Note: Descriptions are shown in the official language in which they were submitted.
CA 02312157 2000-06-23
AN ACTIVE-SUBSTANCE PORTION PACK
Field of the Invention
This invention relates to detergent or cleaner portions, more
particularly those in the form of packed washing preparations, in which part
of the additives are physically embedded in the packaging material. More
particularly, the present invention relates to laundry detergent portion packs
and cleaner portion packs and preferably to machine dishwashing
detergents (dishwasher detergents) in new packs.
Background of the Invention
Detergents and processes for their production have been known for
some considerable time and, accordingly, are widely described in the prior
art literature. Detergents are normally marketed in the form of spray-dried
or granulated solid products or as liquids. In response to consumer
demand for easy dosing, products in pre-portioned form have established
themselves on the market alongside these two conventional variants and
have also been described in the prior art literature, detergents in the form
of
press-agglomerated shaped bodies, i.e. tablets, blocks, briquettes, rings
and the like, and portions of solid or liquid detergents packed in bags being
described in particular.
In the case of individual doses of detergents which are packed in
bags for marketing, bags of water-soluble film, i.e. bags which do not have
to be torn open by the user, have proved successful. In this way, an
individual portion can be conveniently dosed by directly placing the bag in
the dispensing compartment of the washing machine or dishwashing
machine or by throwing the bag into a predetermined quantity of water, for
example in a bucket or in a handwashing or rinsing bowl. The bag
surrounding the detergent dissolves completely when a certain temperature
is reached or when certain other predetermined conditions are established.
Detergents packed in bags of water-soluble film are also described in large
numbers in the prior art literature.
- CA 02312157 2000-06-23
- 2
Thus, DE-AS 11 30 547 (Procter & Gamble) discloses packs of
water-soluble films of polyvinyl alcohol which are filled with non-liquid
synthetic detergents.
An individual dose of a detergent or bleach in a bag comprising one
or more seams of water-sensitive material is described in European patent
application EP 143 476 (Akzo N.V.). A mixture of anionic and/or nonionic
water-binding polymer and cationic polymer adhesive is proposed as the
water-sensitive seam material in this document.
European patent application EP 158 464 (Clorox) describes low-
temperature detergents which can be packed in a bag of water-soluble film.
Extremely large particles wrapped in a water-insoluble film are
described in EP 384 529 (Procter & Gamble). This document discloses a
"jumbo"-particle fabric softener composition of which the 5 to 30 mm large
dryer-activated softener particles are wrapped in a porous water-insoluble
film.
In addition, earlier patent application DE 198 31 703 discloses a
portioned detergent preparation in a bag of water-soluble film, more
particularly a bag of (optionally acetalized) polyvinyl alcohol (PVAL) in
which at least 70% by weight of the particles of the detergent preparation
have particle sizes above 800 Nm.
One factor common to all these publications is that the films in which
the actual detergent/cleaning preparations are wrapped act solely as a
packaging material. They do not have any other technical significance in
regard to the formulation of the detergent portion. Thus, the solubility of
the film in water is merely intended to eliminate the need for manual
unwrapping of the detergent/cleaning preparation.
It is known from other prior-art publications that bitter substances
can be added to water-soluble films surrounding detergent preparations in
order to prevent the preparation from being swallowed by children.
However, bitter substances are not additives which are capable of
- CA 02312157 2000-06-23
' 3
enhancing the properties of the product or their consumer appeal.
Modern detergents are a complex mixture of substances. High-
performance or special-purpose detergents in particular contain additives
which, although relatively expensive, develop the required effect in low
concentrations per detergent dose. In the interests of economy, every
effort is made to use the valuable ingredients of the formulation in the
smallest possible quantities. However, in the interests of dependability, i.e.
the need to be able to obtain the claimed effects with any quantity of a
formulation, a certain excess always has to be used in order to take into
account process-related parameters, such as dosage fluctuations in the
production process, the quality of the process by which the components are
mixed and/or any partial separation of individual components during
packaging of the product.
Accordingly, in the case of detergents consisting of a spray-dried
basic powder, the components to be added in small amounts - providing
they are thermally stable - are normally added via the slurry and can be
dispersed relatively uniformly therein. This basic powder represents the
main constituent of the material of the detergent to be processed in the
subsequent "aftertreatment". Perfume oils and solid raw materials which
cannot be subjected to spray drying on account of their thermal lability are
added and incorporated in the aftertreatment phase. Examples of such
solid raw materials are enzymes, bleaching agents and bleach activators.
Nowadays, raw materials whose thermal properties enable them to be
spray-dried are being increasingly incorporated in the "aftertreatment
stage". This is happening because it is desirable to reduce the number of
components present in the basic powder produced via the slurry as far as
possible in order to be able to make the basic powder the stock component
of as many detergents as possible and thus to enable product changes to
be accommodated more quickly and efficiently in the production or
packaging process.
- CA 02312157 2000-06-23
' 4
Reducing the effort involved in the event of product changes in the
production and packaging process is particularly relevant when the basic
formulations to be successively processed contain raw materials which
adversely affect or even neutralize one another. One example are optical
brighteners which are present in heavy-duty detergents, but are
undesirable in detergents for colored fabrics. Accordingly, in the event of a
product change from heavy-duty detergents to detergents for colored
fabrics, the entire installation, including all the following process stages
and
all the filter units, from which filter dust is recycled into the process,
have to
be laboriously and expensively cleaned. It is much simpler and, hence,
standard practice to incorporate finely crystalline brighteners in the
aftertreatment stage.
Compact detergents are normally aftertreated in the same way
except that the spray-dried basic powder is replaced by granules produced
by pelleting, extrusion, roller compacting or other processes. However,
product changes in the case of compact detergents are attended by the
same problems as described above. One or more components) present in
small quantities in the first product, but unwanted in the second product (for
example optical brighteners) have to be removed from the installation as a
whole, so that the installation has to be shut down and carefully cleaned.
The problems which this involves necessitate separately adding one or
more such components) which in tum raises the problem of their
homogeneous distribution in the product. By comparison with powder-form
detergents, detergents in particle form (granules, beads etc.) have to be
made up in special ways in order to counteract subsequent separation of
the components added in only small quantities. One way of achieving is,
for example, to adapt the particle size to that of the granules, as disclosed
for example in DE-A-19632284 and in DE-A-19847569. In addition, DE A-
19855676 and DE-A-19855677 disclose adjusting the particle size of
detergent additive components added in small quantities in such a way that
CA 02312157 2000-06-23
they adhere as powders to the surface of the granules. Despite these
measures, the necessary uniform distribution of the additive added in small
quantities, as obtainable in spray drying, cannot be achieved with
acceptable outlay on equipment. On the contrary, the addition of powder-
s form optical brightener in the aftertreatment of detergent beads in order to
make the brightener adhere to the surface of the particles, as disclosed in
the above-cited DE-A-19855677, leads to undesirably broad variations in
the concentration of the brightener in different product batches. Tests with
detergent tablets have produced comparable results.
Against the background of this prior art, the problem addressed by
the present invention was to provide a detergent portion which would
contain additives added in small quantities in reliably uniformly distributed
concentrations, even when these additives are only added during the
aftertreatment of the product. In particular, variations in concentration
would be kept to the minimum levels hitherto only achieved with spray-
dried products by adding such additives via the slurry.
Another problem addressed by the invention was to provide
detergent portions in which heat-sensitive detergent components, which
are only required and present in low concentrations, but which cannot be
added via the slung, such as enzymes for example, would be uniformly
distributed in the detergent portions without any significant variations in
concentration occurring within a product batch.
Another problem addressed by the present invention was to assign a
function in the formulation as a whole to the flat plastic wrapper which is
normally used for active-substance portion packs in the field of detergents
or cleaners.
Summary of the Invention
Thus, in one embodiment of the invention, the plastic wrapper
contains additives which are only required in small quantities in the
preparations and which can be uniformly dosed with high precision through
= CA 02312157 2000-06-23
6
their incorporation in the wrapper. In another embodiment of the invention,
use is made of the fact that high molecular weight substances, such as the
polymers used for making plastic films, generally dissolve more slowly than
low molecular weight substances. Thus, on the one hand, the release of
the additives only begins significantly at the dissolving temperature of the
film and, on the other hand, the release of the additives present in the film
can be delayed by the dissolving kinetics.
Accordingly, the present invention relates to an active-substance
portion pack comprising at least one washing or dishwashing or cleaning
preparation and at least one wrapper completely or partly surrounding at
least one washing or dishwashing or cleaning preparation, wherein the
wrapper is soluble under washing, dishwashing or cleaning conditions and
contains at least one individual component of the washing or dishwashing
or cleaning preparation in bound form.
More particularly, the present invention relates to an active-
substance portion pack which contains a washing preparation and a flat
plastic part completely or at least predominantly surrounding the
preparation, characterized in that individual components which control the
effectiveness of the washing preparation or increase its consumer
acceptance (additives) are completely or predominantly present in
physically bound form in the flat plastic part.
The present invention also relates to a process for the production of
active-substance portion packs or at least one washing or dishwashing or
cleaning preparation and at least one wrapper completely or partly
surrounding at least one washing or dishwashing or cleaning preparation,
wherein one or more wrapper materials) is/are converted into a liquid form,
a finely dispersible preparation of at least one individual component of the
washing or dishwashing or cleaning preparation is added to the liquid
wrapper material(s), the mixture is processed to a flat material and the
washing or dishwashing or cleaning preparation is completely or partly
- CA 02312157 2000-06-23
' 7
wrapped in the flat material.
