tablets per hour. The cost of these presses is up to 8 times smaller than the double-stage large presses with a high pressing rate normally used to prepare detergent tablets.
Silicones
The tablets of the invention comprise a silicone, preferably in the form of an emulsion.
The addition of water to the tablet via the emulsion is beneficial because it can prevent the powder from granulating. The granulation of the powder to from granules greater than 10mm is undesirable because it causes difficulties when press feeding press feeding.
The silicones used are preferably polymers or copolymers of dimethyl silicone or aminomethoxy functionalised dimethyl silicone. Mixtures of the polymers may also be used.
It is preferable if the level of silicone emulsion added to the product is from 0.5 wt% to 10 wt% of the total product, preferably from 1 to 3 wt%.
It is also preferable if the level of silicone within the silicone emulsion is from 2 wt% to 50 wt% of the total weight of the silicone emulsion, preferably from 5 to 15 wt%.
To emulsify the silicone in water any emulsifier may be used, preferably the emulsifier is a surfactant, most preferred as the emulsifier a nonionic surfactant.
The silicone emulsions preferentially used in the present invention are those available from Dow Corning under the trademarks Dow Corning 36, 346, and 347; Dow Corning HV-490, Dow Corning 190 and 93; Dow Corning 531 and 536; Dow Corning 8075, 7242, Dow Corning 2-8707 and OSI-SAG 470,
Bleaching Systems
The bleaching systems of the invention are preferably oxygen based.
Peroxy Bleaching Agents
The oxygen bleaching agents of the compositions include organic peroxy acids and diacylperoxides. Typical monoperoxy acids useful herein include alkyl peroxy acids and aryl peroxy acids such as:
  • I) peroxybenzoic acid and ring-substituted peroxybenzoic acids, e.g., peroxy-alpha-naphthoic acid, and magnesium monoperoxyphthalate
  • ii) aliphatic and substituted aliphatic monoperoxy acids, e.g., peroxylauric acid, peroxystearic acid, epsilon-phthalimido-peroxyhexanoic acid and o-carboxybenzamido peroxyhexanoic acid, N-nonylamidoperadipic acid and N-nonylamidopersuccinic acid.
  • iii) Cationic peroxyacids such as those described in US-A-5,422,028, US-A-5,294,362; and US-A-5,292,447.
  • iv) Sulfonyl peroxyacids such as compounds described in US-A-5,039,447 (Monsanto Co.).
    • Typical diperoxy acids useful herein include alkyl diperoxy acids and aryl diperoxy acids, such as:
  • v) 1,12-diperoxydodecanedioic acid
  • vi) 1,9-diperoxyazelaic acid
  • vii) diperoxybrassylic acid; diperoxysecacic acid and diperoxy-isophthalic acid
  • viii)2-decyldiperoxybutan-1,4-dioic acid
  • ix) N,N1-terephthaloyl-di(6-aminopercaproic acid).
    • A typical diacylperoxide useful herein includes dibenzoylperoxide.
    Inorganic peroxygen compounds are especially suitable for the present invention. Examples of these materials useful in the invention are salts of monopersulfate, perborate monohydrate, perborate tetrahydrate, and percarbonate. sodium perborate and sodium percarbonate are particularly preferred.
    The organic peroxy acid is present in the composition in an amount such that the level of organic peroxy acid in the wash solution is 1 ppm to 300 ppm AvOx, preferably 2 ppm to 200 ppm AvOx. Typical levels of organic peroxy acid are from 2 wt% to 15 wt% of the total formulation.
    The oxygen bleaching agent may be incorporated directly into the formulation or may be encapsulated by any number of encapsulation techniques.
    Bleach Precursors
    Suitable peracid precursors for peroxy bleach compounds have been amply described in the literature, including GB Nos. 836,988; 855,735; 907,356; 907;358; 907,950; 1,003,310 and 1,246,339; US-A-3,332,882 and US-A-4,128,494.
    Typical examples of precursors are polyacylated alkylene diamines, such as N,N,N',N'-tetraacetylethylene diamine (TAED) and N,N,N',N'-tetraacetylmethylene diamine (TAMD); acylated glycolurils, such as tetraacetylglycoluril (TAGU); triacetylcyanurate, sodium sulfophenyl ethyl carbonic acid ester, sodium acetyloxybenene sulfonate (SABS), sodium nonanoyloxy benzene sulfonate (SNOBS) and choline sulfophenyl carbonate. Peroxybenzoic acid precursors are known in the art, e.g., as described in GB-A-836,988. Examples of suitable precursors are phenylbenzoate; phenyl p-nitrobenzoate; o-nitrophenyl benzoate; o-carboxyphenyl benzoate; p-bromophenylbenzoate; sodium or potassium benzoyloxy benzene-sulfonate; and benzoic anhydride.
    Preferred peroxygen bleach precursors are sodium p-benzoyloxybenzene sulfonate, N,N,N',N'-tetraacetylethylene diamine, sodium nonanoyloxybenzene sulfonate and choline sulfophenyl carbonate. The peroxygen bleach precursors may be present in the composition in an amount from 1 to 20 wt. %, preferably from 1 to 15 wt. %, most preferably from 2 to 10 weight %. To deliver a functional peroxygen bleach from a precursor, a source of hydrogen peroxide is required. The hydrogen peroxide source is preferably a compound that delivers hydrogen peroxide on dissolution. Preferred sources of hydrogen peroxide are sodium perborate, either as mono- or tetrahydrate and sodium percarbonate. The source of hydrogen peroxide, when included in the composition, is present at a level from 1% to 30% by weight, preferably from 2% to 25% by weight, most preferably from 4% to 20% by weight.
    Bleach Catalyst
    An effective amount of a bleach catalyst can also be present in the first layer. A number of organic catalysts are available such as the sulfonimines as described in US-A-5,041,232; US-A-5,047,163 and US-A-5,463,115.
    Transition metal bleach catalysts are also useful especially those based on manganese, iron, cobalt, titanium, molybdenum, nickel, chromium, copper, ruthenium, tungsten and mixtures thereof. These include simple water-soluble salts such as those of iron, manganese and cobalt as well as catalysts containing complex ligands.
    Suitable examples of manganese catalysts containing organic ligands are described in US-A-4,728,455, US-A-5,114,606, US-A-5,153,161, US-A-5,194,416, US-A-5,227,084, US-A-5,244,594, US-A-5,246,612, US-A-5,246,621, US-A-5,256,779, US-A-5,274,147, US-A-5,280,117 and EP-A-544,440, EP-A-544,490, EP-A-549,271 and EP-A-549,272. Preferred examples of these catalysts include MnIV 2(u-O)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, MnIII 2(u-O)1(u-OAC)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2(CIO4)2, MnIV 4(u-O)6(1,4,7-triazacyclononane)4 (CIO4)4, MnIIIMnIV 4(u-O)1(u-OAC)2(1,4,7-trimethyl-1,4,7triazacyclononane)2(ClO4)3, MnIV(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH3)3(PF6), and mixtures thereof. Other metal-based bleach catalysts include those disclosed in US-A-4,430,243 and US-A-5,l14,611.
