New Zealand No 331906 International No PCT/
TO BE ENTERED AFTER ACCEPTANCE AND PUBLICATION
Priority dates 23 09 1997,
Complete Specification Filed 15 09 1998
Classification (6) C11D3/395, C11D17/00, C11D1/82, B65D1/36, B65D17/00
Publication date 28 October 1999
Journal No 1445
NEW ZEALAND PATENTS ACT 1953
COMPLETE SPECIFICATION
Title of Invention
Machine dish washing composition
Name, address and nationality of apphcant(s) as in international application form
UNILEVER PLC, a British company of Unilever House, Blackfnars, London, EC4P 1BQ, United Kingdom
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The present invention relates to a tablet for use m a dish 5 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 15 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 20 detergent tablets for dish-washing machines contain formulations which are aggressive to the users' skin
Tablets for machine dishwashing are described m EP-A-224,128, EP-A-224,135 EP-A-224,136, WO-91/15568, and 25 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 m the manufacture of a tablet Powders with a low flowability (less than 50 ml/s) can have two negative aspects namely
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Wm.
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 10 the smooth finish of the tablet
Manufacture of tablets can also be difficult due to difficulty m ejecting the tablet from a mold This difficulty means that the mechanical wear on the 15 tablettmg 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 20 disintegrating agents An important property of these such agents is that they are compatible with the active ingredients m 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 m 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, 30 m 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
C3S02
Description of the Invention
The present invention relates to a tablet that dissolves rapidly when added to water and is easy to manufacture 5 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 10 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 15 (3) shaped to receive a tablet and a cover(4) which keeps the tablet m 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 m the dish washing machine but they are easy to process m that the powder used to manufacture the tablets has good flowability, does not adhere to the punch's 25 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 30 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
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@ 10
12t/cnr 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 m 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 ammomethoxy 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 m water any ernulsifier may be used, preferably the ernulsifier is a surfactant, most preferred as the ernulsifier a nonionic surfactant
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_ 5 _
The silicone emulsions preferentially used m the present invention are those available from Dow Corning under the trademarks Dow Corning 36, 346, and 347, Dow Corning HV-490, 5 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 15 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 2 0 acids, e g , peroxy-alpha-naphthoic acid, and magnesium monoperoxyphthalate n) aliphatic and substituted aliphatic monoperoxy acids, e g , peroxylauric acid, peroxystearic acid, 25 epsilon-phthalimido-peroxyhexanoic acid and o-carboxybenzamido peroxyhexanoic acid, N-nonylamidoperadipic acid and N-nonylamido-persuccmic acid
m) 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 m 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 5 vi) 1,9-diperoxyazelaic acid vn) diperoxybrassylic acid, diperoxysecacic acid and diperoxy-isophthalic acid vin)2-decyldiperoxybutan-l,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 15 the present invention Examples of these materials useful m 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 m the composition m an amount such that the level of organic peroxy acid m the wash solution is 1 ppm to 300 ppm AvOx, preferably 2 ppm to 2 00 ppm AvOx Typical levels of organic peroxy acid are 25 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
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BOM &
Bleach Precursors
Suitable peracid precursors :or peroxy bleach compounds have been amply described m the literature, including GB Nos 5 836,988, 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',N1 -tetraacetylethylene diamine 10 (taed) and n,n,n , n'-tetraacatylmethylene diamine (tamd) ,