Finally, the present invention relates to a washing process, wherein
an active-substance portion pack according to the following detailed
description is placed in a washing machine and, by addition of water and
heating of the wash liquor beyond the dissolving point of the wrapper, the
additives present in the wrapper are released through dissolution thereof
and to a machine dishwashing process, wherein an active-substance
portion pack according to the following detailed description is placed in the
metering compartment of a dishwashing machine and, by addition of water
and release of the active-substance portion pack from the dispensing
compartment, the additives are released through dissolution of the wrapper
and to a machine dishwashing process using an active-substance portion
pack according to the invention, wherein a wrapper which only dissolves in
water at temperatures above room temperature is used, the dishwashing
detergent preparation is placed in the interior of the dishwashing machine
and, by addition of water and heating of the wash liquor beyond the
dissolving point of the wrapper, the additives present in the wrapper are
released through dissolution thereof.
Detailed Description of the Invention
An "active-substance portion pack" in the context of the present
invention is understood to be a dose of a laundry detergent, dishwashing
detergent or cleaner which is sufficient for a washing or cleaning process
taking place in an aqueous phase. This may be, for example, a machine
washing or dishwashing process carried out in commercially available
washing or dishwashing machines. However, the expression "active-
substance portion pack" is also understood to encompass handwashing
(carried out for example in a handwashing basin or in a bowl) or manual
dishwashing or any other washing or cleaning process. According to the
invention, the active-substance portion packs are preferably used in
machine washing or cleaning processes or in machine dishwashing
CA 02312157 2000-06-23
processes.
According to the invention, the active-substance portion packs
contain measured quantities of at least one washing or dishwashing or
cleaning preparation, normally measured quantities of several washing or
dishwashing or cleaning preparations. The active-substance portion packs
may only contain washing or dishwashing or cleaning preparations having
a particular composition. According to the invention, however, several,
normally at least two, washing or dishwashing or cleaning preparations
differing in their composition are preferably present in the active-substance
portion packs. The composition may differ both in regard to the
concentration of the individual components of the washing or dishwashing
or cleaning preparation (i.e. quantitatively) and/or in regard to the nature
of
the individual components of the laundry or dishwashing detergent or
cleaning preparation (i.e. qualitatively). In one particularly preferred
embodiment, the components are adapted in regard to type and
concentration to the functions the active-substance portion packs are
intended to perform in the washing or dishwashing or cleaning cycle.
According to the present invention, the part-portions are preferably the
first,
second and optionally third or even fourth, fifth etc. measured quantities of
one or more washing or dishwashing or cleaning preparations which are
wrapped in the same or different water-soluble materials and which are
combined to form an active-substance portion pack according to the
invention.
According to the invention, the active-substance portion packs
comprise at least one washing or dishwashing or cleaning preparation. In
the context of the present invention, the expressions "washing preparation",
"dishwashing preparation" and "cleaning preparation" - these expressions
are sometimes used interchangeably in the present specification - are
understood to be preparations of any conceivable substances that are
relevant to a washing or dishwashing or cleaning process. These are
- CA 02312157 2000-06-23
' 9
primarily the actual detergents or cleaning formulations themselves with
their individual components explained in more detail hereinafter. These
include such active ingredients as surfactants (anionic, nonionic, cationic
and amphoteric surfactants), builders (inorganic and organic builders),
bleaching agents (for example peroxo bleaching and chlorine bleaching
agents), bleach activators, bleach stabilizers, bleach catalysts, enzymes,
special polymers (for example those with co-builder properties),
redeposition inhibitors, dyes and perfumes, although the expression in
question is by no means confined to substances belonging to these groups.
However, the expression "washing or dishwashing or cleaning
preparations" is also understood to encompass washing and cleaning aids
such as, for example, optical brighteners, UV filters, soil repellents, i.e.
polymers which counteract the resoiling of fibers and hard surfaces, and
silver corrosion inhibitors. Laundry treatment compositions, such as fabric
softeners, and dishwasher detergent additives, such as rinse aids, are also
regarded as washing or dishwashing or cleaning preparations in the
context of the present invention.
According to the invention, the active-substance portion pack - in
addition to the washing or dishwashing or cleaning preparation - also
contains at least one wrapper completely or partly surrounding at least one
washing or dishwashing or cleaning preparation. This wrapper has to be
soluble in the particular system, for example in a wash liquor, dishwashing
liquor or cleaning liquor, under washing, dishwashing or cleaning
conditions and must contain at least one individual component of the
washing, dishwashing or cleaning preparation in bound form.
In one preferred embodiment of the invention, the wrapper
comprises a water-soluble polymer material. The wrapper is preferably a
flat plastic part and, more preferably, a plastic pack. Plastic capsules or
bottles are preferred, packs in the form of a water-soluble polymer film
being particularly preferred. Among the plastic film packs, adhesively
CA 02312157 2000-06-23
- 10
bonded and/or sealed plastic film packs are preferred. In one particularly
advantageous embodiment, the wrapper is a water-soluble polymer film
bonded with a water-soluble adhesive.
Such films are known in principle from the prior art and belong, for
example, to the group consisting of (optionally acetalized) polyvinyl alcohol,
polyvinyl pyrrolidone, water-soluble polyacrylates, water-soluble poly-
urethanes, polyethylene oxide, gelatine, cellulose and mixtures thereof.
Polyvinyl alcohols, referred to in short as PVALs, are polymers with
the following general structure:
[-CH2-CH(OH)-]~
which also contain small amounts of structural units of the following type:
[-CH2-CH(OH)-CH(OH)-CH2]
Since the corresponding monomer, vinyl alcohol, is not stable in free form,
polyvinyl alcohols are produced via polymer-analog reactions by hydrolysis
and - on an industrial scale - above all by alkali-catalyzed
transesterification
of polyvinyl acetates with alcohols (preferably methanol) in solution.
PVALs with a predetermined residual percentage of acetate groups -
occasionally also referred to as "acetalized PVALs" - can also be obtained
by these industrial processes.
Commercially available PVALs (for example Mowiol~ types,
products of Hoechst) are marketed as white-yellowish powders or granules
with degrees of polymerization of ca. 500 to 2,500 (corresponding to
molecular weights of ca. 10,000 to 100,000 g/mole) and have different
degrees of hydrolysis starting at around 70 mole-%, for example of 98-99
or 87-89 mole-%. Accordingly, they are partly saponified polyvinyl acetates
with a residual content of acetyl groups of ca. 1-2 or 11-13 mole-%.
CA 02312157 2000-06-23
11
The solubility of PVAL in water can be reduced and thus selectively
adjusted to required values by aftertreatment with aldehydes
(acetalization), by complexing with Ni or Cu salts or by treatment with
dichromates, boric acid, borax. Films of PVAL are largely impervious to
gases, such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but are
permeable to water vapor.
Examples of suitable water-soluble PVAL films are the PVAL films
obtainable under the name of "SOLUBLONO" from Syntana
Handelsgesellschaft E. Harke GmbH & Co. Their solubility in water can be
very precisely adjusted and films of this product series soluble in water in
all the temperature ranges relevant to practical application are obtainable.
Polyvinyl pyrrolidones, referred to in short as PVPs, correspond to
the following general formula:
CH-CH2
N
~O
n
PVPs are produced by radical polymerization of 1-vinyl pyrrolidone.
Commercially available PVPs have molecular weights of ca. 2,500 to
750,000 g/mole and are commercially available as white hygroscopic
powders or as aqueous solutions.
Polyethylene oxides, referred to in short as PEOXs, are polyalkylene
glycols corresponding to the following general formula:
H-[O-C H2-C H2J~-O H
which are produced on an industrial scale by base-catalyzed polyaddition
of ethylene oxide (oxirane) with ethylene glycol as starter molecule in
CA 02312157 2000-06-23
' 12
systems generally containing small quantities of water. They have
molecular weights in the range from ca. 200 to 5,000,000 g/mole,
corresponding to degrees of polymerization n of ca. 5 to >100,000.
Polyethylene oxides have an extremely low concentration of reactive
terminal hydroxy groups and possess only weak glycol properties.
Gelatine is a polypeptide (molecular weight ca. 15,000 - >250,000
g/mole) which is mainly obtained by hydrolysis of the collagen present in
the skin and bones of animals under acidic or alkaline conditions. The
amino acid composition of gelatin largely corresponds to that of the
collagen from which it was obtained and varies according to its
provenance. The use of gelatine as a water-soluble capsule material is
particularly widespread in pharmacy (hard or soft gelatine capsules).
Gelatine is rarely used in the form of films on account of its high price
compared with the polymers mentioned above.
Other preferred portioned detergent compositions according to the
present invention are those of which the bag consists of water-soluble film
of at least one polymer from the group of starch and starch derivatives,
cellulose and cellulose derivatives, more especially methyl cellulose and
mixtures thereof.
Starch is a homoglycan in which the glucose units are attached by
a-glycoside bonds. Starch is made up of two components of different
molecular weight, namely ca. 20-30% straight-chain amylose (molecular
weight ca. 50,000 to 150,000) and 70-80% of branched-chain amylopectin
(molecular weight ca. 300,000 to 2,000,000). Small quantities of lipids,
phosphoric acid and cations are also present. Whereas the amylose - on
account of the bond in the 1,4-position - forms long, helical entwisted
chains containing about 300 to 1,200 glucose molecules, the amylopectin
chain branches through a 1,6-bond after - on average - 25 glucose units to
form a branch-like structure containing about 1,500 to 12,000 glucose
molecules. Besides pure starch, starch derivatives obtainable from starch
CA 02312157 2000-06-23
' 13
by polymer-analog reactions may also be used in accordance with the
invention for the production of water-soluble bags. Such chemically
modified starches include, for example, products of esterification or
etherification reactions in which hydroxy hydrogen atoms were substituted.
However, starches in which the hydroxy groups have been replaced by
functional groups that are not attached by an oxygen atom may also be
used as starch derivatives. The group of starch derivatives includes, for
example, alkali metal starches, carboxymethyl starch (CMS), starch esters
and ethers and amino starches.
