[0001] 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
[0002] 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.
[0003] 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.
[0004] 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.
[0005] 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.
[0006] 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.
[0007] 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.
[0008] 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
[0009] 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.
[0010] 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
[0011] 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.
[0012] 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.
[0013] 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
[0014] 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.
[0015] 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.
[0016] 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.
Silicones
[0017] The tablets of the invention comprise a silicone, preferably in the form of an emulsion.
[0018] 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.
[0019] The silicones used are preferably polymers or copolymers of dimethyl silicone or
aminomethoxy functionalised dimethyl silicone. Mixtures of the polymers may also be
used.
[0020] 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%.
[0021] 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%.
[0022] 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.
[0023] 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
[0024] The bleaching systems of the invention are preferably oxygen based.
Peroxy Bleaching Agents
[0025] 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.).
[0026] 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).
[0027] A typical diacylperoxide useful herein includes dibenzoylperoxide.
[0028] 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.
[0029] 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.
[0030] The oxygen bleaching agent may be incorporated directly into the formulation or may
be encapsulated by any number of encapsulation techniques.
Bleach Precursors
[0031] 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.
[0032] 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.
[0033] 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
[0034] 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.
[0035] 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.
[0036] 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
IIIMn
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. 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.
[0037] 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.
[0038] 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(CF
3SO
3)
2, and binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including
[bipy
2Mn
III(u-O)
2Mn
IVbipy
2]-(CIO
4)
3.
[0039] 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).
[0040] 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 [Co
nL
mX
p]
ZY
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. 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(NH
3)
5OAc]
2+ with Cl
-, OAc
-, PF
6 -, SO
4 =, BF
4 - anions.
[0041] 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.
[0042] 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
[0043] 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.
[0044] 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.
[0045] 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.
[0046] 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.
[0047] Alkali metal citrates, nitrilotriacetates, oxydisuccinates, polyphosphonates, acrylate/maleate
copolymers and acrylate/maleate/vinyl alcohol terpolymers are especially preferred
organic builders.
Buffering System
[0048] 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
[0049] 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.
[0050] Preferred surfactants are one or a mixture of:
Anionic surfactants
[0051] 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.
[0052] Primary Alkyl Sulfates
R1OSO3M
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.
[0053] 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.
[0054] 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.
[0055] 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.
[0056] 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.
[0057] 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.
[0058] 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.
[0059] 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
[0060] 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:
[0061] 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,
[0062] 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.
[0063] 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.
[0064] 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.
[0065] Also included within this category are 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.
[0066] 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. Another preferred nonionic
surfactant is

wherein 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.
[0067] Another nonionic surfactant included within this category are compounds of formula:
R11-(CH2CH2O)qH
wherein 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.
[0068] 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.
[0069] 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.
[0070] polyoxyethylene-polyoxypropylene block copolymers having formula:
HO(CH
2CH
2O)
a(CH(CH
3) CH
2O)
b(CH
2CH
2O)
cH
or
HO(CH(CH
3)CH
2O)
d(CH
2CH
2O)
e(CH(CH
3)CH
2O)
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.
[0071] Amine oxides having formula:
R
12R
13R
14N=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.
[0072] 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.
[0073] 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.
[0074] 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; 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
(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.
[0075] Examples of commercially available materials from Henkel Kommanditgesellschaft 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.
[0076] 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.
[0077] Particularly preferred nonionic surfactants are polyoxyethylene and polyoxypropylene
condensates of linear aliphatic alcohols.
[0078] 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
[0079] 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.
[0080] 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.
[0081] 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.
[0082] 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
[0083] 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
[0084] 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.
[0085] 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
[0086] 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.
[0087] 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
[0088] 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
[0089] The addition order of the components of within the formulation can alter the appearance
of the tablet.
[0090] It is preferable if water and any other liquid is added before the addition of any
tripolyphosphate.
[0091] 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.
[0092] 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
[0093] 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
[0094] 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.
[0095] 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.
[0096] 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.
[0097] the invention will now be illustrated by means of the following non limiting Examples.
Example:
[0098] A detergent tablet according to the present invention (Example 1) was prepared as
follows.
[0099] 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
[0100]
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 |
[0101] 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.
[0102] The obtained values are average values of 3 washes for each product.
[0103] 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.
[0104] Examples A to E are commercially available tablets.
