Note: Descriptions are shown in the official language in which they were submitted.
CA 02314363 2000-07-20
A DETERGENT/CLEANER PORTION WITH A NEW PACK AND A PACK
FOR DETERGENT/CLEANERS
Field of the Invention
This invention relates to a detergent or cleaner portion (hereinafter
referred to as a detergent/cleaner portion) with a new pack, preferably with
a water-soluble pack and more preferably which dissolves in water at a
certain temperature but which does not enter into any adverse interaction
with the ingredients of the detergent/cleaner portion. The invention also
relates to a new pack for detergents/cleaner having improved properties in
relation to the prior art.
Background of the Invention
Detergents and processes for their production have been known for
some considerable time and, accordingly, are widely described in the prior
art literature. Detergents are normally marketed in the form of spray-dried
or granulated solid products or as liquids. In response to consumer
demand for easy dosing, products in pre-portioned form have established
themselves on the market alongside these two conventional variants and
have also been described in the prior art literature, detergents in the form
of
press-agglomerated shaped bodies, i.e. tablets, blocks, briquettes, rings
and the like, and portions of solid and/or liquid detergents packed in bags
being described in particular.
In the case of individual doses of detergents which are packed in
bags for marketing, bags of water-soluble film, i.e. bags which do not have
to be torn open by the user, have proved successful. In this way, an
individual portion can be conveniently dosed by directly placing the bag in
the washing machine or dishwashing machine, particularly in the
dispensing compartment thereof, or by throwing the bag into a
predetermined quantity of water, for example in a bucket or in a
handwashing or rinsing bowl. The bag surrounding the detergent dissolves
CA 02314363 2000-07-20
2
completely when a certain temperature is reached. Detergents packed in
bags of water-soluble film are also described in large numbers in the prior
art literature.
Thus, earlier patent application DE 198 31 703 discloses a portioned
detergent prepar;~tion in a bag of water-soluble film, more particularly a bag
of (optionally acetalized) polyvinyl alcohol (PVAL) in which at least 70% by
weight of the particles of the detergent preparation have particle sizes
above 800 Nm.
The water content and the content of other components present in
the film material is in equilibrium with the content of water (atmospheric
moisture) and optionally other compounds in the surrounding atmosphere.
The same also happens between the film and the interior of the bag. In
other words, a phase equilibrium is gradually established.
Moisture in environment = water content of film = moisture in bag.
So far as the packed product is concerned, this situation is virtually
equivalent to storage of the product in the open air.
This situation brings problems, particularly in connection with the
moisture content or rather the water content of the film, and is particularly
undesirable where percarbonates are used as bleaching agents in the
washing/cleaning formulation. Percarbonates are not permanently stable in
the presence of moisture and undergo significant losses of activity through
the absorption of water. Under certain humidity conditions, therefore,
washing/cleaning preparations containing percarbonate as bleaching agent
are not stable in storage. Although the perborates suitable as alternatives
are less sensitive to moisture than percarbonates, they cannot be used on
account of esterification with the polyvinyl alcohol of the films.
CA 02314363 2000-07-20
3
A known solution is to coat the water-soluble film material with
another layer, for example a vapor barrier layer, which leads to limited
permeability of the pack to water vapor. For example, vapor barrier layers
may be used to protect percarbonate against moisture. In another
example, mechanical and chemical separation of the polyvinyl alcohol
(PVAL) forming the outer pack from the ester with PVAL-forming perborate
can be achieved by an additional layer on the inside of the pack, so that the
pack is stabilized.
Thus, WO 98/40464 (Unilever N.V.) describes combinations of at
least one tablet of a compressed particulate detergent/cleaner preparation
with a closed pack surrounding the tablet which has a water vapor
transmission rate of less than 20 g/m2 per day and, ideally, 5 g/m2 per day.
This pack is said to improve the physical properties of the packed tablet in
storage and to provide the tablet with improved dissolving kinetics on
contact with water.
EP-A 0 899 208 (The Procter & Gamble Company) describes
combinations of detergent/cleaner preparations in the form of a stack of
tablets containing a moisture-sensitive bleaching agent and a water-
insoluble pack surrounding the tablets with a water vapor transmission rate
of less than 20 g/m2 per day and, ideally, 0.5 g/m2 per day. The pack con-
sists, for example:, of monolayers or co-extruded or laminated films of poly-
ethylene, polypropylene, polystyrene and/or polyethylene terephthalate.
A distinct disadvantage of the solutions described in the prior art is
that the production of a film material consisting of one or more (for example
two) layers is complicated and considerably increases the price of the
products. On the other hand, the complete solubility of the pack in water is
generally relinquished in favor of impermeability to water vapor which is
also undesirable ~on account of the residues of the pack accumulating in the
washing/cleaning process.
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4
A logical alternative to the above-described proposals of the prior art
is to use an outer pack. acting as a vapor barrier for moisture-sensitive
and/or hygroscopic products. Although the product is then optimally
protected against water or moisture, a very low equilibrium moisture
content by comparison with the normal air humidity is established in the
container. This equilibrium moisture content is determined by the packed
detergent/cleaner preparation. Water is almost completely removed from
the water-soluble film material so that it becomes brittle and mechanically
sensitive. The bag surrounding detergent/cleaner portions can thus tear,
despite careful handling by the consumer, and releases its contents into
the outer pack forming a vapor barrier. The advantages of a detergent/
cleaner portion packed in a water-soluble film for direct use in a washing or
dishwashing machine are thus lost.
Summary of the Invention
It has now surprisingly been found that both ideal packaging
materials for detergents or cleaners and practical easy-to-dose detergent/
cleaner portions surrounded by the packaging materials mentioned can be
obtained either when detergent/cleaner ingredients which are also present
in the detergent/cleaner to be wrapped are incorporated in the water-
soluble films or when detergent/cleaner-compatible plasticizers which are
also present in the water-soluble film are compounded into the detergent/
cleaner.
The present invention relates to a detergent/cleaner portion, more
particularly for placing in a washing/dishwashing machine for a program
taking place in an aqueous phase, containing at least one measured
quantity of at least one active washing preparation and at least one water-
soluble polymer rnaterial surrounding the measured quantity(ies) of at least
one active washing preparation, one or more components) of at least one
of the active washing preparations also being present in the water-soluble
CA 02314363 2000-07-20
polymer material.
The invention also relates to a detergent/cleaner portion, more
particularly for placing in a washing/dishwashing machine for a program
taking place in an aqueous phase, containing at least one measured
5 quantity of at least one active washing preparation and at least one water-
soluble polymer material surrounding the measured quantity(ies) of at least
one active washing preparation, one or more components) of the water-
soluble polymer materiaN also being present in at least one of the active
washing preparations.
In addition, the invention relates to a wrapper for at least one
measured quantity of an active washing preparation of a detergent/cleaner
portion suitable in particular for placing in a washing/dishwashing machine
in the form of a water-soluble polymer material, one or more components)
of at least one of the active washing preparations also being present in the
water-soluble polymer material.
The invention also relates to a wrapper for at least one measured
quantity of an active washing preparation of a detergent/cleaner portion
suitable in particular for placing in a washing/dishwashing machine in the
form of a water-soluble polymer material, one or more components) of the
water-soluble poNymer material also being present in at least one of the
active washing preparatians.
In addition, the present invention relates to a process for the
production of a detergent/cleaner portion, more particularly for placing in a
washing/dishwashing machine for a program taking place in an aqueous
phase, containing at least one measured quantity of at least one active
washing preparation and at least one water-soluble polymer material
surrounding the measured quantity(ies) of at least one active washing
preparation, characterized by the steps of
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6
- making ready at least one measured quantity of at least one active
washing preparation;
- making ready at least one water-soluble polymer material, at least one
water-soluble polymer material containing one or more components of
at least one of the active washing preparations; and/or
- making ready at least one water-soluble polymer material, at least one
measured quantity of at least one active washing preparation containing
one or more components) of the water-soluble polymer material; and
- at least one measured quantity of at least one active washing
preparation being enveloped in the at least one water-soluble polymer
material.
The present invention also relates to a washing/cleaning process in
which
a detergent portion corresponding to the above definition is placed in a
washing/dishwashing machine;
- at least one active washing preparation is released into the wash liquor
by addition of water and adjustment of the temperature to a first
temperature value at which at least one water-soluble polymer material
surrounding a measured quantity of the active washing preparation of
the detergent portion dissolves; and optionally
- one or more other active washing preparations is/are released into the
wash liquor Iby further additions) of water and adjustment of the
temperature to one or more other temperature values) above the first
temperature value and optionally above other previous temperature
values.
Detailed Description of the Invention
A "detergent portion" in the context of the present invention is
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7
understood to be a dose of a laundry or dishwashing detergent which is
sufficient for a washing or cleaning process taking place in an aqueous
phase. This may be, for example, a machine washing or dishwashing
process carried out in commercially available washing or dishwashing
machines. However, the expression "detergent portion" is also understood
to encompass handwashing (carried out for example in a handwashing
basin or in a bowl) or manual dishwashing or any other washing or cleaning
process. According to the invention, the detergent portions are preferably
used in machine washing or cleaning processes. Detergent portions
according to the invention may also be used, for example, for cleaning
floors and glass, for cleaning fittings, appliances and surfaces in the
kitchen, for cleaning fittings, furniture and surfaces in the bathroom and for
washing the hands. According to the invention, the detergent portions are
preferably used in machine washing or cleaning processes.
A "detergent part-portion" in the context of the invention is
understood to bs~ part of a detergent portion which is present in a phase
separated from other detergent part-portions in spatial combination with
other detergent part-portions of the same detergent portion and which is
prepared by suitable measures in such a way that it can be introduced into
the wash liquor separately from other part-portions of the same detergent
portion and dissolved or suspended therein. A detergent part-portion can
contain the same ingredients as another part-portion of the same detergent
portion. Alternatively, two detergent part portions of the same detergent
portion may contain different ingredients, more particularly different active
washing preparations. However, the invention also encompasses
detergent portions with only one detergent part-portion of uniform
composition, for Example of powders, particles or tablets.
According to the invention, the detergent portions contain measured
quantities of active washing preparations. The detergent portions may only
CA 02314363 2000-07-20
contain active washing preparations having a particular composition.
According to the invention, however, several, normally at least two, active
washing preparations differing in their composition are preferably present in
the detergent portions. The composition may differ both in regard to the
concentration of the individual components of the active washing
preparation (i.e. quantitatively) and/or in regard to the nature of the
individual components of the washing preparation (i.e. qualitatively). In one
particularly preferred embodiment, the components are adapted in regard
to type and concentration to the functions the detergent part-portions are
intended to perform in the washing or cleaning cycle. According to the
present invention, the part-portions are preferably the first, second and
optionally third or' even faurth, fifth etc. measured quantities of one or
more
active washing preparations which are combined to form a detergent
portion according to the invention.
In the context of the present invention, "active washing preparations"
are understood to be preparations of any conceivable substances that are
relevant to a washing or cleaning process. These are primarily the actual
laundry or dishwashing detergents themselves with their individual
components explained in more detail hereinafter. These include such
active ingredients as surfactants (anionic, nonionic, cationic and
amphoteric surfactants}, builders (inorganic and organic builders),
bleaching agents (for example peroxo bleaching and chlorine bleaching
agents), bleach activators, bleach stabilizers, bleach catalysts, enzymes,
special polymers;, dyes and perfumes, although the expression "active
washing preparation" is by no means confined to substances belonging to
these groups.
However, the expression "active washing preparations" is also
understood to encompass washing and cleaning aids. Laundry treatment
compositions, such as fabric softeners, and dishwasher detergent
CA 02314363 2000-07-20
9
additives, such as rinse aids, are also regarded as active washing
preparations in the context of the present invention.