    Iron and manganese salts of aminocarboxylic acids in general are useful herein including iron and manganese aminocarboxylate salts disclosed for bleaching in the photographic color processing arts. A particularly useful transition metal salt is derived from ethylenediaminedisuccinate and any complex of this ligand with iron or manganese.
    Another type of bleach catalyst, as disclosed in US-A-5,114,606 is a water soluble complex of manganese (II), (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, mesoerythritol, meso-inositol, lactose and mixtures thereof. Especially preferred is sorbitol.
    US-A-5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including manganese, cobalt, iron or copper with an non-(macro)-cyclic ligand. Other examples include Mn gluconate, Mn(CF3SO3)2, and binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including [bipy2MnIII(u-O)2MnIVbipy2]-(CIO4)3.
    Other bleach catalysts are described, for example, in EP-A-408,131 (cobalt complexes), EP-A-384,503 and EP-A-306,089 (metallo-porphyrins), US-A-4,728,455 (manganese/multidenate ligand), US-A-4,711,748 (absorbed manganese on aluminosilicate), US-A-4,601,845 (aluminosilicate support with manganese, zinc or magnesium salt), US-A-4,626,373 (manganese/ligand), US-A-4,119,557 (ferric complex), US-A-4,430,243 (Chelants with manganese cations and non-catalytic metal cations), and US-A-4,728,455 (manganese gluconates).
    Useful catalysts based on cobalt are described in WO96/23859, WO96/23860 and WO96/23861 and US-A-5,559,261. WO 96/23860 describe cobalt catalysts of the type [ConLmXp]ZYz, where L is an organic ligand molecule containing more than one heteroatom selected from N, P, O and S; X is a co-ordinating species; n is preferably 1 or 2; m is preferably 1 to 5; p is preferably 0 to 4 and Y is a counterion. One example of such a catalyst is N,N'-Bis(salicylidene)ethylenediaminecobalt (II). Other cobalt catalysts described in these applications are based on Co(III) complexes with ammonia and mon-, bi-, tri- and tetradentate ligands such as [Co(NH3)5OAc]2+ with Cl-, OAc-, PF6 -, SO4 =, BF4 - anions.
    Certain transition-metal containing bleach catalysts can be prepared in the situ by the reaction of a transition-metal salt with suitable chelating agent, for example, a mixture of manganese sulfate and ethylenediaminedisuccinate. Highly colored transition metal-containing bleach catalysts may be co-processed with zeolites to reduce the color impact.
    When present, the bleach catalyst is typically incorporated at a level of 0.0001 to 10% by wt., preferably 0.001 to 5% by weight.
    Detergent Builder Material
    The compositions of this invention can contain all manner of detergent builders commonly taught for use in machine dishwashing or other cleaning compositions. The builders can include any of the conventional inorganic and organic water-soluble builder salts, or mixtures thereof and comprise 5 to 90% by weight, preferably from 10 to 80% by weight of the cleaning composition.
    Typical examples of phosphorus-containing inorganic builders, when present, include the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates and polyphosphates. Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, pyrophosphates and hexametaphosphates.
    Suitable examples of non-phosphorus-containing inorganic builders, when present, include water-soluble alkali metal carbonates, bicarbonates, sesquicarbonates, borates, silicates, including layered silicates such as SKS-6 ex. Hoechst, metasilicates, and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates including layered silicates and zeolites.
    Organic detergent builders can also be used in the present invention. Examples of organic builders include alkali metal citrates, succinates, malonates, fatty acid sulfonates, fatty acid carboxylates, nitrilotriacetates, phytates, phosphonates, alkanehydroxyphosphonates, oxydisuccinates, alkyl and alkenyl disuccinates, oxydiacetates, carboxymethyloxy succinates, ethylenediamine tetraacetates, tartrate monosuccinates, tartrate disuccinates, tartrate monoacetates, tartrate diacetates, oxidized starches, oxidized heteropolymeric polysaccharides, polyhydroxysulfonates, polycarboxylates such as polyacrylates, polymaleates, polyacetates, polyhydroxyacrylates, polyacrylate/polymaleate and polyacrylate/ polymethacrylate copolymers, acrylate/maleate/vinyl alcohol terpolymers, aminopolycarboxylates and polyacetal carboxylates, and polyaspartates and mixtures thereof. Such carboxylates are described in US-A-4,144,226, US-A-4,146,495 and US-A-4,686,062.
    Alkali metal citrates, nitrilotriacetates, oxydisuccinates, polyphosphonates, acrylate/maleate copolymers and acrylate/maleate/vinyl alcohol terpolymers are especially preferred organic builders.
    Buffering System
    The buffering system may be present in order to deliver a pH of about 6 to about 11 in the wash water. Materials which may be selected for the buffering system include water-soluble alkali metal carbonates, bicarbonates, sesquicarbonates, borates, silicates, layered silicates such as SKS-6 ex Hoechst, metasilicates, phytic acid, citric acid, borate and crystalline and amorphous aluminosilicates and mixtures thereof. Preferred examples include sodium and potassium carbonate, sodium and potassium bicarbonates, borates and silicates, including layered silicates
    Surfactants
    Optionally a surfactant may be included in the tablet including anionic, nonionic, cationic, amphoteric, zwitteronic surfactants and mixtures of these surface active agents. However the total level of surfactant in the tablet must not exceed 10% by weight of the total weigh of the tablet. Such surfactants are well known in the detergent arts and are described at length at "Surface Active Agents and Detergents", Vol. 2 by Schwartz, Perry and Birch, Interscience Publishers, Inc., 1959, herein incorporated by reference.
    Preferred surfactants are one or a mixture of:
    Anionic surfactants
    Anionic synthetic detergents can be broadly described as surface active compounds with one or more negatively charged functional groups. An important class of anionic compounds are the water-soluble salts, particularly the alkali metal salts, of organic sulfur reaction products having in their molecular structure an alkyl radical containing from about 6 to 24 carbon atoms and a radical selected from the group consisting of sulfonic and sulfuric acid ester radicals.