Pure cellulose has the formal empirical composition (C6H~o05)n and,
in formal terms, is a ~i-1,4-polyacetal of cellobiose which, in turn, is made
up of two molecules of glucose. Suitable celluloses consist of ca. 500 to
5,000 glucose units and, accordingly, have average molecular weights of
50,000 to 500,000. Other cellulose-based disintegrating agents which may
be used in accordance with the present invention are cellulose derivatives
obtainable from cellulose by polymer-analog reactions. Such chemically
modified celluloses include, for example, products of esteri~cation or
etherification reactions in which hydroxy hydrogen atoms were substituted.
However, celluloses in which the hydroxy groups have been replaced by
functional groups that are not attached by an oxygen atom may also be
used as cellulose derivatives. The group of cellulose derivatives includes,
for example, alkali metal celluloses, carboxymethyl cellulose (CMC),
cellulose esters and ethers and also aminocelluloses.
Preferred wrappers of water-soluble film consist of a polymer with a
molecular weight in the range from 5,000 to 500,000 dalton, preferably in
the range from 7,500 to 250,000 dalton and more preferably in the range
from 10,000 to 100,000 dalton. The water soluble film which forms the bag
has a thickness of 1 to 150 Nm, preferably 2 to 100 arm, more preferably 5
to 75 Nm and most preferably 10 to 50 Nm.
The water-soluble films may be produced by various processes. In
F
CA 02312157 2000-06-23
- 14
principle, they may be produced by blowing, calendering and casting
processes. In one preferred process, which starts out from a melt and uses
a blowing mandrel, the films are blown with air to form a tube. In the
calendering process, which is another preferred production process, the
raw materials plasticized by suitable additives are sprayed to form the films.
It may be necessary in the calendering process to dry the films after
spraying, In the casting process, which is another preferred production
process, an aqueous polymer preparation is applied to a heatable drying
roller, optionally cooled after evaporation of the water and the film formed
is
removed from the roller. This film may optionally be powdered before or
during its removal from the roller. Depending on the stability or rather the
processability of the additives to be used, individual representatives of the
processes described here may be particularly preferred for special
functionalized ~Ims.
According to the invention, the flat plastic parts of the active-
substance portion pack contain individual components (additives) of the
washing-active preparation. In one particularly preferred embodiment, the
individual components) is/are components which control the effectiveness
of the washing, dishwashing or cleaning preparations) or increase its/their
consumer acceptance. Such components are frequently refer-ed to as
additives both in the present specification and in the claims. In one
preferred embodiment of the present invention, additives which are only
required in small quantities in the washing, dishwashing or cleaning
preparations and which are therefore difficult to dose are incorporated.
Additives which, together with the constituent material of the plastic ~Im,
produce a positive increase in washing or cleaning performance may also
be incorporated. Besides these performance additives, perfumes may also
be incorporated. Where perfumes are incorporated, however, it is
important to take suitable measures to prevent their premature
volatilization. Such measures include, for example, encapsulating the
v CA 02312157 2000-06-23
- 15
perfumes or embedding the perfumes in a matrix. In particular, polymers
related to or even identical with the film materials may be used to protect
the perfumes. In another preferred embodiment, however, the perfumes
may even be released before the product is actually used. In this case, the
perfumes are used to provide the packaged product itself with a pleasant
perfume.
A preferred group of additives to be used in accordance with the
invention are optical brighteners. The optical brighteners normally present
in detergents, as individually named hereinafter, may be used. They are
added in the form of an aqueous solution or in the form of a solution in an
organic solvent to the polymer solution which is converted into the film.
Another preferred group of additives to be used in accordance with the
invention are dye transfer inhibitors. Dye transfer inhibitors are special
polymers which normally contain nitrogen-containing monomers. Many
different compounds suitable for use in detergents are known to the expert
in this field.
Another preferred group of additives according to the invention are
UV filters. UV filters are substances which are released in the washing
process or in the subsequent fabric softening process in the wash liquor
and which accumulate on the fibers where they then develop a UV-filtering
effect. Suitable UV filters are, for example, the products commercially
available under the name of Tinosorb from Ciba Speciality Chemicals.
Other possible additives preferred for special embodiments are
surfactants which are capable in particular of influencing the solubility of
the
film and of controlling its wettability and also the formation of foam during
dissolution of the film, foam inhibitors and bitter substances which can
prevent children from accidentally swallowing the packs in question or parts
thereof.
Another preferred group of additives according to the present
invention are dyes, more particularly water-soluble or water-dispersible
CA 02312157 2000-06-23
16
dyes. Dyes of the type normally used to improve visual product appeal in
laundry and dishwashing detergents are preferred.
Another class of additives which may be added to the plastic parts in
accordance with the invention are polymers. Suitable polymers are, on the
one hand, polymers which show co-builder properties during washing,
dishwashing or cleaning, i.e. for example polyacrylic acids, modified
polyacrylic acids and corresponding copolymers. Another group of
polymers are polyvinyl pyrrolidone and other redeposition inhibitors, such
as copolymers of polyvinyl pyrrolidone, cellulose ethers and the like. In
another embodiment of the invention, the polymers may also be soil
repellents. Soil repellents are polymers which are absorbed onto fibers or
hard surfaces where they counteract resoiling. Relevant compounds of this
type are known to the expert on detergents. They are polyesters of
terephthalic acid and ethylene glycol partly modified with sulfonic acid
groups.
Another group of additives are bleach catalysts, more particularly
bleach catalysts for dishwasher detergents or laundry detergents.
Complexes of manganese and cobalt, more particularly with nitrogen-
containing ligands, are used for this purpose.
Another preferred group of additives according to the invention are
silver corrosion inhibitors which may be selected from a number of mostly
cyclic organic compounds which are also familiar to the expert on
detergents.
Another preferred group of additives are enzymes, more particularly
the enzymes described in detail and named by way of example in the
following. Enzymes are incompatible or only conditionally compatible with
a number of washing, dishwashing and cleaning components, so that
efforts have already been made to find ways of separating them from the
remaining formulation of a washing or dishwashing detergent. In addition,
attempts have long been made to make enzymes available at certain,
- CA 02312157 2000-06-23
' 17
precisely definable times in the washing or dishwashing process so that
their activity may be optimally utilized from the perspectives of temperature,
pH and other process parameters. According to the invention, this is
possible when enzymes are incorporated in the water-soluble polymer
material of the wrapper(s).
Another preferred group of additives are the phosphonates, more
particularly hydroxyalkane and aminoalkane phosphonates. Among the
hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP)
is particularly important as a co-builder. It is preferably used in the form
of
a sodium salt, the disodium salt showing a neutral reaction and the
tetrasodium salt an alkaline reaction (pH 9). Preferred aminoalkane
phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP),
diethylenetriamine pentamethylene phosphonate (DTPMP) and higher
homologs thereof. They are preferably used in the form of the neutrally
reacting sodium salts, for example as the hexasodium salt of EDTMP and
as the hepta- and octasodium salt of DTPMP. Within the class of
phosphonates, HEDP is preferably used as builder. The aminoalkane
phosphonates also show a pronounced heavy metal binding capacity.
Accordingly, it can be of advantage to use aminoalkane phosphonates,
more especially DTPMP, or mixtures of the phosphonates mentioned.
Other useful organic co-builders are, for example, the polycarboxylic
acids usable, for example, in the form of their sodium salts, such as citric
acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids,
aminocarboxylic acids, nitrilotriacetic acid (NTA), providing their use is not
ecologically unsafe, and mixtures thereof. Preferred salts are the salts of
the polycarboxylic acids, such as citric acid, adipic acid, succinic acid,
glutaric acid, tartaric acid, sugar acids and mixtures thereof. The acids per
se may also be used.
Other suitable organic co-builders are dextrins, for example
oligomers or polymers of carbohydrates which may be obtained by partial
CA 02312157 2000-06-23
- 18
hydrolysis of starches.
Other preferred builders are polymeric aminodicarboxylic acids, salts
or precursors thereof. Particular preference is attributed to polyaspartic
acids or salts and derivatives thereof which, according to German patent
application DE-A-195 40 086, are also said to have a bleach-stabilizing
effect in addition to their co-builder properties.
Other suitable builders are polyacetals which may be obtained by
reaction of dialdehydes with polyol carboxylic acids. Preferred polyacetals
are obtained from dialdehydes, such as glyoxal, glutaraldehyde, terephthal-
aldehyde and mixtures thereof and from polyol carboxylic acids, such as
gluconic acid and/or glucoheptonic acid.
Other suitable co-builders are oxydisuccinates and other derivatives
of disuccinates, preferably ethylenediamine disuccinate.
Other useful organic co-builders are, for example, acetylated
hydroxycarboxylic acids and salts thereof which may optionally be present
in lactone form and which contain at least 4 carbon atoms, at least one
hydroxy group and at most two acid groups.
Suitable polymeric polycarboxylates are, for example, sodium salts
of polyacrylic acid or polymethacrylic acid, for example those with a relative
molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric
polycarboxylates are, in particular, those of acrylic acid with methacrylic
acid and of acrylic acid or methacrylic acid with malefic acid.
Another preferred group of additives are redeposition inhibitors. The
function of redeposition inhibitors is to keep the soil detached from the
fibers suspended in the wash liquor and thus to prevent the soil from being
re-absorbed by the washing. Suitable redeposition inhibitors are water-
soluble, generally organic colloids, for example the water-soluble salts of
polymeric carboxylic acids, glue, gelatine, salts of ether sulfonic acids of
starch or cellulose or salts of acidic sulfuric acid esters of cellulose or
starch. Water-soluble polyamides containing acidic groups are also
_ CA 02312157 2000-06-23
- 19
suitable for this purpose. Soluble starch preparations and other starch
products than those mentioned above, for example degraded starch,
aldehyde starches, etc., may also be used. Polyvinyl pyrrolidone is also
suitable. However, cellulose ethers, such as carboxymethyl cellulose
(sodium salt), methyl cellulose, hydroxyalkyl cellulose, and mixed ethers,
such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose,
methyl carboxymethyl cellulose and mixtures thereof, are preferably used.