acylated glycolurils, such as tetraacetylglycoluz"il (TAGU) , triacetylcyanurate, sodium sulfophenyl ethyl carbonic acid ester, sodium acetyloxybenene sulfonate (SABS), sodium nonanoyloxy benzene sulfonate (SNOBS) and choline 15 sulfophenyl carbonate Peroxybenzoic acid precursors are known m the art, eg, as described m GB-A-836,988 Examples of suitable precursors are phenylbenzoate, phenyl p-mtrobenzoate, o-nitropbenyl benzoate, o-carboxyphenyl benzoate, p-bromophenylbenzoate, sodium or potassium 20 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 2 5 sulfophenyl carbonate The peroxygen bleach precursors may be present m the composition m an amount from 1 to 2 0 wt %, preferably from 1 to 15 wt. %, most preferably from 2 to 10 weight % To delivei a functional peroxygen bleach from a precursor, a source of hydrogen peroxide is required The 30 hydrogen peroxide sourcej is preferably a compound that delivers hydrogen peroxLde 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 m the composition, is piesent at a level from 1% to 30% by weight, preferably from 2% to 25% by weight, most preferably from 4% to 2 0% by weight
Bleach Catalyst
An effective amount of a bleach catalyst can also be present m the first layer A number of organic catalysts are 10 available such as the sulfonimmes as described m 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, 15 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 m 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, 25 EP-A-549,271 and EP-A-549,272 Preferred examples of these catalysts include MnIV2 (u-O) 2 (1, 4 , 7-tnmethyl-l, 4, 7-triazacyclononane) 2 (PFfc) 2, Mnm2 (u-O) 1 (u-OAc) 2 (1, 4, 7-trimethyl-1, 4, 7-triazacyclononane) 2 (CI04) 2 MniV4 (u-O) 6 (1, 4, 7-triazacyclononane) 4 (CI04)4, MninMnIV4 (u-O) 1 (u-OAc) 2 (1, 4, 7-30 trimethyl-1, 4, 7triazacyclononane) 2 (CIO4) 3 MnIV(l,4,7-trimethyl-1,4,7-triazacyclononane)-
Lj58U2 #
(OCHi) 3 (PFt) , and mi> tures thereof Other xnetal-based bleach catalysts include those disclosed m US-A-4,430,243 and US-A-5, 114,611
Iron and manganese salts of aminocarboxylic acids m general 5 are useful herein including iron and manganese aminocarboxylate salts disclosed for bleaching m the photographic color processing arts A particularly useful transition metal salt is derived from ethylenediammedisuccmate and any complex of this ligand 10 with iron or manganese
Another type of bleach catalyst, as disclosed m 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 15 polyhydroxy compound having at least three consecutive C-OH groups Preferred ligands include sorbitol, lditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol, meso-mositol, 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(CF3S03)2, and binuclear Mn 25 complexed with tetra-N-dentate and bi-N-dentate ligands, including [bipy2MnIIX (u-O) 2MnIvbipy2] - (CI04) 3
Other bleach catalysts are described, for example, m EP-A-408,131 (cobalt complexes), EP-A-384,503 and EP-A-306,089 30 (metallo-porphyrins), US-A-4,728,455 (manganese/multidenate ligand), US-A-4,711,748 (absorbed manganese on alummosilicate) , US-A-4, 601, 845 (alummosilicate support with manganese, zinc or magnesium salt), US-A-4,626,373
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(manganese/ligand), US-A-4,119,557 (ferric complex), US-A-4,430,243 (Chelants with manganese cations and non-catalytic metal cations), and U°-A-4,720,455 (manganese gluconates)
Useful catalysts based on cobalt are described m
W09 6/23859, W096/23860 and W096/23861 and US-A-5,559,261 WO 96/23860 describe cobalt catalysts of the type [ConLmXp] ZY:, where L is <\r organic ligand molecule containing more than one heteroatom selected from N, P, O and S, X is a 10 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)ethylenediammecobalt (II) Other cobalt catalysts described m these applications are based on 15 Co(III) complexes with ammonia and mon-, bi-, tri- and tetradentate ligands such as [Co (NH3) sOAc]2* with CI", OAc", PF6", SO = BF4" anions
Certain transition-metal containing bleach catalysts can be 20 prepared m the situ by the reaction of a transition-metal salt with suitable chelating agent, for example, a mixture of manganese sulfate and ethylenediaminedisuccmate. 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 alJ niajmoi. of detergent builders commonly taught for use m roachihp dishwashing or other cleaning compositions The bua UK -can include any of the conventional inorganic and orqciuic water-soluble builder salts, or mixtures thereof and comprise 5 to 90% by weight, preferably from 10 to CO* by weight of the cleaning composition
Typical examples of phosphorus-containing inorganic builders, when present, include the water-soluble saJl , especially alkali metal pyrophosphates, orthophosplvjt ' <- .jU'I polyphosphates Specific examples of inorganic phosphate 15 builders include sodium and potassium tripolyphosphal^s, pyrophosphates and hexametaphosphates
Suitable examples of non-phosphorus-containing inorganic builders, when present, include water-soluble alkali meta] 20 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 25 carbonate, sodium and potassium bicarbonates, silicates including layered silicates and zeolites