    Primary Alkyl Sulfates R 1 OSO 3 M where R1 is a primary alkyl group of 8 to 18 carbon atoms and M is a solubilizing cation. The alkyl group R1 may have a mixture of chain lengths. It is preferred that at least two thirds of the R1 alkyl groups have a chain length of 8 to 14 carbon atoms. This will be the case if R1 is coconut alkyl, for example. The solubilizing cation may be a range of cations which are in general monovalent and confer water solubility. Alkali metal, notably sodium, is especially envisaged. Other possibilities are ammonium and substituted ammonium ions, such as trialkanolammonium or trialkylammonium.
    Alkyl Ether Sulfates R1O(CH2CH2O)nSO3M
  • where R1 is a primary alkyl group of 8 to 18 carbon atoms, n has an average value in the range from 1 to 6 and M is a solubilizing cation. The alkyl group R1 may have a mixture of chain lengths. It is preferred that at least two thirds of the R1 alkyl groups
  • have a chain length of 8 to 14 carbon atoms. This will be the case if R1 is coconut alkyl, for example. Preferably n has an average value of 2 to 5.
    • Fatty Acid Ester Sulfonates R2CH (SO3M) CO2R3 where R2 is an alkyl group of 6 to 16 atoms, R3 is an alkyl group of 1 to 4 carbon atoms and M is a solubilizing cation. The group R2 may have a mixture of chain lengths. Preferably at least two thirds of these groups have 6 to 12 carbon atoms. This will be the case when the moiety R2CH(-)CO2(-) is derived from a coconut source, for instance. It is preferred that R3 is a straight chain alkyl, notably methyl or ethyl.
    Alkyl Benzene Sulfonates R4ArSO3M where R4 is an alkyl group of 8 to 18 carbon atoms, Ar is a benzene ring (C6H4) and M is a solubilizing cation. The group R4 may be a mixture of chain lengths. Straight chains of 11 to 14 carbon atoms are preferred.
    Paraffin sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms, in the alkyl moiety. These surfactants are commercially available as Hostapur SAS from Hoechst Celanese.
    Olefin sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms. U.S. Patent No. 3,332,880 contains a description of suitable olefin sulfonates.
    Organic phosphate based anionic surfactants include organic phosphate esters such as complex mono- or diester phosphates of hydroxyl- terminated alkoxide condensates, or salts thereof. Included in the organic phosphate esters are phosphate ester derivatives of polyoxyalkylated alkylaryl phosphate esters, of ethoxylated linear alcohols and ethoxylates of phenol. Also included are nonionic alkoxylates having a sodium alkylenecarboxylate moiety linked to a terminal hydroxyl group of the nonionic through an ether bond. Counterions to the salts of all the foregoing may be those of alkali metal, alkaline earth metal, ammonium, alkanolammonium and alkylammonium types.
    Particularly preferred anionic surfactants are the fatty acid ester sulfonates with formula: R2CH(SO3M)CO2R3 where the moiety R2CH(-)CO2(-) is derived from a coconut source and R3 is either methyl or ethyl; primary alkyl sulfates with the formula: R1OSO3M wherein R1 is a primary alkyl group of 10 to 18 carbon atoms and M is a sodium cation; and paraffin sulfonates, preferably with 12 to 16 carbon atoms to the alkyl moiety.
    Nonionic surfactants
    Nonionic surfactants can be broadly defined as surface active compounds with one or more uncharged hydrophilic substituents. A major class of nonionic surfactants are those compounds produced by the condensation of alkylene oxide groups with an organic hydrophobic material which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements. Illustrative, but not limiting examples, of various suitable nonionic surfactant types are:
    polyoxyalkene condensates of aliphatic carboxylic acids, whether linear- or branched-chain and unsaturated or saturated, especially ethoxylated and/or propoxylated aliphatic acids containing from about 8 to about 18 carbon atoms in the aliphatic chain and incorporating from about 2 to about 50 ethylene oxide and/or propylene oxide units. Suitable carboxylic acids include "coconut" fatty acids (derived from coconut oil) which contain an average of about 12 carbon atoms, "tallow" fatty acids (derived from tallow-class fats) which contain an average of about 18 carbon atoms, palmitic acid, myristic acid, stearic acid and lauric acid,
    polyoxyalkene condensates of aliphatic alcohols, whether linear- or branched-chain and unsaturated or saturated, especially ethoxylated and/or propoxylated aliphatic alcohols containing from about 6 to about 24 carbon atoms and incorporating from about 2 to about 50 ethylene oxide and/or propylene oxide units. Suitable alcohols include "coconut" fatty alcohol, "tallow" fatty alcohol, lauryl alcohol, myristyl alcohol and oleyl alcohol.
    Ethoxylated fatty alcohols may be used alone or in admixture with anionic surfactants, especially the preferred surfactants above. The average chain lengths of the alkyl group R5 in the general formula: R5O(CH2CH2O)nH is from 6 to 20 carbon atoms. Notably the group R5 may have chain lengths in a range from 9 to 18 carbon atoms.
    The average value of n should be at least 2. The numbers of ethylene oxide residues may be a statistical distribution around the average value. However, as is known, the distribution can be affected by the manufacturing process or altered by fractionation after ethoxylation. Particularly preferred ethoxylated fatty alcohols have a group R5 which has 9 to 18 carbon atoms while n is from 2 to 8.
    Also included within this category are nonionic surfactants having a formula:
    Figure 00180001
    wherein R6 is a linear alkyl hydrocarbon radical having an average of 6 to 18 carbon atoms, R7 and R8 are each linear alkyl hydrocarbons of about 1 to about 4 carbon atoms, x is an integer of from 1 to 6, y is an integer of from 4 to 20 and z is an integer from 4 to 25.
    One preferred nonionic surfactant of the above formula is Poly-Tergent SLF-187 a registered trademark of the Olin Corporation, New Haven, Conn. having a composition of the above formula where R6 is a C6-C10 linear alkyl mixture, R7 and R8 are methyl, x averages 3, y averages 12 and z averages 16. Another preferred nonionic surfactant is
    Figure 00180002