However, laundry or dishwashing detergents and washing aids such
as, in particular, builder or bleach compositions may be used as washing
preparations. According to the invention, laundry treatment formulations
and dishwasher detergent additives, such as rinse aids, are also regarded
as washing preparations.
The water-soluble polymer materials or plastic parts may also
contain components which have a positive effect on the removability of oil
and fats from textiles by washing (so-called soil repellents). This effect
becomes particularly clear when a textile which has already been
repeatedly washed with a detergent according to the invention containing
this oil- and fat-dissolving component is soiled. Preferred oil- and fat-
dissolving components include, for example, nonionic cellulose ethers,
such as methyl cellulose and methyl hydroxypropyl cellulose containing 15
to 30% by weight of methoxyl groups and 1 to 15% by weight of
hydroxypropoxyl groups, based on the nonionic cellulose ether, and the
polymers of phthalic acid and/or terephthalic acid known from the prior art
or derivatives thereof, more particularly polymers of ethylene terephthalates
and/or polyethylene glycol terephthalates or anionically and/or nonionically
modified derivatives thereof. Of these, the sulfonated derivatives of
phthalic and terephthalic acid polymers are particularly preferred.
All these additives are added to the flat plastic parts according to the
invention in quantities of up to 60% by weight, preferably in quantities of up
to at most 30% by weight and, with particular advantage, in quantities of 2
CA 02312157 2000-06-23
- 20
to 20% by weight. In order to balance the formulation, therefore, the expert
may increase the weight of the plastic part in order either to utilize the
storage effect obtained in accordance with the invention or additionally to
keep the additives mentioned at least partly in the rest of the washing
preparation.
The present invention also relates to processes for producing the
active-substance portion packs. These processes start out from liquid
forms, for example melts or solutions, of the wrapper material or the
wrapper materials, preferably from solutions in a suitable solvent. In
particularly preferred embodiments, this solvent is water. According to the
invention, a finely dispersible preparation of at least one individual
component or at least one additive of a washing, dishwashing or cleaning
preparation is added to the liquid wrapper material(s). The mixture is then
processed to a flat material by methods known per se familiar to the expert
in this field. The flat material thus obtained is used completely or partly to
wrap one or more washing, dishwashing or cleaning preparations and thus
largely to shield the preparations) against outside influences.
In one particularly preferred embodiment of the process according to
the invention, a finely dispersible preparation of one or more additives is
added to the conventionally obtained melt or to a solution, preferably an
aqueous solution, of the wrapper material(s). In one particularly preferred
embodiment, the additives) is/are present in fine-particle form where a
melt of the wrapper material is used. If the wrapper materials are present
in the form of a solution, more particularly an aqueous solution, the
additives) is/are added in the form of solutions or in the form of a
dispersion in the solvent used, preferably water. In one particular
embodiment, aqueous solutions or dispersions of the additives may be
added to the aqueous solutions of one or more polyvinyl alcohols used as
starting material.
The active-substance portion packs, more particularly the detergent
CA 02312157 2000-06-23
21
portions according to the invention, contain one or more ingredients from
the group of surfactants, surfactant compounds, builders, bleaching agents,
bleach activators, enzymes, foam inhibitors, dyes and fragrances and also
binders and disintegration aids. These classes of ingredients are described
in the following.
In order to develop their washing effect, the portioned detergent
compositions according to the invention contain surfactants from the group
of anionic, nonionic, zwitterionic or cationic surfactants, anionic
surfactants
being greatly preferred both for economic reasons and by virtue of their
performance spectrum.
Suitable anionic surfactants are, for example, those of the sulfonate
and sulfate type. Suitable surfactants of the sulfonate type are preferably
C~~3 alkyl benzenesulfonates, olefin sulfonates, i.e. mixtures of alkene and
hydroxyalkane sulfonates, and the disulfonates obtained, for example, from
C~2_~8 monoolefins with an internal or terminal double bond by sulfonation
with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of
the sulfonation products. Other suitable surfactants of the sulfonate type
are the alkane sulfonates obtained from C~2_~a alkanes, for example by
sulfochlorination or sulfoxidation and subsequent hydrolysis or
neutralization. The esters of a-sulfofatty acids (ester sulfonates), for
example the a-sulfonated methyl esters of hydrogenated coconut oil, palm
kernel oil or tallow fatty acids, are also suitable.
Other suitable anionic surfactants are sulfonated fatty acid glycerol
esters. Fatty acid glycerol esters in the context of the present invention are
the monoesters, diesters and triesters and mixtures thereof which are
obtained where production is carried out by esterification of a monoglycerol
with 1 to 3 moles of fatty acid or in the transesterification of triglycerides
with 0.3 to 2 moles of glycerol. Preferred sulfonated fatty acid glycerol
esters are the sulfonation products of saturated fatty acids containing 6 to
22 carbon atoms, for example caproic acid, caprylic acid, capric acid,
CA 02312157 2000-06-23
22
myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
Preferred alk(en)yl sulfates are the alkali metal salts and, in
particular, the sodium salts of the sulfuric acid semiesters of C,2_~8 fatty
alcohols, for example cocofatty alcohol, tallow fatty alcohol, lauryl,
myristyl,
cetyl or stearyl alcohol, or C~o-2o oxoalcohols and the corresponding
semiesters of secondary alcohols with the same chain length. Other
preferred alk(en)yl sulfates are those with the chain length mentioned
which contain a synthetic, linear alkyl chain based on a petrochemical and
which are similar in their degradation behavior to the corresponding
compounds based on oleochemical raw materials. C~2-~s alkyl sulfates,
C~2_~5 alkyl sulfates and C~4_~5 alkyl sulfates are preferred from the point
of
view of washing technology. Other suitable anionic surfactants are 2,3-
alkyl sulfates which may be produced, for example, in accordance with US
3,234,258 or US 5,075,041 and which are commerially obtainable as
products of the Shell Oil Company under the name of DANO.
The sulfuric acid monoesters of linear or branched C~_2~ alcohols
ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched
C~~~ alcohols containing on average 3.5 moles of ethylene oxide (EO) or
C~2_~$ fatty alcohols containing 1 to 4 EO, are also suitable. In view of
their
high foaming capacity, they are only used in relatively small quantities, for
example in quantities of 1 to 5% by weight, in detergents.
Other preferred anionic surfactants are the salts of alkyl
sulfosuccinic acid which are also known as sulfosuccinates or as
sulfosuccinic acid esters and which represent monoesters and/or diesters
of sulfosuccinic acid with alcohols, preferably fatty alcohols and, more
particularly, ethoxylated fatty alcohols. Preferred sulfosuccinates contain
C&~8 fatty alcohol residues or mixtures thereof. Particularly preferred
sulfosuccinates contain a fatty alcohol residue derived from ethoxylated
fatty alcohols which, considered in isolation, represent nonionic surfactants
(for a description, see below). Of these sulfosuccinates, those of which the
CA 02312157 2000-06-23
' 23
fatty alcohol residues are derived from narrow-range ethoxylated fatty
alcohols are particularly preferred. Alk(en)yl succinic acid preferably
containing 8 to 18 carbon atoms in the alk(en)yl chain or salts thereof may
also be used.
Other suitable anionic surfactants are, in particular, soaps. Suitable
soaps are saturated fatty acid soaps, such as the salts of lauric acid,
myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and
behenic acid, and soap mixtures derived in particular from natural fatty
acids, for example coconut oil, palm kernel oil or tallow fatty acids.
The anionic surfactants, including the soaps, may be present in the
form of their sodium, potassium or ammonium salts and as soluble salts of
organic bases, such as mono-, di- or triethanolamine. The anionic
surfactants are preferably present in the form of their sodium or potassium
salts and, more preferably, in the form of their sodium salts. In another
embodiment of the invention, surfactants are used in the form of their
magnesium salts.
According to the invention, preferred portioned detergent
compositions are those which contain 5 to 50% by weight, preferably 7.5 to
40% by weight and more preferably 15 to 25% by weight of anionic
surfactant(s), based on the detergent composition.
So far as the choice of anionic surfactants used in the portioned
detergent compositions according to the invention is concerned, there are
no basic requirements to restrict the freedom of formulation. However,
preferred portioned detergent compositions do have a soap content in
excess of 0.2% by weight, based on the total weight of the detergent
composition. Preferred anionic surfactants are alkyl benzenesulfonates
and fatty alcohol sulfates, preferred detergent compositions containing 2 to
20% by weight, preferably 2.5 to 15% by weight and more preferably 5 to
10% by weight of fatty alcohol sulfate(s), based on the weight of the
detergent composition.
CA 02312157 2000-06-23
24
Preferred nonionic surfactants are alkoxylated, advantageously
ethoxylated, more especially primary alcohols preferably containing 8 to 18
carbon atoms and, on average, 1 to 12 moles of ethylene oxide (EO) per
mole of alcohol, in which the alcohol radical may be linear or, preferably,
methyl-branched in the 2-position or may contain linear and methyl-
branched radicals in the form of the mixtures typically present in oxoalcohol
radicals. However, alcohol ethoxylates containing linear radicals of
alcohols of native origin with 12 to 18 carbon atoms, for example coconut
oil, palm oil, tallow fatty or oleyl alcohol, and on average 2 to 8 EO per
mole
of alcohol are particularly preferred. Preferred ethoxylated alcohols
include, for example, C~2_~4 alcohols containing 3 EO or 4 EO, Cg~~ alcohol
containing 7 EO, C~~~5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO,
C~2_~8 alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such
as mixtures of C~2_~4 alcohol containing 3 EO and C~2_~$ alcohol containing
5 EO. The degrees of ethoxylation mentioned represent statistical mean
values which, for a special product, can be a whole number or a broken
number. Preferred alcohol ethoxylates have a narrow homolog distribution
(narrow range ethoxylates, NRE). In addition to these nonionic surfactants,
fatty alcohols containing more than 12 EO may also be used, examples
including tallow fatty alcohol containing 14 EO, 25 EO, 30 EO or 40 EO.