According to the invention, the detergent/cleaner portion contains at
least one water-soluble polymer material surrounding the measured
quantity(ies) of at least one active washing preparation. This polymer
material is preferably a pack surrounding at least one active washing
preparation. A pack in the context of the invention is understood to be a
flat or three-dimensional structure which completely surrounds at least one
measured quantity of at least one active washing preparation and thus
forms a detergent/cleaner part-portion which is normally (but not
necessarily) arranged very close to another quantity - optionally surrounded
by another water-soluble pack, but at all events measured - of another
active washing preparation in the form of a detergent/cleaner portion. The
exact form of such a pack is not critical and may largely be adapted to the
conditions of uses. For example, plastic films processed to various forms
(such as tubes, pouches" cylinders, bottles, disks or the like), capsules and
other possible forms are suitable. According to the invention, films which
may be bonded ;and/or sealed, for example, to form such packs as tubes,
pouches or the like after they have been filled with part-portions of the
detergent/cleaner portions according to the invention are preferred.
In one preferred embodiment of the invention, the wrapper consists
of a water-soluble polymer material. More preferably, the wrapper is a
sheet-form plastic part. Plastic capsules or bottles and, more particularly,
packs in the form of a water-soluble polymer film are preferred. Among the
plastic film packs, bonded and/or sealed plastic film packs are preferred. In
one particularly advantageous embodiment, the wrapper is a water-soluble
polymer film bonded with a water-soluble adhesive.
Such films are known in principle from the prior art and belong to the
group consisting of (optionally acetalized) polyvinyl alcohol, polyvinyl
CA 02314363 2000-07-20
pyrrolidone, water-soluble polyacrylates, water-soluble polyurethanes,
polyethylene oxide, gelatine, cellulose and mixtures thereof.
Polyvinyl alcohols, referred to in short as PVALs, are polymers with
the following general structure:
5
(-CH2-CH(OH)-]"
which also contain small amounts of structural units of the following type:
10 [-CH2-CH(OH)-CH(OH)-CH2]
Since the corresponding monomer (vinyl alcohol) is not stable in free form,
polyvinyl alcohols are praduced via polymer-analog reactions by hydrolysis
and - on an industrial scale - above all by alkali-catalyzed
transesterification
of polyvinyl acetates with alcohols (preferably methanol) in solution.
PVALs with a predetermined residual percentage of acetate groups -
sometimes also referred to as "acetalized" PVAL - can also be obtained by
these industrial processes.
Commercially available PVALs (for example Mowiol~ types,
products of Hoechst) are marketed as white-yellowish powders or granules
with degrees of polymerization of ca. 500 to 2,500 (corresponding to
molecular weights of ca. 10,000 to 100,000 g/mole) and have different
degrees of hydrolysis of about 70 mole-% or higher, for example 98-99 or
87-89 mole-%. ~4ccordingly, they are partly saponified polyvinyl acetates
with a residual content of acetyl groups of ca. 1-2 or 11-13 mole-%.
The solubility of PVALs in water can be reduced and thus selectively
adjusted to required values by aftertreatment with aldehydes
(acetalization), by complexing with Ni or Cu salts or by treatment with
dichromates, boric acid, borax. Films of PVAL are largely impervious to
CA 02314363 2000-07-20
' 11
gases, such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but are
permeable to water vapor.
Examples of suitable water soluble PVAL films are the PVAL films
obtainable under the name of "SOLUBLONO" from Syntana
Handelsgesellschaft E. Harke GmbH & Co. Their solubility in water can be
very precisely adjusted and films of this product series soluble in water in
all the temperature ranges relevant to practical application are obtainable.
PolyvinyN pyrrolidones, referred to in short as PVPs, correspond to
the following general formula:
CH-CH2
N
~O
n
~ PVPs are produced by radical polymerization of 1-vinyl pyrrolidone.
Commercially available PVPs have molecular weights of ca. 2,500 to
750,000 g/mole and are commercially available as white hygroscopic
powders or as aqueous solutions.
Polyethylene oxides, referred to in short as PEOXs, are polyalkylene
glycols corresponding to the following general formula:
H-[O-CH2-CH2]~-~OH
which are produced on an industrial scale by base-catalyzed polyaddition
of ethylene oxide (oxirane) with ethylene glycol as starter molecule in
systems generally containing small quantities of water. They have
molecular weights in the range from ca. 200 to 5,000,000 g/mole,
corresponding to degrees of polymerization n of ca. 5 to >100,000.
Polyethylene oxides have an extremely low concentration of reactive
CA 02314363 2000-07-20
12
terminal hydroxy groups and possess only weak glycol properties.
Gelatine is a polypeptide (molecular weight ca. 15,000 - >250,000
g/mole) which is mainly obtained by hydrolysis of the collagen present in
the skin and bones of animals under acidic or alkaline conditions. The
amino acid composition of gelatine largely corresponds to that of the
collagen from which it was obtained and varies according to its
provenance. The use of gelatine as a water-soluble capsule material is
particularly widespread in pharmacy (hard or soft gelatine capsules).
Gelatine is rarely used in the form of films on account of its high price
compared with the polymers mentioned above.
Other preferred detergent portions according to the present
invention are those of which the bag consists of water-soluble film of at
least one polymer from the group of starch and starch derivatives, cellulose
and cellulose derivatives, more especially methyl cellulose and mixtures
thereof.
Starch is a homoglycan in which the glucose units are attached by
a-glycoside bonds. Starch is made up of two components of different
molecular weight, namely ca. 20-30% straight-chain amylose (molecular
weight ca. 50,00() to 150,000) and 70-80% of branched-chain amylopectin
(molecular weight ca. 300,000 to 2,000,000). Small quantities of lipids,
phosphoric acid and cations are also present. Whereas the amylose - on
account of the bond in the 1,4-position - forms long, helical entwisted
chains containing about 300 to 1,200 glucose molecules, the amylopectin
chain branches through a 1,6-bond after - on average - 25 glucose units to
form a branch-like structure containing about 1,500 to 12,000 glucose
molecules. Besides pure starch, starch derivatives obtainable from starch
by polymer-analog reactions may also be used in accordance with the
invention for thE; production of water-soluble bags. Such chemically
modified starches include, for example, products of esterification or
CA 02314363 2000-07-20
13
etherification reactions in which hydroxy hydrogen atoms were substituted.
However, starches in which the hydroxy groups have been replaced by
functional groups that are not attached by an oxygen atom may also be
used as starch derivatives. The group of starch derivatives includes, for
example, alkali metal starches, carboxymethyl starch (CMS), starch esters
and ethers and amino starches.
Pure cellulose has the formal empirical composition (CsH~pO5)n and,
in formal terms, its a ~3-1,4-polyacetal of cellobiose which, in tum, is made
up of two molecules of glucose. Suitable celluloses consist of ca. 500 to
5,000 glucose units and, accordingly, have average molecular weights of
50,000 to 500,000. Other cellulose-based disintegrating agents which may
be used in accordance with the present invention are cellulose derivatives
obtainable from cellulose by polymer-analog reactions. Such chemically
modified celluloses include, for example, products of esterification or
etherification reactions in which hydroxy hydrogen atoms were substituted.
However, celluloses in which the hydroxy groups have been replaced by
functional groups that are not attached by an oxygen atom may also be
used as cellulose derivatives. The group of cellulose derivatives includes,
for example, alkali metal celluloses, carboxymethyl cellulose (CMC),
cellulose esters and ethers and also aminocelluloses.
Preferred wrappers of water-soluble film consist of a polymer with a
molecular weight in the range from 5,000 to 500,000 dalton, preferably in
the range from 7,500 to 250,000 dalton and more preferably in the range
from 10,000 to 100,000 dalton. The water-soluble film which forms the
wrapper has a thickness of 1 to 150 Nm, preferably 2 to 100 Nm, more
preferably 5 to 75 Nm and most preferably 10 to 50 Nm.
The water-soluble films may be produced by various processes. In
principle, they rnay be produced by blowing, extrusion and casting
processes. In one preferred process, which starts out from a melt and uses
CA 02314363 2000-07-20
14
a blowing mandrel, the films are blown with air to form a tube. In the
extrusion process, which is another preferred production process, the raw
materials plasticised by suitable additives are sprayed to form the films. It
may be necessary in the extrusion process to dry the films after spraying.
In the casting process, which is another preferred production process, an
aqueous polymer preparation is applied to a heatable drying roller,
optionally cooled after evaporation of the water and the film formed is
removed from the roller. This film may optionally be powdered before or
during its removal from the roller.
According to the invention, the polymer material forming the wrapper
of at least one active washing preparation does not consist solely of one of
the polymers mentioned or a mixture of several polymers, but essentially
contains other substances. According to the invention, there are at least
two possible alternatives in this regard:
- one or more components) of at least one of the active washing
preparations is/are also present in the water-soluble polymer material;
and/or
- one or more c;omponent(s) of the water-soluble polymer material is/are
also present in at least one of the active washing preparations.
According to the invention, either one of the two states prevails as
an alternative, i.e. either one or more components) of at least one of the
active washing preparations is/are also present in the water-soluble
polymer material or, alternatively, one or more components) of the water-
soluble polymer material is/are also present in at least one of the active
washing preparations. In another preferred embodiment of the invention,
however, both states prevail at the same time, in other words both one or
more components) of at least one of the active washing preparations is/are
CA 02314363 2000-07-20
also present in the water-soluble polymer material and, at the same time,
one or more components) of the water-soluble polymer material is/are also
present in at least one of the active washing preparations. In one
particularly preferred embodiment of the invention, both alternatives are
5 applied at the same time.
According to the invention, the fact that one or more components)
of at least one of the active washing preparations is/are also present in the
water-soluble polymer material and/or one or more components) of the
water-soluble polymer material is/are also present in at least one of the
10 active washing preparations ensures that, from the production stage
onwards, a phase equilibrium is established between the ingredients of an
active washing preparation and the water-soluble polymer material
surrounding at least this active washing preparation. Although there is a
continuous exchange of material between these two phases, it does not
15 lead to the enrichment of the particular materials) in one phase exceeding
the concentration of the phase equilibrium and to a resulting depletion of
the particular materials) in another phase which is generally accompanied
by an unwanted change in the particular properties. The repeatedly
observed changes in the properties of one or more ingredients) of one or
even more activE: washing preparations) in regard to the properties, for
example washing or cleaning activity, in the washing/cleaning process
and/or changes in the properties of one or more wrappers) or packs)
surrounding the active washing preparations in regard to the properties, for
example solubility in water or brittleness, do not occur with the detergent/
cleaner portion according to the invention or its wrapper/pack.
Basically, no compulsory limitations emanating from the perspective
of the particular components present in both phases are imposed on the
fact that one or more components) of at least one of the active washing
preparations is/are also present in the water-soluble polymer material
CA 02314363 2000-07-20
16
and/or that one or mare components) of the water-soluble polymer
material is/are ;also present in at least one of the active washing
preparations. Basically, each of the components of the active washing
preparation is suitable for incorporation in the water-soluble polymer
materials) and for the establishment of a phase equilibrium between an
active washing preparation and a polymer material in exactly the same way
as each of the components of the polymer material is suitable for
compounding into the active washing preparations) and for the
establishment of a phase equilibrium between a polymer material and an
active washing preparation.
According to the invention, however, certain ingredients of the
particular phases are advantageous for establishing the equilibrium. The
main advantage is that no other materials foreign to the film need be
incorporated in tlhe film, thus avoiding a complicated production process
and an increase in the weight of the film and also an increase in the cost of
producing of thE; film. In addition, certain ingredients are particularly
suitable becausE: the phase equilibrium can be rapidly and, hence,
advantageously established in regard to such materials so that the
advantages of thE: invention are quickly brought to bear. However, this may
also be due to the fact that the material present in both phases (active
washing preparation and water-soluble polymer material) in one particular
case can be conveniently incorporated in both phases.
In another preferred embodiment of the invention, the materials
present in at least two phases are materials which are liquid or paste-like or
wax-like at room temperature, optionally after the addition of small
quantities of water (less than 20% by weight and advantageously less than
10% by weight, based on the preparation). Substances selected according
to this requirement - to be viewed from the application perspective - lead to
CA 02314363 2000-07-20
17
detergent/cleaner portions with full activity of the active washing
substances and to storage-stable wrappers with improved properties.
According to the invention, one particularly preferred
embodiment of the detergent/cleaner portions is characterized in that the
components) of at least one of the active washing preparations) present
in the water-soluble polymer material is/are selected from the group
consisting of nonionic and anionic surfactants as defined in detail in the
following.