    wherein R9 is a linear, aliphatic hydrocarbon radical having from about 4 to about 18 carbon atoms including mixtures thereof; and R10 is a linear, aliphatic hydrocarbon radical having from about 2 to about 26 carbon atoms including mixtures thereof; j is an integer having a value of from 1 to about 3; k is an integer having a value from 5 to about 30; and z is an integer having a value of from 1 to about 3. Most preferred are compositons in which j is 1, k is from about 10 to about 20 and l is 1. These surfactants are described in WO 94/22800. Other preferred nonionic surfactants are linear fatty alcohol alkoxylates with a capped terminal group, as described in U.S. 4,340,766 to BASF. Particularly preferred is Plurafac LF403 ex. BASF.
    Another nonionic surfactant included within this category are compounds of formula: R11-(CH2CH2O)qH wherein R11 is a C6-C24 linear or branched alkyl hydrocarbon radical and q is a number from 2 to 50; more preferably R11 is a C8-C18 linear alkyl mixture and q is a number from 2 to 15.
    polyoxyethylene or polyoxypropylene condensates of alkyl phenols, whether linear- or branched-chain and unsaturated or saturated, containing from about 6 to 12 carbon atoms and incorporating from about 2 to about 25 moles of ethylene oxide and/or propylene oxide.
    polyoxyethylene derivatives of sorbitan mono-, di-, and tri-fatty acid esters wherein the fatty acid component has between 12 and 24 carbon atoms. The preferred polyoxyethylene derivatives are of sorbitan monolaurate, sorbitan trilaurate, sorbitan monopalmitate, sorbitan tripalmitate, sorbitan monostearate, sorbitan monoisostearate, sorbitan tripalmitate, sorbital tristearate, sorbitan monooleate, and sorbitan trioleate. The polyoxyethylene chains may contain between about 4 and 30 ethylene oxide units, preferably about 10 to 20. The sorbitan ester derivatives contain 1, 2 or 3 polyoxyethylene chains dependent upon whether they are mono-, di- or tri-acid esters.
    polyoxyethylene-polyoxypropylene block copolymers having formula: HO(CH2CH2O)a(CH(CH3) CH2O)b(CH2CH2O)cH    or HO(CH(CH3)CH2O)d(CH2CH2O)e(CH(CH3)CH2O)fH wherein a, b, c, d, e and f are integers from 1 to 350 reflecting the respective polyethylene oxide and polypropylene oxide blocks of said polymer. The polyoxyethylene component of the block polymer constitutes at least about 10% of the block polymer. The material preferably has a molecular weight of between about 1,000 and 15,000, more preferably from about 1,500 to about 6,000. These materials are well-known in the art. They are available under the trademark "Pluronic" and "Pluronic R", a product of BASF Corporation.
    Amine oxides having formula: R12R13R14N=O wherein R12, R13 and R14 are saturated aliphatic radicals or substituted saturated aliphatic radicals. Preferable amine oxides are those wherein R12 is an alkyl chain of about 10 to about 20 carbon atoms and R13 and R14 are methyl or ethyl groups or both R12 and R13 are alkyl chains of about 6 to about 14 carbon atoms and R14 is a methyl or ethyl group.
    Amphoteric synthetic detergents can be broadly described as derivatives of aliphatic tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contain from about 8 to about 18 carbons and one contains an anionic water-solubilizing group, i.e., carboxy, sulpho, sulphato, phosphato or phosphono. Examples of compounds falling within this definition are sodium 3-dodecylamino propionate and sodium 2-dodecylamino propane sulfonate.
    Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium and sulphonium compounds in which the aliphatic radical may be straight chained or branched, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water-solubilizing group, e.g., carboxy, sulpho, sulphato, phosphato or phosphono. These compounds are frequently referred to as betaines. Besides alkyl betaines, alkyl amino and alkyl amido betaines are encompassed within this invention.
    Alkyl Glycosides R15O(R16O)n(Z1)p wherein R15 is a monovalent organic radical (e.g., a monovalent saturated aliphatic, unsaturated aliphatic or aromatic radical such as alkyl, hydroxyalkyl, alkenyl, hydroxyalkenyl, aryl, alkylaryl, hydroxyalkylaryl, arylalkyl, alkenylaryl, arylalkenyl, etc.) containing from about 6 to about 30 (preferably from about 8 to 18 and more preferably from about 9 to about 13) carbon atoms; R16 is a divalent hydrocarbon radical containing from 2 to about 4 carbon atoms such as ethylene, propylene or butylene (most preferably the unit (R16O)n represents repeating units of ethylene oxide, propylene oxide and/or random or block combinations thereof); n is a number having an average value of from 0 to about 12; Z1 represents a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms (most preferably a glucose unit); and p is a number having an average value of from 0.5 to about 10 preferably from about 0.5 to about 5.
    Examples of commercially available materials from Henkel Kommanditgesellschaft Aktien of Dusseldorf, Germany include APG7 300, 325 and 350 with R15 being C9-C11, n is 0 and p is 1.3, 1.6 and 1.8-2.2 respectively; APG7 500 and 550 with R15 is C12-C13, n is 0 and p is 1.3 and 1.8-2.2, respectively; and APG7 600 with R15 being C12-C14, n is 0 and p is 1.3.
    While esters of glucose are contemplated especially, it is envisaged that corresponding materials based on other reducing sugars, such as galactose and mannose are also suitable.
    Particularly preferred nonionic surfactants are polyoxyethylene and polyoxypropylene condensates of linear aliphatic alcohols.
    The preferred range of surfactant is from 0.5 to 30 % by wt., more preferably from 0.5 to 15% by wt of the composition.
    Sequestrants
    The compositions herein may also optionally contain one or more transition metal chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
    Amino carboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraamine-hexaacetates, diethylenetriaminepentaacetates, ethylenediamine disuccinate, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
    Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates), nitrilotris (methylenephosphonates) and diethylenetriaminepentakis (methylenephosphonates). Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See US-A-3,812,044. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
    If utilized, these chelating agents will generally comprise from 0.1% to 10% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from 0.1% to 5.0% by weight of such composition.
    Enzymes
    Enzymes capable of facilitating the removal of soils from a substrate may also be present in an amount of up to 10% by wt., preferably 1 to 5 wt. %. Such enzymes include proteases (e.g., Alcalase7, Savinase7 and Esperase7 from Novo Industries A/S and Purafect OxP7, ex. Genencor), amylases (e.g., Termamyl7 and Duramyl7 from Novo Industries and Purafect OxAm7, ex. Genencor).
