Field of the invention
[0001] The invention relates to household cleaning compositions in unit dose form. More
particularly the invention concerns solid household cleaning compositions in tablet
form. One or a few of such tablets when added to a prescribed amount of water provide
a detergent solution suitable to perform a common household cleaning operation such
as cleaning of floors, walls, or bathroom or kitchen surfaces.
Background of the invention
[0002] Cleaning or detergent compositions in unit dose form, especially tablets, are well
known in the art, particularly for automatic dish washing. Recently they have received
renewed attention for use in laundry washing machines. They provide a clear advantage
in ease of dispensing a standard amount of cleaning composition for a given cleaning
job. Although they have been reported as useful for manual cleaning as well, so far
for this purpose they do not appear to have gained any importance in the marketplace.
[0003] On the one hand detergent tablets must be strong to prevent them from breaking and
crumbling under the mechanical treatment involved in packaging, handling, distribution
and the like. On the other hand they should easily and quickly disintegrate once brought
into contact with water. These two requirements are to a large extent contradictory
and difficult to meet at the same time in one tablet. For tablets suitable for manual
cleaning rapid disintegration and dissolution is even more difficult to attain because
of the absence of the forceful agitation encountered in laundry and dish washing machines.
[0004] For manual cleaning the right amount of cleaning active substances for a limited
quantity of water, usually a bucket or a bowl full, should be contained in one or
a few whole tablets and yet the tablets should be of a sufficient size to be easily
handled by the consumer and to be individually packed if desired.
[0005] Furthermore, tablets should preferably maintain their strength as well as their easy
dissolution properties during storage under conditions of high ambient temperature
and/or humidity.
[0006] Most detergent tablets basically comprise three main ingredients: a carrier material,
one or more detergent surfactants and a disintegration aid. The carrier material may
also be active in the wash process in some way, e.g. as a builder. If these three
components, and any other components which may be present cannot be compacted to a
tablet of the required strength, a binding agent may be present as well.
[0007] The disintegration aid causes the tablet to fall apart on contact with water. It
performs this function in one or more of the three following ways:
a) By causing gas evolution on contact with water. Well known examples are combinations
of a carbonate or bicarbonate salt and an acid, particularly an organic acid such
as citric acid.
b) By quickly dissolving thereby providing inroads for water into the body of the
tablet. Well known examples are easily soluble salts such as alkali metal acetates
and urea.
c) By swelling on contact with water thereby forcing apart the particles which make
up the tablet.
[0008] Tablets are conventionally made by compressing discrete amounts of particulate solids
which solids should be such that they do not stick to the tablet mould. For this reason
the solids should preferably be free flowing and non-pasty. Many detergent surfactants
are either liquids or pasty solids and therefore need a carrier material to convert
them into the required free flowing form. Various carrier materials such as aluminosilicates
and zeolites are known in the art, see e.g. JP-A-10183199. However, for manual cleaning
purposes carrier materials should preferably be completely water soluble so as to
leave no unsightly residue in the bucket or on the cleaned surface.
[0009] In EP 0 221 776 a powder suitable for use as a detergent powder is described which
contains as one of its components crystal-growth-modified sodium carbonate monohydrate
and/or sodium carbonate/sodium sulphate double salt (Burkeite). The powder is prepared
by spray drying a slurry containing the components, among which may be anionic and/or
nonionic detergent actives and is said to be free flowing in spite of the presence
of the detergent active. A polycarboxylate material is used as the crystal growth
modifier.
Brief description of the invention
[0010] The present invention provides solid cleaning compositions in tablet form comprising
one or more detergent surfactants and a solid water-soluble carrier material having
a liquid carrying capacity of at least 6% of its own weight.
Detailed description of the invention.
[0011] The solid cleaning compositions in tablet form according to the invention (hereinafter
for brevity referred to as "detergent tablets") may be of the self-disintegrating
type or of the crumbling type.
[0012] In the former case they spontaneously disintegrate and dissolve on contact with water.
Such tablets will normally contain a disintegrating aid as hereinafter more fully
explained. In the latter case they need mechanical crumbling before or after being
put in water in order to dissolve within a reasonable time. Normally such tablets
will be crumbled by hand force just before being put in water.
[0013] The water soluble carrier material is preferably an inorganic water-soluble salt
which has a porous crystal structure so as to be able to absorb at least 6% of its
own weight of a liquid component without loosing its free flowing properties. It should
also be compatible with the surfactant which means that it should not react therewith
to produce an insoluble compound. An example of a suitable carrier material is sodium
tripolyphosphate.