Another class of prefer-ed nonionic surfactants which may be used
either as sole nonionic surfactant or in combination with other nonionic
surfactants are alkoxylated, preferably ethoxylated or ethoxylated and
propoxylated, fatty acid alkyl esters preferably containing 1 to 4 carbon
atoms in the alkyl chain, more especially the fatty acid methyl esters which
are described, for example, in Japanese patent application JP 581217598
or which are preferably produced by the process described in International
patent application WO A-90113533.
Another class of nonionic surfactants which may advantageously be
used are the alkyl polyglycosides (APGs). Suitable alkyl polyglycosides
CA 02312157 2000-06-23
correspond to the general formula RO(G~ where R is a linear or branched,
more particularly 2-methyl-branched, saturated or unsaturated aliphatic
radical containing 8 to 22 and preferably 12 to 18 carbon atoms and G
stands for a glycose unit containing 5 or 6 carbon atoms, preferably
5 glucose. The degree of glycosidation is between 1.0 and 4.0, preferably
between 1.0 and 2.0 and more preferably between 1.1 and 1.4.
Linear alkyl polyglucosides, i.e. alkyl polyglycosides in which the
polyglycosyl component is a glucose unit and the alkyl component is an n-
alkyl group, are preferably used.
10 The detergent compositions according to the invention may
advantageously contain alkyl polyglycosides, APG contents in the
detergent compositions of more than 0.2% by weight, based on the press-
agglomerated detergent as a whole, being preferred. Particularly preferred
detergent compositions contain APGs in quantities of 0.2 to 10% by weight,
15 preferably in quantities of 0.2 to 5% by weight and more preferably in
quantities of 0.5 to 3% by weight.
Nonionic surfactants of the amine oxide type, for example N-
cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethyl-
amine oxide, and the fatty acid alkanolamide type are also suitable. The
20 quantity in which these nonionic surfactants are used is preferably no more
than the quantity in which the ethoxylated fatty alcohols are used and,
more preferably, no more than half that quantity.
Other suitable surfactants are polyhydroxyfatty acid amides
corresponding to formula (I):
R~
R-CO-N-[Z] (I)
in which RCO is an aliphatic acyl group containing 6 to 22 carbon atoms,
R' is hydrogen, an alkyl or hydroxyalkyl group containing 1 to 4 carbon
atoms and [Z] is a linear or branched polyhydroxyalkyl group containing 3
CA 02312157 2000-06-23
- 26
to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxyfatty acid
amides are known substances which may normally be obtained by
reductive amination of a reducing sugar with ammonia, an alkylamine or an
alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl
ester or a fatty acid chloride.
The group of polyhydroxyfatty acid amides also includes compounds
corresponding to formula (II):
R~-O-R2
R-CO-N-[Z] ( I I )
in which R is a linear or branched alkyl or alkenyl group containing 7 to 12
carbon atoms, R' is a linear, branched or cyclic alkyl group or an aryl group
containing 2 to 8 carbon atoms and R2 is a linear, branched or cyclic alkyl
group or an aryl group or an oxyalkyl group containing 1 to 8 carbon atoms,
C~.~ alkyl or phenyl groups being preferred, and [Z] is a linear polyhydroxy-
alkyl group, of which the alkyl chain is substituted by at least two hydroxyl
groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives
of that group.
[Z] is preferably obtained by reductive amination of a reduced sugar,
for example glucose, fructose, maltose, lactose, galactose, mannose or
xylose. The N-alkoxy- or N-aryloxy-substituted compounds may then be
converted into the required polyhydroxyfatty acid amides by reaction with
fatty acid methyl esters in the presence of an alkoxide as catalyst, for
example in accordance with the teaching of International patent application
WO-A-95107331.
In another preferred embodiment, cationic surfactants may be used
in addition to anionic and nonionic surfactants. They are mainly used as
detergency boosters and need only be used in small quantities. If cationic
surfactants are used, they are present in the detergents in quantities of
preferably 0.01 to 10% by weight and more preferably in quantities of 0.1 to
r CA 02312157 2000-06-23
' 2?
3.0% by weight.
In cases where the active-substance portion packs or
detergent/cleaner portions according to the invention are laundry
detergents, they normally contain one or more surfactants) in total
quantities of 5 to 50% by weight and preferably 10 to 35% by weight,
surfactants optionally being present in relatively large or relatively small
quantities in part-portions of the laundry detergent portions according to the
invention. In other words, the quantity of surfactant is not the same in all
portions, instead part-portions with a relatively large surfactant content and
part-portions with a relatively small surfactant content may be provided.
In cases where the active-substance portion packs or
detergent/cleaner portions according to the invention are cleaning
compositions, more particularly dishwashing detergents, they normally
contain one or more surfactants in total quantities of 0.1 to 10% by weight
and preferably in quantities of 0.5 to 5% by weight, surfactants optionally
being present in relatively large or relatively small quantities in part-
portions
of the laundry detergent portions according to the invention. In other
words, with dishwashing detergents also, the quantity of surfactant is not
the same in all portions, instead part-portions with a relatively large
surfactant content and part-portions with a relatively small surfactant
content may be provided.
Besides the washing-active ingredients, builders are the most
important ingredients of detergents. Any of the builders normally used in
detergents may be present in the detergent compositions according to the
invention, including in particular zeolites, silicates, carbonates, organic co-
builders and also - providing there are no ecological objections to their use
- phosphates.
Suitable crystalline layer-form sodium silicates correspond to the
general formula Na2MSiX02X+~y H20, where M is sodium or hydrogen, x is a
number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x
= CA 02312157 2000-06-23
' 28
being 2, 3 or 4. Crystalline layer silicates such as these are described, for
example, in European patent application EP-A-0 164 514. Preferred
crystalline layer silicates corresponding to the above formula are those in
which M is sodium and x assumes the value 2 or 3. Both ~- and 8-sodium
disilicates Na2Si205y H20 are particularly preferred, ~-sodium disilicate
being obtainable, for example, by the process described in International
patent application WO-A- 91!08171.
Other useful builders are amorphous sodium silicates with a
modulus (Na20:Si02 ratio) of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and more
preferably 1:2 to 1:2.6 which dissolve with delay and exhibit multiple wash
cycle properties. The delay in dissolution in relation to conventional
amorphous sodium silicates can have been obtained in various ways, for
example by surface treatment, compounding, compacting or by overdrying.
In the context of the invention, the term "amorphous" is also understood to
encompass "X-ray amorphous". In other words, the silicates do not
produce any of the sharp X-ray reflexes typical of crystalline substances in
X-ray diffraction experiments, but at best one or more maxima of the
scattered X-radiation which have a width of several degrees of the
diffraction angle. However, particularly good builder properties may even
be achieved where the silicate particles produce crooked or even sharp
diffraction maxima in electron diffraction experiments. This may be
interpreted to mean that the products have microcrystalline regions
between 10 and a few hundred nm in size, values of up to at most 50 nm
and, more particularly, up to at most 20 nm being preferred. So-called X-
ray amorphous silicates such as these, which also dissolve with delay in
relation to conventional waterglasses, are described for example in
German patent application DE-A-44 00 024. Compacted amorphous
silicates, compounded amorphous silicates and overdried X-ray-amorphous
silicates are particularly preferred.
The finely crystalline, synthetic zeolite containing bound water used
CA 02312157 2000-06-23
29
in accordance with the invention is preferably zeolite A and/or zeolite P.
Zeolite MAP~ (for example Doucil, a Crosfield product) is a particularly
preferred P-type zeolite. However, zeolite X and mixtures of A, X and/or P
are also suitable. According to the invention, it is also possible to use, for
example, a commercially obtainable co-crystallizate of zeolite X and zeolite
A (ca. 80% by weight zeolite X) which is marketed by CONDEA Augusta
S.p.A. under the name of VEGOBOND AXC~ and which may be described
by the following formula:
nNa20 ~ (1-n)K20 ~ AI203 ~ (2 - 2.5)Si02 ~ (3.5 - 5.5) H20
Suitable zeolites have a mean particle size of less than 10 ~m (volume
distribution, as measured by the Coulter Counter Method) and contain
preferably 18 to 22% by weight and more preferably 20 to 22% by weight of
combined water.
The generally known phosphates may of course also be used as
builders providing their use should not be avoided on ecological grounds.
The sodium salts of the orthophosphates, the pyrophosphates and, in
particular, the tripolyphosphates are particularly suitable.
Useful organic builders are, for example, polycarboxylic acids usable
in the form of their sodium salts, polycarboxylic acids in this context being
those carboxylic acids which carry more than one acid function. These
include, for example, citric acid, adipic acid, succinic acid, glutaric acid,
malic acid, tartaric acid, malefic acid, fumaric acid, sugar acids, amino-
carboxylic acids, nitrilotriacetic acid (NTA) - providing its use is not
ecologically unsafe - and mixtures thereof. Preferred salts are the salts of
the polycarboxylic acids, such as citric acid, adipic acid, succinic acid,
glutaric acid, tartaric acid, sugar acids and mixtures thereof. The acids per
se may also be used. Besides their builder effect, the acids also typically
have the property of an acidifying component and, hence, also serve to
CA 02312157 2000-06-23
' 30
establish a relatively low and mild pH value in detergent portions according
to the invention. Citric acid, succinic acid, glutaric acid, adipic acid,
gluconic acid and mixtures thereof are particularly mentioned in this regard.