Suitable anionic surfactants are, for example, those of the sulfonate
and sulfate type. Suitable surfactants of the sulfonate type are preferably
cumene sulfonate, C9_~3 alkyl benzenesulfonates, olefin sulfonates, i.e.
mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates
obtained, for example, from C~2_~s monoolefins with an internal or terminal
double bond by sulfonation with gaseous sulfur trioxide and subsequent
alkaline or acidic hydrolysis of the sulfonation products. Other suitable
surfactants of the sulfonate type are the alkane sulfonates obtained from
C~2_~$ alkanes, for example by sulfochlorination or sulfoxidation and
subsequent hydrolysis or neutralization. The esters of a-sulfofatty acids
(ester sulfonates), for example the a-sulfonated methyl esters of
hydrogenated coconut oil, palm kernel oil or tallow fatty acids, are also
suitable.
Other suitable anionic surfactants are sulfonated fatty acid glycerol
esters. Fatty acid glycerol esters in the context of the present invention are
the monoesters, diesters and triesters and mixtures thereof which are
obtained where production is carried out by esterification of a monoglycerol
with 1 to 3 moles of fatty acid or in the transesterification of triglycerides
with 0.3 to 2 moles of glycerol. Preferred sulfonated fatty acid glycerol
esters are the sulfonation products of saturated fatty acids containing 6 to
22 carbon atoms, for example caproic acid, caprylic acid, capric acid,
CA 02314363 2000-07-20
18
myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
Preferred alk(en)yl sulfates are the alkali metal salts and, in
particular, the sodium salts of the sulfuric acid semiesters of C~2_~$ fatty
alcohols, for example cocofatty alcohol, tallow fatty alcohol, lauryl,
myristyl,
cetyl or stearyl alcohol, or C~o_2o oxoalcohols and the corresponding
semiesters of secondary alcohols with the same chain length. Other
preferred alk(en)yl sulfates are those with the chain length mentioned
which contain a synthetic, linear alkyl chain based on a petrochemical and
which are similar in their degradation behavior to the corresponding
compounds based on oleochemical raw materials. C~2_~6 alkyl sulfates,
C~2_~5 alkyl sulfates and C~4_~5 alkyl sulfates are preferred from the point
of
view of washing technology. Other suitable anionic surfactants are 2,3-
alkyl sulfates which may be produced, for example, in accordance with US
3,234,258 or US 5,075,041 and which are commerially obtainable as
products of the Shell Oil Company under the name of DAN~.
The sulfuric acid monoesters of linear or branched C~_2~ alcohols
ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched
C~» alcohols containing on average 3.5 moles of ethylene oxide (EO) or
C~2_~8 fatty alcohols containing 1 to 4 EO, are also suitable. In view of
their
high foaming capacity, they are only used in relatively small quantities, for
example in quantities of 1 to 5% by weight, in dishwashing detergents.
Other suitable anionic surfactants are the salts of alkyl sulfosuccinic
acid which are ;also known as sulfosuccinates or as sulfosuccinic acid
esters and which represent monoesters and/or diesters of sulfosuccinic
acid with alcohols, preferably fatty alcohols and, more particula~iy,
ethoxylated fatty alcohols. Preferred sulfosuccinates contain C8_~8 fatty
alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates
contain a fatty alcohol residue derived from ethoxylated fatty alcohols
which, considered in isolation, represent nonionic surfactants (for a
CA 02314363 2000-07-20
19
description, see below). Of these sulfosuccinates, those of which the fatty
alcohol residues are derived from narrow-range ethoxylated fatty alcohols
are particularly preferred. Alk(en)yl succinic acid preferably containing 8 to
18 carbon atoms in the alk(en)yl chain or salts thereof may also be used.
Other suitable anionic surfactants are, in particular, soaps. Suitable
soaps are saturated fatty acid soaps, such as the salts of lauric acid,
myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and
behenic acid, and soap mixtures derived in particular from natural fatty
acids, for example coconut oil, palm kernel oil or tallow fatty acids.
The anionic surfactants, including the soaps, may be present in the
form of their sodium, potassium or ammonium salts and as soluble salts of
organic bases, such as mono-, di- or triethanolamine. The anionic
surfactants are preferably present in the form of their sodium or potassium
salts and, more preferably, in the form of their sodium salts. In another
embodiment of t;he invention, surfactants are used in the form of their
magnesium salts,.
According to the invention, preferred detergent/cleaner portions are
those which contain 5 to 50% by weight, preferably 7.5 to 40% by weight
and more preferably 15 to 25% by weight of anionic surfactant(s), based on
the detergent portion.
So far as the choice of anionic surfactants used in the detergent
portions according to the invention is concerned, there are no basic
requirements to restrict the freedom of formulation. However, preferred
detergent/cleaner portions according to the invention do have a soap
content in excess of 0.2% by weight, based on the total weight of the
detergent portion. Preferred anionic surfactants are alkyl benzene-
sulfonates and fatty alcohol sulfates, preferred detergent portions
containing 2 to 20% by weight, preferably 2.5 to 15% by weight and more
preferably 5 to '10% by weight of fatty alcohol sulfate(s), based on the
CA 02314363 2000-07-20
weight of the the detergent/cleaner portion.
Preferred nonionic surfactants are alkoxylated, advantageously
ethoxylated or propoxylated, more especially primary alcohols preferably
containing 8 to 18 carbon atoms and, on average, 1 to 80 and preferably 3
5 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol
radical may be linear or, preferably, methyl-branched in the 2-position or
may contain linear and methyl-branched radicals in the form of the mixtures
typically present in oxoalcohol radicals. However, alcohol ethoxylates
containing linear radicals of alcohols of native origin with 12 to 18 carbon
10 atoms, for example coconut oil, palm oil, tallow or oleyl alcohol, and on
average 1 to 80 and preferably 2 to 8 EO per mole of alcohol are partic-
ularly preferred. Preferred ethoxylated alcohols include, for example, C~2_~4
alcohols containing 3 EO or 4 EO, Cg» alcohol containing 7 EO, C~3-15
alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C~2-~8 alcohols containing 3
15 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C~2-~a alcohol
containing 3 EO and C~2_,8 alcohol containing 5 EO. The degrees of
ethoxylation mentioned represent statistical mean values which, for a
special product, can be a whole number or a broken number. Preferred
alcohol ethoxylates have a narrow homolog distribution (narrow range
20 ethoxylates, NRE:). In addition to these nonionic surfactants, fatty
alcohols
containing more 'than 12 EO may also be used, examples including tallow
alcohol containing 14 EO, 25 EO, 30 EO, 40 EO or up to 80 EO.
Another class of preferred nonionic surfactants which may be used
either as sole nonionic surfactant or in combination with other nonionic
surfactants are alkoxylated, preferably ethoxylated or ethoxylated and
propoxylated, fatty acid alkyl esters preferably containing 1 to 8 carbon
atoms in the alkyl chain and 3 to 80 and preferably up to 20 alkoxy groups,
preferably ethoxy groups, in the molecule, more especially the fatty acid
methyl esters which are described, for example, in Japanese patent
CA 02314363 2000-07-20
21
application JP 581217598 or which are preferably produced by the process
described in International patent application WO-A-90113533.
Another class of nonionic surfactants which may advantageously be
used are the alkyl polyglycosides (APGs). Suitable alkyl polyglycosides
correspond to thE; general formula RO(G)Z where R is a linear or branched,
more particularly 2-methyl-branched, saturated or unsaturated aliphatic
radical containing 8 to 22 and preferably 12 to 18 carbon atoms and G
stands for a glycose unit containing 5 or 6 carbon atoms, preferably
glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably
between 1.0 and 2.0 and more preferably between 1.1 and 1.4.
Linear alkyl polyglucosides, i.e. alkyl polyglycosides in which the
polyglycosyl component is a glucose unit and the alkyl component is an n-
alkyl group, are preferably used.
The detergent/cleaner portions according to the invention may
advantageously contain alkyl polyglycosides, APG contents in the
detergent/cleaner portions of more than 0.2% by weight, based on the
tablet as a whole, being preferred. Particularly preferred detergent/cleaner
portions according to the invention contain APGs in quantities of 0.2 to
10% by weight, preferably in quantities of 0.2 to 5% by weight and more
preferably in quantities of 0.5 to 3% by weight.
Nonionic surfactants of the amine oxide type, for example N-
cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethyl-
amine oxide, and the fatty acid alkanolamide type are also suitable. The
quantity in which these nonionic surfactants are used is preferably no more
than the quantity in which the ethoxylated fatty alcohols are used and,
more preferably, no more than half that quantity.
Other suitable surfactants are polyhydroxyfatty acid amides
corresponding to formula (I):
CA 02314363 2000-07-20
22
R'
R-CO-N-[Z] ( I )
in which RCO is an aliphatic acyl group containing 6 to 22 carbon atoms,
R' is hydrogen, an alkyl or hydroxyalkyl group containing 1 to 4 carbon
atoms and [Z] is a linear or branched polyhydroxyalkyl group containing 3
to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxyfatty acid
amides are known substances which may normally be obtained by
reductive amination of a reducing sugar with ammonia, an alkylamine or an
alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl
ester or a fatty acid chloride.
The group of polyhydroxyfatty acid amides also includes compounds
corresponding to formula (II):
R'-O-R2
R-CO-N-[Z] (I I)
in which R is a linear or branched alkyl or alkenyl group containing 7 to 12
carbon atoms, R' is a linear, branched or cyclic alkyl group or an aryl group
containing 2 to 8 carbon atoms and R2 is a linear, branched or cyclic alkyl
group or an aryl group or an oxyalkyl group containing 1 to 8 carbon atoms,
C~~ alkyl or phenyl groups being preferred, and [Z] is a linear polyhydroxy-
alkyl group, of which the alkyl chain is substituted by at least two hydroxyl
groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives
of that group.
[Z] is preferably obtained by reductive amination of a reduced sugar,
for example glucose, fructose, maltose, lactose, galactose, mannose or
xylose. The N-alkoxy- or N-aryloxy-substituted compounds may then be
converted into the required polyhydroxyfatty acid amides by reaction with
fatty acid methyl esters in the presence of an alkoxide as catalyst, for
CA 02314363 2000-07-20
23
example in accordance with the teaching of International patent application
WO-A-95/07331.
According to the invention, nonionic surfactants from the group of
alkoxylated fatty alcohols containing 8 to 20 carbon atoms in the fatty
alcohol alkyl group are even more preferred, fatty alcohols of natural origin,
i.e. linear fatty alcohols predominantly having an even number of carbon
atoms in the alkyl group, being preferred to synthetic fatty alcohols (for
example branched fatty alcohols or fatty alcohols containing an odd
number of carbon atoms). Examples of the fatty alcohols from the
perspective of the availability of the compounds are lauryl alcohol (C~2),
myristyl alcohol (C~4), cetyl alcohol (C~6) etc. and mixtures emanating from
native sources. 'The number of alkoxy groups, above all ethoxy groups or
propoxy groups, more preferably ethoxy groups, may vary within wide limits
and, in one particularly preferred embodiment, is between 3 and 80.
According to the invention, other nonionic surfactants which may also be
present in the water-soluble polymer material are alkoxylated C&2o fatty
acid alkyl esters containing 1 to 8 carbon atoms in the alkyl group and 3 to
80 and preferably up to 20 alkoxy groups in the molecule, the alkoxy
groups preferably being ethoxy groups. From the practical standpoint, a
factor to be advantageously taken into account is that compounds from the
above-mentioned groups which are still liquid or paste-like at the applica-
tion temperatures, despite considerable chain lengths, are used.
According to the invention, anionic surfactants may also preferably
be used for the purpose mentioned. Within the group of these compounds,
alkyl benzenesulfonic acids containing 9 to 13 carbon atoms in the alkyl
groups and salts thereof (mainly present in alkaline medium), cumene
sulfonic acid and salts thereof, fatty alcohol sulfates containing 12 to 18
carbon atoms in the fatty alcohol alkyl group and C8_2o fatty acids and salts
thereof are particularly suitable.