[0014] Very suitable and preferred carrier materials are crystal growth modified sodium
sesquicarbonate (Na
2CO
3.NaHCO
3.2H
2O), sodium carbonate (Na
2CO
3.H
2O), sodium carbonate/sodium sulphate double salt (Na
2CO
3.(Na
2SO
4)
2 burkeite) and mixtures thereof. Such compounds may be prepared by preparing a solution
or slurry of the salt and a crystal growth modifier followed by drying such solution
or slurry by any suitable means known in the art, such as spray drying. Suitable crystal
growth modifiers are polycarboxylate compounds. These may be salts of monomeric polycarboxylic
acids such as EDTA, NTA and citrate. However, preferred crystal growth modifiers are
polymeric polycarboxylates such as homopolymers and copolymers of acrylic acid and/or
maleic acid. Crystal growth modified sodium carbonate, burkeite and mixtures thereof
and their preparation have been fully described in EP-A-0 221 776. The crystal growth
modifiers and the procedure described therein are also applicable to the preparation
of sodium sesquicarbonate.
[0015] Preferred carrier materials are crystal modified burkeite and mixtures of crystal
modified burkeite and crystal modified sodium carbonate. A slurry or solution comprising
sodium sulphate as well as sodium carbonate and crystal growth modifier will on drying
crystallize as much as possible in the form of crystal modified burkeite in which
the carbonate to sulphate weight ratio is 0.37:1. Any excess sulphate will crystallize
as sulphate; any excess carbonate will crystallize as crystal modified carbonate.
To obtain sufficient porosity in the crystal mass the slurry or solution of sodium
carbonate and sodium sulphate should have a carbonate to sulphate weight ratio of
at least 0.03:1, preferably at least 0.1:1 and most preferably between 0.3:1 and 0.45:1.
[0016] The polymeric polycarboxylates are generally used in an amount of 0.1-20% by weight,
preferably 0.2-10% of the total amount of sesquicarbonate or carbonate or carbonate
+ sulphate.
[0017] The minimum amount of carrier material per tablet is of course determined by the
amount of liquid or pasty solid one wishes to put into one unit dose and the carrying
capacity needed to accommodate this dose and the carrying capacity per gram of the
carrier material. The maximum amount is largely determined by the maximum desirable
size of the tablet from a practical point of view. Taking these practical constraints
into account a tablet will generally contain at least 10% by weight of carrier material,
more preferably at least 30%, even more preferably at least 50% or even 70%. On the
other hand a tablet comprising more than 99% of carrier material will contain so little
detergent active material that it will need an unpractically large tablet in order
to supply a useful dose of detergent active in a bucket or bowl of water. Generally,
the amount of carrier material will seldom exceed 95% by weight.
[0018] The surfactant or surfactants in the tablets may be of the anionic, cationic, nonionic,
amphoteric or zwitterionic type. Preferably, the tablets contain at least one anionic
or nonionic detergent surfactant.
[0019] Suitable anionic surfactants are water-soluble salts of organic sulphuric acid esters
and sulphonic acids which have in their molecular structure an aliphatic group containing
from 8 to 22 carbon atoms.
[0020] Suitable examples thereof are the following water-soluble salts:
- long chain aliphatic alcohol sulphates, especially those obtained by sulphating the
higher alcohols produced by reducing the glycerides of vegetable or animal oils or
fats such as tallow or coconut oil;
- alkylbenzene sulphonates, such as those in which the alkyl group contains from 6 to
20 carbon atoms;
- secondary alkanesulphonates;
- alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived
from tallow and coconut oil;
- fatty acid monoglyceride sulphates;
- ethoxylated fatty alcohol sulphates containing 1-6 EO units in the molecule
- ethoxylated alkylphenol sulphates containing 1-8 EO units and in which the alkyl radicals
contain 4-14 C-atoms
- the reaction product of fatty acids, e.g. those derived from coconut oil, esterified
with isethionic acid and neutralised with sodium hydroxide;
and mixtures thereof.
[0021] Very suitable water-soluble synthetic anionic surfactants are the alkali metal (such
as sodium and potassium) and alkaline earth metal (such as calcium and magnesium)
alkyl-benzenesulphonates, olefinsulphonates, alkyl sulphates, and fatty acid mono-glyceride
sulphates.
[0022] One class of suitable nonionic surfactants can be broadly described as compounds
produced by the condensation of alkylene oxide groups, which are hydrophilic in nature,
with an organic hydrophobic compound which may be aliphatic or alkyl aromatic in nature.