Other suitable builders are polymeric polycarboxylates such as, for
example, the alkali metal salts of polyacrylic or polymethacrylic acid, for
example those with a relative molecular weight of 500 to 70,000 g/mole.
The molecular weights mentioned in this specification for polymeric
polycarboxylates are weight-average molecular weights MW of the particular
acid form which, basically, were determined by gel permeation
chromatography (GPC) using a UV detector. The measurement was
carried out against an external polyacrylic acid standard which provides
realistic molecular weight values by virtue of its structural similarity to
the
polymers investigated. These values differ distinctly from the molecular
weights measured against polystyrene sulfonic acids as standard. The
molecular weights measured against polystyrene sulfonic acids are
generally higher than the molecular weights mentioned in this specification.
Particularly suitable polymers are polyacrylates which preferably
have a molecular weight of 2,000 to 20,000 g/mole. By virtue of their
superior solubility, preferred representatives of this group are the short
chain polyacrylates which have molecular weights of 2,000 to 10,000
g/mole and, more particularly, 3,000 to 5,000 g/mole.
Also suitable are copolymeric polycarboxylates, particularly those of
acrylic acid with methacrylic acid and those of acrylic acid or methacrylic
acid with malefic acid. Acrylic acidlmaleic acid copolymers containing 50 to
90% by weight of acrylic acid and 50 to 10% by weight of malefic acid have
proved to be particularly suitable. Their relative molecular weights, based
on the free acids, are generally in the range from 2,000 to 70,000 g/mole,
preferably in the range from 20,000 to 50,000 g/mole and more preferably
in the range from 30,000 to 40,000 g/mole.
The (co)polymeric polycarboxylates may be used either in the form
< CA 02312157 2000-06-23
' 31
of an aqueous solution or in powder form. The laundry/dishwasher
detergent portions according to the invention preferably contain 0.5 to 20%
by weight and more particularly 3 to 10% by weight of (co)polymeric
polycarboxylates.
In order to improve solubility in water, the polymers may also contain
allyl sulfonic acids, such as for example allyloxybenzene sulfonic acid and
methallyl sulfonic acid (cf. EP-B-727 448), as monomer.
Other particularly preferred polymers are biodegradable polymers of
more than two different monomer units, for example those which contain
salts of acrylic acid and malefic acid and vinyl alcohol or vinyl alcohol
derivatives as monomers according to DE-A-43 00 772 or those which
contain salts of acrylic acid and 2-alkylallyl sulfonic acid and sugar
derivatives as monomers according to DE-C-42 21 381.
Other preferred copolymers are those which are described in
German patent applications DE A-43 03 320 and DE-A-44 17 734 and
which preferably contain acrolein and acrylic acid/acrylic acid salts or
acrolein and vinyl acetate as monomers.
Other preferred builders are polymeric aminodicarboxylic acids, salts
or precursors thereof. Particular preference is attributed to polyaspartic
acids or salts and derivatives thereof which, according to German patent
application DE-A-195 40 086, are also said to have a bleach-stabilizing
effect in addition to their co-builder properties.
Other suitable builders are polyacetals which may be obtained by
reaction of dialdehydes with polyol carboxylic acids containing 5 to 7
carbon atoms and at least three hydroxyl groups, for example as described
in European patent application EP-A-0 280 223. Preferred polyacetals are
obtained from dialdehydes, such as glyoxal, glutaraldehyde, terephthal-
aldehyde and mixtures thereof and from polyol carboxylic acids, such as
gluconic acid and/or glucoheptonic acid.
Other suitable organic builders are dextrins, for example oligomers
CA 02312157 2000-06-23
' 32
or polymers of carbohydrates which may be obtained by partial hydrolysis
of starches. The hydrolysis may be carried out by standard methods, for
example acid- or enzyme-catalyzed methods. The end products are
preferably hydrolysis products with average molecular weights of 400 to
500,000 g/mole. A polysaccharide with a dextrose equivalent (DE) of 0.5 to
40 and, more particularly, 2 to 30 is preferred, the DE being an accepted
measure of the reducing effect of a polysaccharide by comparison with
dextrose which has a DE of 100. Both maltodextrins with a DE of 3 to 20
and dry glucose sirups with a DE of 20 to 37 and also so-called yellow
dextrins and white dextrins with relatively high molecular weights of 2,000
to 30,000 g/mole may be used. A preferred dextrin is described in British
patent application 9419 091.
The oxidized derivatives of such dextrins are their reaction products
with oxidizing agents which are capable of oxidizing at least one alcohol
function of the saccharide ring to the carboxylic acid function. Dextrins thus
oxidized and processes for their production are known, for example, from
European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0
472 042 and EP-A-0 542 496 and from International patent applications
WO 92/18542, WO 93108251, WO 93116110, WO 94128030, WO 95/07303,
WO 95112619 and WO 95/20608. An oxidized oligosaccharide
corresponding to German patent application DE A-196 00 018 is also
suitable. A product oxidized at Cs of the saccharide ring can be particularly
advantageous.
Other suitable co-builders are oxydisuccinates and other derivatives
of disuccinates, preferably ethylenediamine disuccinate. Ethylenediamine-
N,N'-disuccinate (EDDS), of which the synthesis is described for example
in US 3,158,615, is preferably used in the form of its sodium or magnesium
salts. The glycerol disuccinates and glycerol trisuccinates described, for
example, in US 4,524,009, in US 4,639, 325, in European patent
application EP-A-0 150 930 and in Japanese patent application JP
~
CA 02312157 2000-06-23
' 33
931339,896 are also particularly preferred in this connection. The
quantities used in zeolite-containing and/or silicate-containing formulations
are from 3 to 15% by weight.
Other useful organic co-builders are, for example, acetylated
hydroxycarboxylic acids and salts thereof which may optionally be present
in lactone form and which contain at least 4 carbon atoms, at least one
hydroxy group and at most two acid groups. Co-builders such as these are
described, for example, in International patent application WO-A-95120029.
Another class of substances with co-builder properties are the
phosphonates, more particularly the hydroxyalkane and aminoalkane
phosphonates described in the foregoing.
In addition, any compounds capable of complexing alkaline earth
metal ions may be used as co-builders.
In addition to the ingredients - surfactants and builders - mentioned
above, the detergents according to the invention may contain other typical
detergent ingredients, for example from the group of bleaching agents,
bleach activators, enzymes, perfumes, perfume can-iers, fluorescing
agents, dyes, foam inhibitors, silicone oils, redeposition inhibitors, optical
brighteners, discoloration inhibitors, dye transfer inhibitors and corrosion
inhibitors.
Among the compounds yielding H202 in water which serve as
bleaching agents, sodium perborate tetrahydrate and sodium perborate
monohydrate are particularly important. Other useful bleaching agents are,
for example, sodium percarbonate, peroxypyrophosphates, citrate perhy-
drates and H202-yielding peracidic salts or peracids, such as
perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or
diperdodecane dioic acid. If detergent or bleaching compositions for
dishwashing machines are being produced, bleaching agents from the
group of organic bleaches may also be used. Typical organic bleaching
agents are diacyl peroxides, such as dibenzoyl peroxide for example.
CA 02312157 2000-06-23
34
Other typical organic bleaching agents are the peroxy acids, of which alkyl
peroxy acids and aryl peroxy acids are particularly mentioned as examples.
Preferred representatives are (a) peroxybenzoic acid and ring-substituted
derivatives thereof, such as alkyl peroxybenzoic acids, but also peroxy-a-
naphthoic acid and magnesium monoperphthalate, (b) aliphatic or
substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic
acid, s-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid
(PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic
acid and N-nonenylamidopersuccinates. and (c) aliphatic and araliphatic
peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-
diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid,
diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic acid, N,N-
terephthaloyl-di(6-aminopercaproic acid).
Other suitable bleaching agents in compositions for dishwashing
machines are chlorine- and bromine-releasing substances. Suitable
chlorine- or bromine-releasing materials are, for example, heterocyclic N
bromamides and N-chloramides, for example trichloroisocyanuric acid,
tribromoisocyanuric acid, dibromoisocyanuric acid and/or dichloro
isocyanuric acid (DICA) and/or salts thereof with cations, such as
potassium and sodium. Hydantoin compounds, such as 1,3-dichloro-5,5-
dimethyl hydantoin, are also suitable.
In order to obtain an improved bleaching effect where washing is
carried out at temperatures of 60°C or lower, bleach activators may be
incorporated in the detergents according to the invention. The bleach
activators may be compounds which form aliphatic peroxocarboxylic acids
containing preferably 1 to 10 carbon atoms and more preferably 2 to 4
carbon atoms and/or optionally substituted perbenzoic acid under
perhydrolysis conditions. Substances bearing O- and/or N-acyl groups with
the number of carbon atoms mentioned and/or optionally substituted
benzoyl groups are suitable. Preferred bleach activators are polyacylated
, CA 02312157 2000-06-23
- 35
alkylenediamines, more particularly tetraacetyl ethylenediamine (TAED),
acylated triazine derivatives, more particularly 1,5-diacetyl-2,4-dioxohexa-
hydro-1,3,5-triazine (DADHT), acylated glycolurlls, more particularly
tetraacetyl glycolurll (TAGU), N-acylimides, more particularly N-nonanoyl
succinimide (NOSI), acylated phenol sulfonates, more particularly n-
nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic
anhydrides, more particularly phthalic anhydride, acylated polyhydric
alcohols, more particularly triacetin, ethylene glycol diacetate and 2,5-
diacetoxy-2,5-dihydrofuran.
In addition to or instead of the conventional bleach activators
mentioned above, so-called bleach catalysts may also be incorporated in
the detergents according to the invention. Bleach catalysts are bleach-
boosting transition metal salts or transition metal complexes such as, for
example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen
complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium,
molybdenum, titanium, vanadium and copper complexes with nitrogen-
containing tripod ligands and cobalt-, iron-, copper- and ruthenium-ammine
complexes may also be used as bleach catalysts.