Organic detergent builders can also be used m the present invention Examples of organic builders include alkali 30 metal citrates, succinates, malonates, fatty acid sulfonates, fatty acid carboxylates, nitrilotriacetates, phytates, phosphonates, alkanehydroxyphosphonates, oxydisuccinates, alkyl and alkenyl disuccinates,
oxydiacetates, carboxymethyloxy succinates, ethylenediamme tetraacetates, tartrate monosuccinates, tartrate disuccmates, tartrate monoacetates, tartrate diacetates, oxidized starches, oxidized heteropolymenc polysaccharides, 5 polyhydroxysulfonates, polycarboxylates such as polyacrylates, polymaleates, polyacetates, polyhydroxyacrylates, polyacrylate/polymaleate and polyacrylate/ polymethacrylate copolymers, acrylate/maleate/vmyl alcohol terpo] /mers, 10 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/vmyl alcohol terpolymers are especially preferred organic builders
Buffering System
The buffering system may be present m order to deliver a pH of about 6 to about 11 m the wash water Materials which may be selected for the buffering system include 25 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 alummosilicates and mixtures thereof Preferred examples include sodium and 30 potassium carbonate, sodium and potassium bicarbonates, borates and silicates, including layered silicates
CIS 02 jSP
Surfactants
Optionally a surfactant may be included in the tablet including anionic, nonionic, cationic, amphoteric, 5 zwitteronic surfactants and mixtures of these surface active agents However the total level of surfactant m the tablet must not exceed 10% by weight of the total weigh of the tablet Such surfactants are well known m the detergent arts and are described at length at "Surface Active Agents 10 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 20 functional groups An important class of anionic compounds are the water-soluble salts, particularly the alkali metal salts, of organic sulfur reaction products having m their molecular structure an alkyl radical containing from about 6 to 24 carbon atoms and a radical selected from the group 25 consisting of sulfonic and sulfuric acid ester radicals
Primary Alkyl Sulfates
R20S03M
where R1 is a primary alkyl group of 8 to 18 carbon atoms and 30 M is a solubilizmg 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
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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 5 envisaged Other possibilities are ammonium and substituted ammonium ions, such as tnalkanolammonium or tnalkylammonium
Alkyl Ether Sulfates where is a primary alkyl group of 8 to 18 carbon atoms, n has an average value m the range from 1 to 6 and M is a solubilizing cation The alkyl group R1 may have a mixture 15 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 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
2 5 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(-)C02(~) is derived from a coconut source, for instance It is preferred that R3 is a straight chain alkyl, notably methyl
3 0 or ethyl
R20(CH;CH;0) nS03M
R2CH(S03M) CO2R3
802
4lJcyI Benzene Sulfonates
R*ArSO,M
where R'1 is an alkyl group of 8 to 18 carbon atoms, Ar is a benzene ring (CbH4) 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, m 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 20 phosphate esters such as complex mono- or diester phosphates of hydroxyl- terminated alkoxide condensates, or salts thereof Included m the organic phosphate esters are phosphate ester derivatives of polyoxyalkylated alkylaryl phosphate esters, of ethoxylated linear alcohols and 25 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 30 metal, ammonium, alkanolammonium and alkylammonium types
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Particularly preferred anionic surfactants are the fatty acid ester sulfonates with formula
R'CH (SOiM) C02Rj
where the moiety R'CH(-) CO; (-) is derived from a coconut source and R3 is either methyl or ethyl, primary alkyl sulfates with the formula
r:oso3m 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 20 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 2 5 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 ahphatjc carboxylic acids, whether linear- or branched-cham 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 5 (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-cham and unsaturated or saturated, especially ethoxylated and/or propoxylated aliphatic alcohols containing from about 6 to about 24 carbon atoms 15 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 m admixture with anionic surfactants, especially the preferred surfactants above The average chain lengths of the alkyl group Rb in the general formula
2 5 R50(CH2CH20) nH
