Note: Descriptions are shown in the official language in which they were submitted.
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LAUNDRY, DISHWASHING OR CLEANING PRODUCT DETERGENT
PORTIONS WITH CONTROLLED RELEASE OF ACTIVE SUBSTANCE
The present invention relates to laundry, dishwashing
or cleaning product detergent portions with controlled
release of active substance. In particular, the present
invention relates to laundry, dishwashing or cleaning
product detergent portions possessing a system
permitting controlled release of at least one active
substance in the laundering, dishwashing, cleaning, or
aftertreatment process. The invention also relates to a
process for producing such laundry, dishwashing or
cleaning product detergent portions. The invention also
relates to laundering, dishwashing or cleaning
processes using said laundry, dishwashing or cleaning
product detergent portions.
For a long time it was the norm to provide the consumer
with laundry detergents, dishwashing detergents or
cleaning product detergents in the form of bulk-
packaged goods and to leave it up to the consumer at
the time of use to dose the laundry detergent,
dishwashing detergent or cleaning product detergent in
accordance with the requirements of the application,
which depended on the water hardness, the nature,
amount, and/or degree of soiling of the laundry, ware
or article to be cleaned, on the amount of the washing
or cleaning liquor, and on other parameters.
In view of the consumer's desire to have laundry,
dishwashing or cleaning product detergents which are
easier and more convenient to dose, these detergents
were increasingly provided in a form which obviates the
need for ad hoc dosing: laundry detergents, dishwashing
detergents or cleaning product detergents were
formulated in predetermined portions comprising all of
the components required for one washing or cleaning
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cycle or operation. In the case of solid products, such
portions were frequently formed into shapes (sometimes
comprising two or more phases) such as granules, beads,
tablets ("tabs"), cubes, briquettes, etc., which are
dosed as a whole into the liquor. Liquid products were
placed in water-soluble enclosures which dissolve on
contact with the aqueous liquor and release the
contents into the .Liquor.
A disadvantage of these solutions is that all of the
components required in the course of a wash or cleaning
cycle or operation pass simultaneously into the aqueous
liquor. In this case, not only are there problems of
incompatibility of certain components of a laundry
detergent, dishwashing detergent or cleaning product
detergent with other components, but also it becomes
impossible deliberately to dose certain components into
the liquor at a defined point in time.
The prior art has since described means by which
individual laundry detergent, dishwashing detergent or
cleaning product detergent components may be dosed
deliberately and at a defined point in time during use.
For example, the temperature controlled release of
active substances is described, permitting active
substances such as surfactants, bleaches, soil release
polymers and the hike to be released either in the main
wash or cleaning cycle or operation or even in an
aftertreatment cycle or operation - for example, in the
rinse cycle in the case of machine dishwashing.
There have been a plurality of descriptions of the use
of paraffins having a melting point of more than 50°C.
One product on the market, in a dishwashing detergent
tablet, makes use of a paraffin core as carrier or
matrix in order to cause a rinse aid surfactant
incorporated therein to be released not in the wash
cycle but only in the rinse cycle of a dishwasher. In
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the case of premature release, such as during the wash
cycle, for example, the rinse aid surfactant is to a
very great extent pumped away during intermediate
washing, and is then able to develop little if any of
its activity in the rinse cycle. If the matrix material
has a melting point at the temperature of the rinse
cycle, this ensures that the rinse aid surfactant -
which is emulsified or, ideally, distributed in
molecularly disperse form in the matrix - remains
enclosed in the matrix during the wash cycle, which
takes place at temperatures up to 55°C, and is released
only in the rinse .cycle, in which temperatures of up to
about 65°C are attained, following melting of the
matrix material.
This solution to protect the rinse aid surfactant has
become established in practice. However, a disadvantage
is that the proportion of the matrix material in the
core, consisting of paraffin and rinse aid surfactant,
of the dishwashing detergent tablet accounts for
between 30 and 95% of the overall mass of the core,
generally about 50% of the overall mass. The matrix
material, especially in this amount, may leave residues
on the articles to be cleaned, such as on the kitchen-
and tableware, for example, and may also impair the
activity of the rinse aid surfactant it contains, which
is released when the paraffin melts. One reason for
this might be that: after the paraffin has melted, the
rinse aid surfactant remains bound at the interface
between lipophilic carrier material and the wash liquor
and so does not develop the desired action.
A further disadvantage of the temperature controlled
release of active substances in detergents is that, in
the washing machines and dishwashers that are typically
used within households there is a relatively large
number of programs, which differ significantly in
temperature and time, in particular. For example, the
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programs nowadays used most frequently in dishwashers
have peak temperatures in the wash cycle of from 50 to
60°C or from 60 to 70°C, the exact level of the
temperature possibly being different depending on
manufacturer and machine type. However effective the
functioning of a temperature controlled active
substance release per se, the effect achieved is
frequently still dependent on the type of machine used
and on consumer behavior.
As one approach, this fact can be dealt with by means
of systems which, rather than a certain maximum
achievable temperature, which is subject to the breadth
of range described above, react to the control
parameter of cooling and use it for the targeted
release of active substances from laundry detergent,
dishwashing detergent or cleaning product detergent
portions. For instance, one of the applicant's earlier
German patent applications, unpublished at the priority
date of the present specification, describes laundry
detergents, dishwashing detergents or cleaning product
detergents comprising polymers which are called LOST
polymers and possess the particular property that they
are insoluble above a certain temperature (flocculation
point) and dissolve only at lower temperatures. This
principle may be used for all applications where
release of certain components is to take place during
the cooling phase in the laundering, dishwashing or
cleaning process after the temperature has gone below
the flocculation point of the LCST polymers.
Applications which meet these criteria are, for
example, machine dishwashing and machine laundering,
provided the wash liquor is pumped off in intermediate
wash cycles and replaced by cold or relatively cold
washing or rinsing water.
Another principle which has been described is based on
the fact that when a volume of air heated to a certain
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temperature is cooled there is a volume decrease by
approximately 1/2'72 per ° Kelvin. By means of an
appropriate embodiment, such as a perforated capsule,
for example, material may be drawn from the immediate
environment into the embodiment as a result of the
underpressure resulting from the air volume
contraction. This step may then trigger secondary
processes such as corrosion, dissolution, heating or
gas formation, which allow release of the desired
ingredients.
Disadvantages of said controlled active substance
release by means of a temperature switch lie in the
dependency they exhibit on certain temperature programs
and/or on the need for cooling during the laundering,
dishwashing or cleaning process.
It is an object of the invention, then, to provide
switch systems which do not have the aforementioned
disadvantages.
It was also an object of the invention to provide a
system for the controlled release of laundry,
dishwashing or cleaning product detergent components
into the liquor, from a laundry, dishwashing or
cleaning product detergent portion which ensures that
the relevant component passes into the liquor at a
defined point in time with, as far as possible, a
minimal amount if any of auxiliaries needed for
compounding.
A further object of the invention was to provide a
system for separating individual components of a
laundry, dishwashing or cleaning product detergent from
other components of the same detergent for the purpose
of avoiding incompatibilities of the individual
components during production, storage and/or transit
and thus to ensure that the components pass into the
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washing or cleaning liquor without loss of activity at
a defined point in time, together if desired with
other, precisely defined components.
A further object of the invention was to provide the
possibility of supplying not only naturally solid
components of a laundry detergent, dishwashing
detergent or cleaning product detergent for a utility
but also those components which are in a nonsolid form,
for example, in liquid, gel or paste form, or for a
utility with such components in a different aggregate
state.
The invention accordingly provides a laundry,
dishwashing or cleaning product detergent portion
having two or more detersive components of which at
least two are to be released into the liquor at
different points in time in a laundering, dishwashing
or cleaning process, said portion comprising at least
one release controlling (physico)chemical switch which
is not subject or not exclusively subject to
temperature control, and also one or more substances
for increasing the extent of the shift in pH.
In one preferred embodiment the invention provides a
laundry, dishwashing or cleaning product detergent
portion of tree stated type wherein the
(physico)chemical switches) controlling the release of
at least one detersive component is(are) one or more
components, when there is a change in the electrolyte
concentration in the wash or cleaning liquor, undergo a
change in physical and/or chemical properties.
Further preference is given in accordance with the
invention to a laundry, dishwashing or cleaning product
detergent portion wherein the (physico)chemical
switches) controlling the release of at least one
detersive component is(are) one or more components,
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when there is a change in the H+ ion concentration (the
pH) in the wash or cleaning liquor, undergo a change in
physical and/or chemical properties.
The invention further provides a process for producing
a laundry, dishwashing or cleaning product detergent
portion having two or more detersive components of
which at least two are to be released into the liquor
at different points in time in a washing or cleaning
process, which comprises compounding the detersive
components) for release into the liquor at a later
point in time in the washing or cleaning process with a
release controlling (physico)chemical switch and
processing the detersive components) thus compounded
with one or more other detersive components to give a
laundry, dishwashing or cleaning product detergent
portion.
The invention additionally provides a laundering,
dishwashing or cleaning process using the laundry,
dishwashing or cleaning product detergent portions
which are described in detail below.
The invention primarily provides laundry detergent
portions, dishwashing detergent portions or cleaning
product detergent portions. In the context of the
present invention, the term "laundry detergent portion"
or "dishwashing detergent portion" or "cleaning product
detergent portion" refers to an amount of a laundry,
dishwashing or cleaning product detergent that is
sufficient for one washing or cleaning procedure which
takes place in an aqueous phase. This may be, for
example, a machine washing or cleaning procedure, as
carried out with standard commercial washing machines
or dishwashers. In accordance with the invention,
however, this term also embraces a handwash laundry
operation or manual dishwashing operation (carried out,
for example, in a wash basin or in a bowl) or some
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other laundering, dishwashing or cleaning procedure. In
accordance with the invention, the laundry, dishwashing
or cleaning product detergent portions are used in
machine laundering, dishwashing or cleaning procedures.
In the context of the present invention, the term
"laundry detergent subportion", "dishwashing detergent
subportion" or "cleaning product detergent subportion"
refers to a component amount of a laundry detergent
portion, dishwashing detergent portion or cleaning
product detergent portion which is present in a phase
separate from other laundry, dishwashing or cleaning
product detergent subportions, in spatial communication
with other laundry, dishwashing or cleaning product
detergent subportions of the same laundry, dishwashing
or cleaning product detergent portion and which by
means of appropriate measures has been formulated or
compounded in such a way that it may be placed into the
liquor and, if desired, dissolved or suspended in it
separately from other laundry, dishwashing or cleaning
product detergent subportions of the same laundry,
dishwashing or cleaning product detergent portion. One
laundry, dishwashing or cleaning product detergent
subportion may comprise the same ingredients as another
laundry, dishwashing or cleaning product detergent
subportion of the same laundry, dishwashing or cleaning
product detergent portion; preferably, however, two
laundry, dishwashing or cleaning product detergent
subportions of the same laundry, dishwashing or
cleaning product detergent portion comprise different
ingredients, in particular different detersive
formulations.
In accordance with the invention, the laundry,
dishwashing or cleaning product detergent portions
comprise measured amounts of at least one detersive
formulation, usually measured amounts of two or more
detersive formulations. It is possible for the portions
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to comprise only detersive formulations of one
particular make-up. In accordance with the invention it
is preferred, however, for two or more, usually at
least two, detersive formulations of different make-up
to be present in the laundry, dishwashing or cleaning
product detergent. portions. The make-up may be
different in terms of the concentration of the
individual components of the detersive formulation
(quantitatively) and/or in terms of the nature of the
individual components of the detersive formulation
(qualitatively). It is particularly preferred for the
components to be adapted in terms of nature and
concentration to the tasks which the laundry,
dishwashing or cleaning product detergent subportions
are required to fulfill in the laundering, dishwashing
or cleaning procedure.
In the context of the present invention, the term
"detersive formulation/component" embraces formulations
or components of all conceivable substances that are
relevant in the context of a laundering, dishwashing or
cleaning procedure. These substances are, primarily,
the laundry detergents, dishwashing detergents or
cleaning product detergents themselves, with their
individual components which are elucidated further in
the ongoing course of the description. These include
active substances such as surfactants (anionic,
nonionic, cationic and amphoteric surfactants), builder
substances (organic and inorganic builder substances),
bleaches (such as peroxo bleaches and chlorine
bleaches, for example), bleach activators, bleach
stabilizers, bleaching catalysts, enzymes, special
polymers (for example, those having cobuilder
properties), graying inhibitors, dyes and fragrances
(perfumes), without the term being restricted to these
groups of substances.
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The term "detersive formulation/component" also,
however, embraces laundering assistants, dishwashing
assistants and cleaning assistants. Examples of these
assistants are optical brighteners, UV protection
substances, soil repellants, i.e., polymers which
counter redirtying of fibers or hard surfaces, and
silver protectants. In accordance with the invention,
laundry treatment compositions such as fabric
softeners, and dishwashing composition additions such
as rinse aids, are also regarded as detersive
formulations or components.
The laundry, dishwashing or cleaning product detergent
portions of the invention comprise one or more
substances from the group consisting of surfactants,
compounded surfactants, builders, bleaches, bleach
activators, enzymes, foam inhibitors, dyes and
fragrances and also - where the laundry, dishwashing or
cleaning product detergent portions are present at
least in part as shaped bodies - binders and
disintegration aids as well. These classes of substance
are described below.
To develop the wash performance, the laundry,
dishwashing and cleaning product detergent portions of
the invention may comprise surface-active substances
from the group consisting of anionic, nonionic,
zwitterionic and cationic surfactants, distinct
preference being given to anionic surfactants on
economic grounds and because of their performance
spectrum.
Anionic surfactants used are, for example, those of the
sulfonate and sulfate type. Preferred surfactants of
the sulfonate type are C9_13 alkylbenzenesulfonates,
olefinsulfonates, i.e., mixtures of alkenesulfonates
and hydroxyalkanesulfonates, and also disulfonates, as
are obtained, for example, from Cla-la monoolefins having
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a terminal or internal double bond by sulfonating with
gaseous sulfur trioxide followed by alkaline or acidic
hydrolysis of the sulfonation products. Also suitable
are alkanesulfonates, which are obtained from Clz-la
alkanes, for example, by sulfochlorination or
sulfoxidation with subsequent hydrolysis or
neutralization, respectively. Likewise suitable, in
addition, are the esters of 2-sulfo fatty acids (ester
sulfonates), e.g., the 2-sulfonated methyl esters of
hydrogenated coconut, palm kernel or tallow fatty
acids.
Further suitable anionic surfactants are sulfated fatty
acid glycerol esters. Fatty acid glycerol esters are
the monoesters, diesters and triesters, and mixtures
thereof, as obtained in the preparation by
esterification of a monoglycerol with from 1 to 3 mol
of fatty acid or in the transesterification of
triglycerides with from 0.3 to 2 mol of glycerol.
Preferred sulfated fatty acid glycerol esters are the
sulfation products of saturated fatty acids having 6 to
22 carbon atoms, examples being those of caproic acid,
caprylic acid, capric acid, myristic acid, lauric acid,
palmitic acid, stearic acid, or behenic acid.
Preferred alk(en)yl sulfates are the alkali metal
salts, and especially the sodium salts, of the sulfuric
monoesters of Clz--Cla fatty alcohols, examples being
those of coconut fatty alcohol, tallow fatty alcohol,
lauryl, myristyl, cetyl or stearyl alcohol, or of
Cio-Czo oxo alcohols, and those monoesters of secondary
alcohols of these chain lengths. Preference is also
given to alk (en) yl sulfates of said chain length which
contain a synthetic straight-chain alkyl radical
prepared on a petrochemical basis, these sulfates
possessing degradation properties similar to those of
the corresponding compounds based on fatty-chemical raw
materials. From a detergents standpoint, the Clz-Cls
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alkyl sulfates and Clz-Cls alkyl sulfates, and also
C14-Cls alkyl sulfates, are preferred. In addition,
2,3-alkyl sulfates, which may for example be prepared
in accordance with US Patents 3 234 258 or 5 075 041
and obtained as commercial products from Shell Oil
Company under the name DAN~, are suitable anionic
surfactants.
Also suitable are the sulfuric monoesters of the
straight-chain or branched C~_zl alcohols ethoxylated
with from 1 to 6 mol of ethylene oxide, such as
2-methyl-branched C9_11 alcohols containing on average
3.5 mol of ethylene oxide (EO) or Clz-18 fatty alcohols
containing from 1. to 4 EO. Because of their high
foaming behavior they are used in detergents only in
relatively small amounts, for example, in amounts of
from 1 to 5% by weight.