CA 02314363 2000-07-20
24
In another particularly preferred embodiment of the detergent/
cleaner portions according to the invention, the components) of the water-
soluble polymer material also present in at least one active washing
preparation is/are selected from the group of hydrophilic plasticizers.
According to the invention, polyols containing 1 to 20 carbon atoms and 2
to 6 hydroxy groups, polyalkylene glycols containing 2 to 4 (preferably
linear) alkylene carbon atoms (i.e. ethylene groups, propylene groups or
butylene groups) in the molecule, preferably polyethylene glycols and/or
polypropylene glycols and more preferably polyethylene glycols and/or
polypropylene glycols with molecular weights of 200 to 12,000 and
preferably with molecular weights of less than 1500 are particularly
preferred. Amines structurally analogous to the polyalkylene glycols
mentioned above, i.e. compounds in which the glycol -O- group is replaced
by an amine -NH~- group, may also be used with advantage. The molecular
weight ranges mentioned above also apply to the amines. From the
practical perspective, compounds which are still liquid or paste-like at the
(elevated) application temperatures may be used with advantage.
In another preferred embodiment of the detergent/cleaner portions
according to the invention, the components) of the water-soluble polymer
material also prEaent in at least one active washing preparation is/are
selected from the group of perfumes and perfume preparations. Suitable
perfume oils or perfumes include individual perfume compounds, for
example synthetic products of the ester, ether, aldehyde, ketone, alcohol
and hydrocarbon type. Perfume compounds of the ester type are, for
example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.butyl cyclohexyl
acetate, linalyl acetate, dimethyl benzyl carbinyl acetate, phenyl ethyl
acetate, linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate,
allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The
ethers include, for example, benzyl ethyl ether; the aldehydes include, for
CA 02314363 2000-07-20
example, the linear alkanals containing 8 to 18 carbon atoms, citral,
citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxy-
citronellal, lilial and bourgeonal.
The ketones include, for example, the ionones, a-isomethyl ionone
5 and methyl cedryl ketone. The alcohols include anethol, citronellol,
eugenol, geraniol, linalool, phenyl ethyl alcohol and terpineol. The
hydrocarbons include, above all, the terpenes, such as limonene and
pinene. However, mixtures of various perfumes which together produce an
attractive perfume note are preferably used. Perfume oils such as these
10 may also contain natural perfume mixtures obtainable from vegetable
sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang
oil. Also suitable are clary oil, camomile oil, clove oil, melissa oil, mint
oil,
cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum
oil, galbanum oil and labdanum oil and orange blossom oil, neroli oil,
15 orange peel oil and sandalwood oil.
In another preferred embodiment of the invention, low molecular
weight polyacrylates or polymethacrylates or polymaleates (acids or - under
the alkaline in-use conditions - preferably their salts, including their amine
or (even organic) ammonium salts) or copolymers of polyacrylates/
20 polymethacrylates and polymaleates may also be used.
The concentrations of the particular compounds in the particular
phases, i.e. in the active washing preparations) and in the water-soluble
polymer materials) surrounding them, depend entirely on the particular
individual case. The concentration values are of course influenced by the
25 character of the material present in the two phases in question, optionally
interactions between two or more materials present, interactions) thereof
with the other components of the particular phase, the temperature, the
pressure and optionally other parameters. The phase equilibrium
concentration in one of the two phases in question is generally between 0.5
CA 02314363 2000-07-20
26
and 50% by weight, based on the total weight of the particular phase,
preferably between 1 and 30% by weight and more preferably between 3
and 25% by weight. The only critical factor so far as the concentration of a
suitable substance is concerned is that a phase equilibrium of the
concentration of 'the particular substance(s), at which the properties of the
active washing preparations) on the one hand and the water-soluble
polymer materials) on the other hand are in a desirable range, is
established between the phases.
According to the invention, it is of course also possible to design the
detergent/cleaner portion and/or its pack or the wrapper surrounding a part-
portion in such a way that one of the two phases does not contain any of
the substances subsequently producing the expected property(ies) in the
equilibrium whereas the other phase contains so much that, over a
controlled period (for example of a few hours or a few days), a phase
equilibrium is established between the two phases (at least one active
washing preparation and/or at least one wrapper) without the substance in
question being so heavily depleted in the phase in which it is initially
present that its desired or already optimized properties unacceptably
deteriorate or without the properties of the phase in which the substance in
question is initially not present at all or in a quantity below the
equilibrium
concentration deteriorating so seriously that subsequent establishment of a
phase equilibrium no longer improves the properties to an acceptable
extent. In this case, one or more components) alone may also be incorpo-
rated in one of the two phases while one or more other substances) alone
is/are incorporatf:d in the other phase. After the two phases have been
combined in the production of the detergent/cleaner portion according to
the invention by introducing one or more active washing preparations) into
one or more wrappers) of one or more water-soluble polymer material(s), a
phase equilibrium of the particular substance in the two phases (active
CA 02314363 2000-07-20
27
washing substance or water-soluble polymer material), which does not
adversely affect the required properties of the two phases, even in the
event of prolonged storage, is established under control through diffusion
or adsorption effects.
In the detergent/cleaner portions according to the invention, the
water-soluble material surrounding the active washing preparations) is in
the form of a film, capsule or coating.
According to the invention, particularly preferred wrappers for the at
least one active washing preparation are polyvinyl alcohol films. The PVAL
films preferably used are soluble at the temperature of cold water, i.e. at
about 12 to 18°C. In another preferred embodiment, the PVAL films used
are soluble at a temperature in a range which corresponds to the
temperature range of the washing/dishwashing cycle in which the second
measured quantity of a washing preparation is used. The temperature in
question, for example in the case where the measured quantity of an active
washing preparation in question is a preparation for the main wash cycle of
a dishwashing machine, is the temperature of the main wash cycle, for
example a temperature in the range from > about 20 to about 55°C,
preferably >25°C to below 45°C and more preferably a temperature
above
30°C to, for example, 40°C. In the case where the particular
measured
quantity of an active washing preparation is a preparation for the clear-rinse
cycle of a dishwashing machine, the temperature at which the film
dissolves in water is the temperature of the clear-rinse cycle, for example a
temperature of >45°C, for example in the range from 50 to 55°C
or even
higher. In line with the requirements and typical settings of the machines,
other temperature ranges are relevant to washing processes carried out in
washing machines, for example up to about 25°C for the prewash cycle,
up
to about 90°C for the main wash cycle and up to about 30°C for
the final
wash cycle. The temperatures at which the water-soluble ~Im dissolves
CA 02314363 2000-07-20
28
can of course be adjusted within wide limits. In addition, films adjusted to a
certain water-solubility temperature range (cf. the above-mentioned films of
the MOWIOL~ type or the SOLUBLON~ type) are commercially
obtainable. The expert is thus able to select such films according to
requirements and to incorporate the components used in the films in
accordance with the invention in those films or to allow them to enter the
films through establishment of the phase equilibrium.
In another preferred embodiment of the present invention, the water-
soluble material surrounding the particular measured quantity of an active
washing preparation is a water-soluble capsule. Such capsules are also
known from the prior art. They may be, for example, capsules of PVAL,
gelatine or similar materials, but are by no means confined to materials
such as these. Such capsules are commercially obtainable and are widely
used in connection with pharmaceutical preparations and food additives.
Capsules of hard gelatine or soft gelatine have proved to be particularly
successful and, accordingly, are particularly preferred for the purposes of
the invention.
In another preferred embodiment of the invention, the water-soluble
material surrounding the particular measured quantity of an active washing
preparation is a water-soluble coating. Such coatings or membrane
materials are used for coating washing substances in the prior art and, like
the film materials, may be adjusted in their physical and chemical
properties, for example their solubility in water, melting point or melting
range, to meet certain technical requirements. For the purposes of the
present invention, coatings soluble in water in the narrower sense are as
suitable for coating active washing preparations as coatings which dissolve
in an aqueous environment providing certain physical or chemical
conditions, for example a certain temperature or a certain pH, are
established because, for example, they melt and the membrane materials
CA 02314363 2000-07-20
29
are then dispersE:d in water so that the ingredients, i.e. the active washing
preparation(s), previously surrounded by the coating or membrane are
released.
In this sense, the term "water-soluble" in the context of the present
invention generally encompasses not only the ability of the coatings/
membranes of the active washing preparations to be dissolved by an
aqueous medium (in the narrower sense), but also their ability (in the
broader sense) to change when certain or physical or chemical conditions
are established in the aqueous environment so that their physical integrity
is lost and the coating/membrane releases the ingredients into the aqueous
phase. The melting and subsequent dispersion of the membrane/coating
material in the aqueous phase is a typical (but non-limiting) example of this.
Basically, the coatings or capsule materials should have a melting
range at temperatures at which the active substances to be
coated/encapsulated are not exposed to significant thermal stressing. On
the other hand, however, the melting range must be high enough still to
afford the encapsulated active washing preparations effective protection at
at least slightly elevated temperatures. According to the invention, the
coating/encapsulating materials have melting ranges between about 45°C
and about 75°C., The expression "melting range" in the present case
means that the melting range lies within the temperature range mentioned
and does not denote the width of the melting range. Coatings of waxes
have proved to be particularly effective in this connection where they can
be directly applied to the active washing preparation or its individual
components. Accordingly, such coatings are particularly preferred because
they are easy to apply and because their solubility in water can be exactly
adjusted and hence optimally adapted to meet particular requirements and
a phase equilibrium can be established between the coating and the
coated active washing preparation.
CA 02314363 2000-07-20
"Waxes" in the context of the present invention are understood to
be any of a number of natural or synthetic substances which generally melt
above 40°C without decomposing and, even just above their melting
point,
are of relatively low viscosity and non-stringing. Their consistency and
5 solubility are dependent to a large extent on temperature.
Waxes are divided into three groups according to their origin,
namely: natural waxes, chemically modified waxes and synthetic waxes.
The natural waxes include, for example, vegetable waxes, such as
candelilla wax, carnauba wax, Japan wax, esparto grass wax, cork wax,
10 guaruma wax, rice oil wax, sugar cane wax, ouricury wax or montan wax,
animal waxes, such as bees wax, shellac wax, spermaceti, lanolin (wool
wax) or uropygial fat, mineral waxes, such as ceresine or ozocerite (earth
wax), or petrochemical waxes, such as petrolatum, paraffin waxes or
microwaxes.
15 The chemically modified waxes include, for example, hard waxes,
such as montan f;ster waxes, sassol waxes or hydrogenated jojoba waxes.
Synthetic waxes are generally understood to be polyalkylene waxes
or polyalkylene glycol waxes.
Compounds from other classes which satisfy the above-mentioned
20 softening point requirements may also be used as coating/encapsulating
materials. For example, higher esters of phthalic acid, more particularly the
dicyclohexyl phthalate commercially available under the name of Unimoll~
66 (Bayer AG), have proved to be suitable synthetic compounds. Synthetic
waxes of lower carboxylic acids and fatty alcohols, for example the
25 dimyristyl tartrate commercially available under the name of
Cosmacol~ETLP (Condea), are also suitable. Conversely, synthetic or
partly synthetic esters of lower alcohols with fatty acids from native sources
may also be used. This class of substances includes, for example, Tegin~
90 (Goldschmidt), a glycerol monostearate palmitate. Schellack-KPS-
CA 02314363 2000-07-20
31
Dreiring-SP (Kalkhoff GmbH) may also be used as a coating/encapsulating
material in accordance with the invention.
In the context of the invention, the waxes also include, for example,
the so-called wax alcohols. Wax alcohols are relatively high molecular
weight water-insoluble fatty alcohols generally containing about 22 to 40
carbon atoms. 'The wax alcohols are used as a principal constituent of
many natural waxes, for example in the form of wax esters of relatively high
molecular weighs: fatty acids (wax acids). Examples of wax alcohols are
lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or
melissyl
alcohol. The coating of the washing preparations may also contain wool
wax alcohols which are understood to be triterpenoid and steroid alcohols,
for example the lanolin obtainable, for example, under the name of
Argowax~ (Pamentier ~ Co.). According to the invention, fatty acid
glycerol esters or fatty acid alkanolamides and also water-insoluble or
substantially water-insoluble polyalkylene glycol compounds may also be
used at least partly as an encapsulating material.