is from 6 to 2 0 carbon atoms Notably the group i?5 may have chain lengths m a range from 9 to 18 carbon atoms
3 0 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 Rs 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
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 01in Corporation, New Haven, Conn having a composition of the above formula where R6 is a C6-Cio linear alkyl mixture, R7 20 and R8 are methyl, x averages 3, y averages 12 and z averages 16 Another preferred nonionic surfactant is
R«®(CH,CH»)J(CH1CH,*)k(CH1CH(®H)Ri»)l
<k wherein R9 is a linear, aliphatic hydrocarbon radical having from about 4 to about 18 carbon atoms including mixtures 25 thereof, and R10 is a linear, aliphatic hydrocarbon radical
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havirg 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 5 Most preferred are compositons m which j is 1, k is from about 10 to about 20 and 1 is 1 These surfactants are described m WO 94/22800 Other preferred nonionic surfactants are linear fatty alcohol alkoxylates with a capped terminal group, as described in U S 4,340,7 66 10 to BASF Particularly preferred is Plurafac LF403 ex BASF
Another nonionic surfactant included within this category are compounds of formula
R11—(CH.CH.O^H
wherein Rn is a C6-C24 linear or branched alkyl hydrocarbon radical and q is a number from 2 to 50, more preferably Ru is a C8-Ci8 linear alkyl mixture and q is a number from 2 to 15
polyoxyethylene or polyoxypropylene condensates of alkyl phenols, whether linear- or branched-cham 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-r 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, 30 sorbitan trilaurate, sorbitan monopalmitate, sorbitan tripalmitate, sorbitan monostearate, sorbitan monoisostearate, sorbitan tripalmitate, sorbital
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tnstearate, 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 (CH2CH20) a (CH (CH3) CH20) b (CH2CH20) CH
or
HO (CH (CH3) CH20)d (CH2CH20) e (CH (CH3) CH20) rH
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 m the art They are available under the trademark "Pluronic" and "Pluronic Ru, a product of BASF Corporation
Amine oxides having formula
R12R13R14N=0
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
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about 10 to about 2 0 carbon atoms and R1J and R14 are methyl or ethyl groups or both R12 and Rn 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, m which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contain from about 10 8 to about 18 carbons and one contains an anionic water-solubilizmg group, i e , carboxy, sulpho, sulphato, phosphato or phosphono Examples of compounds falling within this definition are sodium 3-dodecylamino propionate and sodium 2-dodecylammo propane sulfonate
Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium and sulphomum compounds m which the aliphatic radical may be straight chained or branched, and wherein one of the 20 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 25 amido betaines are encompassed within this invention.
Alkyl Glycosides
R1"0(R:60)n(Z1)p wherein R15 is a monovalent organic radical (eg, a 30 monovalent saturated aliphatic, unsaturated aliphatic or aromatic radical such as alkyl, hydroxyalkyl, alkenyl, hydroxyalkenyl, aryl, alkylaryl, hydroxyalkylaryl,
arylalkyl, alkenylaryl, arylalkenyl, etc ) containing from
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about 6 to about 30 (preferably from about 8 to 18 and more preferably from about 9 to about 13) carbon atoms, R1C is a divalent hydrocarbon radical containing from 2 to about 4 carbon atoms such as ethylene, propylene or butylene (most 5 preferably the unit (RlD0)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, Z2 represents a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms (most 10 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 15 Kommanditgesellschaft Aktien of Dusseldorf, Germany include APG7 300, 325 and 350 with R15 being C9-Cn, n is 0 and p is
1 3, 1 6 and 1 8-2 2 respectively, APG7 500 and 550 with R15 is Ci2-Cn, n is 0 and p is 1 3 and 1 8-2 2, respectively, and APG7 600 with R15 being C^-Cn, 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
Ammo carboxylates useful as optional chelating agents include ethylenediammetetraacetates, N-
hydroxyethylethylenediammetriacetates, nitrilotriacetates, ethylenediamme tetraproprionates, tnethylenetetraamme-hexaacetates, diethylenetriarnmepentaacetates, ethylenediamme disuccinate, and ethanoldiglycmes, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein
