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Patent 2317182 Summary

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(12) Patent Application: (11) CA 2317182
(54) English Title: DETERGENT COMPONENT
(54) French Title: COMPOSANT DE DETERGENT
Status: Deemed Abandoned and Beyond the Period of Reinstatement - Pending Response to Notice of Disregarded Communication
Bibliographic Data
(51) International Patent Classification (IPC):
  • C11D 3/20 (2006.01)
  • C11D 1/72 (2006.01)
  • C11D 1/722 (2006.01)
  • C11D 1/83 (2006.01)
  • C11D 17/00 (2006.01)
  • C11D 17/02 (2006.01)
  • C11D 17/06 (2006.01)
(72) Inventors :
  • SCHMIEDEL, PETER (Germany)
  • BAYERSDOERFER, ROLF (Germany)
  • HOLDERBAUM, THOMAS (Germany)
  • KESSLER, ARND (Germany)
  • SUNDER, MATTHIAS (Germany)
  • RICHTER, BERND (Germany)
  • HAERER, JUERGEN (Germany)
  • NITSCH, CHRISTIAN (Germany)
(73) Owners :
  • HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN
(71) Applicants :
  • HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN (Germany)
(74) Agent: NORTON ROSE FULBRIGHT CANADA LLP/S.E.N.C.R.L., S.R.L.
(74) Associate agent:
(45) Issued:
(22) Filed Date: 2000-08-31
(41) Open to Public Inspection: 2001-02-28
Availability of licence: N/A
Dedicated to the Public: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): No

(30) Application Priority Data:
Application No. Country/Territory Date
199 41 264.2 (Germany) 1999-08-31
199 57 504.5 (Germany) 1999-11-30

Abstracts

English Abstract


Mixtures which possess long-term stability, which have
little propensity to separate and which give effective
and stable detergent components, comprise from 10 to
90% by weight surfactant (s) , from 10 to 90% by weight
fatty substance(s), from 0 to 70% by weight meltable
substance(s) having a melting point above 30°C, and
from 0 to 15% by weight further active substances
and/or auxiliaries.


Claims

Note: Claims are shown in the official language in which they were submitted.


What is claimed is:
1. A detergent component comprising
a) from 10 to 90% by weight of surfactant(s),
b) from 10 to 90% by weight of fatty
substance(s),
c) from 0 to 70% by weight of meltable
substance (s) having a melting point above 30°C,
and
d) from 0 to 15% by weight of further active
substances and/or auxiliaries.
2. The component as claimed in claim 1, comprising
as ingredient a) from 15 to 80, preferably from
20 to 70, with particular preference from 25 to
60, and in particular from 30 to 50% by weight of
surfactant (s).
3. The component as claimed in either of claims 1
and 2, comprising as ingredient b) from 12.5 to
85, preferably from 15 to 80, with particular
preference from 17.5 to 75, and in particular
from 20 to 70% by weight of fatty substance(s).
4. The component as claimed in any of claims 1 to 3,
comprising as ingredient c) from 0 to 65,
preferably from 0 to 60, with particular
preference from 0 to 55, and in particular from 0
to 50% by weight of meltable substance(s).
5. The component as claimed in any of claims 1 to 4,
comprising as ingredient a) anionic and/or
nonionic surfactant(s), preferably nonionic
surfactant (s).
91

6. The component as claimed in any of claims 1 to 5,
comprising as ingredient a) nonionic
surfactant(s) having a melting point above 20°C,
preferably above 25°C, with particular preference
between 25 and 60°C, and in particular between
26.6 and 43.3°C.
7. The component as claimed in any of claims 1 to 6,
comprising as ingredient a) ethoxylated nonionic
surfactant (s) obtained from C6-20 monohydroxy-
alkanols or C6-20 alkylphenols or C16-20 fatty
alcohols and more than 12 mol, preferably more
than 15 mol, and in particular more than 20 mol,
of ethylene oxide per mole of alcohol.
8. The component as claimed in any of claims 1 to 7,
comprising as ingredient a) 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.
9. The component as claimed in any of claims 1 to 8,
comprising as ingredient a) nonionic surfactants
of the formula
R1O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(OH)R2]
in which R1 is a linear or branched aliphatic
hydrocarbon radical having 4 to 18 carbon atoms,
or mixtures thereof, R2 is a linear or branched
hydrocarbon radical having 2 to 26 carbon atoms,
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or mixtures thereof, and x is between 0.5 and
1.5, and y is at least 15.
10. The component as claimed in any of claims 1 to 9,
comprising as ingredient a) endgroup-capped
poly(oxyalkylated) nonionic surfactants of the
formula
R1O[CH2CH(R3)O]x[CH2]kCH(OH)[CH2]jOR2
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
R1O[CH2CH(R3)O]xCH2CH(OH)CH2OR2
where x is from 1 to 30, preferably from 1 to 20,
and in particular from 6 to 18.
11. The component as claimed in any of claims 1 to
10, comprising as ingredient b) one or more
substances from the groups of the fatty alcohols,
fatty acids, and fatty acid esters.
12. The component as claimed in any of claims 1 to
11, comprising as ingredient b) one or more C10-30
fatty alcohols, preferably C12-24 fatty alcohols,
with particular preference 1-hexadecanol,
1-octadecanol, 9-cis-octadecen-1-ol, all-cis-9,12-
-93-