The length of the hydrophilic or polyoxyalkylene radical which is attached to any
particular hydrophobic group can be readily adjusted to yield a water-soluble compound
having the desired balance between hydrophilic and hydrophobic elements. This enables
the choice of nonionic surfactants with the right HLB.
[0023] Particular examples include:
- the condensation products of aliphatic alcohols having from 8 to 22 carbon atoms in
either straight or branched chain configuration with ethylene oxide, such as coconut
alcohol ethylene oxide condensates having from 2 to 15 moles of ethylene oxide per
mole of coconut alcohol;
- condensates of alkylphenols whose alkyl group contains from 6 to 12 carbon atoms with
2 to 25 moles of ethylene oxide per mole of alkylphenol;
- condensates of the reaction product of ethylenediamine and propylene oxide with ethylene
oxide, the condensates containing from 40 to 80% of ethyleneoxy groups by weight and
having a molecular weight of from 5,000 to 11,000.
[0024] Other classes of nonionic surfactants are:
- tertiary amine oxides of general structure RRRN0, where one R is an aliphatic group
of 8 to 18 carbon atoms and the other Rs are each alkyl or hydroxyalkyl groups of
1 to 3 carbon atoms, for instance dimethyldodecylamine oxide;
- tertiary phosphine oxides of structure RRRP0, where one R is an aliphatic group of
8 to 18 carbon atoms and the other Rs are each alkyl or hydroxyalkyl groups of 1 to
3 carbon atoms, for instance dimethyl-dodecylphosphine oxide;
- dialkyl sulphoxides of structure RRS0 where one R is an alkyl group of from 10 to
18 carbon atoms and the other is methyl or ethyl, for instance methyltetradecyl sulphoxide;
- fatty acid alkylolamides;
- alkylene oxide condensates of fatty acid alkylolamides;
- alkyl mercaptans.
[0025] Ethoxylated aliphatic alcohols are particularly preferred as nonionic surfactants.
[0026] Suitable amphoteric surfactants are derivatives of aliphatic secondary and tertiary
amines containing a C8-C18 alkyl group and an aliphatic group substituted by an anionic
water-solubilising group, for instance sodium 3-dodecylamino-propionate, sodium 3-dodecylaminopropane
sulphonate and sodium N-2-hydroxydodecyl-N-methyl taurate.
[0027] Suitable cationic surfactants are quaternary ammonium salts having at least one C8-C22
aliphatic or alkyl-aromatic group, e.g. dodecyl-trimethylammonium bromide or chloride,
cetyltrimethyl-ammonium bromide or chloride, didecyl-dimethyl-ammonium bromide or
chloride, octyl-benzyl-dimethyl-ammonium bromide or chloride, dodecyl-benzyl-dimethyl-ammonium
bromide or chloride and (higher alkyl)-benzyldimethyl-ammonium bromide or chloride.
[0028] Suitable zwitterionic surfactants are derivatives of aliphatic quaternary ammonium,
sulphonium and phosphonium compounds having a C8-C18 aliphatic group and an aliphatic
group substituted by an anionic water-solubilising group, for instance 3-(N,N-dimethyl-N-hexadecylammonium)-propane-1-sulphonate
betaine, 3-(dodecyl-methyl-sulphonium)-propane-1-sulphonate betaine and 3-(cetylmethyl-phosphonium)-ethane-sulphonate
betaine.
[0029] Further examples of suitable surfactants are given in the well-known textbooks "Surface
Active Agents", Volume I by Schwartz and Perry and "Surface Active Agents and Detergents",
Volume II by Schwartz, Perry and Berch.
[0030] The amount of surfactant per tablet is again determined by the desired size of the
tablet and the required amount of surfactant per unit dose. In general the amount
of surfactant will be at least 1% by weight, preferably at least 3%. The maximum amount
is largely determined by the carrying capacity of the carrier material. In practice
it will seldom exceed 50% by weight and preferably be below 30%.
[0031] As outlined above, the preferred surfactants are anionic or nonionic or mixtures
thereof. Ethoxylated alcohols are preferred nonionics, particularly those having at
most 16 carbon atoms in the aliphatic chain.
[0032] If the tablets are of the self-disintegrating type they preferably contain a disintegration
aid (disintegrant). This may be one of the effervescent mixtures well known in the
art, such as an organic acid, particularly citric acid, in combination with a carbonate
or bicarbonate salt. Other examples are described in WO 98/46715 and the literature
cited therein.