Further suitable anionic surfactants include the salts
of alkylsulfosuccinic acid, which are also referred to
as sulfosuccinates or as sulfosuccinic esters and which
constitute monoesters and/or diesters of sulfosuccinic
acid with alcohols, preferably fatty alcohols and
especially ethoxylated fatty alcohols. Preferred
sulfosuccinates comprise C8_1a fatty alcohol radicals or
mixtures thereof. Especially preferred sulfosuccinates
contain a fatty alcohol radical derived from
ethoxylated fatty alcohols which themselves represent
nonionic surfactants (for description, see below).
Particular preference is given in turn to
sulfosuccinates whose fatty alcohol radicals are
derived from ethoxylated fatty alcohols having a
narrowed homolog distribution. Similarly, it is also
possible to use alk(en)ylsuccinic acid containing
preferably 8 to 18 carbon atoms in the alk(en)yl chain,
or salts thereof.
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Further suitable anionic surfactants are, in
particular, soaps. Suitable soaps include saturated
fatty acid soaps, such as the salts of lauric acid,
myristic acid, palmitic acid, stearic acid,
hydrogenated erucic acid and behenic acid, and, in
particular, mixtures of soaps derived from natural
fatty acids, e.g., coconut, palm kernel, or tallow
fatty acids.
The anionic surfactants, including the soaps, may be
present in the form of their sodium, potassium or
ammonium salts and also as soluble salts of organic
bases, such as mono-, di- or triethanolamine.
Preferably, the anionic surfactants are in the form of
their sodium or potassium salts, in particular in the
form of the sodium salts. In a further embodiment of
the invention, surfactants are used in the form of
their magnesium sa-'~ts.
In the context of the present invention, preference is
given to laundry, dishwashing and cleaning product
detergent portions comprising from 5 to 50% by weight,
preferably from 7.5 to 40% by weight, and in particular
from 15 to 25% by weight, of one or more anionic
surfactants, based in each case on the detergent
portion.
Regarding the selection of the anionic surfactants
employed in the laundry, dishwashing or cleaning
product detergent portions of the invention, there are
no restrictions to be observed that stand in the way of
formulation freedom. Preferred laundry, dishwashing or
cleaning product detergent portions of the invention,
however, have a soap content which exceeds 0.2% by
weight, based on the overall weight of the detergent
portion. Anionic surfactants for use with preference
are the alkylbenzenesulfonates and fatty alcohol
sulfates, preferred laundry, dishwashing and cleaning
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product detergent portions comprising from 2 to 20% by
weight, preferably from 2.5 to 15% by weight, and in
particular from 5 to loo by weight, of fatty alcohol
sulfate(s), based in each case on the weight of the
detergent portion.
Nonionic surfactants used are preferably alkoxylated,
advantageously ethoxylated, especially primary,
alcohols having preferably 8 to 18 carbon atoms and on
average from 1 to 12 mol of ethylene oxide (EO) per
mole of alcohol, in which the alcohol radical may be
linear or, preferably, methyl-branched in position 2
and/or may comprise linear and methyl-branched radicals
in a mixture, as are commonly present in oxo alcohol
radicals. In particular, however, preference is given
to alcohol ethoxylates containing linear radicals from
alcohols of natural origin having 12 to 18 carbon
atoms, e.g., from coconut, palm, tallow fatty or oleyl
alcohol and on average from 2 to 8 EO per mole of
alcohol. Preferred ethoxylated alcohols include, for
example, Clz-i4 alcohols containing 3 EO or 4 EO, C9_11
alcohol containing 7 EO, C13-is alcohols containing 3 EO,
5 EO, 7 EO or 8 EO,. Clz-la alcohols containing 3 EO, 5 EO
or 7 EO, and mixtures thereof, and also mixtures of
Clz-14 alcohol containing 3 EO and Clz-la alcohol
containing 5 EO. The stated degrees of ethoxylation
represent statistical mean values, which for a specific
product may be an integer or a fraction. Preferred
alcohol ethoxylates have a narrowed homolog
distribution (nar:row range ethoxylates, NREs). In
addition to these nonionic surfactants it is also
possible to use fatty alcohols containing more than 12
EO. Examples thereof are tallow fatty alcohol
containing 14 EO, 25 EO, 30 EO or 40 EO.
A further class of nonionic surfactants used with
preference, which are used either as sole nonionic
surfactant or in combination with other nonionic
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surfactants, are alkoxylated, preferably ethoxylated,
or ethoxylated and propoxylated, fatty acid alkyl
esters, preferably having 1 to 4 carbon atoms in the
alkyl chain, especially fatty acid methyl esters, as
are described, for example, in Japanese Patent
Application JP 58/217598, or those prepared preferably
by the process described in International Patent
Application WO-A-90/13533.
A further class of nonionic surfactants which may be
used advantageously are the alkyl polyglycosides (APG).
Useful alkyl polyglycosides are of the general formula
RO(G)Z, where R is a linear or branched aliphatic
radical, especially an aliphatic radical methyl-
branched in position 2, saturated or unsaturated and
containing 8 to 22, preferably 12 to 18, carbon atoms,
and G is the symbol representing a glycose unit having
5 or 6 carbon atoms, preferably glucose. The degree of
glycosidization, z, is between 1.0 and 4.0, preferably
between 1.0 and 2.0, and in particular between 1.1 and
1.4.
Preference is given to the use of linear alkyl
polyglucosides, i.e., alkyl polyglycosides in which the
polyglycosyl residue is a glucose residue and the alkyl
radical is an n-alkyl radical.
The laundry, dishwashing or cleaning product detergent
portions of the invention may preferably include alkyl
polyglycosides, preference being given to APG contents
of more than 0.2% by weight in the detergent portions,
based on the overall shaped body. Particularly
preferred laundry, dishwashing and cleaning product
detergent portions comprise APGs in amounts of from 0.2
to 10-°s by weight, preferably in amounts of from 0.2 to
5% by weight, and in particular in amounts of from 0.5
to 3% by weight.
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Nonionic surfactants of the amine oxide type, examples
being N-cocoalkyl-N,N-dimethylamine oxide and
N-tallowalkyl-N,N-<iihydroxyethylamine oxide, and of the
fatty acid alkanolamide type, may be also be suitable.
The amount of these nonionic surfactants is preferably
not more than that, of the ethoxylated fatty alcohols,
in particular not more than half thereof.
Further suitable surfactants are polyhydroxy fatty acid
amides of the formula (I),
R1
R-CO-N- [Z] ( I )
where RCO is an aliphatic acyl radical having 6 to 22
carbon atoms, R-~ is hydrogen or an alkyl or
hydroxyalkyl radical having 1 to 4 carbon atoms, and
[Z] is a linear or branched polyhydroxyalkyl radical
having 3 to 10 cax-bon atoms and from 3 to 10 hydroxyl
groups. The polyhydroxy fatty acid amides are known
substances which are customarily obtainable 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 the polyhydroxy fatty acid amides also
includes compounds of the formula (II)
Ri-O-R2
R-CO-N- [Z] ( I I )
where R is a linear or branched alkyl or alkenyl
radical having 7 to 12 carbon atoms, R1 is a linear,
branched or cyclic alkyl radical or an aryl radical
having 2 to 8 carbon atoms and R2 is a linear, branched
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or cyclic alkyl radical or an aryl radical or an
oxyalkyl radical having 1 to 8 carbon atoms, preference
being given to C1_~ alkyl radicals or phenyl radicals,
and [Z] is a linear polyhydroxyalkyl radical whose
alkyl chain is substituted by at least two hydraxyl
groups, or alkoxylated, preferably ethoxylated or
propoxylated, derivatives of said radical.
[Z] is preferably obtained by reductive amination of a
reduced sugar, e.g., glucose, fructose, maltose,
lactose, galactose, mannose, or xylose. The N-alkoxy-
or N-aryloxy-substituted compounds may then be
converted to the desired polyhydroxy fatty acid amides,
for example, in accordance with the teaching of
International Patent Application WO-A-95/07331 by
reaction with fatty acid methyl esters in the presence
of an alkoxide as catalyst.
Furthermore, it may be preferable to use not only
anionic and nonionic surfactants but also cationic
surfactants. In this context they are used preferably
as wash performance boosters, with only small amounts
of cationic surfactants being required. Where cationic
surfactants are used, they are present in the
compositions preferably in amounts of from 0 . O1 to 10 0
by weight, in particular from 0.1 to 3.0% by weight.
Where the laundry, dishwashing or cleaning product
detergent portions of the invention comprise laundry
detergents, they normally comprise one or more
surfactants in total amounts of from 5 to 50% by
weight, preferably in amounts of from 10 to 35% by
weight, it being possible for surfactants to be present
in a greater or smaller amount in subportions of the
laundry detergent portions of the invention. In other
words: the amount of surfactant is not identical in all
subportions; instead, subportions with a relatively
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high surfactant content and subportions with a
relatively low surfactant content may be provided.
Where the laundry, dishwashing or cleaning product
detergent portions of the invention comprise cleaning
products, especially dishwashing compositions, more
preferably warewashing compositions, they normally
comprise one or more surfactants in total amounts of
from 0.1 to 10% by weight, preferably in amounts of
from 0.5 to 5o by weight, it being possible for
surfactants to be present in a greater or smaller
amount in subportions of the cleaning product or
dishwashing detergent portions of the invention. In
other words: even in the case of cleaning products or
dishwashing compositions, the amount of surfactant is
not identical in all subportions; instead, subportions
with a relatively high surfactant content and
subportions with a relatively low surfactant content
may be provided.
Besides the detersive substances, builders are the most
important ingredients of laundry, dishwashing and
cleaning product detergents. The laundry, dishwashing
or cleaning product detergent portions of the invention
may comprise all of the builders commonly used in
laundry, dishwashing detergent and cleaning product
detergents, i.e., in particular, zeolites, silicates,
carbonates, organic cobuilders, and - where there are
no ecological prejudices against their use - phosphates
as well.
Suitable crystalline, layered sodium silicates possess
the general formula NaMSiXOzX+uyHzO, where M is sodium or
hydrogen, x is a number from 1.9 to 4, y is a number
from 0 to 20, and preferred values for x are 2, 3 or 4.
Crystalline phyllosilicates of this kind are described,
for example, in European Patent Application
EP-A-0 164 514. Preferred crystalline phyllosilicates
CA 02328326 2000-12-13
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of the formula indicated are those in which M is sodium
and x adopts the value 2 or 3. In particular, both (S-
and 8-sodium disilicates Na2Si205~yH20 are preferred,
(3-sodium disilicate, for example, being obtainable by
the process described in International Patent
Application WO-A-91/08171.
It is also possib7_e to use amorphous sodium silicates
having an Na20:Si02 modulus of from 1:2 to 1:3.3,
preferably from 1:2 to 1:2.8, and in particular from
1:2 to 1:2 .6, which are dissolution-retarded and have
secondary washing properties. The retardation of
dissolution relative to conventional amorphous sodium
silicates
may have
been brought
about in
a variety
of
ways - for example, by surface treatment, compounding,
compacting, or overdrying. In the context of this
invention, the term "amorphous" also embraces "X-ray-
amorphous". This means that in X-ray diffraction
experiments the silicates do not yield the sharp X-ray
reflections typical of crystalline substances but
instead yi eld at best one or more maxima of the
scattered -radiation, having a width of several degree
X
units of
the diffraction
angle. However,
good builder
properties may result, even particularly good builder
properties, if the silicate particles in electron
diffraction experiments yield vague or even sharp
diffraction maxima. The interpretation of this is that
the product s have microcrystalline regions with a size
of from 10 to several hundred nm, values up to max.
50 nm and in particular up to max. 20 nm being
preferred. So-called X-ray-amorphous silicates of this
kind, which
likewise
possess
retarded
dissolution
relative to the conventional waterglasses, are
described, for example, in German Patent Application
DE-A-44 00 024. Particular preference is given to
compacted amorphous silicates, compounded amorphous
silicates, and overdried X-ray-amorphous silicates.
CA 02328326 2000-12-13
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Any finely crystalline, synthetic zeolite used,
containing bound water, is preferably zeolite A
and/or P. A particularly preferred zeolite of type P is
zeolite MAP (e. g., commercial product Doucil A24 from
Crosfield). Also suitable, however, are zeolite X and
also mixtures of the zeolites A, X and/or P. A product
available commercially and able to be used with
preference in the context of the present invention, for
example, is a cocrystallizate of zeolite X and zeolite
A (approximately 80% by weight zeolite X), which is
sold by CONDEA Augusta S.p.A. under the brand name
VEGOBOND AX~ and may be described by the formula
nNa20~ (1-n) K~O~AlZ03~ (2-2 .5) SiOz~ (3 .5-5.5) H20.
Suitable zeolites have an average particle size of less
than 10 ~m (volume distribution; measurement method:
Coulter counter) and contain preferably from 18 to 22%
by weight, in particular from 20 to 22% by weight, of
bound water.
Of course, in laundry detergents the widely known
phosphates may also be used as builder substances,
provided such a use is not to be avoided on ecological
grounds. The sodium salts of the ortho-phosphates, the
pyrophosphates, and in particular the tripolyphosphates
are particularly suitable.
Organic builder substances which may be used are, for
example, the polycarboxylic acids, usable in the form
of their sodium salts, the term polycarboxylic acids
meaning those carboxylic acids which carry more than
one acid function. Examples of these are citric acid,
adipic acid, succinic acid, glutaric acid, malic acid,
tartaric acid, malefic acid, fumaric acid, sugar acids,
amino carboxylic acids, nitrilotriacetic acid (NTA),
provided such use is not objectionable on ecological
grounds, and also mixtures thereof. Preferred salts are
CA 02328326 2000-12-13
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the salts of the polycarboxylic acids such as citric
acid, adipic acid, succinic acid, glutaric acid,
tartaric acid, sugar acids, and mixtures thereof. The
acids per se may also be used. In addition to their
builder effect, the acids typically also possess the
property of an acidifying component and thus also serve
to establish a lower and milder pH of laundry and
cleaning product detergent portions in accordance with
the invention. In this context, mention may be made in
particular of citric acid, succinic acid, glutaric
acid, adipic acid, gluconic acid, and any desired
mixtures thereof.
Also suitable as builders are polymeric poly-
carboxylates. These are, for example, the alkali metal
salts of polyacrylic acid or of polymethacrylic acid,
examples being those having a relative molecular mass
of from 500 to 70 000 g/mol.
The molecular masses reported for polymeric
polycarboxylates, for the purposes of the present
invention, are weight-average molecular masses, MW, of
the respective acid form, determined basically by means
of gel permeation chromatography (GPC) using a UV
detector. The measurement was made against an external
polyacrylic acid standard, which owing to its
structural similarity to the polymers under
investigation provides realistic molecular weight
values. These figures differ markedly from the
molecular weight values obtained using poly-
styrenesulfonic acids as the standard. The molecular
masses measured against polystyrenesulfonic acids are
generally much higher than the molecular masses
reported in the context of the present invention.
Suitable polymers are, in particular, polyacrylates,
which preferably have a molecular mass of from 2 000 to
20 000 g/mol. Owing to their superior solubility,
CA 02328326 2000-12-13
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preference in this group may be given in turn to the
short-chain polyacrylates, which have molecular masses
of from 2 000 to 10 000 g/mol, and with particular
preference from 3 000 to 5 000 g/mol.
Also suitable are copolymeric polycarboxylates,
especially those of acrylic acid with methacrylic acid
and of acrylic acid or methacrylic acid with malefic
acid. Copolymers which have been found particularly
suitable are those of acrylic acid with malefic acid
which contain from 50 to 90% by weight acrylic acid and
from 50 to 10% by weight malefic acid. Their relative
molecular mass, based on free acids, is generally from
2 000 to 70 000 g/mol, preferably from 20 000 to
50 000 g/mol, and in particular from 30 000 to
40 000 g/mol.
The (co)polymeric polycarboxylates can be used either
as powders or as aqueous solutions. The (co)polymeric
polycarboxylate content of the laundry, dishwashing or
cleaning product detergent portions is preferably from
0.5 to 20s by weight, in particular from 3 to 10% by
weight.
In order to improve the solubility in water, the
polymers may also contain allylsulfonic acids, such as
in EP-B-0 727 448, allyloxybenzenesulfonic acid and
methallylsulfonic acid, for example, as monomers.
Particular preference is also given to biodegradable
polymers comprising more than two different monomer
units, examples being those as in DE-A 43 00 772
comprising, as monomers, salts of acrylic acid and of
malefic acid, and also vinyl alcohol or vinyl alcohol
derivatives, or those as in DE-C 42 21 381 comprising,
as monomers, salts of acrylic acid and of
2-alkylallylsulfonic acid, and also sugar derivatives.
CA 02328326 2000-12-13
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Further preferred copolymers are those described in
German Patent Applications DE-A-43 03 320 and
DE-A-44 17 734, whose monomers are preferably acrolein
and acrylic acid/acrylic acid salts, and, respectively,
acrolein and vinyl acetate.
Similarly, further preferred builder substances that
may be mentioned include polymeric amino dicarboxylic
acids, their salts or their precursor substances.