    Process Aids
    Suitable binding and disintegrating agents for use in tablets are described in the literature (see, for example, "Pharmaceutical Dosage Forms : Volume 1", 1989, Marcel Dekker Inc., ISBN 0-8246-804402). Both natural and synthetic polymeric materials are suitable. These include starch such as corn, rice and potato starch and starch derivatives such as U-Sperse M™ and U-Sperse™ provided by National Starch Primojel™, carboxymethyl starch and sodium glycolate such as Explotab™, pre-gelatinized corn starches such as National™ 1551 and Starch ™ 1500; cellulose and cellulose derivatives including carboxymethyl cellulose such as Courlose™ and Nymcel™, reticulated sodium carboxymethyl cellulose, such as Ac-Di-Sol™ provided by FMC Corporation, microcystalline cellulose fibres such as Hanfloc™, microcrystalline cellulose such as Lattice™ NT provided by FMC Corporation and Avicel™ PH provided by FMC Corporation, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose and hydroxyprorylmethyl cellulose. Other useful polymers as binding/disintegrating agents are polyvinylpolypyrrolidone products such as Plasdone™, PVP™ K-30 and PVP™ K-60 all provided by International Specialty Products; polyvinylpolypyrrolidine products, a crosslinked product of N-vinyl-2-pyrrolidone such as Polyplasdone™ XL provided by International Specialty Products; polymethacrylates, polyvinyl alcohol and polyethylene glycols. Gums such as acacia, tragacanth, guar, locust bean gum and pectin, gelatin, sucrose and alginates are also suitable as binding/disintegrating agents. Suitable inorganic materials include magnesium-aluminium silicate such as Veegum™ HV provided by R.T. Vanderbilt Co.Inc., bentonite and montmorillonite such as Gelwhite™ provided by Southern Clay Products. Other suitable binding agents include monoglycerids such as Imwitor™ 191 provided by Huls America Inc., glyceril sterates such as Imwitor™ 900 provided by Huls America Inc., and palmoil glycerides such as Imwitor™ 940 provided by Huls America Inc.. The most preferred binding/disintegrating agents are microcrystalline cellulose and polyethylene glycols. The most preferred polyethylene glycols have a molecular weight of about 2000 to about 15000.
    Other tablet additives commonly used are lubricant agents for aiding the tablet's processing, such as stearates, waxes, hydrogenated vegetable oils and polyethylene glycols and charges such as sugars, sodium sulphate and sodium chloride.
    Tablet Form
    The tablet may be in the form of a layered product. The level of components may vary in each layer. In some instances it may be desirable to have no or low levels of bleaching ingredient with bleach sensitive ingredients such as perfume in one layer and the bleaching ingredient in a separate layer.
    it is highly preferable if the tablets of the invention completely dissolve in 6 litres of water(4oFH) at 65°C within 14 minutes.
    Particle Size
    In the present invention, the total solid material within the tablet is preferably in the range from 0.005 to 1.0mm. in order to maximize the dissolution rate and increase the tablet's resistance.
    Mixture and Addition Process
    The addition order of the components of within the formulation can alter the appearance of the tablet.
    It is preferable if water and any other liquid is added before the addition of any tripolyphosphate.
    In the context of the present invention a tablet can be defined as any particulate material compacted to form a solid material, the tablet comprising at least one thousand particulates. Preferably the tablet has a diameter of 0.5 cm.
    In a typical tablet formulation the addition of components are preferably as follows:
  • 1st - filler
  • 2nd - surfactant
  • 3rd - silicone emulsion
  • 4th - perfume
  • 5th - buffering system
  • 6th - bleaching system
  • 7th - builder
    • Particularly preferred are formulations prepared by the addition of components in the following order:
  • 1st - sodium carbonate
  • 2nd - non-ionic surfactant
  • 3rd - silicone emulsion
  • 4th - perfume
  • 5th - sodium disilicate
  • 6th - tetraacetylene diamine (TAED)
  • 7th - sodium perborate
  • 8th - sodium tripolyphosphate
  • 9th - enzymes
    • Tablet's Packaging
    The packaging system of the present invention comprises a body (3) shaped to receive a tablet and a cover(4) which keeps the tablet in the body. Preferably the cover covering the tablet is metallic.
    It is particularly advantageous if the packaging system avoids the physical contact of a user with the detergent tablet when placing the tablet in the dish washing machine.
    Another important aspect of the present invention is the combined use of the detergent material of the present invention with a packaging of the type here illustrated in figure 1 and 2, as examples.
    the invention will now be illustrated by means of the following non limiting Examples.
    Example:
    A detergent tablet according to the present invention (Example 1) was prepared as follows.
    In a mixer sodium carbonate was added. Under agitation non-ionic surfactant, silicone emulsion and perfume were added followed by the remaining powders in the sequence sodium disilicate, tetraacetylene diamine, sodium perborate, sodium tripolyphosphate and finally enzymes. The resulting mixture was left under agitation until homogeneous then transferred to a press and compacted.
    Example 1
    formulation w/w(%)
    Sodium tripolyphosphate 22.63
    Sodium disilicate 28.00
    Sodium carbonate 24.50
    Alcohol ethoxypropoxylate 1.00
    Sodium perborate 6.00
    Tetracetylene diamine 2.00
    Enzyme protease 2.50
    Enzyme amylase 2.50
    Silicon emulsion 2.00
    perfume/moisture/impurity to 100
    A dissolution test was performed in actual use conditions by placing a tablet in a plastic basket within a dish-washing machine Enxuta brand - Futura model, acquired in 1996. The selected cycle was set to a complete wash and the time taken for the tablet to completely dissolve was measured.
    The obtained values are average values of 3 washes for each product.
    The table given below demonstrates the tablet according to the invention dissolves completely within 14 minutes, while the comparative examples take longer than 14 minutes to completely dissolve.
    Examples A to E are commercially available tablets.
    Figure 00300001