octadecadien-1-ol, all-cis-9,12,15-octadecatrien-1-ol,
1-docosanol, and mixtures thereof.
13. The component as claimed in any of claims 1 to
12, comprising as ingredient c) one or more
substances having a melting range between 30 and
100°C, preferably between 40 and 80°C, and in
particular between 50 and 75°C.
14. The component as claimed in any of claims 1 to
13, comprising as ingredient c) at least one
paraffin wax having a melting range of from 30°C
to 65°C.
15. The component as claimed in any of claims 1 to
14, comprising as ingredient c) at least one
substance from the group of the polyethylene
glycols (PEGS) and/or polypropylene glycols
(PPGs).
16. The component as claimed in any of claims 1 to
15, comprising as ingredient d) further active
substances and/or auxiliaries from the groups of
the dyes, fragrances, antisettling agents,
suspension agents, antifloating agents,
thixotropic agents, and dispersing auxiliaries in
amounts of from 0 to 10% by weight, preferably
from 0.25 to 7.5% by weight, with particular
preference from 0.5 to 5% by weight, and in
particular from 0.75 to 2.5% by weight.
17. The component as claimed in any of claims 1 to
16, having a melting point of between 50 and
80°C, preferably between 52.5 and 75°C, and in
particular between 55 and 65°C.
-94-

18. A process for producing a particulate detergent
component, which comprises applying a melt
comprising
a) from 10 to 90% by weight of surfactant(s),
b) from 10 to 90% by weight of fatty
substance (s) ,
c) from 0 to 70% by weight of meltable
substance(s) having a melting point above
30°C, and
d) from 0 to 15% by weight of further active
substances and/or auxiliaries
to one or more support materials and shaping the
mixture.
19. The process as claimed in claim 18, wherein the
shaping operation takes place by granulating,
compacting, pelletizing, extruding, or tableting.
20. A process for preparing a prilled detergent
component, which comprises spraying a melt
comprising
a) from 10 to 90% by weight of surfactant(s),
b) from 10 to 90% by weight of fatty
substance (s),
c) from 0 to 70% by weight of meltable
substance(s) having a melting point above 30°C,
and
d) from 0 to 15% by weight of further active
substances and/or auxiliaries
into a cold gas stream.
21. A process for preparing a pelletized detergent
component, which comprises metering a melt
comprising
-95-

a)from 10 to 90% by weight of surfactant(s),
b)from 10 to 90% by weight of fatty
substance(s),
c)from 0 to 70% by weight of meltable
substance(s)having a melting point above 30°C,
and
d)from 0 to 15% by weight of further active
substances and/or auxiliaries
onto cooled pelletizing plates.
22. A process for preparing a particulate detergent
component,which comprises applying a melt
comprising
a)from 10 to 90% by weight of surfactant(s),
b)from 10 to 90% by weight of fatty
substance(s),
c)from 0 to 70% by weight of meltable
substance(s) having a melting point above 30C;
and
d)from 0 to 15% by weight of further active
substances and/or auxiliaries
by spraying or otherwise to a cooling roll,
scraping off the solidified melt, and comminuting
the scrapings if necessary.
23. The use of a particulate detergent component
comprising
a)from 10 to 90% by weight of surfactant(s),
b)from 10 to 90% by weight of fatty
substance(s),
c) from 0 to 70% by weight of meltable
substance(s) having a melting point above 30C,
and
d)from 0 to 15% by weight of further active
substances and/or auxiliaries
-96-

in a detergent for machine dishwashing.
24. A particulate machine dishwashing composition
comprising builders and also, optionally, further
detergent ingredients, said composition
comprising particulate detergent components
comprising, based on their weight,
a) from 10 to 90% by weight of surfactant(s),
b) from 10 to 90% by weight of fatty
substance(s),
c) from 0 to 70% by weight of meltable
substance(s) having a melting point above 30°C,
and
d) from 0 to 15% by weight of further active
substances and/or auxiliaries.
25. The composition as claimed in claim 24,
comprising builders in amounts of from 20 to 80%
by weight, preferably from 25 to 75% by weight,
and in particular from 30 to 70% by weight, based
in each case on the weight of the composition.
26. The composition as claimed in either of claims 24
and 25, further comprising one or more substances
from the groups of the bleaches, bleach
activators, bleaching catalysts, surfactants,
corrosion inhibitors, polymers, dyes, fragrances,
pH modifiers, complexing agents, and enzymes.
27. The composition as claimed in any of claims 24 to
26, comprising the particulate detergent
component in amounts of from 0.5 to 30% by
weight, preferably from 1 to 25% by weight, and
in particular from 3 to 15% by weight, based in
each case on overall composition.
-97-