Particular preference is given to polyaspartic acids
and their salts and derivatives, which are disclosed in
German Patent Application DE-A-195 40 086 to have not
only cobuilder properties but also a bleach-stabilizing
action.
Further suitable builder substances are polyacetals,
which may be obtained by reacting dialdehydes with
polyol carboxylic acids having 5 to 7 carbon atoms and
at least 3 hydroxyl groups, as described for example in
EP-A 0 280 223. Preferred polyacetals are obtained from
dialdehydes such as glyoxal, glutaraldehyde,
terephthalaldehyde and mixtures thereof and from polyol
carboxylic acids such as gluconic acid and/or
glucoheptonic acid.
Further suitable organic builder substances are
dextrins, examples being oligomers and polymers of
carbohydrates, which may be obtained by partial
hydrolysis of starches. The hydrolysis can be conducted
by customary processes; for example, acid-catalyzed or
enzyme-catalyzed processes. The hydrolysis products
preferably have average molecular masses in the range
from 400 to 500 000 g/mol. Preference is given here to
a polysaccharide having a dextrose equivalent (DE) in
the range from 0.5 to 40, in particular from 2 to 30,
DE being a common measure of the reducing effect of a
polysaccharide in comparison to dextrose, which
possesses a DE of 100. It is possible to use both
CA 02328326 2000-12-13
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maltodextrins having a DE of between 3 and 20 and dried
glucose syrups having a DE of between 20 and 37, and
also so-called yellow dextrins and white dextrins
having higher molecular masses, in the range from 2 000
to 30 000 g/mol. A preferred dextrin is described in
GB-A 94 19 091.
The oxidized derivatives of such dextrins comprise
their products of reaction with oxidizing agents which
are able to oxidize at least one alcohol function of
the saccharide ring to the carboxylic acid function.
Oxidized dextrins of this kind, and processes for
preparing them, are known, for example, from European
Patent Applications EP-A-0 232 202, EP-A-0 427 349,
EP-A-0 472 042 an~~ EP-A-0 542 496 and from Inter-
national Patent Applications WO 92/18 542,
WO 93/08 251, WO 93/16 110, WO 94/28 030, WO 95/07 303,
WO 95/12 619 and WO 95/20 608. Likewise suitable is an
oxidized oligosaccharide in accordance with German
Patent Application DE-A 196 00 018. A product oxidized
at C6 of the saccharide ring may be particularly
advantageous.
Oxydisuccinates and other derivatives of disuccinates,
preferably ethylenediamine disuccinate, are further
suitable cobuilders. Ethylenediamine N,N'-disuccinate
(EDDS), whose synthesis is described for example in the
document US-A 3 158 615, is used preferably in the form
of its sodium or magnesium salts. Further preference in
this context is given to glycerol disuccinates and
glycerol trisuccinates as well, as described for
example in US Patents US-A 4 524 009 and
US-A 4 639 325, in EP-A 0 150 930 and in
JP-A 93/339,896. Suitable use amounts in formulations
containing zeolite and/or silicate are from 3 to 15% by
weight.
CA 02328326 2000-12-13
- 25 -
Examples of further useful organic cobuilders are
acetylated hydroxy carboxylic acids and their salts,
which may also be present in lactone form and which
contain at least 4 carbon atoms, at least one hydroxyl
group, and not more than two acid groups. Such
cobuilders are described, for example, in International
Patent Application WO 95/20 029.
A further class of substance having cobuilder
properties is represented by the phosphonates. The
phosphonates in question are, in particular,
hydroxyalkane- and aminoalkanephosphonates. Among the
hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphos-
phonate (HEDP) is of particular importance as a
cobuilder. It is used preferably as the sodium salt,
the disodium salt being neutral and the tetrasodium
salt giving an alkaline (pH 9) reaction. Suitable
aminoalkanephosphonates are preferably ethylenediamine-
tetramethylenephosphonate (EDTMP), diethylenetriamine-
pentamethylenephosphonate (DTPMP), and their higher
homologs. They are used preferably in the form of the
neutrally reacting sodium salts, e.g., as the
hexasodium salt of EDTMP or as the hepta- and octa-
sodium salt of DTPMP. As a builder in this case,
preference is given to using HEDP from the class of the
phosphonates. Furthermore, the aminoalkanephosphonates
possess a pronounced heavy metal binding capacity.
Accordingly, and especially if the laundry, dishwashing
and cleaning product detergent portions of the
invention also contain bleach, it may be preferred to
use aminoalkanephosphonates, especially DTPMP, or to
use mixtures of said phosphonates.
Furthermore, all compounds capable of forming complexes
with alkaline earth metal ions may be used as
cobuilders.
CA 02328326 2000-12-13
- 26 -
In addition to the abovementioned constituents,
surfactant and builder, the laundry, dishwashing and
cleaning product detergent portions of the invention
may further comprise further customary laundry,
dishwashing and cleaning product detergent ingredients
from the group consisting of bleaches, bleach
activators, enzymes, fragrances, perfume carriers,
fluorescers, dyes, foam inhibitors, silicone oils,
antiredeposition agents, optical brighteners, graying
inhibitors, color transfer inhibitors, and corrosion
inhibitors.
Among the compounds used as bleaches which yield H20L in
water, particular importance is possessed by sodium
perborate tetrahydrate and sodium perborate
monohydrate. Further bleaches which may be used are,
for example, sodium percarbonate, peroxypyrophosphates,
citrate perhydrates, and H202-donating peracidic salts
or peracids, such as perbenzoates, peroxophthalates,
diperazelaic acid, phthaloiminoper acid or
diperdodecanedioic acid. If cleaning or bleach
formulations are produced for machine dishwashing,
bleaches from the group of organic bleaches may also be
used. Typical organic bleaches are the diacyl
peroxides, such as dibenzoyl peroxide, for example.
Further typical organic bleaches are the peroxy acids,
particular examples being the alkyl peroxy acids and
the aryl peroxy acids. Preferred representatives are
(a) peroxybenzoic acid and its ring-substituted
derivatives, such <~s alkylperoxybenzoic acids, and also
peroxy-a-naphthoic acid and magnesium monoperphthalate,
(b) aliphatic or substituted aliphatic peroxy acids,
such as peroxylauric acid, peroxystearic acid, E-
phthalimidoperoxy caproic acid [phthaloiminoperoxy-
hexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic
acid, N-nonenylamidoperadipic acid and N-nonenylamido-
persuccinates, and (c) aliphatic and araliphatic peroxy
dicarboxylic acids, such as 1,12-diperoxydecane-
CA 02328326 2000-12-13
- 27 -
dicarboxylic acid, 1,9-diperoxyazelaic acid, diperoxy-
sebacic acid, diperoxybrassylic acid, the diperoxy-
phthalic acids, 2-decyldiperoxybutane-1,4-dioic acid
and N,N-terephthaloyldi(6-aminopercaproic acid) may be
used.
Bleaches used in compositions for machine dishwashing
may also be substances which release chlorine or
bromine. Among suitable chlorine- or bromine-releasing
materials, examples include heterocyclic N-bromoamides
and N-chloroamides, examples being trichloroisocyanuric
acid, tribromoisocyanuric acid, dibromoisocyanuric acid
and/or dichloroisocyanuric acid (RICA) and/or salts
thereof with can ons such as potassium and sodium.
Hydantoin compounds, such as 1,3-dichloro-5,5-di-
methylhydantoin, are likewise suitable.
In order to achieve an improved bleaching action when
washing or cleaning at temperatures of 60°C and below,
it is possible to incorporate bleach activators into
the laundry, dishwashing and cleaning product detergent
portions of the invention. Bleach activators which may
be used are compounds which under perhydrolysis
conditions give rise to aliphatic peroxo carboxylic
acids having preferably 1 to 10 carbon atoms, in
particular 2 to 4 carbon atoms, and/or substituted or
unsubstituted perbenzoic acid. Suitable substances are
those which carry O-acyl and/or N-aryl groups of the
stated number of carbon atoms, and/or substituted or
unsubstituted benzoyl groups. Preference is given to
polyacylated alkylenediamines, especially tetraacetyl-
ethylenediamine (TAED), acylated triazine derivatives,
especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-
triazine (DADHT), acylated glycolurils, especially
tetraacetylglycoluril (TAGU), N-acyl imides, especially
N-nonanoylsuccinimlde (NOSI), acylated phenol-
sulfonates, especially n-nonanoyl- or isononanoyl-
oxybenzenesulfonate (n- or iso-NOBS), carboxylic
CA 02328326 2000-12-13
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anhydrides, especially phthalic anhydride, acylated
polyhydric alcohols, especially triacetin, ethylene
glycol diacetate, and 2,5-diacetoxy-2,5-dihydrofuran.
In addition to the conventional bleach activators, or
instead of them, it is also possible to incorporate
what are known as bleaching catalysts into the laundry,
dishwashing or cleaning product detergent portions.
These substances are bleach-boosting transition metal
salts or transition metal complexes such as, for
example, Mn-, Fe-, Co-, Ru- or Mo-salen complexes or
-carbonyl complexes. Other bleaching catalysts which
can be used include Mn, Fe, Co, Ru, Mo, Ti, V and Cu
complexes with N-containing tripod ligands, and also
Co-, Fe-, Cu- and Ru-amine complexes.
Suitable enzymes include those from the class of the
proteases, lipases, amylases, cellulases, and mixtures
of said enzymes. Especially suitable enzymatic active
substances are those obtained from bacterial strains or
fungi, such as Bacillus subtilis, Bacillus
licheniformis, and Streptomyces griseus. Preference is
given to the use of proteases of the subtilisin type,
and especially to proteases obtained from Bacillus
lentus. Of particular interest in this context are
enzyme mixtures, examples being those of protease and
amylase or protease and lipase or protease and
cellulase or cellulase and lipase, or of protease,
amylase and lipase, or protease, lipase and cellulase,
but especially cellulase-containing mixtures.
Peroxidases or oxidases have also proven suitable in
some cases. The enzymes may be adsorbed on carrier
substances and/or embedded in coating substances in
order to protect them against premature decomposition.
The proportion of the enzymes, enzyme mixtures or
enzyme granules in the compositions of the invention
may be, for example, from about 0.1 to 5% by weight,
preferably from 0.1 to about 2% by weight.
CA 02328326 2000-12-13
- 29 -
In accordance with the prior art, enzymes are added
primarily to a cleaning product formulation, especially
to a dishwashing composition, which is intended for the
main wash cycle. A disadvantage in this case was that
the activity optimum of enzymes used restricted the
choice of temperature and also that problems occurred
in connection with the stability of the enzymes in the
strongly alkaline medium. With the laundry, dishwashing
or cleaning product detergent portions of the invention
it is possible to use enzymes in the prewash cycle as
well and so to utilize the prewash cycle, in addition
to the main wash cycle, for the enzymes to act on ware
soiling.
In accordance with the invention, therefore, it is
particularly preferred to add enzymes to the detersive
formulation or subportion - intended for the prewash
cycle - of a cleaning product detergent portion and
then - with further preference - to enclose such a
formulation with a material which dissolves in water
even at low temperature, in order, for example, to
protect the enzyme-containing formulation against a
loss of activity caused by immediate-environment
conditions. With further preference, the enzymes are
optimized for use under the conditions of the prewash
cycle, i.e., in cold water, for example.
The dishwashing detergent or cleaning product detergent
portions of the invention may be advantageous when the
enzyme formulations are in liquid form, as are
available commercially in some cases, since in that
case it is possible to expect a rapid action which
takes place as early as in the prewash cycle (which is
relatively short and is carried out in cold water).
Even when - as is usual - the enzymes are used in solid
form and are provided with an enclosure of a water-
soluble material which is soluble even in cold water,
CA 02328326 2000-12-13
- 30 -
the enzymes may develop their activity even before the
main wash cycle or main cleaning operation. An
advantage of using an enclosure comprising water-
soluble material, especially comprising cold-water-
soluble material, is that the enzymes) acts(act)
rapidly in cold water following dissolution of the
enclosure. By this means it is possible to extend their
activity time, to t:he benefit of the wash.
In accordance with one particularly preferred
embodiment, the laundry, dishwashing or cleaning
product detergent portions of the invention comprise
further additives as known from the prior art as
additives for laundry, dishwashing and cleaning product
detergent formulations. These additives may be added to
either one or more, or else if necessary to all,
subportions (detersive formulations) of the laundry,
dishwashing or cleaning product detergent portions of
the invention, or may - as described in the parallel
pending patent application No. 199 29 098.9 with the
title "Active substance portion pack" - be incorporated
into water-soluble materials comprising the detersive
formulations, i.e., for example, into water-soluble
enclosure films, or else into the capsules or coatings
of the invention.
One preferred group of additives used in accordance
with the invention are optical brighteners. In this
case it is possible to use the optical brighteners
customary in laundry detergents. They are added as an
aqueous solution or a solution in an organic solvent to
the polymer solution which is converted into the film,
or are added in solid or liquid form to a subportion
(detersive formulation) of a detergent. Examples of
optical brighteners are derivatives of
diaminostilbenedisulfonic acid and the alkali metal
salts thereof. Suitable, for example, are salts of
4,4'-bis(2-anilino--4-morpholino-1,3,5-triazinyl-6-
CA 02328326 2000-12-13
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amino)stilbene-2,2'-disulfonic acid or compounds of
similar structure carrying a diethanolamino group, a
methylamino group, and anilino group, or a
2-methoxyethylamino group in place of the morpholino
group. Moreover, brighteners of the substituted
diphenylstyryl type may be present in the subportions
(detersive formulations) of the laundry, dishwashing or
cleaning product detergent portions of the invention,
examples being the 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)bi-
phenyl. Mixtures of the aforementioned brighteners may
also be used.
A further group of additives which is preferred in
accordance with the invention are UV protection
substances. These are substances which during the
washing process or during the subsequent fabric
softening process are released in the wash liquor and
accumulate on the fiber, subsequently achieving a W
protection effect. The products available commercially
under the designation Tinosorb from Ciba Specialty
Chemicals are suitable.
Further additives which are conceivable and are
preferred in specific embodiments are surfactants,
which may in particular influence the solubility of the
water-soluble film, but may also control the
wettability thereof and the formation of foam during
dissolution, and foam inhibitors, and also bitter
substances, which may prevent accidental swallowing of
such packaging or parts of such packaging by children.
A further group of additives which is preferred in
accordance with the invention are dyes, especially
water-soluble or water-dispersible dyes. Preference is
given here to dyes as commonly used in order to enhance
the visual appeal of the product in laundry detergents,
dishwashing detergents, and cleaning product
CA 02328326 2000-12-13
- 32 -
detergents. The selection of such dyes causes no
difficulty to the skilled worker, especially since
customary dyes of this kind have a high level of
storage stability and insensitivity to the other
ingredients of the detersive formulations, and with
respect to light, and also have no pronounced affinity
for textile fibers, so as not to stain them. In
accordance with the invention, the dyes are present in
amounts of less than 0.01% by weight in the laundry,
dishwashing or cleaning product detergent portions.
A further class of additives which may be added in
accordance with the invention to the laundry,
dishwashing or cleaning product detergent portions are
polymers. Suitable such polymers include, firstly,
polymers which in the course of washing or cleaning
exhibit cobuilder properties, i.e., for example,
polyacrylic acids, including modified polyacrylic
acids, or corresponding copolymers. Another group of
polymers are polyvinylpyrrolidone and other graying
inhibitors, such as polyvinylpyrrolidone copolymers,
cellulose ethers, and the like. In accordance with
another embodiment of the invention, suitable polymers
also include what are known as soil repellents, as are
known to the skilled laundry, dishwashing or cleaning
products worker and described in detail below.
Another group of additives are bleaching catalysts,
especially bleaching catalysts for machine dishwashing
compositions or laundry detergents. Use is made here of
complexes of manganese and of cobalt, especially with
nitrogenous ligands.
A further group of additives which is preferred in the
context of the invention is silver protectants. This
group comprises a large number of usually cyclic
organic compounds, which again are familiar to the
skilled worker in question here and which contribute to
CA 02328326 2000-12-13
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preventing the tarnishing of articles containing silver
during the cleaning process. Specific examples may be
triazoles, benzotriazoles, and complexes thereof with
metals such as Mn, Co, Zn, Fe, Mo, W or Cu, for
example.