Suitable enzymes are those from the class of proteases, lipases,
amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial
strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and
Streptomyces griseus, are particularly suitable. Proteases of the subtilisin
type are preferred, proteases obtained from Bacillus lentus being
particularly preferred. Enzyme mixtures, for example of protease and
amylase or protease and lipase or protease and cellulase or of cellulase
and lipase or of protease, amylase and lipase or of protease, lipase and
cellulase, but especially cellulase-containing mixtures, are of particular
interest. Peroxidases or oxidases have also proved to be suitable in some
cases. The enzymes may be adsorbed to supports and/or encapsulated in
membrane materials to protect them against premature decomposition.
CA 02312157 2000-06-23
36
The percentage content of the enzymes, enzyme mixtures or enzyme
granules in the detergents according to the invention may be, for example,
from about 0.1 to 5% by weight and is preferably from 0.1 to about 2% by
weight.
According to the prior art, enzymes are added primarily to a
detergent preparation, more particularly a dishwasher detergent intended
for the main wash cycle. The disadvantage was that the action optimum of
the enzymes used restricted the choice of temperature and problems with
the stability of the enzymes in strongly alkaline medium also occurred.
With the detergent portions according to the invention, enzymes may also
be used in the pre-rinse cycle so that the pre-rinse cycle may be used in
addition to the main wash cycle for enzymes to act on tableware soil.
In a particularly preferred embodiment of the invention, therefore,
enzymes are added to the washing preparation intended for the pre-rinse
cycle or to a part-portion of a detergent portion and the preparation in
question may preferably be wrapped in a material which dissolves in water
at low temperatures in order, for example, to protect the enzyme-containing
preparation against a loss of action by environmental conditions. The
enzymes are preferably optimized for use under the conditions of the pre-
rinse cycle, i.e. for example in cold water.
The detergent portions according to the invention can be of
advantage when the enzyme preparations are present in the liquid form
sometimes available on the market because, in that case, a quick effect -
already occurring in the pre-rinse cycle (relatively brief and carried out in
cold water) - can be expected. Even if the enzymes are used in solid form,
as they normally are, and are provided with a wrapping of a water-soluble
material dissolving in cold water, the enzymes are able to develop their
effect before the main wash cycle. The advantage of using a wrapper of a
water-soluble material, more particularly a cold-water-soluble material, is
that the enzymes) quickly become active in cold water after the wrapper
' CA 02312157 2000-06-23
37
dissolves. Their action time can thus be extended to the benefit of the
washing/cleaning result.
In one particularly preferred embodiment, the detergent portions
according to the invention contain other additives known from the prior art
as additives for washing or dishwashing preparations. These other
additives may either be added to one or more, if necessary even all, of the
part-portions (washing preparations) of the detergent portions according to
the invention or may be incorporated in the water-soluble materials in which
the washing preparations are wrapped, i.e. for example in the water-soluble
films, but also in capsules or coatings which may act as wrappers.
A preferred group of additives used in accordance with the invention
are optical brighteners. The optical brighteners normally present in
detergents may be used. They are added in the form of an aqueous
solution or in the form of a solution in an organic solvent to the polymer
solution which is converted into the film or are added to a part-portion
(washing preparation) of a detergent/cleaner in solid or liquid form.
Examples of optical brighteners are derivatives of diamino-
stilbenedisulfonic acid or alkali metal salts thereof. Suitable optical
brighteners are, for example, salts of 4,4'-bis-(2-anilino-4-morpholino-1,3,5-
triazinyl-6-amino)-stilbene-2,2'-disulfonic acid or compounds of similar
composition which contain a diethanolamino group, a methylamino group,
an anilino group or a 2-methoxyethylamino group instead of the morpholino
group. Brighteners of the substituted diphenyl styryl type, for example
alkali metal salts of 4,4'-bis-(2-sulfostyryl)-diphenyl, 4,4'-bis-(4-chloro-3-
sulfostyryl)-diphenyl or 4-(4-chlorostyryl)-4'-(2-sulfostyryl)-diphenyl, may
also be present in the part-portions (laundry detergent prepqarations) of the
detergent/cleaner portions according to the invention. Mixtures of the
brighteners mentioned above may also be used.
UV filters, surfactants capable in particular of influencing the
solubility of the water-soluble film and also controlling its wettability and
' CA 02312157 2000-06-23
38
foaming during dissolution, foam inhibitors, bitter substances for preventing
children from accidentally swallowing the packs or parts thereof, polymers
and bleach catalysts were mentioned in the foregoing as further groups of
additives preferably used in accordance with the invention.
Another group of additives preferably used in accordance with the
invention are dyes, more particularly water-soluble or water-dispersible
dyes. Dyes of the type normally used to improve visual product appeal in
detergents/cleaners are preferred. Such dyes are not difficult for the expert
to choose, above all because they have high stability in storage, are not
affected by the other ingredients of the laundry detergent preparations or
by light and do not have any pronounced substantivity for textile fibers so
as not to color them. According to the invention, the dyes are present in
the detergent/cleaner portions in quantities of less than 0.01 % by weight.
Another group of additives preferably used in accordance with the
invention are silver corrosion inhibitors, i.e. any of various, mostly cyclic
organic compounds which are also familiar to the expert and which
contribute towards preventing silver-containing articles from tarnishing
during the dishwashing process. Special examples of silver corrosion
inhibitors are triazoles, benzotriazoles and complexes thereof with metals
such as, for example, Mn, Co, Zn, Fe, Mo, W or Cu.
The detergent/cleaner portions may also contain soil repellents, i.e.
polymers which are absorbed onto fibers or hard surfaces (for example
onto china and glass) and which positively influence the removal of oils and
fats from textile and thus counteract resoiling, as further additives
according to the invention. This effect becomes particularly clear when a
textile or a hard object (china, glass) which has already been repeatedly
washed with a detergent according to the invention containing this oil- and
fat-dissolving component is soiled. Preferred oil- and fat-dissolving
components include, for example, nonionic cellulose ethers, such as methyl
cellulose and methyl hydroxypropyl cellulose containing 15 to 30% by
' CA 02312157 2000-06-23
39
weight of methoxy groups and 1 to 15% by weight of hydroxypropoxy
groups, based on the nonionic cellulose ether, and the polymers of phthalic
acid and/or terephthalic acid known from the prior art or derivatives thereof,
more particularly polymers of ethylene terephthalates and/or polyethylene
glycol terephthalates or anionically and/or nonionically modified derivatives
thereof. Of these, the sulfonated derivatives of phthalic acid and
terephthalic acid polymers are particularly preferred.
All these additives are added to the detergent/cleaner portions
according to the invention in quantities of up to at most 30% by weight and
preferably 2 to 20% by weight. According to the invention, they may be
added to a material of a water-soluble wrapper which comprises the, or one
of the, detergent preparation(s). In order to balance the formulation, the
expert may also increase the weight of the plastic material for the wrapper
in order thus to utilize the storage effect obtained in accordance with the
invention by incorporating the additives in the wrappers) or additionally to
keep the additives mentioned at least partly in the remaining detergent
preparation.
Perfumes are added to the detergent/cleaner portions according to
the invention to improve the aesthetic impression created by the products
and to provide the consumer not only with the required technical
performance (fabric softening result) but also with a visually and sensorially
"typical and unmistakable" product. Suitable perfume oils or perfumes
include individual perfume compounds, for example synthetic products of
the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Perfume
compounds of the ester type are, for example, benzyl acetate,
phenoxyethyl isobutyrate, p-tert.butyl cyclohexyl acetate, linalyl acetate,
dimethyl benzyl carbinyl acetate, phenyl ethyl acetate, linalyl benzoate,
benzyl formate, ethyl methyl phenyl glycinate, ally) cyclohexyl propionate,
styrallyl propionate and benzyl salicylate. The ethers include, for example,
benzyl ethyl ether; the aldehydes include, for example, the linear alkanals
- CA 02312157 2000-06-23
containing 8 to 18 carbon atoms, citral, citronellal, citronellyloxy-
acetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal.
The ketones include, for example, the ionones, a-isomethyl ionone
and methyl cedryl ketone. The alcohols include anethol, citronellol,
5 eugenol, geraniol, linalool, phenyl ethyl alcohol and terpineol. The
hydrocarbons include, above all, the terpenes, such as limonene and
pinene. However, mixtures of various perfumes which together produce an
attractive perfume note are preferably used. Perfume oils such as these
may also contain natural perfume mixtures obtainable from vegetable
10 sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang
oil. Also suitable are clary oil, camomile oil, clove oil, melissa oil, mint
oil,
cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum
oil, galbanum oil and labdanum oil and orange blossom oil, neroli oil,
orange peel oil and sandalwood oil.
15 The perfume content is normally up to 2% by weight, based on the
detergent portion as a whole. Accordingly, these are typical additives
which, in view of their small quantity, are difficult to disperse uniformly in
normal formulations, but which according to the invention may ideally be
added to the material of the wrappers) and hence are present in uniform
20 distribution in the active-substance portion packs according to the
invention.
The perfumes may be directly incorporated in the detergents
according to the invention, although it can also be of advantage to apply
the perfumes to supports which strengthen the adherence of the perfume
25 to the washing and which provide the textiles with a long-lasting perfume
through a slower release of the perfume. Suitable support materials are,
for example, cyclodextrins, the cyclodextrin/perfume complexes optionally
being coated with other auxiliaries.