In one preferred embodiment, the coatings used in accordance with
the invention prE;dominantly contain paraffin wax. In another preferred
embodiment, at least 50% by weight of the total of encapsulating materials
present and preferably more consists of paraffin wax. Paraffin wax
contents (based on total enapsulating material) of about 60% by weight,
about 70% by weight or about 80% by weight are particularly suitable, even
higher contents of, for example, more than 90% by weight being particularly
preferred. In one: particular embodiment of the invention, the total quantity
of encapsulating material used consists of paraffin wax. So far as the
present invention is concerned, paraffin waxes have the advantage over
the other natural waxes mentioned that the waxes do not undergo
hydrolysis in an alkaline detergent environment (as might be expected, for
example, in the ease of the wax esters), because a paraffin wax does not
CA 02314363 2000-07-20
32
contain any hydrolyzable groups.
Paraffin waxes consist principally of alkanes and small amounts of
iso- and cycloalkanes. The paraffin waxes preferably used in accordance
with the invention preferably contain virtually no constituents with a melting
point above 70°C: and, more preferably, above 60°C. If the
temperature in
the washing/cleaning solution falls below this melting temperature, high-
melting alkanes in the paraffin can leave unwanted wax residues behind
on the laundry to be washed or the ware to be cleaned. Wax residues
such as these generally leave the cleaned surface with an unattractive
appearance and should therefore be avoided. The encapsulating
substances used in accordance with the invention contain a paraffin wax
with a melting range of 50°C to 60°C.
The paraffin wax used preferably has a high content of alkanes,
isoalkanes and cycloalkanes solid at ambient temperature (generally about
10 to about 30°(:). The higher the percentage of solid wax constituents
present in a wax at room temperature, the more useful that wax is for the
purposes of the present invention. The higher the percentage of solid wax
constituents, the greater the resistance of the coated particles to impact or
friction with othe~~r surfaces, which leads to better protection of the active
washing substances present in the particles.
Besides paraffin as principal constituent, the coating material may
also contain one or more of the waxes or wax-like substances mentioned
above. Basically, the composition of the mixture forming the
encapsulating/coating material should be such that the coated particles are
at least substantially insoluble in water. Their solubility in water should
not
exceed about 10 mg/l at a temperature of about 30°C and should
preferably be below 5 mg/l. At all events, the coating should have very low
solubility in water, even in water at elevated temperature, in order largely
to
avoid the active washing substances being released independently of
CA 02314363 2000-07-20
33
temperature.
The principle described above facilitates the delayed release of
active washing preparations at a certain time in the washing or cleaning
cycle and may be applied with particular advantage when the main wash
cycle, for example in dishwashing, is carried out at a relatively low
temperature (for example 45°C), so that the active washing substance is
only released from the coated particles comprising a rinse aid in the final
rinse cycle at relatively high temperatures (for example > 55°C).
Membrane materials or coatings preferably used in accordance with
the invention comprise one or more substances with a melting range of
40°C to 75°C in quantities of 6 to 30% by weight, preferably 7.5
to 25% by
weight and more preferably 10 to 20% by weight, based on the weight of
the particles.
In another preferred embodiment of the invention, the detergent/
cleaner portion in which one or more components) of at least one of the
active washing preparations is/are also present in the water-soluble
polymer material and/or in which one or more components) of the water-
soluble polymer material is/are also present in at least one of the active
washing preparations additionally comprises a wrapper or outer pack
which, in one particular embodiment, is less permeable to water vapor
and/or to the particular components) present in the phase equilibrium
and/or subjected to the establishment of a phase equilibrium than the
wrappers) immediately surrounding the active washing preparation(s).
This additional wrapper may be a wrapper surrounding only one detergent/
cleaner portion or a wrapper surrounding several detergent/cleaner
portions. The second of these two cases is preferred: several detergent
portions may be offered to the consumer so to speak in a "portion pack".
Not only does this solve a transport-related problem of simultaneously
supplying several (for example six, ten or more) detergent/cleaner portions,
CA 02314363 2000-07-20
34
it also affords the individual detergent/cleaner portions optimal protection
against exchange with water vapor or substances from the interior of the
wrapper or substances from the surrounding environment. Particularly high
stability in storage can thus be guaranteed. The permeability of this
additional wrapper to water and to the components) present in the phase
equilibrium in accordance with the invention may be entirely different.
Thus, the permeability to one or more of the components may (optionally)
be slightly greater or smaller than to water. In another preferred
embodiment of the invention, the additional wrapper in question is
reclosable after opening and removal of one or more detergent portions.
This can be guaranteed in known manner, for example as described in EP-
A 0 899 208. 'The expert in this packaging field is familiar with such
devices for reclosing a wrapper of the type in question and may select them
unconditionally according to his own expert knowledge.
In another preferred embodiment of the invention, an outer pack as
described herein with only limited permeability to water vapor is used.
Desirable packs which may be used with particular advantage in
accordance with 'the invention have a water vapor transmission rate of <_ 10
g/m2 per day at 23°C/85% relative humidity and preferably a water vapor
transmission rate of <_ 5 g/m2 per day. Outer packs which do not have an
measurable permeability to water vapor as measured to DIN EN 53122 are
particularly preferred. Suitable materials for these purposes are also
known from the prior art and may be, for example, single-layer, multilayer,
laminated or co-extruded films of such materials as polyethylene, poly-
propylene, polystyrene, polyethylene terephthalate, copolymers thereof or
mixtures thereof. Polyethylene or polypropylene films with one or more
layers are particularly advantageous.
In the detergent/cleaner portions according to the invention, several,
for example first, second and optionally further (third, fourth, etc.),
CA 02314363 2000-07-20
measured quantities of active washing preparations independently of one
another are preferably laundry/ dishwasher detergent formulations in the
form of shaped bodies, powders, gels or liquids. Detergent/cleaner
preparations in the form of shaped bodies may be present as granules,
5 tablets, blocks, briquettes, rings or other shaped bodies. More
particularly,
tablets, blocks or briquettes may be plain shaped bodies or shaped bodies
with depressions, cavities, grooves or the like which are used to
accommodate particular components of the preparations or which may
even have a performance-related function. Liquid detergent/cleaner
10 preparations may be solutions, suspensions or other liquid systems known
for washing and cleaning purposes.
The deterc~ent/cleaner portions contain one or more ingredients from
the group of surfactants, surfactant compounds, builders, bleaching agents,
bleach activators, enzymes, foam inhibitors, dyes and perfumes and -
15 where the detergent/cleaner portions are at least partly present as tablets
-
binders and disintegration aids. These classes of ingredients are described
in the following.
In order to develop their washing effect, the laundry/dishwasher
detegent portions according to the invention contain surfactants from the
20 group of anionic:, nonionic, zwitterionic or cationic surfactants, anionic
surfactants being greatly preferred both for economic reasons and by virtue
of their performance spectrum.
The anionic and nonionic surfactants suitable for use in the
detergent portions according to the invention were broadly described in the
25 foregoing. As mE:ntioned, anionic surfactants are preferably used.
In another preferred embodiment, cationic surfactants may be used
in addition to anionic and nonionic surfactants. They are mainly used as
detergency boosters and need only be used in small quantities. If cationic
surfactants are used, they are present in the detergents in quantities of
CA 02314363 2000-07-20
36
preferably 0.01 to 10% by weight and more preferably in quantities of 0.1 to
3.0% by weight.
In cases where the detergent/cleaner portions according to the
invention are laundry detergents, they normally contain one or more
surfactants) in total quantities of 5 to 50% by weight and preferably 10 to
35% by weight, surfactants optionally being present in relatively large or
relatively small quantities in part-portions of the laundry detergent portions
according to the invention. In other words, the quantity of surfactant is not
the same in all portions, instead part-portions with a relatively large
surfactant content and part-portions with a relatively small surfactant
content may be provided.,
In cases where the detergent/cleaner portions according to the
invention are cleaning compositions, more particularly dishwashing
detergents, they normally contain one or more surfactants in total quantities
of 0.1 to 10% by weight and preferably in quantities of 0.5 to 5% by weight,
surfactants optionally being present in relatively large or relatively small
quantities in part-portions of the laundry detergent portions according to the
invention. In other words, with dishwashing detergents also, the quantity of
surfactant is not the same in all portions, instead part-portions with a
relatively large surfactant content and part-portions with a relatively small
surfactant content may be provided.
Besides the active washing ingredients, builders are the most
important ingredients of detergents. Any of the builders normally used in
detergents may be present in the detergent/cleaner portions according to
the invention, including in particular zeolites, silicates, carbonates,
organic
co-builders and also - providing there are no ecological objections to their
use - phosphates.
Suitable crystalline layer-form sodium silicates correspond to the
general formula f~aMSiXO~+~y H20, where M is sodium or hydrogen, x is a
CA 02314363 2000-07-20
37
number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x
being 2, 3 or 4. Crystalline layer silicates such as these are described, for
example, in European patent application EP-A-0 164 514. Preferred
crystalline layer silicates corresponding to the above formula are those in
which M is sodium and x assumes the value 2 or 3. Both Vii- and 8-sodium
disilicates Na2Si;z05y H20 are particularly preferred, ~-sodium disilicate
being obtainable, for example, by the process described in International
patent application WO-A- 91108171.
Other useful builders are amorphous sodium silicates with a
modulus (Na20:Si02 ratio) of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and more
preferably 1:2 to 1:2.6 which dissolve with delay and exhibit multiple wash
cycle properties. The delay in dissolution in relation to conventional
amorphous sodium silicates can have been obtained in various ways, for
example by surface treatment, compounding, compacting or by overdrying.
In the context of the invention, the term "amorphous" is also understood to
encompass "X-ray amorphous". In other words, the silicates do not
produce any of the sharp X-ray reflexes typical of crystalline substances in
X-ray diffraction experiments, but at best one or more maxima of the
scattered X-radiation which have a width of several degrees of the
diffraction angle. However, particularly good builder properties may even
be achieved where the silicate particles produce crooked or even sharp
diffraction maxima in electron diffraction experiments. This may be
interpreted to mean that the products have microcrystalline regions
between 10 and a few hundred nm in size, values of up to at most 50 nm
and, more particularly, up to at most 20 nm being preferred. So-called X-
ray amorphous silicates such as these, which also dissolve with delay in
relation to conventional waterglasses, are described for example in
German patent application DE-A-44 00 024. Compacted amorphous
silicates, compounded amorphous silicates and overdried X-ray-amorphous
CA 02314363 2000-07-20
38
silicates are particularly preferred.
A finely crystalline, synthetic zeolite containing bound water
optionally is preferably zeolite A and/or zeolite P. Zeolite MAP~ (for
example Doucil A24, a Crosfield product) is a particularly preferred P-type
zeolite. However, zeolite X and mixtures of A, X and/or P are also suitable.
According to thE: invention, it is also possible to use, for example, a
commercially obtainable co-crystallizate of zeolite X and zeolite A (ca. 80%
by weight zeolite X) which is marketed by CONDEA Augusta S.p.A. under
the name of VEGOBOND AX~ and which may be described by the
following formula:
nNa20 ~ (1-n)K2O ~ AI203 ~ (2 - 2.5)Si02 ~ (3.5 - 5.5) H20
Suitable zeolites have a mean particle size of less than 10 pm (volume
distribution, as rneasured by the Coulter Counter Method) and contain
preferably 18 to 22% by weight and more preferably 20 to 22% by weight of
bound water.
The generally known phosphates may of course also be used as
builders providinc,~ their use should not be avoided on ecological grounds.
The sodium salty of the orthophosphates, the pyrophosphates and, in
particular, the trip~olyphosphates are particularly suitable.