As further additives in accordance with the invention
the laundry, dishwashing or cleaning product detergent
portions may also comprise what are known as soil
repellents, i.e., polymers which attach to fibers or
hard surfaces (to porcelain and glass, for example),
which have a positive effect on the capacity for oil
and fat to be washed off from textiles, and which
therefore act specifically to counter recoiling. This
effect is particularly marked if a textile or a hard
article (porcelain, glass) which has already been
washed or cleaned a number of times beforehand with a
laundry, dishwashing or cleaning product detergent of
the invention comprising this oil- and fat-dissolving
component becomes soiled. The preferred oil- and fat-
dissolving components include, for example, nonionic
cellulose ethers such as methylcellulose and
methylhydroxypropylcellulose having a methoxy group
content of from 15 to 30% by weight and a
hydroxypropoxy group content of from 1 to 15% by
weight, based in each case on the nonionic cellulose
ether, and also the prior art polymers of phthalic acid
and/or of terephthalic acid and/or of derivatives
thereof, especially polymers of ethylene terephthalates
and/or polyethylene glycol terephthalates or
anionically and/or nonionically modified derivatives of
these. Of these compounds, particular preference is
given to the sulfonated derivatives of the phthalic
acid and terephthalic acid polymers.
All of these additives are added to the laundry,
dishwashing or cleaning product detergent portions of
the invention in amounts of not more than 30% by
CA 02328326 2000-12-13
- 34 -
weight, preferably from 2 to 20% by weight. As already
stated, the addition may also be made to a material of
a water-soluble enclosure which encloses the - or one
of the - detersive formulations. In order to maintain
the balance of the recipe, therefore, it is possible
for the skilled worker either to increase the weight of
the polymer material for the enclosure, in order to
utilize the depot effect which is achieved in
accordance with the invention, or else to keep the
aforementioned additives additionally, at least
fractionally, in the remaining detersive formulation.
This, however, is less preferred.
Fragrances are added to the laundry, dishwashing or
cleaning product detergent portions of the invention in
order to enhance overall esthetic appeal of the
products and to provide the consumer with not only the
performance (fabric softening, clear rinsing) but also
a sensorially typical and unmistakable product. As
perfume oils or fragrances it is possible to use
individual odorant compounds, examples being the
synthetic products of the ester, ether, aldehyde,
ketone, alcohol, and hydrocarbon types. Odorant
compounds of the ester type are, for example, benzyl
acetate, phenoxyet.hyl isobutyrate, p-tert-butylcyclo-
hexyl acetate, linalyl acetate, dimethylbenzylcarbinyl
acetate, phenylethyl acetate, linalyl benzoate, benzyl
formate, ethyl methylphenylglycinate, allyl
cyclohexylpropionate, styrallyl propionate, and benzyl
salicylate. The ethers include, for example, benzyl
ethyl ether. The aldehydes include, for example, the
linear alkanals having 8 to 18 carbon atoms, citral,
citronellal, citronellyloxyacetaldehyde, cyclamen
aldehyde, hydroxycitronellal, filial and bourgeonal.
The ketones include, for example, the ionones,
a-isomethylionone and methyl cedryl ketone. The
alcohols include anethole, citronellol, eugenol,
CA 02328326 2000-12-13
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geraniol, linalool, phenylethyl alcohol, and terpineol.
The hydrocarbons include primarily terpenes such as
limonene and pinene. Preference is given to the use of
mixtures of diffex-ent odorants, which are blended so
that together they produce an appealing fragrance. Such
perfume oils may a:Lso contain natural odorant mixtures,
as obtainable from plant sources. Examples are pine
oil, citrus oil, jasmine oil, patchouli oil, rose oil
or ylang-ylang oil. Likewise suitable are nutmeg oil,
sage oil, chamomile oil, clove oil, balm oil, mint oil,
cinnamon leaf oil, lime blossom oil, juniperberry oil,
vetiver oil, olibanum oil, galbanum oil and labdanum
oil, and also orange blossom oil, neroli oil, orange
peel oil, and sandalwood oil.
Normally, the fragrance content is in the region of up
to 2% by weight of the overall detergent portion.
The fragrances may be incorporated directly into the
detersive formulations; alternatively, it may be
advantageous to apply the fragrances to carriers which
intensify the adhesion of the perfume on the laundry
and, by means of slower fragrance release, ensure long-
lasting fragrance of the textiles. Materials which have
become established as such carriers are, for example,
cyclodextrins, it being possible in addition for the
cyclodextrin-perfume complexes to be additionally
coated with further- auxiliaries.
The perfumes and fragrances may in principle be present
in any of the subportions (detersive formulations) of
the laundry, dishwashing or cleaning product detergent
portions of the invention. With particular preference,
however, they are present - in a laundry detergent - in
a detergent subportion intended for the afterwash cycle
or fabric softening cycle or rinse cycle, or - in a
cleaning product, especially in a dishwashing
composition - in a detergent subportion intended for
CA 02328326 2000-12-13
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the afterwash cycle or rinse cycle. In accordance with
the invention, therefore, they must be enveloped by a
material which :is water-soluble only under the
conditions (especially the temperature) of the
afterwash cycle, and which is water-insoluble under the
conditions (especially temperature) of the preceding
wash cycles, especially by a corresponding film or
capsule or by a corresponding coating. In accordance
with the invention this can be done, for example, using
a pouch consisting of a plurality of chambers and made
from films differing in their water-solubility.
To combat microorganisms, the laundry, dishwashing or
cleaning product detergent portions of the invention
may comprise active antimicrobial substances. A
distinction is made here, according to antimicrobial
spectrum and mechanism of action, between bacteriostats
and bacteriocides, fungiostats and fungicides, etc.
Important substances from these groups are, for
example, benzalkonium chlorides, alkylarylsulfonates,
halophenols, and phenylmercuric acetate. The terms
antimicrobial activity and antimicrobial substance in
the context of the teaching of the invention have the
customary meaning in the art, which is given, for
example, by K.H. Wallhausser in "Praxis der
Sterilisation, Desinfektion - Konservierung: Keimiden-
tifizierung - Betriebshygiene" (5th edition -
Stuttgart; New York: Thieme, 1995), it being possible
to use all of the substances described therein
possessing antimicrobial activity. Suitable active
antimicrobial substances are preferably selected from
the groups of the alcohols, amines, aldehydes,
antimicrobial acids and their salts, carboxylic esters,
acid amides, phenols, phenol derivatives, biphenyls,
diphenylalkanes, urea derivatives, oxygen and nitrogen
acetals and forrrials, benzamidines, isothiazolines,
phthalimide derivatives, pyridine derivatives,
antimicrobial surface-active compounds, guanidines,
CA 02328326 2000-12-13
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antimicrobial amphoteric compounds, quinolines,
1,2-dibromo-2,4-dic:yanobutane, iodo-2-propyl butyl-
carbamate, iodine, iodophores, peroxo compounds,
halogen compounds, and any desired mixtures of the
above compounds and/or groups of compounds.
The active antimicrobial substance may be selected from
the group of the compounds given below, it being
possible to use one or more of the stated compounds:
ethanol, n-propanol, i-propanol, 1,3-butanediol,
phenoxyethanol, 1,2-propylene glycol, glycerol,
undecylenic acid, benzoic acid, salicylic acid,
dihydroacetic acid, o-phenylphenol, N-methylmorpholine-
acetonitrile (MMA), 2-benzyl-4-chlorophenol, 2,2'-
methylenebis(6-bromo-4-chlorophenol), 4,4'-dichloro-2'-
hydroxydiphenyl ether (diclosan), 2,4,4'-trichloro-2'-
hydroxydiphenyl ether (triclosan), chlorhexidine, N-(4-
chlorophenyl)-N-(3,4-dichlorophenyl)urea, N,N'-(1,10-
decanediyldi-1-pyridinyl-4-ylidene)bis(1-octanamine)
dihydrochloride, N,N'-bis(4-chlorophenyl)-3,12-diimino-
2,4,11,13-tetraazatetradecanediimideamide, glucopro-
tamines, antimicrobial surface-active quaternary
compounds, guanidines, including the biguanidines and
polyguanidines, such as, for example, 1,6-bis(2-ethyl-
hexylbiguanidohexane) dihydrochloride, 1,6-di(N1,N1'-
phenyldiguanido-NS, NS'-)hexane tetrahydrochloride, 1,6-
di (N1, N1' -phenyl-N1, N1' -methyldiguanido-N5, NS' - ) hexane
dihydrochloride, 1,6-di(N1,N1'-o-chlorophenyldiguanido-
NS,NS' -) hexane dihydrochloride, l, 6-di (N1,N1' -2, 6-di-
chlorophenyldiguanido-NS, NS'-)hexane dihydrochloride,
1, 6-di- [N1,N1' -beta- (p-methoxyphenyl) diguanido-NS,NS' -] -
hexane dihydrochloride, 1,6-di(N1,N1'-alpha-methylbeta-
phenyldiguanido-NS, NS'-)hexane dihydrochloride, 1,6-
di (N1,N1' -p-nitrophenyldiguanido-NS,NS' -) hexane di-
hydrochloride, omega,omega'-di(N1,N1'-phenyldiguanido-
NS,NS'-)di-n-propyl ether dihydrochloride, omega,omega'-
di (N1, N1' -p-chlorophenyldiguanido-N5, NS' - ) di-n-propyl
ether tetrahydrochloride, 1,6-di(N1,N1'-2,4-dichloro-
CA 02328326 2000-12-13
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phenyldiguanido-NS, NS'-)hexane tetrahydrochloride, 1,6-
di (N1, N1' -p-methylphenyldiguanido-N5, NS' -) hexane di-
hydrochloride, 1,6-di(N1,N1'-2,4,5-trichlorophenyldi-
guanido-NS, NS'-)hexane tetrahydrochloride, 1,6-
di [N1,N1' -alpha- (p-chlorophenyl) ethyldiguanido-NS,NS' -] -
hexane dihydrochloride, omega,omega-di(N1,N1'-p-
chlorophenyldiguanido-NS, NS'-)m-xylene dihydrochloride,
1, 12-di (N1,N1' -p-chlorophenyldiguanido-NS,NS' -) dodecane
dihydrochloride, 1, 10-di (N1,N1' -phenyldiguanido-NS,N.S' -)
decane tetrahydrochloride, 1,12-di(N1,N1'-phenyl-
diguanido-NS, NS'-)dodecane tetrahydrochloride, 1,6-
di (N1, N1' -o-chlorophenyldiguanido-N5, NS' - ) hexane dihydro-
chloride, 1, 6-di (N1,N1' -o-chlorophenyldiguanido-NS,NS' -) -
hexane tetrahydrochloride, ethylenebis(1-tolyl-
biguanide), ethylenebis(p-tolylbiguanide), ethylenebis-
(3,5-dimethylphenylbiguanide), ethylenebis(p-tent-amyl-
phenylbiguanide), ethylenebis(nonylphenylbiguanide),
ethylenebis(phenylbiguanide), ethylenebis(N-butyl-
phenylbiguanide), ethylenebis(2,5-die-
thoxyphenylbiguanide), ethylenebis(2,4-dimethylpheny-
lbiguanide), ethylenebis(o-diphenylbiguanide), ethy-
lenebis(mixed-amyl--naphthylbiguanide), N-butylethy-
lenebis(phenylbiguanide), trimethylenebis(o-toly-
lbiguanide), N-butyltrimethylenebis(phenylbiguanide)
and the corresponding salts such as acetates,
gluconates, hydrochlorides, hydrobromides, citrates,
bisulfites, fluorides, polymaleates, N-coco-
alkylsarcosinates, phosphates, hypophosphites, per-
fluorooctanoates, silicates, sorbates, salicylates,
maleates, tartrates, fumarates, ethylenediamine-
tetraacetates, iminodiacetates, cinnamates, thio-
cyanates, arginat.es, pyromellitates, tetracarboxy-
butyrates, benzoates, glutarates, monofluorophosphates,
perfluoropropionates, and any desired mixtures thereof.
Also suitable are halogenated xylene and cresol
derivatives, such as p-chloro-meta-cresol or p-chloro-
meta-xylene, and also natural active antimicrobial
substances of plant origin (e.g., from spices or
CA 02328326 2000-12-13
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herbs), animal origin, and microbial origin. With
preference it is possible to use antimicrobial surface-
active quaternary compounds, a natural active
antimicrobial substance of plant origin and/or a
natural active antimicrobial substance of animal
origin, very great preference being given to at least
one active natural antimicrobial substance of plant
origin from the group consisting of caffeine,
theobromine and theophylline and also essential oils
such as eugenol, t:hymol and geraniol, and/or at least
one natural active antimicrobial substance of animal
origin from the group consisting of enzymes such as
milk protein, lysozyme and lactoperoxidase, and/or at
least one antimicrobial surface-active quaternary
compound containing an ammonium, sulfonium,
phosphonium, iodonium or arsonium group, peroxo
compounds, and chloro compounds. It is also possible to
use substances of microbial origin, known as
bacteriocins.
The quaternary ammonium compounds (QAC) suitable as
active antimicrobial substances have the general
formula (R1) (RZ) (R3) (R4)N+X where R1 to R4 are identical
or different C1 to C22 alkyl radicals, C-, to C28 aralkyl
radicals or heterocyclic radicals, where two - or, in
the case of an aromatic incorporation as in pyridine,
even three - radicals, together with the nitrogen atom,
form the heterocycle, e.g., a pyridinium or
imidazolinium compound, and X- are halide ions, sulfate
ions, hydroxide ions or similar ions. For an optimum
antimicrobial activity, at least one of the radicals
preferably has a chain length of from 8 to 18, in
particular from 12 to 16, carbon atoms.
QACs may be prepared by reacting tertiary amines with
alkylating agents, such as methyl chloride, benzyl
chloride, dimethyl sulfate, dodecyl bromide, but also
ethylene oxide, for example. The alkylation of tertiary
CA 02328326 2000-12-13
- 40 -
amines with a long alkyl radical and two methyl groups
is particularly easy. The quaternization of tertiary
amines having two long radicals and one methyl group
may also be carried out under mild conditions with the
aid of methyl chloride. Amines having three long alkyl
radicals or hydroxy-substituted alkyl radicals are
relatively unreactive and are preferably quaternized
using dimethyl sulfate.
Suitable QACs are, for example, benzalkonium chloride
(N-alkyl-N,N-dimethylbenzylammonium chloride, CAS
No. 8001-54-5), benzalkone B (m,p-dichlorobenzyl-
dimethyl-C12-alkylammonium chloride, CAS No. 58390-78-
6), benzoxonium chloride (benzyldodecylbis(2-
hydroxyethyl)ammonium chloride), cetrimonium bromide
(N-hexadecyl-N,N-trimethylammonium bromide, CAS No. 57-
09-0) , benzetonium chloride (N,N-dimethyl-N- [2- [2- [p-
( 1, 1, 3 , 3 -tetramethylbutyl ) phenoxy] ethoxy] ethyl ) -
benzylammonium chloride, CAS No. 121-54-0),
dialkyldimethylammonium chlorides such as di-n-
decyldimethylammonium chloride (CAS No. 7173-51-5-5),
didecyldimethylammonium bromide (CAS No. 2390-68-3),
dioctyldimethylammonium chloride, 1-cetylpyridinium
chloride (CAS No. 123-03-5) and thiazoline iodide (CAS
No. 15764-48-1), and mixtures thereof. Particularly
preferred QACs are the benzalkonium chlorides having C8
to Cla alkyl radicals, especially C12 to C14 alkyl-
benzyldimethylammonium chloride.
Benzalkonium halides and/or substituted benzalkonium
halides are available commercially, for example, as
Barquat~ from Lonza, Marquat~ from Mason, Variquat~
from Witco/Sherex and Hyamine~ from Lonza, and also
Bardac~ from Lonza. Further commercially available
active antimicrobial substances are N-(3-
chloroallyl)hexaminium chloride such as Dowicide~ and
Dowicil~ from Dow, benzethonium chloride such as
Hyamine~ 1622 from Rohm & Haas, methylbenzethonium
CA 02328326 2000-12-13
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chloride such as Hyamine~ lOx from Rohm & Haas, and
cetylpyridinium chloride such as cepacol chloride from
Merrell Labs.
The active antir~iicrobial substances are used in
laundry, dishwash_Lng or cleaning product detergent
portions of the invention in amounts of from 0.0001% by
weight to 1% by weight, preferably from 0.001% by
weight to 0.8% by weight, with particular preference
from 0.005% by weight to 0.3% by weight, and in
particular from 0.01 to 0.2% by weight.
In accordance with the invention, the laundry,
dishwashing or c:Leaning product detergent portions
comprise at least two, but if desired even more than
two, detersive components or formulations, for example,
those as described in detail above, which are intended
for release into the liquor at different points in
time. For example, in the case of a laundry detergent
portion of the invention, these may be detersive
formulations or components for the prewash cycle of a
wash operation on the one hand and for the main wash
cycle of a wash operation on the other hand, or
detersive components or formulations for the main wash
cycle of a wash operation on the one hand and for the
afterwash cycle of a wash operation on the other hand.
In this case it is preferred for the respective cycles
to be cycles of a wash operation in a washing machine.