[0033] Alternatively, it may be a quickly dissolving compound as is also widely known in
the art. Well known examples are: sodium citrate dihydrate, potassium carbonate, urea,
sodium acetate, sodium acetate trihydrate, magnesium sulphate heptahydrate, potassium
acetate, sodium chloride and sorbitol. Preferred compounds have a solubility of at
least 50g in 100g of de-ionised water at 20°C.
[0034] Furthermore it may be a material which swells on contact with water, or first swells
and later dissolves. Known materials include various natural and synthetic polymers,
such as polyethylene glycol (e.g. PEG 1500), cellulose derivatives (sodium CMC) and
swelling clays such as bentonite, smectites and montmorillonites
[0035] A suitable minimum level of disintegrant is 0.5, preferably at least 1% by weight;
a suitable maximum level is 50%, preferably at most 30% by weight. Preferred disintegrants
are swelling clays since they not only act as a disintegrant on contact with water
but also act as a binder in the dry tablet. They are conveniently used in an amount
of 1.5-10%.
[0036] Optionally the detergent tablets may contain a hygiene agent which deals with microbial
contamination of the surfaces to be cleaned. Particularly, many quaternary ammonium
salts are known to have antimicrobial properties. Well known examples are benzalkonium
salts, cetyl-trimethyl ammonium salts, didecyl-dimethyl ammonium salts. Such quaternary
ammonium salts are preferably used in combination with a nonionic surfactant.
[0037] Other compounds with antimicrobial properties may be used instead of, or in addition
to antimicrobially active quaternary ammonium salts. Examples are: Triclosan™ and
similar antibacterials, iodine/NaI, solid chlorine bleaching agents such as the chlorinated
cyanuric acid salts.
[0038] The detergent tablets according to the invention may additionally contain other ingredients
known in the art to be beneficial for cleaning hard surfaces, such as components which
facilitate second time cleaning or components which improve shine of the cleaned surface.
Furthermore they may contain components to increase the attractiveness of the tablets
and/or the cleaning solution to the consumer such as perfumes and dyes.
[0039] For the purposes of this invention tablets are defined as macroscopic shaped objects
of such minimum dimensions that they can be handled individually by the consumer.
Therefore the minimum dimension of such objects should preferably not be less than
2 mm. Tablets are normally flat shaped objects in which the minimum dimension (thickness)
is normally substantially less than the diameter (for round shaped tablets) or the
length of the sides (for tablets with a rectangular, triangular or other shape). However,
for the purposes of this invention, pills, balls, bullets and similarly shaped objects
are comprised in the definition of a tablet.
Examples
Example 1
[0040] A base powder was prepared having the following composition (in % by weight):
- 6.00%
- Neodol 91-5™ (ethoxylated alcohol)
- 2.25%
- Benzalkonium chloride
- 2.25%
- water
- 2.50%
- Bentonite clay
- 0.20%
- Eriochrome black (dye)
- 0.60%
- perfume
- 86.20%
- Burkeite powder
[0041] The base powder was prepared by mixing all liquid components with the burkeite powder
using a Forniture Sirman™ high shear mixer until a homogeneous free flowing mixture
was obtained. This was mixed with the bentonite clay.
[0042] 10 g tablets were stamped from this base powder using an Instron™ tensiometer Model
5566 fitted with a 10 kN load cell and a 35 mm round die.
[0043] The burkeite carrier material was prepared from a mixture of 290.6 kg water, 213.8
kg of Na sulphate, 80 kg of Na carbonate and 15.7 kg of CP5 (40% aqueous solution
of maleic/acrylic acid copolymer) by spray drying according to the procedure described
in Examples 2-5 of EP 0 221 776.
1. Solid cleaning compositions in tablet form comprising one or more detergent surfactants
and a solid water-soluble carrier material having a liquid carrying capacity of at
least 6% of its own weight.
2. Cleaning composition according to claim 1 wherein the carrier material is chosen from
sodium tripolyphosphate and crystal growth modified sodium sesquicarbonate, sodium
carbonate, sodium carbonate/sodium sulphate double salt (burkeite) and mixtures thereof.
3. Cleaning composition according to claim 2 wherein the carrier material comprises crystal
growth modified burkeite.
4. Cleaning compositions according to claims 1-3 wherein the surfactants are anionic
and/or nonionic surfactants.
5. Cleaning composition according to claims 1-4 which further comprises a disintegrant.
6. Cleaning composition according to claim 5 wherein the disintegrant is a swelling clay.
7. Cleaning composition according to claims 1-6 which further comprises a hygiene agent.
8. Cleaning composition according to claim 7 wherein the hygiene agent is a quaternary
ammonium salt.