Useful organic builders are, for example, polycarboxylic acids usable
in the form of their sodium salts, polycarboxylic acids in this context being
those carboxylic acids which carry more than one acid function. These
include, for example, citric acid, adipic acid, succinic acid, glutaric acid,
malic acid, tartaric acid, malefic acid, fumaric acid, sugar acids, amino-
carboxylic acids,, nitrilotriacetic acid (NTA) - providing its use is not
ecologically unsafe - and mixtures thereof. Preferred salts are the salts of
the polycarboxylic acids, such as citric acid, adipic acid, succinic acid,
CA 02314363 2000-07-20
39
glutaric acid, tartaric acid, sugar acids and mixtures thereof. The acids per
se may also be used. Besides their builder effect, the acids also typically
have the property of an acidifying component and, hence, also serve to
establish a relatively low and mild pH value in detergent portions according
to the invention. Citric; acid, succinic acid, glutaric acid, adipic acid,
gluconic acid and mixtures thereof are particularly mentioned in this regard.
Other suitable builders are polymeric polycarboxylates such as, for
example, the alkali metal salts of polyacrylic or polymethacrylic acid, for
example those with a relative molecular weight of 500 to 70,000 g/mole.
The molecular weights mentioned in this specification for polymeric
polycarboxylates are weight-average molecular weights MW of the particular
acid form which, basically, were determined by gel permeation
chromatography (GPC) using a UV detector. The measurement was
carried out against an external polyacrylic acid standard which provides
realistic molecular weight values by virtue of its structural similarity to
the
polymers investiclated. These values differ distinctly from the molecular
weights measured against polystyrene sulfonic acids as standard. The
molecular weights measured against polystyrene sulfonic acids are
generally higher than the molecular weights mentioned in this specification.
Particularlyr suitable polymers are polyacrylates which preferably
have a molecular weight of 2,000 to 20,000 g/mole. By virtue of their
superior solubility, preferred representatives of this group are the short-
chain polyacrylates which have molecular weights of 2,000 to 10,000
g/mole and, more: particularly, 3,000 to 5,000 g/mole.
Also suitable are copolymeric polycarboxylates, particularly those of
acrylic acid with methacrylic acid and those of acrylic acid or methacrylic
acid with malefic <~cid. Acrylic acid/maleic acid copolymers containing 50 to
90% by weight of acrylic acid and 50 to 10% by weight of malefic acid have
proved to be particularly suitable. Their relative molecular weights, based
CA 02314363 2000-07-20
on the free acids, are generally in the range from 2,000 to 70,000 g/mole,
preferably in the range from 20,000 to 50,000 g/mole and more preferably
in the range from 30,000 to 40,000 g/mole.
The (co)polymeric polycarboxylates may be used either in the form
5 of an aqueous solution or in powder form. The detergent/cleaner portions
according to the invention preferably contain 0.5 to 20% by weight and
more particularly 3 to 10% by weight of (co)polymeric polycarboxylates.
In order to improve solubility in water, the polymers may also contain
allyl sulfonic acids, such as for example allyloxybenzene sulfonic acid and
10 methallyl sulfonic acid (cf. EP-B-727 448), as monomer.
Other particularly preferred polymers are biodegradable polymers of
more than two different monomer units, for example those which contain
salts of acrylic acid and malefic acid and vinyl alcohol or vinyl alcohol
derivatives as monomers according to DE-A-43 00 772 or those which
15 contain salts of acrylic acid and 2-alkylallyl sulfonic acid and sugar
derivatives as monomers according to DE-C-42 21 381.
Other preferred copolymers are those which are described in
German patent applications DE-A-43 03 320 and DE-A-44 17 734 and
which preferably contain acrolein and acrylic acid/acrylic acid salts or
20 acrolein and vinyl acetate as monomers.
Other preferred builders are polymeric aminodicarboxylic acids, salts
or precursors thereof. Particular preference is attributed to polyaspartic
acids or salts and derivatives thereof which, according to German patent
application DE-A-195 40 086, are also said to have a bleach-stabilizing
25 effect in addition to their co-builder properties.
Other suitable builders are polyacetals which may be obtained by
reaction of dialdehydes with polyol carboxylic acids containing 5 to 7
carbon atoms and at least three hydroxyl groups, for example as described
in European patent application EP-A-0 280 223. Preferred polyacetals are
CA 02314363 2000-07-20
41
obtained from dialdehydes, such as glyoxal, glutaraldehyde, terephthal-
aldehyde and mixtures thereof and from polyol carboxylic acids, such as
gluconic acid and/or glucoheptonic acid.
Other suitable organic builders are dextrins, for example oligomers
or polymers of carbohydrates which may be obtained by partial hydrolysis
of starches. ThE: hydrolysis may be carried out by standard methods, for
example acid- or enzyme-catalyzed methods. The end products are
preferably hydrolysis products with average molecular weights of 400 to
500,000 g/mole. A polysaccharide with a dextrose equivalent (DE) of 0.5 to
40 and, more particularly, 2 to 30 is preferred, the DE being an accepted
measure of the reducing effect of a polysaccharide by comparison with
dextrose which has a DE of 100. Both maltodextrins with a DE of 3 to 20
and dry glucose sirups with a DE of 20 to 37 and also so-called yellow
dextrins and while dextrins with relatively high molecular weights of 2,000
to 30,000 g/mole may be used. A preferred dextrin is described in British
patent application 9419 091.
The oxidized derivatives of such dextrins are their reaction products
with oxidizing agents which are capable of oxidizing at least one alcohol
function of the saccharide ring to the carboxylic acid function. Dextrins thus
oxidized and processes for their production are known, for example, from
European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0
472 042 and EP-A-0 542 496 and from International patent applications
WO 92/18542, WO 93108251, WO 93116110, WO 94128030, WO 95107303,
WO 95/12619 and WO 95120608. An oxidized oligosaccharide
corresponding to~ German patent application DE A-196 00 018 is also
suitable. A product oxidized at C6 of the saccharide ring can be particularly
advantageous.
Other suitable co-builders are oxydisuccinates and other derivatives
of disuccinates, G>referably ethylenediamine disuccinate. Ethylenediamine-
CA 02314363 2000-07-20
42
N,N'-disuccinate (EDDS), of which the synthesis is described for example
in US 3,158,615, is preferably used in the form of its sodium or magnesium
salts. The glycerol disuccinates and glycerol trisuccinates described, for
example, in US 4,524,009, in US 4,639, 325, in European patent
application EP-A-0 150 930 and in Japanese patent application JP
931339,896 are also particularly preferred in this connection. The
quantities used in zeolite-containing and/or silicate-containing formulations
are from 3 to 15% by weight.
Other useful organic co-builders are, for example, acetylated
hydroxycarboxylic acids and salts thereof which may optionally be present
in lactone form and which contain at least 4 carbon atoms, at least one
hydroxy group and at most two acid groups. Co-builders such as these are
described, for example, in International patent application WO-A-95120029.
Another class of substances with co-builder properties are the
phosphonates, more particularly hydroxyalkane and aminoalkane phos
phonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1
diphosphonate (HEDP) is particularly important as a co-builder. It is
preferably used in the form of a sodium salt, the disodium salt showing a
neutral reaction and the tetrasodium salt an alkaline reaction (pH 9).
Preferred aminoalkane phosphonates are ethylenediamine tetramethylene
phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate
(DTPMP) and higher homologs thereof. They are preferably used in the
form of the neutrally reacting sodium salts, for example as the hexasodium
salt of EDTMP and as the hepta- and octasodium salt of DTPMP. Within
the class of phosphonates, HEDP is preferably used as builder. The
aminoalkane phosphonates also show a pronounced heavy metal binding
capacity. Accordingly, it can be of advantage to use aminoalkane
phosphonates, more especially DTPMP, or mixtures of the phosphonates
mentioned, particularly if the detergent/cleaner portions according to the
CA 02314363 2000-07-20
43
invention also contain bleach.
In addition, any compounds capable of complexing alkaline earth
metal ions may be used as co-builders.
In addition to the ingredients - surfactants and builders - mentioned
above, the dete~rgentlcleaner portions according to the invention may
contain other typical detergent ingredients, for example from the group of
bleaching agents, bleach activators, enzymes, perfumes, perfume carriers,
fluorescing agents, dyes, foam inhibitors, silicone oils, redeposition
inhibitors, optical brighteners, discoloration inhibitors, dye transfer
inhibitors
and corrosion inhibitors.
Among the compounds yielding H202 in water which serve as
bleaching agents, sodium perborate tetrahydrate and sodium perborate
monohydrate are particularly important. Other useful bleaching agents are,
for example, sodium percarbonate, peroxypyrophosphates, citrate pefiy-
drates and H~~02-yielding peracidic salts or peracids, such as
perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or
diperdodecane dioic acid. If detergent or bleaching compositions for
dishwashing machines are being produced, bleaching agents from the
group of organic bleaches may also be used. Typical organic bleaching
agents are diacyl peroxides, such as dibenzoyl peroxide for example.
Other typical organic bleaching agents are the peroxy acids, of which alkyl
peroxy acids and aryl peroxy acids are particularly mentioned as examples.
Preferred representatives are (a) peroxybenzoic acid and ring-substituted
derivatives thereof, such as alkyl peroxybenzoic acids, but also peroxy-a-
naphthoic acid and magnesium monoperphthalate, (b) aliphatic or
substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic
acid, s-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid
(PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic
acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic
CA 02314363 2000-07-20
44
peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-
diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid,
diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic acid, N,N-
terephthaloyl-di(~i-aminopercaproic acid).
Other suitable bleaching agents in compositions for dishwashing
machines are chlorine- and bromine-releasing substances. Suitable
chlorine- or bromine-releasing materials are, for example, heterocyclic N-
bromamides and N-chloramides, for example trichloroisocyanuric acid,
tribromoisocyanurlc acid, dibromoisocyanuric acid and/or dichloro-
isocyanuric acid (DICA) and/or salts thereof with cations, such as
potassium and sodium. Hydantoin compounds, such as 1,3-dichloro-5,5-
dimethyl hydantoin, are also suitable.
In order to obtain an improved bleaching effect where washing is
carried out at temperatures of 60°C or lower, bleach activators may be
incorporated in l:he detergents according to the invention. The bleach
activators may be compounds which form aliphatic peroxocarboxylic acids
containing preferably 1 to 10 carbon atoms and more preferably 2 to 4
carbon atoms and/or optionally substituted perbenzoic acid under
perhydrolysis conditions. Substances bearing O- and/or N-acyl groups with
the number of carbon atoms mentioned and/or optionally substituted
benzoyl groups are suitable. Preferred bleach activators are polyacylated
alkylenediamines, more particularly tetraacetyl ethylenediamine (TAED),
acylated triazine derivatives, more particularly 1,5-diacetyl-2,4-dioxohexa-
hydro-1,3,5-triazine (DADHT), acylated glycolurils, more particularly
tetraacetyl glycoluril (TAGU), N-acylimides, more particularly N-nonanoyl
succinimide (NOSI), acylated phenol sulfonates, more particularly n-
nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic
anhydrides, more particularly phthalic anhydride, acylated polyhydric
alcohols, more particularly triacetin, ethylene glycol diacetate and 2,5-
CA 02314363 2000-07-20
diacetoxy-2,5-dihydrofuran.
In addition to or instead of the conventional bleach activators
mentioned above, so-called bleach catalysts may also be incorporated in
the detergent/cleaner portions. Bleach catalysts are bleach-boosting
5 transition metal salts or transition metal complexes such as, for example,
manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or
carbonyl comple:Kes. Manganese, iron, cobalt, ruthenium, molybdenum,
titanium, vanadium and copper complexes with nitrogen-containing tripod
ligands and cobalt-, iron-, copper- and ruthenium-ammine complexes may
10 also be used as bleach catalysts.
Suitable enzymes are those from the class of proteases, lipases,
amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial
strains or fungi,, such as Bacillus subtilis, Bacillus licheniformis and
Streptomyces griseus, are particularly suitable. Proteases of the subtilisin
15 type are preferred, proteases obtained from Bacillus lentus being
particularly preferred. Enzyme mixtures, for example of protease and
amylase or protease and lipase or protease and cellulase or of cellulase
and lipase or of protease, amylase and lipase or of protease, lipase and
cellulase, but especially cellulase-containing mixtures, are of particular
20 interest. Peroxidases or oxidases have also proved to be suitable in some
cases. The enzymes may be adsorbed to supports and/or encapsulated in
membrane materials to protect them against premature decomposition.