In the case of a dishwashing detergent according to the
invention - to name a further preferred example of the
invention - the at least two components may be
detersive components or formulations for the prewash
cycle and main wash cycle or for the main wash cycle
and afterwash cycle of a wash operation, preferably in
a dishwasher.
The laundry, dishwashing or cleaning product detergent
portion of the invention, comprising two or more
CA 02328326 2000-12-13
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detersive components of which at least two are to be
released into the :Liquor at different points in time of
a washing or cleaning operation, comprise at least one
release controlling (physico)chemical switch which is
not subject or not exclusively subject to temperature
control.
By the term "(physico)chemical switch" in the context
of the present invention, in the most general
embodiment, it .is understood that the laundry,
dishwashing or cleaning product detergent portion may
be induced to release at least two detersive components
it comprises into the respective liquor at different
points in time of the washing or cleaning operation by
means of appropriate components it comprises, on the
basis of one or more changes in its surrounding wash
liquor or cleaning liquor, this change or changes being
controllable by the user in accordance with the
conditions or in accordance with the desired results -
for example, in accordance with the wash program or
cleaning program of a machine.
In preferred embodiments of the invention, such
components may, for example, be structural components.
By this is meant that the structural composition of the
laundry, dishwashing or cleaning product detergent
portion is such that release of one or more detersive
components of the respective portion into the wash
liquor or cleaning liquor may take place independently
of one or more other detersive components of the
respective portion. In one preferred embodiment of the
wash liquor or cleaning liquor of the invention, this
structural composition may be a composition in layers
or in disks, in which - to name only one of numerous
conceivable and practicable examples, without
restricting the invention hereto - one or more
detersive components of a laundry, dishwashing or
cleaning product detergent portion, which is or are to
CA 02328326 2000-12-13
- 43 -
be released into the liquor later, is or are present in
one or more layers of a portion present in the form of
a tablet, said layer or layers not being exposed to the
ingress of an aqueous liquor until later than one or
more other detersive components of a laundry,
dishwashing or cleaning product detergent portion which
is or are to be released into the liquor at an earlier
point in time of the washing or cleaning operation. The
structural components may also comprise, for example, a
composition in which particles of individual (or else
of two or more) detersive components, or aggregates of
such particles, which are to be released into the
liquor at a late point in time of a washing or cleaning
operation are surrounded by one or more layers of one
or more detersive components which may be released into
the liquor at an early point in time. Similarly, the
structural components may comprise a composition in
which one or more components for later release into the
respective liquor is or are surrounded by a coating
which dissolves poorly in water or dissolves only under
certain conditions in water, but one or more components
for earlier release into the respective liquor is or
are not so surrounded, or in which one or more
components for release into the liquor at a later point
in time of the washing or cleaning operation has or
have been compacted to a greater extent, and/or more
closely, to an agglomerate of particles or one or more
layers thereof or to a tablet or one or more layers
thereof, than has or have one or more other components
of a laundry, dishwashing or cleaning product detergent
portion which is or are to be released into the liquor
at an earlier point in time. Of course, combinations of
two or more such (or else different) structural
components are pos:~ible.
In another preferred embodiment of the laundry,
dishwashing or cleaning product detergent portion of
the invention, the (physico)chemical switches)
CA 02328326 2000-12-13
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controlling the release of at least one detersive
component is/are one or more structural or substantive
components of the laundry, dishwashing or cleaning
product detergent portion. This means that the laundry,
dishwashing or cleaning product detergent portion
comprises at least one substance component which in
reaction to changes in the immediate environment of the
laundry, dishwashing or cleaning product detergent
portion, for example, to changes in certain properties
of the wash liquor or cleaning liquor - possible
examples being the electrolyte concentration or the H+
ion concentration (i.e., the pH) - prevents or retards
release of one or more detersive components into the
wash liquor or cleaning liquor, while one or more other
components of the respective laundry, dishwashing or
cleaning product detergent portion or subportion have
been released into the liquor. The substantive
components) which brings) about prevention or
retardation of the release may itself/themselves be
nondetersive substances; however, a preferred
embodiment of the laundry, dishwashing or cleaning
product detergent portion of the invention is that
wherein one or more such release preventing or
retarding substantive components is/are itself/-
themselves (a) detersive component(s).
Of course, combinations of the abovementioned preferred
embodiments of the invention are also possible. For
instance, the (physico)chemical switches) controlling
the release of at least one detersive component may be
one or more structural components or one or more
substantive components or else a combination of one or
more structural components with one or more substantive
components of the laundry, dishwashing or cleaning
product detergent portion.
Further preference is given in accordance with the
invention to laundry, dishwashing or cleaning product
CA 02328326 2000-12-13
- 45 -
detergent portions wherein the (physico)chemical
switches) controlling the release of at least one
detersive component is/are one or more components
which, when there is a change in the electrolyte
concentration in the washing or cleaning liquor,
undergo a change in physical and/or chemical
properties. In the context of the present invention,
therefore, it is possible with preference to use a
(physico)chemical switch which brings about electrolyte
controlled active substance release. In the case, for
example, of laundry detergents or dishwashing
compositions for use in washing machines or
dishwashers, the difference in the electrolyte content
of the liquor of, for example, the cleaning cycle and
the rinse cycle may be utilized.
One preferred embodiment of the invention therefore
relates to a laundry, dishwashing or cleaning product
detergent portion comprising an active substance or a
combination of active detersive substances which is
compounded with one or more electrolyte sensitive
substances, the active substances) being released at a
certain point in time or during a certain period of
time, in the case of two or more active substances
preferably at different points in time or during
different periods of time, during the laundry,
dishwashing or cleaning process, as a consequence of a
change which occur: in the electrolyte concentration in
the respective liquor.
It has in fact surprisingly been found that it is
possible, for example, to release an active substance
in the course of use, by compounding or coating with a
material which dissolves better at low ionic strength
than at high ionic strength, referred to below as
"electrolyte sensitive material", as a function of the
salinity. Examples of classes of substance for
consideration as electrolyte sensitive materials are
CA 02328326 2000-12-13
- 46 -
the following, without the invention being restricted
to these:
a) Cellulose derivatives, e.g., methylcellulose,
hydroxyethylcellulose, hydroxypropylcellulose,
methylhydroxyethylcellulose, carboxymethyl-
cellulose with various degrees of substitution;
b) Polyvinyl alcohols with different degrees of
hydrolysis and molecular weights;
c) Polyelectrolyt=es such as, for example,
polyacrylates and, with particular preference,
polystyrenesulfonate.
These electrolyte sensitive materials possess good
solubility in pure water or at low ionic concentration,
but become difficult to dissolve or even insoluble in
the presence of higher concentrations of ions, for
example, at relatively high salt concentrations. The
concentration of ions per unit volume of the respective
liquor, for example, the salt concentration, which is
required to render insoluble the electrolyte sensitive
materials or substances depends on a number of
parameters, a particular example being the nature of
the electrolyte sensitive material used.
In accordance with the invention, laundry, dishwashing
or cleaning product detergent portions which may be
used with particular advantage and are therefore
further preferred are those wherein the
(physico)chemical switches) controlling the release of
at least one detersive component is/are one or more
components which, when there is a change in the H+ ion
concentration (the pH) in the washing or cleaning
liquor, undergo a change in physical and/or chemical
properties.
CA 02328326 2000-12-13
- 47 -
Considering the process of machine laundering or
dishwashing, the pH of the wash liquor during the wash
cycle is approximately 10. The reason why this is so is
that the major products available on the market for
machine laundering or dishwashing contain alkali.
In the great majority of the washing machines and
dishwashers that are presently available on the market,
the wash processes are programmed in such a way that
the wash liquor is pumped off after the main wash cycle
and replaced by fresh water. In this case,
independently of the temperature of the water that is
passed in, there is a drop in pH by approximately 1 to
2 pH units. The precise value of the pH drop is
dependent on the amount of residual liquor remaining in
the machine, which is approximately 2%. It has now been
found that the pH change occurring in this stage of the
washing process may be utilized in order to effect
targeted release of active detersive substances at
certain points in time or during certain periods of
time of the washing or cleaning operation.
In one particularly preferred embodiment of the
invention, therefore, the laundry, dishwashing or
cleaning product detergent portions comprise those
(physico)chemical switches which, when there is a
change in the pH of the application liquor, undergo a
change in the physicochemical properties. Particular
preference is given to using (physico)chemical switch
substances which, as a consequence of a change in pH
occurring in the application liquor, undergo a change
in solubility, more preferably still exhibiting an
increased solubility in water. Alternatively or in
addition, preference is given to those switch
substances which, when there is a change in the pH of
the application liquor, undergo a change, especially a
decrease, in the diffusion density and/or a change,
with particular preference an acceleration, in the
CA 02328326 2000-12-13
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dissolution kinetics and/or a change, with particular
preference a decrease, in the mechanical stability.
Advantageous - and therefore particularly preferred -
are compositions, especially detergents for machine
laundering or dishwashing, which comprise a
(physico)chemical switch substance which, when there is
a change in pH occurring in the application liquor in
the range from 11 to 6, preferably from 10 to 7, more
preferably still in the range from 10 to 8, undergoes a
change in its physicochemical properties and in doing
so preferably has an increased solubility in water in
the case of a decrease in pH in the range from 10 to 7,
in particular from 10 to 8, and/or undergoes a decrease
in the diffusion density and/or undergoes an
acceleration of the dissolution kinetics and/or
undergoes a decrease in the mechanical stability. A
decrease in the diffusion density may have the effect,
for example, that, when there is a change in the
electrolyte concentration and/or the pH, a film or a
matrix material undergoes partial dissolution and
permits ingress of the aqueous liquor to the detersive
formulation, or two or more such formulations, through
the resultant pores, cracks or holes. Similarly, an
acceleration in the dissolution kinetics as a result of
the change in electrolyte concentration and/or the
change in pH has the effect that a film or a matrix
material dissolves more rapidly and in the case of a
decrease in the mechanical stability when there is a
change in the electrolyte concentration or the pH it is
found that tablets comprising detersive components
disintegrate more readily.
Suitable substances which may be used as such
(physico)chemical switches are basic in nature and are,
in particular, basic polymers and/or copolymers.
The principle of pH-dependent water solubility is based
in general on a protonation or deprotonation of
CA 02328326 2000-12-13
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functional groups of the polymer molecules, with a
corresponding change in their charge state as a result.
The polymer, then, must be such that it dissolves in
water in the charged state which is stable at a certain
pH but precipitates in the uncharged state at a
different pH. In the context of the present invention,
it is preferred for the polymers used in accordance
with the invention to have a lower water solubility at
a relatively high pH than at lower pH values, or even
to be insoluble in water at a relatively high pH.
Polymers with pH--dependent solubility are known in
particular from pharmacy. Here, use is made, for
example, of acid-insoluble polymers in order to give
tablets a coating which resists gastric fluid but is
soluble in the intestinal fluid. Acid-insoluble
polymers of this kind are mostly based on derivatives
of polyacrylic acid, which is present in undissociated
and hence insoluble form in the acidic range, but is
neutralized in the alkaline range, typically at a pH of
8, and goes into solution as a polyanion.
For the opposite case as well - soluble in the acidic
range, insoluble in the alkaline range - there are
known examples in the prior art. These substances,
where the polymer molecules usually carry amino-
substituted functional groups or sidechains, are used,
for example, to produce tablet coatings that are
soluble in gastric fluid. They generally dissolve at a
pH of less than 5. Polymers where the change from
soluble to insoluble occurs at a higher pH are unknown
in pharmacy, since such pH values are of no
physiological significance.
Suitable substances which are particularly preferred in
the context of the present invention are basic
(co)polymers containing amino groups or aminoalkyl
groups. Comonomers may be, for example, customary
CA 02328326 2000-12-13
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acrylates, methacrylates, maleates or derivatives of
these compounds. A particularly suitable aminoalkyl
methacrylate copolymer is marketed by the company Rohm
and carries the commercial designation/brand name
Eudragit~.
Besides the thermodynamic solubility, the dissolution
kinetics of a film-coated substance, or the decrease in
its mechanical stability, may be of importance for the
application. The dissolution kinetics of the switch
substances used in accordance with the invention is pH
dependent at room temperature up into the alkaline
range, i.e., the films are stable for significantly
longer at a pH of 10 than at a pH of 8.5, although they
are thermodynamically soluble at both pH values.
In a further embodiment of the present invention,
therefore, use is made of polymers whose water
solubility reverses between a pH of 7 and a pH of 6 and
which at relatively high pH values are less readily
soluble than at lower values. As already described
above, suitable po=Lymers contain basic groups, examples
being primary, secondary or tertiary amino groups,
imino groups, amido groups or pyridine groups - in
general, groups which possess a quaternizable nitrogen
atom. V~Ihen the pH is lowered, the quaternizable
nitrogen atoms are protonated, and the polymer becomes
soluble as a result. In relatively high pH, the
molecule is in the uncharged state and is therefore
insoluble. In general, the transition - referred to
below as the "switching point" - takes place in the
range of acidic pH values, depending on the pKb value
of the basic groups and also dependent on their density
along the polymer chain. The laundry, dishwashing or
cleaning product detergent portions of the present
invention therefore further comprise portions
comprising a polymer for which the switching point is
in a pH range between 6 and 7.
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This shift in the switching point of a polymer suitable
for the purposes of the present invention proceeds in
principle as follows: depending on the pKb value of the
functional groups of the polymer, there is only a very
slight change in the charge state of the polymer in
solution in the range of relatively high pH. Therefore,
the solubility of the polymer must be able to
decisively influence the solubility of the polymer with
a slight change in the charge state of the polymer. In
other words, the polymer must, to be exact, have a
hydrophilicity such that it is insoluble in the fully
uncharged state but becomes soluble when there is even
a slight charging, such as by protonation, for example.
To adjust the hydrophilicity it is possible to use the
following methods:
~ Copolymerization of a monomer having a basic function
with a more hydrophilic monomer. The ratio in which
the respective comonomers are incorporated influences
the switching point.
~ Hydrophilicization of the polymer carrying basic
groups by means of a polymer-analogous reaction. The
degree of modification influences the switching point.
In addition to simple hydrophilicization it is also
possible to introduce basic functions having different
pKb values. The switching point may be influenced by
the ratio of the two groups and the resulting
hydrophilicity of t=he molecule.
A particularly preferred polymer of this class of
substance is an N-oxidized polyvinylpyridine.
The pH shift sensitive switches of the invention, and
those used in accordance with the invention, may be
CA 02328326 2000-12-13
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employed for all applications, especially in the
laundry, dishwashing or cleaning product sector, in
which an active substance is to be released when there
is a reduction in pH from the alkaline into the neutral
range. This may be the case both in the field of
laundering in the washing machine and in the case of
machine dishwashing. Included in particular in
accordance with the invention are detergent portions in
which components of a detergent recipe for machine
dishwashing (e. g., surfactants, perfume, soil
repellent, acid, complexing agents, builder substances,
etc., or formulations comprising these active
substances) are formulated with the polymer of the
invention in such a way that these components are not
released into the wash liquor at high pH in the main
wash cycle but are released in the subsequent rinse
cycle with lower pH, where the polymer becomes soluble
in water.
The polymer of pH-dependent solubility may be used
either as a coating or as a matrix material, binder or
disintegrant for the components intended for release at
a later point in time or over a later period of time.
It is not necessary in this case for the polymer to
dissolve completely in order to release the active
substance under the inherent pH conditions for the
polymer. Rather, it is sufficient if, for example, the
permeability of a polymer film changes and, for
example, the penetration of water into the active
substance formulation and an expulsion of the dissolved
components through the holes or pores formed is made
possible. By this means, in a further preferred
embodiment of the laundry, dishwashing or cleaning
product detergent portions of the invention, a
secondary effect, e.g., the activation of an
effervescent system or the swelling of a water-
swellable disintegrant, which are known in particular
CA 02328326 2000-12-13
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in pharmacy, may ensure the complete release of the
active detersive substance(s).
In conformity with the present invention, so-called pH
shift boosters are used in addition to the
abovementioned switches. By this means it is possible,
at least to a predominant extent, to prevent the
incidence in the application liquor after the rinse
cycle of residues consisting, in particular, of the
polymer substance of pH-dependent solubility itself.
Suitable pH shift boosters for the purposes of this
invention are all substances and formulations which are
able to increase the extent of the shift in pH (the pH
shift) either locally, i.e., in the immediate
environment of the particular pH shift sensitive
substance, or else in a generalized way, i.e., in the
wash liquor as a whole. Such substances include - to
name one group of substances particularly suitable as
pH shift boosters in accordance with the invention -
all organic and/or inorganic, water-soluble acids or
acidically reacting salts, in particular at least one
substance from the group of the alkylbenzenesulfonic
acids, alkylsulfuric acids, citric acid, oxalic acid
and/or alkali metal hydrogen sulfates. These substances
may be used alone or in a combination of two or more
thereof .