Basically the perfumes may be present in each of the part-portions
30 (detergent preparations) of the detergent/cleaner portions according to the
CA 02312157 2000-06-23
41
invention. In one particularly preferred embodiment, however, they are
present in a detergent in a laundry detergent part-portion intended for the
after-wash cycle or fabric-softening cycle or in a cleaner, particularly a
dishwashing detergent, in a cleaner part-portion, particularly a dishwashing
detergent part-portion, intended for the anal rinse or clear rinse cycle.
According to the invention, therefore, they have to be surrounded by a
material which only dissolves in water under the conditions (more
particularly at the temperature) of the after-wash or final rinse cycle, but
which is insoluble in water under the conditions (more particularly at the
temperature) of the preceding wash cycles, more particularly a
corresponding film or capsule. According to the invention, this is possible
for example with a multi-compartment bag of films differing in their water
solubility.
The present invention also relates to a washing process wherein an
active-substance portion pack as described in detail in the foregoing is
placed in a washing machine and, by addition of water and heating of the
wash liquor beyond the dissolving point of the wrapper, the additives
contained in the wrapper are released through dissolution thereof. The
invention also relates to a machine dishwashing process, wherein an
active-substance portion pack as described in detail in the foregoing is
placed in the dispensing compartment of a dishwashing machine and, by
addition of water and release of the active-substance portion pack from the
dispensing compartment, the additives are released through dissolution of
the wrapper. Finally, the present invention also relates to a machine
dishwashing process using an active-substance portion pack as describe in
detail in the foregoing, wherein a wrapper which only dissolves in water
above room temperature is selected, the dishwashing detergent
preparation is placed in the interior of the dishwashing machine and, by
addition of water and heating of the wash liquor beyond the dissolving point
of the wrapper, the additives contained in the wrapper are released through
' CA 02312157 2000-06-23
42
dissolution thereof.
The invention is illustrated by the following Examples.
Commercial names used: ,
Aerosil 8972, Degussa-Huls: silicon dioxide
Dehydol LT 7, Cognis: fatty alcohol ethoxylate (EO = 7)
Mowiol, Mowilith, Clariant: polyvinyl alcohol, partly saponified
Optiblanc, Sigma: optical brightener
Polyviol, Wacker: polyvinyl alcohol
Sokalan HP 53, BASF: polyvinyl pyrrolidone
Tinopal CBS-X, Ciba: 4,4'-bis-(2-sulfostyryl)-biphenyl, disodium
salt (optical brightener)
Examples 1 to 7 and Comparison Example
I. Comparison Example
1000 parts by weight polyvinyl alcohol,
2.5 parts by weight stearic acid (sodium salt)
100 parts by weight glycerol,
6 parts by weight fine-particle Si02 and
60 parts by weight sorbitol
are stirred to form an approximately 40% aqueous solution. A 10 to 50 Nm
thick film is produced from this solution by thermocalendering. The film is
used for packaging dishwasher tablets or a laundry detergent tablet by
wrapping the tablets in the film and sealing the edges of the film. The
dissolving point of the film can be varied between 0 and 80°C through
the
choice of the polyvinyl alcohol used. In the present case, a film dissolving
at 20°C was used.
II. Examples according to the invention
Similar films were produced as described in the Comparison
' CA 02312157 2000-06-23
- 43
Example with the following additions:
Example 1: 5% by weight of an optical brightener
Example 2: 5% by weight of a UV filter
Example 3: 5% by weight of a blue detergent dye
Examale 4: 10% by weight of a detergent perfume mixture
Example 5: 20% by weight of a soil repellent polymer based on ethylene
glycol and terephthalic acid
Example 6: 3% by weight of a cobalt ammine complex
Example 7: 10% by weight of benzotriazole.
The substances mentioned above may readily be incorporated in the
polymer films using mechanical energy. Where possible, they are incorpo-
rated in the form of aqueous solutions, otherwise in the form of an aqueous
dispersion. The films formed are uniform and dissolve completely in
washing tests so that the additives are released.
Example 8
A portion bag for detergents in the form of beads ("Megaperls")
contains 37.5 g of washing preparations. Two portion bags (= 75 g of
washing preparations) are used for one wash cycle. The film in which the
preparations were wrapped was 30 Nm thick and 1.5 g of film was used for
both bags (corresponding to 2% by weight).
(a) A film containing (a) 13.5% by weight of Optiblanc 2MG (9% active
content), (~i) 2.2% by weight Tinopal CBS-X (2% active content) and (r)
84.3% by weight PVAL and auxiliaries was produced. Accordingly, 1.5
g of film contained exactly the quantity of brightener intended for the
Megaperls. The film was transparent with an opalescent appearance,
but was not disturbingly colored.
' CA 02312157 2000-06-23
i
44
{b) A film containing (a) 25% by weight polyvinyl pyrrolidone {active
content from an aqueous Sokalan HP53 solution) and (~i) 75% by
weight PVAL and auxiliaries was produced. Accordingly, 1.5 g of film
contained exactly the quantity of redeposition inhibitor (PVP) intended
for Megaperls Color. The film was colorless and transparent.
Different formulations of various detergents could be produced with
both films without aftertreatment mixers and transport paths of the raw
materials being contaminated with unwanted additives because the
brighteners and redeposition inhibitors were incorporated in the film
material. Accordingly, the effort involved in a product change in the
production process was confined to changing the film in the packaging
machine.
Example 9
PVA films for detergent wrappers containing various detergent
ingredients or plasticizers were produced. Films 1 and 2 were blown films
while films 3 to 9 were pressed films. The mixtures identified below were
processed in a Brabender 42/7 twin-screw kneader. The twin-screw
kneader had contrarotating screws for extremely thorough mixing. The
temperatures at which the mixtures were processed were 140°C in the
three zones present along the screw and 147°C in the die.
Mixtures 1 and 2 were processed and granulated at 50 r.p.m. The
granules obtained were processed in a film blowing machine (Brabender
single-screw kneader). The temperature profile from the feed zone to the
die was adjusted as follows: heating zones 1 to 6: 180, 175, 160, 150, 120,
120°C. The screw was driven at 50 r.p.m. which produced a torque of 80
Nm. A film take-off rate of 1.3 was adjusted.
Mixtures 3 to 9 were extruded at 50 r.p.m. through a ribbon nozzle.
The dimensions of the nozzle were 50 x 0.5 mm so that a 45 mm wide and
' CA 02312157 2000-06-23
0.5 mm thick ribbon was obtained. The ribbon obtained was pressed in a
heatable press (Webre) to form films. The pressing temperatures were in
the range from 120 to 180°C; the pressure applied was 50 to 60 bar.
5 Film 1:
Polyviol 051290 83.0% SRP for cotton
Glycerol 11.3%
Sorbitol 5.1
Aerosil 0.5%
10 Stearic acid 0.1
100.0%
Film 2:
15 Polyviol 05/290 37.6% SRP for cotton
Mowilith 8/88 37.6%
Glycerol 16.7%
Sorbitol 4.6%
Dist. Water 2.8%
20 Aerosil 0.5%
Stearin 0.2%
100.0%
25 Film 3:
Mowiol 8/88 41.4%
Mowiol 4/88 41.4%
Glycerol 8.3%
Sorbitol 5.0%
30 Dist. Water 3.2%
' CA 02312157 2000-06-23
46
Aerosil 8972 0.5%
Stearic acid 0.2%
100.0%
Film 4
Mowiol 8/88 42.5%
Mowiol 4/88 42.5%
Glycerol 4.3%
Sorbitol 2.6%
PEG400 6.8% (plasticizer)
Dist. Water 0.5%
Aerosil 8972 0.5%
Stearic acid 0.3%
100.0%
Film 5:
Mowiol 8/88 41.4%
Mowiol4/88 41.4%
Glycerol 4.1
Sorbitol 2.5%
Dehydol LS 4 6.6% (surfactant)
Dist. Water 3.3%
Aerosil8972 0.5%
Stearic acid 0.2%
100.0%
' CA 02312157 2000-06-23
47
Film 6:
Mowiol 8/88 41.4%
Mowiol 4/88 41.4%
Glycerol 4.1
Sorbitol 2.5%
Dehydol LT7 6.6% (surfactant)
Dist. Water 3.3%
Aerosil 8972 0.5%
Stearic acid 0.2%
100.0%
Film 7:
Mowiol 8/88 40.5%
Mowiol4/88 40.5%
Tinopal CBS 2.2% (brightener)
Glycerol 8.0%
Sorbitol 4.9%
Dist. Water 3.2%
Aerosil8972 0.5%
Stearic acid 0.2%
100.0%
Film 8:
Mowiol 8/88 35.8%
Mowiol 4/88 35.8%
Optiblanc 13.4% (brightener)
Glycerol 7.2%
Sorbitol 4.3%
CA 02312157 2000-06-23
48
Dist. Water 2.8%
Aerosil 8972 0.4%
Stearic acid 0.2%
100.0%
Film 9:
Mowiol 8/88 34.0%
Mowiol4/88 34.0%
Optiblanc 13.5% (brightener)
Tinopal CBS 4.4% (brightener)
Glycerol 9.5%
Sorbitol 4.1
Aerosil8972 0.3%
Stearic acid 0.2%
100.0%
The films obtained contained the particular additives) in a uniform
concentration, i.e. the additives) was/were uniformly distributed in the
particular film material. The films showed outstanding properties in the
production of active-substance portion packs and could readily be
processed in the existing machines. The films of the active-substance
portion packs obtained dissolved as well and as completely in aqueous
phase as the corresponding additive-free films. The additives in the films
produced the same effect as the additives in the detergent preparation. In
contrast to the film additives, however, a higher concentration of the
additives was necessary in the known preparations for compensating the
variations in concentration attributable to the non-uniform distribution.
CA 02312157 2000-06-23
49
The invention may be varied in any number of ways as would
be apparent to a person skilled in the art and all obvious equivalents and
the like are meant to fall within the scope of this description and claims.
The description is meant to serve as a guide to interpret the claims and not
to limit them unnecessarily.