    Claims (14)

    1. A machine dish washing tablet comprising a bleaching system, a silicone and less than 10 wt% of surfactant.
    2. A machine dish washing tablet according to claim 1 or claim 2 in which the bleaching system comprises sodium perborate or sodium percarbonate.
    3. A machine dish washing tablet according to any preceding claim wherein the silicone is selected from the group consisting of a polymers or copolymers of dimethyl silicone, aminomethoxy functionalised dimethyl silicone and mixtures thereof.
    4. A machine dish washing tablet according to any preceding claim in which the particle size of the total solid material within the tablet is in the range from 0.005 to 1.0mm.
    5. A machine dish washing composition according to any preceding claim in which the silicone is in the form of a silicone emulsion.
    6. A machine dish washing tablet according to claim 5 in which the level of silicone emulsion added to the product is from 0.5 wt% to 10 wt% of the total product.
    7. A machine dish washing tablet according to claims 5 or 6 in which the level of silicone within the silicone emulsion is from 2 wt% to 50 wt% of the total weight of the silicone emulsion.
    8. A machine dish washing tablet according to any one of claims 5 , 6 or 7 in which the silicone is emulsified with a nonionic surfactant.
    9. A process for preparing machine dish washing tablets comprising the step of adding a silicone emulsion to a formulation that is to be tabletted.
    10. A dish washing tablet(1) and a packaging system (2) the packaging system comprising a body (3) shaped to receive a tablet and a cover(4) which keeps the tablet in the body.
    11. A dish washing tablet and a packaging system according to claim 1 in which the cover(3) is metallic.
    12. A dish washing tablet packaging system according to claim 10 or claim 11 in that the packaging system avoids the physical contact of a user with the detergent tablet when using the tablet.
    13. Detergent composition package as illustrated by figures 1 and 2.
    14. Use of a packaging system comprising a body (3) shaped to receive a tablet and a cover(4) which keeps the tablet in the body, to store a machine dish washing tablet.
    EP98307432A 1997-09-23 1998-09-14 Machine dish washing composition Withdrawn EP0903405A3 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    BR9704788-0A BR9704788A (en) 1997-09-23 1997-09-23 Process for increasing the dissolution of detergent tablets for dishwashers, combination of detergent composition with packaging system, and, packaging
    BR9704788 1997-09-23