The pH shift booster may be incorporated into the
laundry, dishwashing or cleaning product detergent. In
a further embodiment of the invention, however, it is
possible to supply the pH shift booster from the
outside, either after the end of the main wash cycle or
at the beginning of the afterwash cycle or rinse cycle,
for example, to introduce it into the corresponding
filling shaft or the corresponding dosing compartment
of the machine or to release it by means of a special
delivery system (by coating with a slow-dissolving
CA 02328326 2000-12-13
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coating material) or by diffusion from a matrix
material or enclosure material in connection with a
tablet or its enclosure.
In another embodiment, the invention provides for the
laundry, dishwashing or cleaning product detergent
portion of the invention to comprise not only the pH
shift booster but also at least two switches, of which
with advantage not more than one is subject to
temperature control. The use of two or more switches
makes it possible for at least two switches differing
in action to improve or even fine-tune the controlled
release of an active detersive substance or of a
combination of such active substances. Alternatively,
however, it is also conceivable for two switches
differing in action to bring about the controlled
release of two or more different active detersive
substances or combinations of different active
substances at different points in time or within
different periods of time of the washing or cleaning
process.
In the context of this embodiment of the invention it
is particularly preferred for at least two switches
which are not subject to temperature control or not
subject to temperature control alone to be present in
the laundry, dishwashing or cleaning product detergent
portion, for example, in the case of a tablet having a
cavity or depression, to be present as cavity filling
or depression filling. In this case it may well be of
advantage if two or more (physico)chemical switches of
which at least one is not subject to temperature
control or not subject to temperature control alone are
present in the cavity filling or depression filling.
In a very particularly preferred embodiment of the
invention, one of the abovementioned (physico)chemical
switches, for example, a pH shift sensitive switch or
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electrolyte sensitive switch, is combined with a switch
which is subject to temperature control. Preference is
given in this case in particular to what are known as
inverse temperature switches, which may be realized by
means of so-called LOST substances. LOST substances are
substances which have a better solubility at low
temperatures than at higher temperatures. They are also
referred to as substances with a low lower critical
separation temperature (low critical solubility
temperature) or w=ith a low lower turbidity point or
flocculation point. Depending on application
conditions, the lower critical separation temperature
should lie between room temperature and the temperature
of the heat treatment in the respective washing or
cleaning process, for example, between 20°C and 120°C,
preferably between 30°C and 100°C, in particular
between 30°C and 50°C. The LCST substances are selected
preferably from alkylated and/or hydroxyalkylated
polysaccharides, cellulose ethers, polyisopropyl-
acrylamide, copolymers of polyisopropylacrylamide, and
mixtures of two or more of these substances.
Examples of alkylated and/or hydroxyalkylated
polysaccharides are hydroxypropylmethylcellulose
(HPMC), ethyl(hydroxyethyl)cellulose (EHEC), hydroxy-
propylcellulose (HPC), methylcellulose (MC), ethyl-
cellulose (EC), carboxymethylcellulose (CMC), carboxy-
methylmethylcellulose (CMMC), hydroxybutylcellulose
(HBC), hydroxybutylmethylcellulose (HBMC), hydroxy-
ethylcellulose (HEC), hydroxyethylcarboxymethyl-
cellulose (HECMC), hydroxyethylethylcellulose (HEEL),
hydroxypropylcarboxymethylcellulose (HPCMC), hydroxy-
ethylmethylcellulose (HEMC), methylhydroxyethyl-
cellulose (MHEC), methylhydroxyethylpropylcellulose
(MHEPC) and propylcellulose (PC).
Further examples of LCST substances are cellulose
ethers and also mixtures of cellulose ethers with
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carboxymethylcellulose (CMC). Further polymers which
exhibit a lower critical separation temperature in
water and which are likewise suitable are polymers of
mono- or di-N-substituted acrylamides with acrylates
and/or acrylic acids, or mixtures of interpenetrating
networks of the abovementioned (co)polymers. Also
suitable are polyethylene oxide or copolymers thereof,
such as ethylene oxide-propylene oxide copolymers,
graft copolymers of alkylated acrylamides with
polyethylene oxide, polymethacrylic acid, polyvinyl
alcohol and copolymers thereof, polyvinyl methyl
ethers, certain proteins such as poly(VATGW), a
repeating unit of the natural protein elastin and
certain alginates. Mixtures of these polymers with
salts or surfactants may likewise be used as LCST
substance. By means of such additions or by the degree
of crosslinking of the polymers it is possible to
modify the lower critical separation temperature
(LCST) .
In a further preferred embodiment of the laundry,
dishwashing or cleaning product detergent portions of
the invention, a pH sensitive switch is combined with
an LCST substance, it being possible in accordance with
the invention for this combination to comprise a pH
shift booster as well.
In accordance with another, likewise preferred
embodiment of the invention, a laundry, dishwashing or
cleaning product detergent portion of the present
invention may also comprise other switches. Suitable,
for example, are switches which are able to bring about
an enzyme controlled release of active detersive
substances at at least two different points in time or
during at least two different periods of time. Enzyme
controlled active substance release switches of this
kind are described in the parallel patent application
bearing the title "Detergent portion with enzyme
CA 02328326 2000-12-13
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controlled release of active substance". Appropriate
enzymes in particularly preferred embodiments of the
invention are proteases, amylases, cellulases and/or
lipases, whereas enzyme sensitive substances which may
be used include cellulose and its derivatives, starch
and its derivatives, partially oxidized starch
derivatives, glycerides, proteins, and mixtures
thereof. Enzyme controlled switches of this kind may be
used in combination with the switches of the laundry,
dishwashing or cleaning product detergent portions of
the present invention.
In a further preferred embodiment, an enzyme sensitive
switch is combined with an LCST substance.
In another preferred embodiment of the invention, a pH
shift sensitive switch, in combination in accordance
with the invention with a pH shift booster, is combined
with an enzyme sensitive switch.
With particular advantage it is possible to use both a
pH shift sensitive switch, in combination in accordance
with the invention with a pH shift booster, and an
enzyme sensitive switch and an LOST substance.
Other appropriate switches besides enzyme sensitive
switches include redox switches, i.e., switches by
means of which the release of active detersive
substances may be brought about at at least two
different points in time or during at least two
different periods of time in the context of a redox
reaction. Redox sensitive switches of this kind are
described in the parallel patent application bearing
the title "Detergent portion with redox controlled
release of active substance". In particularly preferred
embodiments of they invention, suitable redox sensitive
materials include oxidation sensitive organic and
inorganic substances and polymers. One example of a
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redox sensitive material is polyvinylpyridine.
Oxidizing agents used may be, for example, a
percarbonate, the latter in particular in combination
with a bleach activator such as TAED, for example.
Switches of this kind, controlled by a redox reaction,
may be used in combination with the switches of the
laundry, dishwashing or cleaning product detergent
portions of the present invention.
In a further advantageous embodiment of the invention,
a redox sensitive switch is used together with an LCST
substance and/or a pH shift sensitive switch, in
combination in accordance with the invention with a pH
shift booster. It .is further preferred to use all three
switches, i.e., a pH shift sensitive switch, a redox
sensitive switch, and a switch subject to temperature
control, such as an LCST substance, for example, in
combination in accordance with the invention with a pH
shift booster.
A further preferred embodiment of the invention
provides for combining a redox sensitive switch with an
enzyme sensitive switch. In addition, this combination
may again include an LOST substance and/or a pH shift
sensitive switch, in combination in accordance with the
invention with a pH shift booster.
In another embodiment of the invention, the laundry,
dishwashing or cleaning product detergent portion of
the invention comprises an electrolyte sensitive switch
and one or more of the aforementioned pH shift
sensitive switches, in combination in accordance with
the invention with a pH shift booster, an enzyme
sensitive switch, a redox sensitive switch, and an LCST
substance.
In one preferred embodiment of the invention, the
laundry, dishwashing or cleaning product detergent
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portions of the invention are present in solid form,
for example, as powders, granules, agglomerates,
pellets, roll compacts and/or extrudates. A
particularly preferred embodiment, however, is that of
a shaped body constituting one laundry, dishwashing or
cleaning product detergent portion, it being possible
to use one or more shaped bodies per application in a
washing or cleaning process. A particularly
advantageous configuration is as a tablet or as a
capsule. In this case it is also possible to use one or
more tablets and/or one or more capsules, together if
desired with powder, granules, agglomerates, pellets,
roll compacts and/or extrudates. Advantageously, two or
more shaped bodies or the mixtures referred to of
different configurations are supplied in an enclosure
such as in a pouch or in a film which either is opened
prior to use, so that the laundry, dishwashing or
cleaning product detergent portion may be introduced
into the dosing compartment of the washing machine or
dishwasher, or is soluble in water, so that it may be
introduced into the machine together with the detersive
formulation, without residues thereof remaining after
the washing or cleaning operation. In this case, dosing
both by way of the dosing compartment and by way of the
detergent compartment of the respective machine is
possible.
One particularly preferred embodiment is a tablet with
a circular, oval or rectangular to square basal
surface, which may have rounded corners and edges. The
embodiment in question may comprise single-layer white
or colored tablets, which preferably have different-
colored speckles, or else multilayer, at least two-
layer, tablets which in particular comprise at least
two colors, of which one may be white.
In a further embodiment of the invention, the single-
layer or multilayer shaped bodies, and especially
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tablets, have at least one cavity. The design of this
cavity may be such that it extends from the upper
surface to the lower basal surface and the shaped body,
accordingly, forms a ring around a hollow space. In
another preferred embodiment of the invention, the
design of the cavity is such that it does not extend
from the upper surface to the lower basal surface but
instead merely forms a depression, which may be formed
either only over one layer or else over two or more
layers of the tablet. In particular, such depressions
have a circular, oval or rectangular to square basal
surface.
In one particularly preferred embodiment of the
invention, the cavity and preferably the depression
comprises one part of the overall composition of the
detergent. This part of the overall composition may
fill a part of the cavity or depression or the whole
cavity or depression. In a preferred embodiment of the
invention, one or more mixtures liquid at room
temperature, which may comprise detersive components
besides carriers and auxiliaries, in the form, for
example, of a melt, is or are inserted in the cavity or
depression. The melt solidifies on cooling.
As an alternative to this, it is also possible to
prepare the cavity filling or depression filling
separately and then to insert it in the cavity or
depression, respectively. The cavity filling or
depression filling may then be present in the cavity or
depression in solid form, for example by adhesive
bonding, or looser for example in the form of a plug
connection. The separately prepared cavity filling or
depression filling may be prepared in a variety of
ways. Preferred methods include the preparation of an
uncompressed shaped body, especially a solidified melt
body, or of a compressed body. In particular, the
separately prepared filling bodies may adopt a shape
CA 02328326 2000-12-13
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other than that predetermined by the cavity or
depression. Thus it is possible, for example, for the
depression to constitute a semicircular opening in a
tablet and for the filling to be present in spherical
form but for the latter to have, possibly, a smaller
diameter than the semicircular depression.
Alternatively, it is also conceivable for the
depression to have an oval basal surface, but for the
filling to have a spherical form. In particular,
however, it is preferred for the shaped body, including
the cavity filling or depression filling, to have a
planar or virtually planar surface.
In a further embodiment of the invention it is
envisaged that the cavity is internal and that its
filling is not visible from the outside. The actual
shaped body, and especially the actual tablet,
therefore, constitute a sheath which completely
encloses the cavity - which in particular is filled.
The cavity filling may again have been prepared in the
manner already described, either separately as a melt
body or compressed body, and may then have been cast or
compressed to form the ultimate shaped body, or else
the cavity filling is inserted in melt form into a
precompressed shaped body, and this is subsequently
compressed to form the ultimate shaped body.
In one particularly preferred embodiment, the invention
envisages the cavity filling or depression filling
comprising at least one switch for controlled active
substance release which is not subject to temperature
control or not to temperature control alone.
In another embodiment of the invention, the shaped body
is present as a capsule. Where only parts of the
overall composition are encapsulated, it is possible
for the aforementioned switch systems to be
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incorporated into the capsule shell. For pouches,
similar comments apply.
In the context of the present invention it is
particularly preferred to carry out controlled release
of surfactants, fragrances, dyes, bleaches, preferably
an active chlorine carrier, acids, preferably citric
acid, amidosulfonic acid or hydrogen sulfate,
phosphonates, complexing agents, surfactants having
complexing properties, builders, and cobuilders. An
embodiment of the invention which is very particularly
preferred in practice involves providing machine
dishwashing compositions which simultaneously comprise
a rinse aid which is released controllably in the rinse
cycle. Particularly preferred active substances are
nonionic surfactants which have a clear-rinse effect
and a melting point above room temperature, i.e., above
20°C, with particular preference between 25 and 60°C,
and in particular between 26.6 and 43.3°C.
Suitable nonionic surfactants having melting or
softening points within the stated temperature range
are, for example, low-foaming nonionic surfactants
which may be solid or highly viscous at room
temperature. If nonionic surfactants which are highly
viscous at room temperature are used, then it is
preferred that they have a viscosity above 20 Pas,
preferably above 35 Pas, and in particular above
40 Pas. Also preferred are nonionic surfactants which
possess a waxlike consistency at room temperature.
Preferred nonionic surfactants for use that are solid
at room temperature originate from the groups of
alkoxylated nonionic surfactants, especially the
ethoxylated primary alcohols, and mixtures of these
surfactants with surfactants of more complex
construction such as polyoxypropylene/polyoxyethylene/
polyoxypropylene (PO/EO/PO) surfactants. Such
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(PO/EO/PO) nonionic surfactants are notable,
furthermore, for good foam control.
In one preferred embodiment of the present invention,
the nonionic surfactant having a melting point above
room temperature is an ethoxylated nonionic surfactant
originating from the reaction of a monohydroxy alkanol
or alkylphenol having 6 to 20 carbon atoms with
preferably at least 12 mol, with particular preference
at least 15 mol, in particular at least 20 mol, of
ethylene oxide per mole of alcohol or alkylphenol,
respectively.
A particularly preferred nonionic surfactant for use
that is solid at room temperature is obtained from a
straight-chain fatty alcohol having 16 to 20 carbon
atoms (C16-zo alcohol) , preferably a C18 alcohol, and at
least 12 mol, preferably at least 15 mol, and in
particular at least 20 mol of ethylene oxide. Of these,
the so-called "narrow range ethoxylates" are
particularly preferred.
Particularly preferred are C6_2o monohydroxyalkanols or
Cs-ao alkyl phenols or Cls-2o fatty alcohols with more than
12 mol, preferably more than 15 mol, and in particular
more than 20 mol, of ethylene oxide per mole of
alcohol.
The nonionic surfactant which is solid at room
temperature preferably further possesses propylene
oxide units in the molecule. Preferably, such PO units
account for up to 25o by weight, with particular
preference up to 20% by weight, and in particular up to
15% by weight, of the overall molecular mass of the
nonionic surfactant. Particularly preferred nonionic
surfactants are ethoxylated monohydroxy alkanols or
alkylphenols, which additionally comprise
polyoxyethylene-polyoxypropylene block copolymer units.
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The alcohol or alkylphenol moiety of such nonionic
surfactant molecules in this case makes up preferably
more than 30% by weight, with particular preference
more than 50% by weight, and in particular more than
70% by weight, of the overall molecular mass of such
nonionic surfactants. Preferred processes are those in
which the core tablet comprises as ingredient
ethoxylated and propoxylated nonionic surfactants
wherein the propylene oxide units in the molecule
account for up to 25% by weight, preferably up to 20%
by weight, and in particular up to 15% by weight, of
the overall molecular mass of the nonionic surfactant.
Further nonionic surfactants whose use is particularly
preferred, with melting points above room temperature,
contain from 40 to 70% of a polyoxypropylene/
polyoxyethylene/polyoxypropylene block polymer blend
which comprises 75% by weight of an inverted block
copolymer of polyoxyethylene and polyoxypropylene
containing 17 mol of ethylene oxide and 44 mol of
propylene oxide and 25% by weight of a block copolymer
of polyoxyethylene and polyoxypropylene, initiated with
trimethylolpropane and containing 24 mol of ethylene
oxide and 99 mol of propylene oxide per mole of
trimethylolpropane.
Nonionic surfactants which may be used with particular
preference are, for example, obtainable under the name
Poly Tergent~ SLF-18 from Olin Chemicals.
Further preferred are nonionic surfactants of the
following formula
R10 [CHZCH (CH3) O] X [CHzCH20] y [CH2CH (OH) R2]
in which R1 is a linear or branched aliphatic
hydrocarbon radical having 4 to 18 carbon atoms, or
mixtures thereof, Rz is a linear or branched
CA 02328326 2000-12-13
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hydrocarbon radical having 2 to 26 carbon atoms, or
mixtures thereof, and x is between 0.5 and 1.5, and y
is at least 15.