Ammo phosphonates are also suitable for use as chelating agents m the compositions of the invention when at least low levels of total phosphorus are permitted m detergent compositions, and include ethylenediammetetrakis (methylenephosphonates), rutrilotris (methylenephosphonates) and diethylenetriammepentakis (methylenephosphonates) Preferably, these ammo phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms Polyfunctionally-substituted aromatic chelating agents are also useful m the compositions herein See US-A-3,812,044. Preferred compounds of this type m acid form are
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dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene
If utilized, these chelating agents will generally comprise 5 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 m an amount of up to 10% by wt , preferably 1 to 5 wt % Such enzymes include 15 proteases (eg , Alcalase7, Savmase7 and Esperase7 from Novo Industries A/S and Purafect OxP7, ex Genencor), amylases (eg , Termamyl7 and Duramyl7 from Novo Industries and Purafect OxAm7, ex Genencor)
Process Aids
Suitable binding and disintegrating agents for use m tablets are described m the literature (see, for example, 25 "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 30 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
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as Courlose™ and Nymcel1", reticulated sodium carboxymethyl cellulose, such as Ac-Di-Sol™ provided by FMC Corporation, microcystalline cellulose fibres such as Hanfloc™ microcrystallme cellulose such as Lattice™ NT provided by 5 FMC Corporation and Avicel™ PH provided by FMC Corporation, methyl cellulose, ethyl cellulose, hydroxypropy1 cellulose and hydroxyprorylmethy1 cellulose Other useful polymers as binding/disintegrating agents are polyvmylpolypyrrolidone products such as Plasdone™, PVP™ K-3 0 and PVP™ K-60 all 10 provided by International Specialty Products,
polyvmylpolypyrrolidme products, a crosslmked product of N-vinyl-2-pyrrolidone such as Polyplasdone™ XL provided by International Specialty Products, polymethacrylates, polyvinyl alcohol and polyethylene glycols Gums such as 15 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 20 montmonllonite such as Gelwhile™ provided by Southern Clay Products Other suitable binding agents include monoglycends 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™ 25 940 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
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and charges such as sugars, sodium sulphate and sodium chloride
Tablet Form
The tablet may be m the form of a layered product The level of components may vary m each layer In some instances it may be desirable to have no or low levels of bleaching ingredient with bleach sensitive ingredients such 10 as perfume in one layer and the bleaching ingredient m a separate layer it is highly preferable if the tablets of the invention completely dissolve m 6 litres of water(4oFH) at 65°C 15 within 14 minutes
Particle Size
In the present invention, the total solid material within 20 the tablet is preferably m the range from 0 005 to 1 0mm m 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
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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 5 0 5 cm
In a typical tablet formulation the addition of components are preferably as follows 1st - filler 10 2nd - surfactant
3rd - silicone emulsion 4th - perfume 5th - buffering system 6th - bleaching system 15 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 25 6th - tetraacetylene diamine (TA.ED)
7th - sodium perborate 8th - sodium tripolyphosphate 9th - enzymes
3 0 Tablet's Packaging
The packaging system of the present invention comprises a body (3) shaped to receive a tablet and a cover(4) which
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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 m 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 nonionic surfactant, silicone emulsion and perfume were added followed by the remaining powders m 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
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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 m actual use conditions by placing a tablet in a plastic basket within a dish-washing machine Enxuta brand - Futura model, acquired in 1996 The 20 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 Droduct
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
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Tablet A
Tablet B
Tablet C
Tablet D
Tablet E
Invention's Tablet
Weight Dissolution
(mm)
(g)
%(m/m)
Weight Dissolution (g) %(m/m)
Weight Dissolution Weight Dissolution Weight Dissolution Weight Dissolution
(g>
(%m/m)
(g)
(%m/in)
(g)
(%in/m)
(%n/in)
0
0
0
0
0
0
18
0
2
23
9
23
23
9
23
23
7
14
4
18
18
22
13
13
29
6
18
27
18
18
27
18
43
7
17
32
16
17
32
16
19
23
9
50
8
16
36
40
16
36
40
18
27
8
57
14
45
13
50
14
45
13
50
17
33
71
12
11
55
60
11
55
60
40
3
86
14
9
64
8
70
9
64
8
70
13
47
0
100
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