The percentage content of the enzymes, enzyme mixtures or enzyme
granules in the compositions according to the invention may be, for
25 example, from about 0.1 to 5% by weight and is preferably from 0.1 to
about 2% by weight.
In one p<~rticularly preferred embodiment, the detergent/cleaner
portions according to the invention contain other additives known from the
prior art as additives for laundry-dishwasher detergent preparations. These
CA 02314363 2000-07-20
46
other additives may either be added to one or more, if necessary even all,
of the part-portions (active washing preparations) of the detergent/cleaner
portions according to the invention or, as described in co-pending patent
application 199 29 098.8 with the title "Active-substance portion pack", may
be incorporated in the water-soluble wrappers surrounding the active
washing preparations, i.e. for example in the water-soluble films, but also in
the capsules or coatings according to the invention.
A preferred group of additives used in accordance with the invention
are optical brighteners. The optical brighteners normally present in
detergents may be used. They are added in the form of an aqueous
solution or in the form of a solution in an organic solvent to the polymer
solution which i~; converted into the film or are added to a part-portion
(active washing preparation) of a detergent/cleaner in solid or liquid form.
Examples of optical brighteners are derivatives of diamino-
stilbenedisulfonic acid or alkali metal salts thereof. Suitable optical
brighteners are, for example, salts of 4,4'-bis-(2-anilino-4-morpholino-1,3,5-
triazinyl-6-amino)-stilbene-2,2'-disulfonic acid or compounds of similar
composition which contain a diethanolamino group, a methylamino group,
an anilino group or a 2-methoxyethylamino group instead of the morpholino
group. Brighteners of the substituted Biphenyl styryl type, for example
alkali metal salts of 4,4'-bis-(2-sulfostyryl)-Biphenyl, 4,4'-bis-(4-chloro-3-
sulfostyryl)-Biphenyl or 4-(4-chlorostyryl)-4'-(2-sulfostyryl)-Biphenyl, may
also be present in the part-portions (active washing preparations) of the
detergent/cleaner portions according to the invention. Mixtures of the
brighteners mentioned above may also be used.
According to the invention ,another preferred group of additives are
UV filters. These are substances which are released into the wash liquor
during the washing process or in the subsequent fabric-softening process
and accumulate on the fibers where they have a UV-filtering effect. The
CA 02314363 2000-07-20
47
products commercially available under the name of Tinosorb from Ciba
Speciality Chemicals are suitable UV filters.
Other possible additives - preferred in special embodiments - are
foam inhibitors and also bitter substances for preventing children from
accidentally swallowing the packs or parts thereof.
Another group of additives preferably used in accordance with the
invention are dyes, more particularly water-soluble or water-dispersible
dyes. Dyes of the type normally used to improve visual product appeal in
detergents/cleaners are preferred. Such dyes are not difficult for the expert
to choose, above all because they have high stability in storage, are not
affected by the other ingredients of the active washing preparations or by
light and do not have any pronounced substantivity for textile fibers so as
not to color them. According to the invention, the dyes are present in the
detergent/cleaner portions in quantities of less than 0.01 % by weight.
Another class of additives which may be added to the
detergentlcleaner portions according to the invention are polymers.
Suitable polymers are; on the one hand, polymers which show co-builder
properties during washing, dishwashing or cleaning, i.e. for example
polyacrylic acids, modified polyacrylic acids and corresponding copolymers.
Another group of polymers are polyvinyl pyrrolidone and other redeposition
inhibitors, such as copolymers of polyvinyl pyrrolidone, cellulose ethers and
the like. In another embodiment of the invention, the polymers may also be
soil repellents. Soil repellents are polymers which are absorbed onto fibers
or hard surfaces where they counteract resoiling. Relevant compounds of
this type are known to the expert on detergents. They are polyesters of
terephthalic acid and ethylene glycol partly modified with sulfonic acid
groups.
Another group of additives are bleach catalysts, more particularly
bleach catalysts; for dishwasher detergents or laundry detergents.
CA 02314363 2000-07-20
48
Complexes of manganese and cobalt, more particularly with nitrogen-
containing ligands, are used for this purpose.
Another group of additives preferably used in accordance with the
invention are silver corrosion inhibitors, i.e. any of various, mostly cyclic
organic compounds which are also familiar to the expert and which
contribute towards preventing silver-containing articles from tarnishing
during the dishwashing process.
Other additives which may be present in the detergent/cleaner
portions according to the invention are components which positively
influence the removal of oils and fats from textiles, so-called soil
repellents.
This effect becomes particularly clear when a textile which has already
been repeatedly washed with a detergent according to the invention
containing this oil- and tat-dissolving component is soiled. Preferred oil-
and fat-dissolving components include, for example, nonionic cellulose
ethers, such as methyl cellulose and methyl hydroxypropyl cellulose
containing 15 to 30% by weight of methoxy groups and 1 to 15% by weight
of hydroxypropo~;y groups, based on the nonionic cellulose ether, and the
polymers of phthalic acid and/or terephthalic acid known from the prior art
or derivatives thereof, mare particularly polymers of ethylene terephthalates
and/or polyethylene glycol terephthalates or anionically and/or nonionically
modified derivatives thereof. Of these, the sulfonated derivatives of
phthalic acid and terephthalic acid polymers are particularly preferred.
All these additives are added to the detergent/cleaner portions
according to the invention in quantities of up to at most 30% by weight and
preferably 2 to 20% by weight. As already mentioned, they may also be
added to a material of a water-soluble wrapper which comprises the, or one
of the, active washing preparation(s). In order to balance the formulation,
therefore, the expert may also increase the weight of the plastic material for
the wrapper in order thus to utilize the storage effect obtained in
CA 02314363 2000-07-20
49
accordance with the invention by incorporating the additives in the
wrappers) or additionally to keep the additives mentioned at least partly in
the remaining active washing preparation. However, this is less preferred.
Perfumes are added to the detergent/cleaner portions according to
the invention to improve the aesthetic impression created by the products
and to provide the consumer not only with the required technical
performance (fabric softening result) but also with a visually and sensorially
"typical and unmistakable" product.
The perfumes and perfume preparations suitable for use in the
detergent/cleaner portions according to the invention were broadly
described in the foregoing.
The perfume content is normally up to 2% by weight, based on the
detergent/cleaner portion as a whole.
The perfumes may be directly incorporated in the active washing
preparations according to the invention, although it can also be of
advantage to apply the perfumes to supports which strengthen the
adherence of thE; perfume to the washing and which provide the textiles
with a long-lasting perfume through a slower release of the perfume.
Suitable support materials are, for example, cyclodextrins, the
cyclodextrin/perfume complexes additionally being coated with other
auxiliaries. '
Basically, the perfumes may be present in each of the part-portions
(active washing preparations) of the detergent/cleaner portions according
to the invention. In one particularly preferred embodiment, however, they
are present in a detergent in a laundry detergent part-portion intended for
the final wash cycle or fabric-softening cycle or in a cleaner, particularly a
dishwashing detergent, in a cleaner part-portion, particularly a dishwashing
detergent part-portion, intended for the final rinse or clear rinse cycle.
According to the invention, therefore, they have to be surrounded by a
CA 02314363 2000-07-20
material which only dissolves in water under the conditions (more
particularly at the temperature) of the final wash or final rinse cycle, but
which is insoluble in water under the conditions (more particularly at the
temperature) of the preceding wash cycles, more particularly a
5 corresponding film or capsule. According to the invention, this is possible
for example with a multi-compartment bag of films differing in their water
solubility.
The detergent/cleaner portions according to the invention may be
present in a wide variety of forms. These various forms are dependent on
10 the particular Components used, more particularly by the washing
preparations, but may also be freely selected within certain limits.
Thus, numerous active washing preparations are present in the form
of powders, powder mixtures or in the form of particles, for example beads
or granules, so that detergent/cleaner portions according to the invention
15 may be made up as single-portion packs or as packs of combinations of
powder-form or particulate components, for example as combinations of
powder-form or particulate components in film bags with one or more
compartments or layers or as single portions or combinations of powder-
form components in capsules. In another preferred embodiment of the
20 invention, the solid, for example powder-form, components may be present
as granules or beads and - like the powders - may be packed in the form of
granules or beads in film bags with several layers or compartments or in
capsules and may then be directly used in this form for washing or
cleaning.
25 In another preferred embodiment of the invention, the
detergent/cleaner portions may also be present in the form of solids
compressed to form shaped bodies of any form; such shaped bodies (such
as tablets, blocks, briquettes, rings or the like) are known from the prior
art
and may also bE~ used within the scope of the present invention. More
CA 02314363 2000-07-20
51
particularly, shaped bodies of the type in question may also have cavities,
depressions, indentations or the like for accommodating individual washing
substances. Shaped bodies in combination with powders, in combination
with liquids (for example in a wrapper of a water-soluble material according
to the invention) or in combination with an active washing preparation
embedded in a fusible matrix are of course also within the scope of the
present invention.
The following are preferred, but not limiting examples of active
washing preparations which may be combined to form detergent/cleaner
portions according to the invention:
- one or more active washing preparations in powder, particulate or
granular form and/or liquid form for one or more cycles of the washing/
cleaning process in one or more wrappers of one or more water-soluble
polymer material(s), preferably in an individual bag of polymer material
or in interconnected bags of polymer material differing in their solubility
in water, preferably as a function of temperature; active washing
preparations differing in their composition for one and the same
washing/cleaning cycle may be surrounded by one of these prepara-
tions, i.e. for example three active washing preparations of which, for
example, one is intended for the preliminary (washing or cleaning) cycle
and two for the main (washing or cleaning) cycle or, for example, two for
the main (washing or cleaning) cycle and one for the final (washing or
cleaning) cycle;
- an active washing preparation in powder form and an active washing
preparation in the form of a body melting at high temperature in a
wrapper which dissolves in water at the temperature at which the
detergent/cleaner part-portion present in powder form is needed in the
liquor;
CA 02314363 2000-07-20
52
- an active washing preparation in the form of a shaped body and an
active washing preparation in the form of a body melting at high
temperature in a wrapper which dissolves in water at the temperature at
which the detergent/cleaner part-portion present in solid form is needed
in the liquor; this embodiment may encompass a shaped body which
dissolves partly or completely with delay, for example by compression
or coating with a coating resistant to water for a certain time or at a
certain temperature; if, in this case, the wrapper is soluble in cold water,
the tablet is released into the liquor early in the washing/cleaning cycle
and may contain quick-dissolving components for a preliminary
(washing or cleaning) cycle and (through the delay in dissolution) slowly
dissolving components for a main (washing or cleaning) cycle or even
quick-dissolving components for a first part of the main (washing or
cleaning) cycle and (through the delay in dissolution) slowly dissolving
components for a second part of the main (washing or cleaning) cycle;
at all events, the active washing preparation emanating from the fusible
body is intended for the final (washing or cleaning) cycle;
- an active washing preparation in the form of a shaped body (optionally
surrounded by a water-soluble polymer material and optionally dissolv-
ing with delay) in combination with an active washing preparation, for
example in liquid form, surrounded by a water-soluble polymer material;
- an active washing preparation in the form of a shaped body (optionally
dissolving with delay) with a cavity in which another active washing
preparation is held in the form of a powder of a polymer material
dissolving in water at a certain temperature;
- an active washing preparation in the form of a shaped body (optionally
dissolving with delay) with a cavity in which another active washing
preparation is held in the form of a shaped body of a polymer material
dissolving in water at a certain temperature; by adjusting the solubility of
CA 02314363 2000-07-20
53
the second shaped body, components dissolving under certain
conditions (for example at a certain temperature) can be dosed into the
wash liquor; several active washing preparations in the form of shaped
bodies (optionally dissolving with delay) are combined in water-soluble
polymer materials differing in their solubility in water to form a detergent/
cleaner portion, optionally together with other components in other
polymer materials soluble in water (under different conditions).
As mentioned above, these cases are non-limiting examples of
detergent portions according to the invention.