Further nonionic surfactants which may be used with
preference are the endgroup-capped poly(oxyalkylated)
nonionic surfactants of the formula
R10 [CHzCH (R3) O] X [CHz] kCH (OH) [CHZ] ~ORz
in which R1 and RZ are linear or branched, saturated or
unsaturated, aliphatic or aromatic hydrocarbon radicals
having 1 to 30 carbon atoms, R3 is H or a methyl,
ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or
2-methyl-2-butyl radical, x is between 1 and 30, k and
j are between 1 and 12, preferably between 1 and 5.
Where x = 2, each R3 in the above formula may be
different. R1 and R2 are preferably linear or branched,
saturated or unsaturated, aliphatic or aromatic
hydrocarbon radicals having 6 to 22 carbon atoms,
radicals having 8 to 18 carbon atoms being particularly
preferred. For the radical R3, H, -CH3 or -CHzCH3 are
particularly preferred. Particularly preferred values
for x lie within the range from 1 to 20, in particular
from 6 to 15.
As described above, each R3 in the above formula may be
different if x - 2. By this means it is possible to
vary the alkylene oxide unit in the square brackets. If
x, for example, is 3, the radical R3 may be selected in
order to form ethylene oxide (R3 - H), or propylene
oxide (R3 - CH3) units, which may be added on to one
another in any sequence, examples being (EO)(PO)(EO),
(EO) (EO) (PO) , (EO) (EO) (EO) , (PO) (EO) (PO) , (PO) (PO) (EO)
and (PO) (PO) (PO) . The value of 3 for x has been chosen
by way of example in this case and it is entirely
possible for it to be larger, the scope for variation
increasing as the values of x go up and embracing, for
CA 02328326 2000-12-13
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example, a large number of (EO) groups, combined with a
small number of (PO) groups, or vice versa.
Particularly preferred endgroup-capped poly(oxy-
alkylated) alcohols of the above formula have values of
k - 1 and j - l, thereby simplifying the above formula
to
R10 [CHZCH (R3) O] XCHZCH (OH) CH20R2 .
In the last-mentioned formula, R1, RZ and R3 are as
defined above and x stands for numbers from 1 to 30,
preferably from 1 to 20, and in particular from 6 to
18. Particular preference is given to surfactants
wherein the radicals R1 and Rz have 9 to 14 carbon
atoms, R3 is H, and x adopts values from 6 to 15.
Summarizing the last-mentioned statements, preference
is given to endgroup-capped poly(oxyalkylated) nonionic
surfactants of the formula
R10 [CH2CH (R3) O] X [CHZ] kCH (OH) [CHz] ~OR2
in which R1 and R2 are linear or branched, saturated or
unsaturated, aliphatic or aromatic hydrocarbon radicals
having 1 to 30 carbon atoms, R3 is H or a methyl,
ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or
2-methyl-2-butyl radical, x is between 1 and 30, k and
j are between 1 and 12, preferably between 1 and 5,
particular preference being given to surfactants of the
type
R10 [CHzCH (R3) O] XCH2CH (OH) CH20R2
where x is from 1 to 30, preferably from 1 to 20, and
in particular from 6 to 18.
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In one preferred embodiment of the invention, cavity
fillings or depression fillings are used which comprise
a nonionic surfactant or a surfactant mixture with
clear-rinse effect in amounts of from 20 to 50% by
weight, one or more (physico)chemical switches, in
combination if desired with a temperature sensitive
switch in amounts of from 40 to 70% by weight and,
optionally, a pH shift booster in amounts of from 2 to
15o by weight, in particular in amounts of up to 10% by
weight, the percentages by weight being based on the
fillings.
Otherwise, the - in particular, solid - laundry,
dishwashing or cleaning product detergent portions may
comprise conventional ingredients in conventional
amounts. Here, reference is made to the relevant
technical literature and to the detailed description
above. In particular, it is preferred to equip the
laundry, dishwashing or cleaning product detergent
portions of the invention with a conventional
effervescent system, comprising carbonate and citric
acid, for example, in which context it may be
particularly preferred for the cavity filling or
depression filling as well to have such an effervescent
system. This effervescent system may be activated by a
change in the water permeability of the coating with
the material of the (physico)chemical switch as a
result of the change in the respective relevant
parameter during the washing or cleaning operation.
Alternatively to an effervescent system it is also
possible to use a disintegrant known, for example, from
pharmacy or from laundry detergent technology.
The following are suitable for use in textile laundry
detergents with release at a certain point in time in
the wash process, e.g., in the rinse cycles:
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Textile hand components, enzymes, alkalis, acids,
fragrances, dyes, fluorescers, optical brighteners,
shrinkage preventatives, anticrease agents, active
antimicrobial substances, germicides, fungicides,
antioxidants, antistats, easy-iron auxiliaries,
repellents, impregnating agents, UV absorbers, and any
desired mixtures of the aforementioned detersive
components.
Especially in the case of solid machine dishwashing
compositions, the present invention may be utilized in
order to transport active substances through the main
wash cycle into the rinse cycle. In this case, a
formulation comprising, for example, rinse aid
surfactant or else other of the abovementioned active
ingredients may be coated with an electrolyte sensitive
material and/or a pH shift sensitive material or may be
incorporated into a matrix comprising an electrolyte
sensitive material and/or pH shift sensitive material.
This formulation is subsequently formulated together
with the customary detersive component(s), e.g., added
to a powder cleaner or combined with a shaped body. As
for the pH shift sensitive switch, it is not absolutely
necessary for the electrolyte sensitive material to
dissolve completely under the corresponding electrolyte
or pH conditions in the rinse cycle in order to release
the active detersive substance. Rather, it is
sufficient for there to be a change in the permeability
of the electrolyte or pH shift sensitive film or of the
corresponding matrix and, for example, for the
penetration of water into the active substance
formulation to be made possible. As a result, a
secondary effect, for example, the activation of an
effervescent system, may ensure the complete release of
the active substance.
In a particularly preferred embodiment of the
invention, laundry, dishwashing or cleaning product
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detergent formulations are provided with two or more
detersive components, in which components for release
into the respective liquor at a later stage of the
washing or cleaning process, such as, for example,
rinse aid surfactants, acids (such as citric acid, for
example), fragrances, soil repellents, enzymes,
catalysts, bleaches, etc., in compositions for machine
dishwashing are provided with a pH shift sensitive
coating, are compounded into a detersive formulation
using a pH shift sensitive binder, or are compounded
into a detersive formulation using a pH shift sensitive
matrix material. The resulting coated or compounded
product further comprises other customary detersive
components of laundry, dishwashing or cleaning product
detergent portions, as have been described in detail
above.
Setting the switching point to a pH which can be used
for practical purposes of from 10 to 8, very
particularly from 10 to 8.5, is done by copolymerizing
conventional basic monomers of the general formula (A)
H2C = C (-R) COO (CHZ) XN (R1) (RZ) (A)
where R is H or CH3, R1 and R2 independently of one
another are alkyl radicals having 1 to 3 carbon atoms,
and x is an integer from 1 to 4, as repeating units
with a hydrophobic monomer which is insoluble or
sparingly soluble i.n water, of the general formula (B)
HzC = C (-R3) - (CHz) Y-B-R4 (B)
where R3 is H, CH3 or COOH, R4 is a straight-chain or
branched alkyl radical having 1 to 8 carbon atoms, B is
C(O)O or OC(O), and y is 0 or 1, and a water-soluble
monomer of the general formula (C)
H2C = C (-RS) -C (O) -R6 (C)
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where RS is H or CH3 and R6 is an amino group which is
unsubstituted or substituted, for example, with an N,N-
dimethylaminopropyl group or is a hydroxyalkyl group
having 1 to 3 carbon atoms in the alkylene radical or
is a polyethylene glycol radical, it being possible to
adjust the solubility of the copolymer by way of the
molar ratio of the abovementioned monomer units.
Preferred compounds of the general formula (A) are, for
example, N,N-dimethylaminoethyl (meth)acrylate and N,N-
dimethylaminopropyl (meth)acrylate. Preferred compounds
of the above general formula (B) include, for example,
(meth)acrylic esters having preferably 1 to 8 carbon
atoms, vinyl acetate or alkyl itaconates having 1 to 8
carbon atoms in the alkyl radical. Suitable compounds
of the general formula (C) include N,N-dimethyl-
aminopropyl(meth)acrylamide, 2-hydroxyethyl (meth)-
acrylate or (meth)acrylic esters of polyethylene
glycols. The ratio of the repeating units (A):(B):(C)
to the sum of the three components is in the range from
[from 0.1 to 0.7] : [from 0.05 to 0.6] : [from 0.1 to 0.7] ,
based on [ (A) + (B) + (C) ] .
Using a pH shift sensitive copolymer of this kind it is
possible to coat, compound or embed detersive
components whose release into the liquor is desired not
until a relatively late point in time in the washing or
cleaning process. As a result, the detersive substances
thus treated are released only in a relatively late
process step, when the pH of the application liquor has
dropped from > 10 to < 8.5 or below and the copolymer
has become soluble owing to the shift in pH.
Said active detersive substances may be compounded
conventionally. By way of example, mention may be made
of the following procedures: the active substances)
may be adsorbed onto an appropriate carrier material.
Examples of the carriers are highly porous substances
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from different classes of substance, such as highly
disperse silica, for example; zeolites (e. g., Wessalith
types such as P or XD), porous polymer gels such as the
commercial product with the designation Polypore E200
(from Chemdal Corp.; allyl methacrylate crosspolymer);
template structures such as highly porous silicatic
substances obtained by ceramicization of surfactant
associates, or bentonite. The carrier/active substance
ratio may be, preferably, in the range from 3:1 to 1:5,
based on the weight . The product should retain a free-
flowing, granular structure, it being possible to
effect subsequent compression, in which case the pH
shift sensitive copolymer may be incorporated as a
binder or applied as a coating.
In other preferred embodiments of the invention, the
substances) intended for later release in the washing
or cleaning process such as, for example - without,
however, restricting the invention - a rinse aid in a
composition for machine dishwashing, may be compounded
with an appropriate polymer in such a way that the
resultant formulation may be extruded. Appropriate
polymers for these purposes are, for example, partially
hydrolyzed polyvinyl alcohols (PVALs) and fully
hydrolyzed polyvinyl alcohol (PVALs) with the addition
of polyvinyl acetate (PVAc) or polyethylene glycol
(PEG). The resultant extrudate is subsequently provided
coatingswise with a coating comprising, for example, a
pH shift sensitive component, e.g., a pH shift
sensitive polymer.
In another embodiment of the invention, the
substances) intended for later release in the washing
process is/are incorporated, alone or else together
with one or more other detersive substances, into a
capsule made from a water-soluble polymer such as, for
example, gelatin. A filled gelatin capsule of this kind
is then provided with the coating comprising, for
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example, a pH shift sensitive component such as, for
example, a pH shift sensitive polymer.
In order to ensure that the pH shift sensitive coating
does not dissolve in the earlier steps of the washing
or cleaning operation, for example, at the beginning of
the main wash cycle in the case of machine dishwashing,
when fresh water is passed in but the laundry,
dishwashing or cleaning product detergent subportions
intended for the cycle in question have not yet fully
released their alkaline components into the application
liquor in order to establish a high (alkaline) pH,
various techniques may be employed, in order to avoid
losses of active substances:
(a) The coating may be made sufficiently thick or the
molecular weight of the polymer sufficiently high.
In accordance with the invention, the coat
thickness is in the range from 5 ~,m to 50 Vim, but
in order to avoid active substance losses is
preferably adjusted to a range from 20 ~m to
40 mm. In accordance with the invention, the
molecular weight of the polymer coating should be
at least 50 kD, preferably at least 1 000 kD.
Combinations of both parameters are possible and
are particularly preferred.
An active substance loss may also be avoidable by
admixing to the coating material a further polymer
which lowers the solubility of the blend. Examples
of such addit_Lonal polymers are, in general, those
which are less hydrophilic/more hydrophobic than
the coating polymer.
(b) In accordance with the invention, it is also
possible to coat a coat which is sensitive to a pH
shift from 10 to pH values lying further in the
acidic range by applying a further pH shift
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sensitive coat which only dissolves when the pH of
the aqueous :liquor used for the wash cycle has
risen to 10.
In accordance with a similar principle, an
additional coat which dissolves less rapidly or
less effectively at a relatively low temperature
may also be applied. This may be, for example, a
paraffin which melts on reaching a relatively high
temperature (which is traversed only in the
subsequent step) ("melt coating"), or else a
hydrophilic polymer which becomes soluble on
reaching a certain temperature ("polymer
coating").
(c) The formulation comprising the substances)
intended for later release in the washing or
cleaning process may be incorporated in its
entirety into the formulation comprising the other
components of the laundry, dishwashing or cleaning
product detergent portion, this latter formulation
being present., for example, in the form of a
tablet, so that the substances) intended for
later release in the washing or cleaning process
come into contact with the liquor or with the
fresh water only when the components used earlier
have already been drawn off with the liquor.
In accordance with a further embodiment of the
invention, electrolyte sensitive switches, for example,
electrolyte sensitive polymer coats, may be optimized
by adding to them further components which bring about
not only an improvement in the behavior of the coat
following application to detersive formulations but
also improved release characteristics of said
formulations at t:he desired point in time of the
washing or cleaning cycle. Electrolyte sensitive
polymers of this embodiment of the invention may be,
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for example, polyvinyl alcohols with different degrees
of hydrolysis (i.e., polyvinyl alcohols having
different residual vinyl acetate group contents); the
degrees of hydrolysis are in the range from 70 to
98 mol% (residual vinyl acetate groups: 30 to 2 mol%).
The polymers are mixed with one or more auxiliaries
from the pigments, lubricants group. The amount of said
auxiliaries is in the range from 1 to 40o by weight,
based on the sum of all such auxiliaries present; in
the case of two or more of them, the weight ratio of
the individual auxiliaries to one another is not
critical, but may be in the range from 5:1 to 1:5. A
preferred example of such auxiliaries is talc. In a
particularly preferred embodiment of the invention it
is also possible to incorporate detersive components
into such a coating composition (coating). With
advantage it is possible for this purpose to use, for
example, plasticizers, pearlescence agents, color
pigments, dyes, perfume oils, aroma substances and/or
fragrances, and other detersive substances, as recited
in detail above.
Such polymers are applied in coating thicknesses in the
range from 10 to 500 Vim, preferably in the range from
100 to 350 Vim, with further preference in the range
from 150 to 300 Vim, to the detersive formulations
intended for release later in the washing or cleaning
process: for example, to shaped bodies of such
formulations, to granules of such formulations, to
particles of such formulations, or to portions which
have been filled into enclosures, such as capsules or
pouches, for example. Said polymer/auxiliary mixtures
are preferably applied to shaped bodies or capsules, in
order to permit controlled release of individual
detersive components or mixtures of such components
from these bodies or capsules into the respective
application liquor. It will be understood that - as is
further preferred - such coatings may be produced not
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only (or not solely) with electrolyte sensitive
components but also with other components (for example,
heat sensitive, pH shift sensitive, enzyme sensitive
and/or redox sensitive components) . In the same way it
is possible to combine an electrolyte sensitive coating
of composition as described above with one or more
separate, different coats) (for example, heat, pH
shift, enzyme and/or redox sensitive coat(s)) in any
desired combination and sequence.
The aforementioned materials may be used not only as
coatings for detersive formulations in capsules or in
the form of shaped bodies (granules, tablets, etc.) but
also for fixing in recesses of shaped bodies (e. g.,
depression tabs, ring tabs, etc.) or else in water-
soluble polymer pouches, together with other components
of detersive formulations.
The invention also relates to a process for producing
the laundry, dishwashing or cleaning product detergent
portions described in detail above, preferably those
comprising two or more detersive components of which at
least two are to be released into the liquor at
different points in time or in two different periods of
time in a washing or cleaning operation. In accordance
with the invention, the detersive components) to be
released into the liquor at a later point in time in
the washing or cleaning operation is/are compounded
with a release controlling (physico)chemical switch and
with one or more substances for increasing the extent
of the shift in pH (preferably, the pH shift booster)
and the detersive components) thus compounded is/are
processed with one or more other detersive components
to form a laundry, dishwashing or cleaning product
detergent portion.
In one preferred procedure in accordance with the
invention, the (physico)chemical switches) controlling
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the release of at least one detersive component is/are
chosen to comprise one or more structural or
substantive components of a laundry, dishwashing or
cleaning product detergent portion. Appropriate
structural and substantive components of the laundry,
dishwashing or cleaning product detergent portion have
been described in detail above.