    Publications (2)

    Publication Number Publication Date
    EP0903405A2 true EP0903405A2 (en) 1999-03-24
    EP0903405A3 EP0903405A3 (en) 1999-08-11

    Family

    ID=4068055

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP98307432A Withdrawn EP0903405A3 (en) 1997-09-23 1998-09-14 Machine dish washing composition

    Country Status (7)

    Country Link
    EP (1) EP0903405A3 (en)
    AR (1) AR017131A1 (en)
    AU (1) AU8522598A (en)
    BR (1) BR9704788A (en)
    CA (1) CA2247017A1 (en)
    NZ (1) NZ331906A (en)
    ZA (1) ZA988506B (en)

    Cited By (28)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    WO1999063045A1 (en) * 1998-06-03 1999-12-09 Henkel Kommanditgesellschaft Auf Aktien Fracture-stable, fast-dissolving detergent shaped bodies
    EP1041138A1 (en) * 1999-04-02 2000-10-04 Unilever Plc Household cleaning compositions
    GB2355245A (en) * 1999-10-12 2001-04-18 Mcbride Robert Ltd Detergent packaging system
    WO2002051704A1 (en) * 2000-12-22 2002-07-04 Henkel Kommanditgesellschaft Auf Aktien Method for producing a packaging filled with tablets and one such packaging
    US6540081B2 (en) 2001-09-06 2003-04-01 Ecolab Inc. Unit dose blister pack product dispenser
    US6610643B1 (en) * 1998-10-05 2003-08-26 Henkel Kommanditgesellschaft Auf Aktien Detergent tablet packaging for dishwashers
    WO2003074647A1 (en) * 2002-03-06 2003-09-12 Reckitt Benckiser N.V. Improvements in or relating to a container
    US6673765B1 (en) 1995-05-15 2004-01-06 Ecolab Inc. Method of making non-caustic solid cleaning compositions
    US6962266B2 (en) 2002-10-04 2005-11-08 Ecolab Inc. Method and apparatus for using a unit dose dispenser
    WO2007007034A1 (en) * 2005-07-08 2007-01-18 Reckitt Benckiser N.V. Cleaning article and cleaning method
    WO2012049053A1 (en) * 2010-10-14 2012-04-19 Unilever Plc Package comprising a laundry composition, dispenser for said package and method for washing using said dispenser and said package
    US8329112B2 (en) 2006-10-30 2012-12-11 Reckitt Benckiser N.V. Multi-dosing detergent delivery device
    US8338357B2 (en) 2006-01-21 2012-12-25 Reckitt Benckiser N.V. Multiple dosing ware washing article
    US8375962B2 (en) 2006-01-21 2013-02-19 Reckitt Benckiser N. V. Dosage element and chamber
    US8815018B2 (en) 2007-05-30 2014-08-26 Reckitt Benckiser N.V. Detergent dosing device
    US9062281B2 (en) 2010-10-14 2015-06-23 Conopco, Inc. Particulate detergent compositions comprising fluorescer
    US9273271B2 (en) 2010-10-14 2016-03-01 Conopco Inc. Laundry detergent particles
    US9284517B2 (en) 2010-10-14 2016-03-15 Conopco Inc. Laundry detergent particle
    US9290723B2 (en) 2010-10-14 2016-03-22 Conopco Inc. Laundry detergent particles
    US9290724B2 (en) 2010-10-14 2016-03-22 Conopco, Inc. Laundry detergent particles
    US9290725B2 (en) 2010-10-14 2016-03-22 Conopco Inc. Laundry detergent particles
    US9365811B2 (en) 2010-10-14 2016-06-14 Conopco Inc. Manufacture of coated particulate detergents
    WO2017009422A1 (en) 2015-07-14 2017-01-19 Henkel Ag & Co. Kgaa Blister packaging and method for removing a product from the blister packaging
    DE102015218216A1 (en) 2015-09-22 2017-03-23 Henkel Ag & Co. Kgaa Blister packaging and method for removing a tablet from the blister pack
    DE102015218217A1 (en) 2015-09-22 2017-03-23 Henkel Ag & Co. Kgaa Blister pack with asymmetric tablet and asymmetric tablet
    DE102015218214A1 (en) 2015-09-22 2017-03-23 Henkel Ag & Co. Kgaa Blister packaging, outer packaging for blister packaging and containers with outer packaging
    DE102016203354A1 (en) 2016-03-01 2017-09-07 Henkel Ag & Co. Kgaa Blister packaging with asymmetrical blister hood
    EP4303290A1 (en) * 2022-07-05 2024-01-10 Capsule Minimal Ltd. Readily dissolvable cartridge complex and industrial systems and processes of fabricating the same

    Family Cites Families (14)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    GB1297087A (en) * 1969-10-15 1972-11-22
    FR2249949A1 (en) * 1973-11-06 1975-05-30 Saporta Francois De Compacting detergent powder into pellets - packaged e.g. in continuous tapes, for accurate dosage in washing machine
    GB1508297A (en) * 1974-06-24 1978-04-19 Sagapha Ag Method of storing stain-removing agents
    US4136045A (en) * 1976-10-12 1979-01-23 The Procter & Gamble Company Detergent compositions containing ethoxylated nonionic surfactants and silicone containing suds suppressing agents
    US4219436A (en) * 1977-06-01 1980-08-26 The Procter & Gamble Company High density, high alkalinity dishwashing detergent tablet
    DE3326459A1 (en) * 1983-07-22 1985-01-31 Etol-Werk GmbH & Co KG Chemische Fabrik, 7603 Oppenau Process for the production of a dishwashing composition and device for the processing of the latter
    US4690305A (en) * 1985-11-06 1987-09-01 Ecolab Inc. Solid block chemical dispenser for cleaning systems
    GB2200365A (en) * 1987-01-26 1988-08-03 Goodjet Ltd Detergent composition
    CA1293708C (en) * 1987-10-02 1991-12-31 Jeffrey B. Anderson Blister package and its manufacture
    DE3911363B4 (en) * 1989-04-07 2005-02-03 Freytag Von Loringhoven, Andreas Process for the preparation of fragrances to be enriched with fragrances or perfume and fragrance adding agents for carrying out the process
    DE4010524A1 (en) * 1990-04-02 1991-10-10 Henkel Kgaa STABLE, BIFUNCTIONAL, PHOSPHATE-FREE DETERGENT TABLETS FOR THE MACHINE DISHWASHER
    GB9425926D0 (en) * 1994-12-22 1995-02-22 Procter & Gamble Silicone compositions
    WO1997000311A1 (en) * 1995-06-16 1997-01-03 The Procter & Gamble Company Bleach compositions comprising cobalt catalysts
    DE19606765A1 (en) * 1996-02-23 1997-08-28 Henkel Kgaa Process for the production of dishwasher tablets