The process for the production of a detergent/cleaner portion, more
particularly for placing in a washing/dishwashing machine for a program
taking place in an aqueous phase, containing at least one measured
quantity of at lea t one active washing preparation and at least one water-
soluble polymer material surrounding the measured quantity(ies) of at least
one active washing preparation is characterized by the steps of
- making ready at least one measured quantity of at least one active
washing preparation;
- making ready at least one water-soluble polymer material, at least one
water-soluble polymer material containing one or more components of
at least one of the active washing preparations; and/or
- making ready at least one water-soluble polymer material, at least one
measured quantity of at least one active washing preparation containing
one or more components) of the water-soluble polymer material; and
- at least one measured quantity of at least one active washing
preparation being enveloped in the at least one water-soluble polymer
material.
The process steps depend on whether a single measured quantity or
whether several measured quantities of active washing preparations is/are
CA 02314363 2000-07-20
54
present in the detergent/cleaner portion to be produced. Basically, the
processes suitable for the production of detergent/cleaner portions
comprising one active washing preparation or detergent/cleaner portions
comprising several active washing preparations. The second case is the
preferred case according to the invention. Detergent/cleaner portions in
which several active washing preparations are combined to form a portion
are generally produced.
In the most simple method of production, each active washing
preparation is surrounded by a separate water-soluble polymer material.
However, several active washing preparations may also be surrounded by
a polymer material. The particular water-soluble polymer material used in
the production process according to the invention must be selected
according to the temperature at which the particular polymer material is
intended to dissolve in the washing/cleaning liquor and thus to release the
contents of the part-pack into the liquor. According to the invention,
however, another criterion governing the choice of the water-soluble
polymer material is what active washing preparation is to be surrounded by
the particular polymer material. This is important because it determines the
decision as to which components) of the active washing preparation, for
which the polymE;r material is intended to serve as a "pack", is/are also to
be present in the polymer material or alternatively or additionally which
components) of the water-soluble polymer material is/are also to be
present in the active washing preparation.
Accordingly, the invention provides at least one water-soluble
polymer material for the active washing preparations) which contains one
or more components) that is/are present in at least one of the packed
active washing preparations. Alternatively or even at the same time, one or
more active washing preparations is/are compounded so that they contain
at least one or Even several components) of the water-soluble polymer
CA 02314363 2000-07-20
material surrounding them. In one particularly preferred embodiment, one
or more of the components mentioned which are present in both phases
(polymer materials) and active washing preparation(s)) is/are selected
from the group of hydrophilic plasticizers and substances which are present
5 in liquid or paste-like or wax-like form at room temperature, optionally
after
addition of small quantities of water (less than 20% by weight and
advantageously less than 10% by weight, based on the preparation).
Particular preference is attributed to the above-mentioned surfactant
components or polyols, polyalkylene glycols and structurally analogous
10 amines, particularly the representatives specially described above. One or
more of these may be present in both phases.
The content of one or more of the components mentioned in the
process according to the invention is selected so that it corresponds to the
particular concentration of the phase equilibrium in each of the phases.
15 Accordingly, both phases may be involved in a reciprocal dynamic ex-
change of the particular components) from the outset. In another embodi-
ment of the invention, however, the concentration of the components) is
selected so that one phase contains the predominant quantity or even the
entire quantity of the particular components) while the other phase
20 contains a relatively small quantity of the same component or does not
contain the components) in question at all when the equilibrium between
the two phases involved (active washing preparation and water-soluble
polymer material) is established under controlled conditions after produc-
tion of the detergent/cleaner portion according to the invention. Through
25 diffusion and/or adsorption, the component in question migrates, for
example (but not necessarily) in hours or a few days into the phase in
which the concentration is below the phase equilibrium concentration.
Thus, the phase equilibrium is established after a short time acceptable for
practical purposE;s, so that both stable active washing preparations and
CA 02314363 2000-07-20
56
storage-stable wrappers for the active washing preparations) are thus
obtained in combination.
It is of course also possible in the production process according to
the invention for several active washing preparations to be surrounded by
one water-soluble polymer material. Corresponding examples were
mentioned in the foregoing. In this case, the polymer material may contain
one or more components of one or more active washing substances;
alternatively or at the same time, several active washing substances may
also contain one or more components of the polymer material.
The invention also relates to the new wrappers for the detergent
portions according to the invention.
These wrappers are particularly suitable for wrapping the detergent/
cleaner portions according to the invention or part-portions thereof. These
wrappers are either designed in such a way that one or more components)
of at least one of the (subsequently wrapped) active washing preparations
is/are also present in the water-soluble polymer material of the wrapper or
in such a way that one or more components) of the water-soluble polymer
material is/are also present in at least one of the "subsequently wrapped"
active washing preparations. In another preferred embodiment of the
invention, both one or more components) of at least one of the active
washing preparations is/are also present in the water-soluble polymer
material and one or more components) of the water-soluble polymer
material is/are also present in at least one of the active washing
preparations.
In preferred embodiments of the wrappers which may be used with
advantage, the components) which is/are also present in the water-soluble
polymer material is/are selected from the group of substances which are
present in liquid or paste-like or wax-like form at room temperature,
optionally after addition of small quantities of water.
CA 02314363 2000-07-20
57
In another' preferred embodiment of the wrappers according to the
invention, the c:omponent(s) of at least one of the active washing
preparations) also present in the water-soluble polymer material is/are
selected from the group consisting of nonionic and anionic surfactants, as
defined in detail in the foregoing. According to the invention, nonionic
surfactants from the group of alkoxylated fatty alcohols containing 8 to 20
carbon atoms in the fatty alcohol alkyl group are more preferred, fatty
alcohols of natural origin, i.e. linear fatty alcohols predominantly
containing
an even number of carbon atoms in the alkyl group, being preferred to
synthetic fatty alcohols (for example branched fatty alcohols or fatty
alcohols containing an odd number of carbon atoms). Examples of fatty
alcohols from the perspective of availability of the compounds are lauryl
alcohol (C~2), myristyl alcohol (C~4), cetyl alcohol (C~s) etc. or mixtures of
such fatty alcohols emanating from native sources and correspondingly
processed. The number of alkoxy groups - according to the invention
primarily ethoxy or propoxy groups, preferably ethoxy groups - may vary
within wide limits and, in one particularly preferred embodiment, is between
3 and 80. According to the invention, other nonionic surfactants which may
also be present in the water-soluble polymer material are alkoxylated C&2o
fatty acid alkyl esters containing 1 to 8 carbon atoms in the alkyl group and
3 to 80, preferably up to 20 alkoxy groups, preferably ethoxy groups, in the
molecule. From the practical standpoint, a factor which may advanta-
geously be taken into account is that substances from the above-
mentioned groups which are still liquid or paste-like at the application
temperatures, despite considerable chain lengths, are used.
According to the invention, anionic surfactants may also be used for
the purpose mentioned. Within the group of anionic surfactants, alkyl
benzenesulfonic .acids containing 9 to 13 carbon atoms in the alkyl groups
and salts thereof (mainly present in alkaline medium), cumene sulfonic acid
CA 02314363 2000-07-20
58
and salts thereof" C~2_~a fatty alcohol sulfates and C&zo fatty acids and
salts
thereof are particularly suitable.
Another particularly preferred embodiment of the wrappers for
cleaner/detergent portions according to the invention is characterized in
that the components) of the water-soluble polymer material which is/are
also present in at least one active washing preparation is/are selected from
the group of hydrophilic plasticizers.
According to the invention, particularly preferred hydrophilic plasti-
cizers are polyols containing 1 to 20 carbon atoms and 2 to 6 hydroxy
groups, polyalkylene glycols containing 2 to 4 (preferably linear) alkylene
carbon atoms (i.e. ethylene groups, propylene groups or butylene groups)
in the molecule, preferably polyethylene glycols and/or polypropylene
glycols and more preferably polyethylene glycols and/or polypropylene
glycols with molecular weights in the range from 200 to 12,000 and
preferably with molecular weights of less than 1500. Amines structurally
analogous to the polyalkylene glycols mentioned, i.e. compounds in which
the glycol -O- group is replaced by an amine -NH- group, may also be used
with advantage. The above-mentioned molecular weight ranges also apply
to the amines. I=rom the practical standpoint, compounds which are still
liquid or paste-like at the (high) application temperatures may be used with
advantage in the wrapper according to the invention.
In another' preferred embodiment of the invention, low molecular
weight polyacrylates or polymethacrylates or polymaleates (acids or - under
the alkaline in-use conditions - preferably salts thereof, including amine or
(even organic) ammonium salts) or copolymers of polyacrylates/polymeth-
acrylates and polymaleates may also be used.
As mentioned above, the concentrations of the particular
components) in the wrapper according to the invention are subjected to
hardly any limitations, but do depend upon a number of parameters. In
CA 02314363 2000-07-20
59
general, the pha;>e equilibrium concentration in the wrapper is between 0.5
and 50% by weight, based on the total weight of the material of the
wrapper, preferably between 1 and 30% by weight and more preferably
between 3 and 25% by weight. In the case discussed above where, in the
production of the cleaner/detergent portion, the wrapper still contains none
of the required components, the concentration at the beginning of the
production step can of course be 0% by weight. However, a phase
equilibrium concentration of the corresponding components) in the
wrapper which corresponds to a concentration in the above-mentioned
ranges will subsequently be established over a controllable, comparatively
short period of time.
In another preferred embodiment of the invention, the material of the
wrapper is a polymer material selected from the group consisting of
(optionally acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene
oxide, gelatin, starch, cellulose and derivatives and mixtures thereof.
Details of these materials were provided in the foregoing.
According to the invention, water-soluble polymer materials present
in the form of films, Capsules or coatings are used with particular
advantage. Particulars of these forms were also provided in the foregoing
in connection with the detergent/cleaner portions.
The present invention also relates to a washing process using the
above-described detergent portions and to a dishwashing process using
the above-described detergent portions. Both processes are characterized
by the use of wrappers in which one or more components) of at least one
of the (subsequently wrapped) active washing preparations is/are also
present in the water-soluble polymer material of the wrapper and/or in
which one or more components) of the water-soluble polymer material
is/are also present in at least one of the (subsequently wrapped) active
washing preparations.
CA 02314363 2000-07-20
The washing process according to the invention is, in particular, a
machine washing process, in which
- a detergent portion as described in detail in the foregoing is placed in a
washing machine;
5 - at least one active washing preparation is released into the wash liquor
by addition of water and adjustment of the temperature to a first
temperature value at which at least one water-soluble polymer material
surrounding a measured quantity of the active washing preparation of
the detergent portion dissolves; and optionally
10 - one or more other active washing preparations is/are released into the
wash liquor by further additions) of water and adjustment of the
temperature to one or more other temperature values) above the first
temperature value and optionally above other previous temperature
values.
15 The cleaning process according to the invention is, in particular, a
machine dishwashing process, in which
- a detergent portion as described in detail in the foregoing is placed in a
dishwashing machine;
- at least one active washing preparation is released into the wash liquor
20 by addition of water and adjustment of the temperature to a first
temperature value at which at least one water-soluble polymer material
surrounding a~ measured quantity of the active washing preparation of
the detergent portion dissolves; and optionally
- one or more other active washing preparations is/are released into the
25 wash liquor by further additions) of water and adjustment of the
temperature to one or more other temperature values) above the first
temperature value and optionally above other previous temperature
values.
Accordingly, the washing or cleaning process seeks to achieve
CA 02314363 2000-07-20
61
optimal conditioning of the washing/cleaning liquor through the release of
corresponding detergent/cleaner portions into the liquor under conditions,
primarily and hence preferably under temperature conditions, which enable
the properties of the active washing preparation released to be optimally
developed, i.e. in particular at the staggered (first, second and optionally
higher) temperatures of the particular washing or cleaning steps.
The present invention therefore provides detergent/cleaner portions
and wrappers ~;uitable for accommodating them which, even in the
wrappers, contain at least one component which is present in one of the
active washing preparations of the detergent/cleaner portions and/or even
in at least one active washing preparation of the detergent portions contain
at least one component which is present in a water-soluble polymer
material forming the wrapper. Not only ideal packaging or
wrapping/coating materials for active washing preparations, but also
practical detergent/cleaner portions convenient to dose by the consumer
with improved properties in relation to the prior art are obtained in this
way.