Further preferred in accordance with the invention is a
process wherein the (physico)chemical switch(.es)
controlling the release of at least one detersive
component is/are chosen to comprise one or more
components which, when there is a change in the
electrolyte concentration in the wash liquor or
cleaning liquor, undergo a change in the physical
and/or chemical properties. With particular advantage,
and therefore very particularly preferred, is a process
wherein the (physico)chemical switches) controlling
the release of at least one detersive component is/are
chosen to comprise one or more components which, when
there is a change in the H+ ion concentration (the pH)
in the wash liquor or cleaning liquor, undergo a change
in the physical and/or chemical properties.
In a procedure which may be employed with particular
advantage, the (physico)chemical switch chosen
comprises one or more substances which, when there is a
change in the electrolyte concentration, preferably a
change in the pH, in the wash liquor or cleaning
liquor,
(a) undergo a change in solubility in water; and/or
(b) undergo a change in diffusion density; and/or
(c) undergo a change in dissolution kinetics; and/or
(d) undergo a change in mechanical stability.
More preferably still, the change in pH is a change of
the pH in the wash liquor or cleaning liquor in the
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range from 11 to 6, preferably in the range from 10 to
7, more preferably a decrease in the pH in the range
between 10 and 8. Further preference is given to
procedures using as (physico)chemical switches one or
more substances which in the case of said changes in
pH, preferably in the case of said decrease in pH,
(a) undergo an increase in solubility in water; and/or
(b) undergo a decrease in diffusion density; and/or
(c) undergo an acceleration in dissolution kinetics;
and/or
(d) undergo a decrease in mechanical stability.
As already described above, the (physico)chemical
switch used comprises one or more substances from the
group consisting of basic polymers and/or copolymers,
preferably basic polymers and/or copolymers containing
amino groups and/or aminoalkyl groups, imino groups
and/or pyridine groups, more preferably still an
aminoalkyl methacrylate copolymer.
Ultimately, the invention also relates to a washing
process, especially a washing process in a washing
machine, in which a laundry detergent portion as
described in detail above is brought into contact with
laundry, being inserted in particular into the
detergent compartment of a commercially customary
washing machine, and is rinsed into the wash liquor
with water of the first wash cycle, the early steps of
the wash operation are conducted as normal and then
conditions are established under which the release
controlling (physico)chemical switch(es), which is/are
not subject or not subject exclusively to temperature
control, releases/release into the wash liquor the
components) intended for later release into the wash
liquor.
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Furthermore, the invention also relates to a washing
process, especially a washing process in a dishwashing
machine, in which a dishwashing detergent portion as
described in detail above is brought into contact with
ware, being inserted in particular into the detergent
compartment of a commercially customary dishwashing
machine, and is rinsed into the wash liquor with water
of the first wash cycle, the early steps of the wash
operation are conducted as normal and then conditions
are established under which the release controlling
(physico)chemical switch(es), which is/are not subject
or not subject exclusively to temperature control,
releases/release into the wash liquor the components)
intended for later release into the wash liquor.
Finally, the invention also relates to a cleaning
process, in which a cleaning product detergent portion
as described in detail above is brought into contact
with material to be cleaned, the early steps of the
cleaning operation are conducted as normal and then
conditions are established under which the release
controlling (physico)chemical switch(es), which is/are
not subject or not subject exclusively to temperature
control, releases/release into the cleaning liquor the
components) intended for later release into the
cleaning liquor.
The invention is illustrated by the following examples,
but without being restricted to these examples, which
represent preferred embodiments of the invention.
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Examples
Example 1
A mixture of 60% by weight aminoalkyl methacrylate
copolymer (Eudragit E~, Rohm) and 40% by weight of a
nonionic surfactant (Poly Tergent SLF 18 B~, Olin
Chemicals) was prepared with heating and the homogenous
composition formed was poured into the three-
dimensional recess, configured in the form of a
depression, of a conventionally produced detergent
tablet. Following solidification, the filled-depression
tablets thus obtained underwent a 65°C wash program in
a commercially customary dishwasher from Bosch, the
tablets being introduced by way of the dosing
compartment. Following the end of the wash program, the
depression filling was still virtually undissolved, but
at the end of the rinse cycle had very substantially
dissolved. A distinct rinse-clean effect was obtained.
Example 2
Tablets and capsules were prepared with an effective
amount of rinse aid surfactant (500 mg of Poly Tergent
SLF~ 18B45). The product was subsequently film coated
with aminoalkyl methacrylate copolymer (Eudragit E~).
The tablets and capsules thus produced underwent a 65°C
wash program as in Example 1 together with a
commercially customary tableted machine ware cleaner
(Somat Profi~) as in Example 1. After the wash cycle,
the coated tablets and capsules containing rinse aid
were virtually undissolved. After the rinse cycle, the
tablets and capsules had very largely dissolved, the
discernible residues consisting predominantly of
coating material. A distinct clear-rinse effect on
kitchen- and tableware was found.
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Example 3
Example 1 was repeated. However, in this case the
depression filling used was 57.5% by weight
Eudragit E~, 37.5% by weight Poly Tergent SLF~ 18 B,
and 5o by weight alkylbenzenesulfonic acid, and was
poured into the depression of the detergent tablets in
the form of a melted homogenous composition. Following
solidification, the wash program was conducted in a
dishwasher as described above. After the end of the
wash cycle, the depression filling remained virtually
undissolved. At the end of the rinse cycle, the
depression filling was very substantially dissolved.
Significantly little to no residues were found in the
dishwasher. A distinct clear-rinse effect on kitchen-
and tableware was found.
Example 4
In accordance with Example 2 above, coated tablets or
capsules were produced which contained additionally 5%
by weight of different acids (alkylbenzenesulfonic acid
and/or oxalic acid). while the clear-rinse effects were
comparable with the results of Example 2, very
substantial dissolution of the tablets or capsules was
found after the rinse cycle. Residues were either
absent or minimal, but in any case significantly lower
than in Example 2.
Example 5
Examples 1 and 2 were repeated; the pH shift booster,
citric acid (2.5 g), was either supplied externally
after the end of the wash cycle and/or at the beginning
of the rinse cycle, or released by means of a specific
delivery system (by coating with a slow-dissolving
coating agent). This allowed residues to be minimized.
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Example 6: Preparation of polymers having a switching
point in the pH range between 6 and 7
As an example of a pH shift switching polymer whose
switching point is in the pH range between 6 and 7,
polyvinylpyridine with an average molecular mass
Mn = 90 000, partially converted to the N-oxide, was
synthesized. The synthesis is in accordance with the
following examples:
Initial introduction of polyvinylpyridine (PVPy)
In a four-necked flask with KPG stirrer, thermometer,
reflux condenser and N2 blanketing, 105.3 g of
4-vinylpyridine were dissolved in 210 ml of methanol at
150 rpm under the Nz atmosphere. Azobis(isobutyro-
nitrile) AIBN (1.05 g) dissolved under reflux at 65°C
in 105 ml of methanol was perfused over the course of
3 h. Polymerizat10I1 took place at 65°C over a period of
10 h. The polyvinylpyridine (PVPy) was precipitated
from ethyl acetate. The yield was 900.
Example 6.1
In a 500 ml four-necked flask with KPG stirrer,
thermometer and reflux condenser, 2.5 g of PVPy were
dissolved in 25 g of glacial acetic acid at 60°C with
stirring. 1 drop of concentrated HZS04 and 3.2 g of 30%
strength Hz02 were dissolved in 12.5 g of glacial acetic
acid and this solution was added dropwise at 25°C with
stirring to the first solution. This was followed by
stirring at 25°C for 30 minutes and then by heating to
80 to 85°C. At this temperature, full oxidation took
place within 6 h. Since H202 was used in excess, the
peroxide content was > 25 mg/1.
Example 6.2
Oxidation was carried out as in Ex. 6.1. At 60%
oxidation, the H~OZ content was reduced to 1.6 g.
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Oxidation was quantitative. The peroxide content was
< 5 mg/1.
Example 6.3
Oxidation was carried out as in Ex. 6.1. At 30%
oxidation, the H20~ content was reduced correspondingly
to 0.8 g. Oxidation was quantitative. The peroxide
content was < 1 mg/l.
The corresponding procedure was carried out using the
polyvinylpyridine N-oxides having a degree of oxidation
of 48%, 50%, 51%, 52%, and 53%.
The pH dependent solubility of all PVPy N-oxides
prepared was initially detected without workup and
separation of the acetate. Following complete
conversion, a sample of each batch was diluted with
water and titrated with concentrated sodium hydroxide
solution. The initial pH at which the solution was
completely clear was approximately 3. The pure
substance was obtained by dialyzing the aqueous polymer
solution after separating off the water.
In Table 1 below, the pH at which the 10% strength by
weight polymer solution underwent marked clouding and
flocculation during the titration with 1N NaOH at room
temperature is stated as a function of the degree of
oxidation of the polyvinylpyridine before and after
dialysis.
It was observed that the switching point may be shifted
into the neutral range by oxidation. After that point,
the hydrophilicity of the polymer had increased so
greatly that it was soluble at virtually any pH.
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Table 1
Degree of PVPy N-oxide, not PVPy N-oxide
oxidation worked up, clouding after dialysis
PVPy [%] [pH clouding] [pH clouding]
0 4.8 4.8
30 5.0 -
48 6.6 5.9
50 6.4-7.0 6.5
51 6.4-7.2 6.5
52 6.4-7.8 6.5
53 12 12
60 >12 -
100 Soluble at any pH Soluble at any pH
However, as already mentioned, the dissolution kinetics
are more important than the solubility for the purpose
of practical application as a pH switch. The following
example shows that these kinetics retain a marked pH
sensitivity even at. substantially higher pH values.
Example 6.4:
To investigate the dissolution kinetics of PVPy N-oxide
films as a function of pH, the PVPy N-oxide with a
degree of oxidation of 51o was filmed.
Preparing the polymer films:
For filming, an aqueous solution of the dialyzed PVPy
N-oxide with the composition 26% by weight PVPy N-
oxide, 0.1% by weight Perenol S5 additive and 0.5% by
weight Cibacron Brilliant Red dye was used. Using a
knife coater, the solution was applied to glass plates
to give films 150 ~m thick. The plates were
subsequently dried at RT for 12 h before being placed
in aqueous solutions whose pH had been adjusted to 10
and 8.5 using sodium carbonate. At a pH of 10, the
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polymer film was fully dissolved after 21 minutes, at a
pH of 8.5 after just 12 minutes.
This effect was utilized in order to transport a
formulation component, containing rinse aid, of a
machine dishwashing composition through the main wash
cycle into the rinse cycle. For this purpose, a rinse
aid surfactant (Poly Tergent SLF 18B) was applied to a
carrier material and coated with a film of partly
oxidized polyvinylpyridine. The thickness of the film
was adjusted such that the film dissolved only partly
in the main wash cycle at high pH but became detached
in the rinse cycle at a lower pH and thus released the
rinse aid.
Example 7
Example 1 was repeated. However, in this case the
depression filliTlg used was 46.8% by weight
Eudragit E~, 31.3% by weight Poly Tergent SLF~ 18 B,
7.8% by weight alkylbenzenesulfonic acid and 14.1% by
weight methylcellulose, and was poured into the
depression of the detergent tablets in the form of a
melted homogeneous composition. Following solidi-
fication, the wash program was conducted in a
dishwasher as described above. After the end of the
wash cycle, the depression filling remained virtually
undissolved. At the end of the rinse cycle, the
depression filling was very substantially dissolved and
with virtually no residue.
Example 8
As in Example 2 above, coated tablets or capsules were
produced which contained an effective amount of rinse
aid surfactant (500 mg of Poly Tergent SLF~ 18B45).
These products were subsequently film coated with
aminoalkyl methacrylate copolymer. Amylose in an amount
of 10% by weight, based on the overall coating
material, was dispersed in the coating material as a
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finely powdered solid. The products were tested as in
Example 2.
After the wash Cycle, the coated tablets and capsules
were undissolved. At the points where there were
amylose domains in the coating material, small holes
were discernible.
After the rinse cycle, the tablets and capsules were
fully dissolved. This was evidently achieved by the
combination of the two control mechanisms.
Example 9
Rinse aid surfactant (Poly Tergent SLF~ 18B) was
applied to a carrier material and coated with a film of
polystyrenesulfonate (MW = 1 000 000) or polyvinyl
alcohol or methylcellulose. The coat thickness was
adjusted such that the film dissolved only partly in
the main wash cycle, owing to the high electrolyte
concentration prevailing there, as a result of the
ionic constituents of the cleaner, but detached in the
presence of clean water and so released the rinse aid
surfactant.
Example 10
18 parts by weight of PolyPore, 10 parts by weight of
PEG 6000 and 72 parts by weight of Poly Tergent (rinse
aid surfactant), based in each case on 100 parts by
weight of the overall mixture, were kneaded to form a
homogeneous mixture which was subsequently shaped to
form beads having a mass of 1 g.
The beads were dip-coated with a pH shift sensitive
copolymer of N,N-dimethylaminoethyl methacrylate
(DMAEMA), methyl methacrylate (MMA), N,N-dimethylamino-
propylmethacrylamide (DMAPMAm) and hydroxyethyl
methacrylate (HEMA) in a molar ratio of 35:25:30:10 as
a 30% (w/w) formulation in acetone/isopropanol (40:60;
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v/v) and had been further colored with a dye, and then
were dried at 40°C for 30 minutes. The coating step was
repeated.
The pH dependent solubility of the coating was tested
in the pH range from 10 to 8.5, which is relevant for
practical use, using two buffer solutions having a pH
of 10 and 8.5. For this purpose, one coated bead with
the rinse aid sux-factant was placed in a wire mesh
basket which was immersed into the respective buffer
solution. The solution was stirred at 700 rpm. The
point in time at which the pH shift sensitive coating
dissolved was recorded. The results are reported in
Table 2 below.
Table 2
Time pH 8.5 at RT pH 10 at RT pH 10 at
[min] 55C
10 Bead decolors; No change. Swelling
of
solution takes on the coating
color of the
coating.
Coating dissolves; No change. No change.
solution becomes
milkily cloudy.
60 Bead dissolves No change. No change.
slowly; solution
becomes very cloudy.
95 Bead has dissolved. Experiment Experiment
terminated: coating terminated;
has swollen but has bead
not dissolved from remains
the bead. stable.
Example 11
20 The following coating recipes were prepared:
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(a) Polyvinyl alcohol (degree of hydrolysis
approximately 70%; product Erkol M05/280 from
Erkol S.A.); l0o strength aqueous solution;
(b) Polyvinyl alcohol (degree of hydrolysis
approximately 98%; product Erkol M05/20 from Erkol
S.A.); 15% strength aqueous solution;
(c) Polyvinyl alcohol (degree of hydrolysis
approximately 98%; product Erkol M05/20 from Erkol
S.A.); 15% strength aqueous solution; and 40o by
weight talc, based on the PVAL dry weight.
Soft gelatin capsules as used for enclosing detersive
components (weight approximately 0.8 g; filling volume:
0.5 g) were coated in a fluidized bed in a coating
vessel with the aforementioned coatings (a) to (c).
A film which would have been sufficiently thick and
defect-free could not be applied to the capsules using
coatings (a) and (b). During the process of applying
the coating, the capsules stuck to one another, so
likewise disrupting the uniformity of the coating.
The recipe (c) was applied to the capsules as a film
without problems. 0.05 g of coating (coating thickness
approximately 150 Vim), 0.08 g of coating (coating
thickness approximately 240 Vim) and 0.11 g of coating
(coating thickness approximately 350 Vim) were applied
per gelatin capsule.
3 each of the gelatin capsules thus coated were
supplied to a dishwasher (Bosch 5712) by way of the
dosing flap together with a conventional detergent
depression tab. The results can be seen from Table 3
below. As the table reveals in detail, it was possible
using the combination of PVAL (degree of hydrolysis:
98%) and talc to produce electrolyte sensitive coatings
for capsules filled with dishwashing components (rinse
aid) which do not dissolve in the (electrolyte rich)
CA 02328326 2000-12-13
_ 88 _
wash medium of the main wash cycle and so prevent
release of the rinse aid surfactant in this cycle. Only
in the low electrolyte water of the rinse cycle is the
coating of the capsules dissolved, and then permits
dissolution of the gelatin capsule and thus release of
the rinse aid surfactant into the wash liquor.
Table 3
Coating 50 program 65 program
weight
0.05 g Capsules do not dissolveCapsules dissolve in
the
in the main wash cycle main wash cycle.
but dc> dissolve
(completely) in the
rinse cycle.
0.08 g Capsules do not dissolveCapsules dissolve in
in the main wash cycle part in the main wash
but do dissolve cycle (residues of the
(completely) in the coating after main wash
rinse cycle. cycle). There are no
longer any coating
residues after the rinse
cycle.
0.11 g Capsules do not dissolveCapsules do not dissolve
in the main wash cycle in the main wash cycle
but do dissolve but do dissolve
(completely) in the (completely) in the
rinse cycle. rinse cycle.