    Cited By (35)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US6673765B1 (en) 1995-05-15 2004-01-06 Ecolab Inc. Method of making non-caustic solid cleaning compositions
    WO1999063045A1 (en) * 1998-06-03 1999-12-09 Henkel Kommanditgesellschaft Auf Aktien Fracture-stable, fast-dissolving detergent shaped bodies
    US6610643B1 (en) * 1998-10-05 2003-08-26 Henkel Kommanditgesellschaft Auf Aktien Detergent tablet packaging for dishwashers
    EP1041138A1 (en) * 1999-04-02 2000-10-04 Unilever Plc Household cleaning compositions
    GB2355245A (en) * 1999-10-12 2001-04-18 Mcbride Robert Ltd Detergent packaging system
    WO2002051704A1 (en) * 2000-12-22 2002-07-04 Henkel Kommanditgesellschaft Auf Aktien Method for producing a packaging filled with tablets and one such packaging
    US6540081B2 (en) 2001-09-06 2003-04-01 Ecolab Inc. Unit dose blister pack product dispenser
    US7407925B2 (en) 2002-03-06 2008-08-05 Reckitt Benckiser N.V. Packaged detergent composition or additive and method for packaging the same
    WO2003074647A1 (en) * 2002-03-06 2003-09-12 Reckitt Benckiser N.V. Improvements in or relating to a container
    US6962266B2 (en) 2002-10-04 2005-11-08 Ecolab Inc. Method and apparatus for using a unit dose dispenser
    GB2428247A (en) * 2005-07-08 2007-01-24 Reckitt Benckiser Nv Reduced mass detergent tablet and packaging
    WO2007007034A1 (en) * 2005-07-08 2007-01-18 Reckitt Benckiser N.V. Cleaning article and cleaning method
    US8338357B2 (en) 2006-01-21 2012-12-25 Reckitt Benckiser N.V. Multiple dosing ware washing article
    US8375962B2 (en) 2006-01-21 2013-02-19 Reckitt Benckiser N. V. Dosage element and chamber
    US8329112B2 (en) 2006-10-30 2012-12-11 Reckitt Benckiser N.V. Multi-dosing detergent delivery device
    US8815018B2 (en) 2007-05-30 2014-08-26 Reckitt Benckiser N.V. Detergent dosing device
    CN103153813A (en) * 2010-10-14 2013-06-12 荷兰联合利华有限公司 Package containing laundry composition, dispenser of said package and method of washing using said dispenser and said package
    US9365811B2 (en) 2010-10-14 2016-06-14 Conopco Inc. Manufacture of coated particulate detergents
    US9062281B2 (en) 2010-10-14 2015-06-23 Conopco, Inc. Particulate detergent compositions comprising fluorescer
    CN103153813B (en) * 2010-10-14 2015-08-19 荷兰联合利华有限公司 Package containing laundry composition, dispenser of said package and method of washing using said dispenser and said package
    US9273271B2 (en) 2010-10-14 2016-03-01 Conopco Inc. Laundry detergent particles
    US9284517B2 (en) 2010-10-14 2016-03-15 Conopco Inc. Laundry detergent particle
    US9290723B2 (en) 2010-10-14 2016-03-22 Conopco Inc. Laundry detergent particles
    US9290724B2 (en) 2010-10-14 2016-03-22 Conopco, Inc. Laundry detergent particles
    US9290725B2 (en) 2010-10-14 2016-03-22 Conopco Inc. Laundry detergent particles
    WO2012049053A1 (en) * 2010-10-14 2012-04-19 Unilever Plc Package comprising a laundry composition, dispenser for said package and method for washing using said dispenser and said package
    WO2017009422A1 (en) 2015-07-14 2017-01-19 Henkel Ag & Co. Kgaa Blister packaging and method for removing a product from the blister packaging
    DE102015213199A1 (en) 2015-07-14 2017-01-19 Henkel Ag & Co. Kgaa Blister packaging and method for removing a product from the blister package
    DE102015218216A1 (en) 2015-09-22 2017-03-23 Henkel Ag & Co. Kgaa Blister packaging and method for removing a tablet from the blister pack
    DE102015218217A1 (en) 2015-09-22 2017-03-23 Henkel Ag & Co. Kgaa Blister pack with asymmetric tablet and asymmetric tablet
    DE102015218214A1 (en) 2015-09-22 2017-03-23 Henkel Ag & Co. Kgaa Blister packaging, outer packaging for blister packaging and containers with outer packaging
    WO2017050538A1 (en) * 2015-09-22 2017-03-30 Henkel Ag & Co. Kgaa Blister packaging with asymmetric tablet and asymmetric tablet
    DE102016203354A1 (en) 2016-03-01 2017-09-07 Henkel Ag & Co. Kgaa Blister packaging with asymmetrical blister hood
    WO2017148698A1 (en) 2016-03-01 2017-09-08 Henkel Ag & Co. Kgaa Blister packaging having an asymmetric blister cap
    EP4303290A1 (en) * 2022-07-05 2024-01-10 Capsule Minimal Ltd. Readily dissolvable cartridge complex and industrial systems and processes of fabricating the same

    Also Published As

    Publication number Publication date
    ZA988506B (en) 2000-03-22
    AU8522598A (en) 1999-04-15
    CA2247017A1 (en) 1999-03-23
    EP0903405A3 (en) 1999-08-11
    AR017131A1 (en) 2001-08-22
    BR9704788A (en) 1999-09-08
    NZ331906A (en) 1999-10-28

    Similar Documents

    Publication Publication Date Title
    EP0903405A2 (en) Machine dish washing composition
    US5783540A (en) Machine dishwashing tablets delivering a rinse aid benefit
    US5900395A (en) Machine dishwashing tablets containing an oxygen bleach system
    EP0893491B1 (en) Automatic dishwashing compositions
    US5837663A (en) Machine dishwashing tablets containing a peracid
    EP0998548B1 (en) Automatic dishwashing compositions containing water soluble cationic or amphoteric polymers
    US20040058846A1 (en) Copolymers that prevent glass from corroding
    US5705465A (en) Anti-foam system for automatic dishwashing compositions
    US5480576A (en) 1,3-N azole containing detergent compositions
    US20100144576A1 (en) Dish detergent
    EP0846757B1 (en) Machine dishwashing gel composition
    JP3171856B2 (en) Bleach additive composition and bleaching composition containing anhydrous glycine activator
    US6345633B1 (en) Automatic dishwashing compositions containing water soluble cationic surfactants
    AU729402B2 (en) An anti-foam system based on hydrocarbon polymers and hydrophobic particulate solids
    AU9258498A (en) Machine dishwashing compositions and rinse aid compositions
    US6334452B1 (en) Automatic dishwashing compositions containing water soluble cationic surfactants
    WO1994019445A1 (en) Machine dishwashing composition
    EP1325105B1 (en) Process for preparing tablets
    WO1996036687A1 (en) Automatic dishwashing compositions containing aluminum salts

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    AK Designated contracting states

    Kind code of ref document: A2

    Designated state(s): DE ES FR GB IT

    AX Request for extension of the european patent

    Free format text: AL;LT;LV;MK;RO;SI

    PUAL Search report despatched

    Free format text: ORIGINAL CODE: 0009013

    AK Designated contracting states

    Kind code of ref document: A3

    Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    AX Request for extension of the european patent

    Free format text: AL;LT;LV;MK;RO;SI

    17P Request for examination filed

    Effective date: 19990906

    RAP1 Party data changed (applicant data changed or rights of an application transferred)

    Owner name: UNILEVER N.V.

    Owner name: UNILEVER PLC

    AKX Designation fees paid

    Free format text: DE ES FR GB IT

    17Q First examination report despatched

    Effective date: 20020712

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

    18D Application deemed to be withdrawn

    Effective date: 20030805