28. The composition as claimed in any of claims 24 to
27, wherein the particulate detergent component
has particle sizes of between 1 and 40 mm,
preferably between 1.5 and 30 mm, and in
particular between 2 and 20 mm.
29. The composition as claimed in any of claims 24 to
28, having (without taking into account the
particulate detergent component) particle sizes
of between 100 and 3000 µm, preferably between
300 and 2500 µm, and in particular between 400
and 2000 µm.
30. The composition as claimed in any of claims 24 to
29, wherein a dosing unit is welded in a
watersoluble film pouch.
31. A multiphase detergent tablet for machine
dishwashing, comprising builders and also,
optionally, further detergent ingredients,
wherein at least one phase comprises
a) from 10 to 90% by weight of surfactant(s),
b) from 10 to 90% by weight of fatty
substance(s),
c) from 0 to 70% by weight of meltable
substance(s) having a melting point above 30°C,
and
d) from 0 to 15% by weight of further active
substances and/or auxiliaries.
32. The tablet as claimed in claim 31, wherein the
phases have the form of layers and the tablet has
2, 3 or 4 phases.
-98-

33. The tablet as claimed in claim 31, comprising a
base tablet, which has a cavity, and a part
present at least partly in the cavity.
34. The tablet as claimed in claim 33, wherein the
part present in the cavity comprises
a) from 10 to 90% by weight of surfactant(s),
b) from 10 to 90% by weight of fatty
substance(s),
c) from 0 to 70% by weight of meltable
substance(s) having a melting point above 30°C,
and
d) from 0 to 15% by weight of further active
substances and/or auxiliaries.
35. A combination comprising (a) particulate
detergent(s) as claimed in any of claims 24 to 30
and/or (a) detergent tablet(s) as claimed in any
of claims 31 to 34 and a packaging system
containing said detergent and/or said detergent
tablet(s), wherein said packaging system has a
moisture vapor transmission rate of from 0.1
g/m2/day to less than 20 g/m2/day if said
packaging system is stored at 23°C and a relative
equilibrium humidity of 85%.
36. A method of cleaning kitchen- and tableware in a
dishwasher, which comprises placing one or more
particulate detergents as claimed in any of
claims 24 to 30 and/or one or more detergent
tablets as claimed in any of claims 31 to 34 into
the dispensing compartment of the dishwasher and
running a wash program in the course of which the
dispensing compartment opens and the detergent(s)
and/or tablet(s) is or are dissolved.
-99-

37. A method of cleaning kitchen- and tableware in a
dishwasher, which comprises placing one or more
particulate detergents as claimed in any of
claims 24 to 30 and/or one or more detergent
tablets as claimed in any of claims 31 to 34,
with or without a dosing aid, in the washing
compartment of the dishwasher and running a wash
program in the course of which the detergent(s)
and/or the tablets) is or are dissolved.
-100-

Description

Note: Descriptions are shown in the official language in which they were submitted.


CA 02317182 2000-08-31
"Detergent component"
The present invention is situated in the field of
machine dishwashing compositions for customary
domestic dishwashing machines. It relates to detergent
components for use in machine dishwashing compositions
(MDWCs) and also to detergent compositions and
detergent tablets which comprise such components.
The machine cleaning of kitchen- and tableware in
domestic dishwashing machines normally involves a
prewash cycle, a main wash cycle and a rinse cycle,
interrupted by intermediate wash cycles. With the
majority of machines, the prewash cycle may be
selected for highly soiled ware, but is selected by
the user only in exceptional cases, so that in the
majority of machines a main wash cycle, an
intermediate wash cycle with clean water, and a rinse
cycle are conducted. The temperature of the main wash
cycle varies, according to machine type and program
step choice, between 40 and 65°C. In the rinse cycle,
rinse aids are added from a dosing tank within the
machine, these rinse aids normally comprising nonionic
surfactants as their principal constituent. Rinse aids
of this kind are in liquid form and have been widely
described in the prior art. Their primary object is to
prevent lime spots and deposits on the cleaned ware.
Besides water and low-foaming nonionic surfactants,
these rinse aids often also include hydrotropes, pH
modifiers such as citric acid, or scale-inhibiting
polymers.
The reservoir tank within the dishwashing machine has
to be filled up at regular intervals with rinse aid,
one fill being sufficient for from 10 to 50 cycles,
1

CA 02317182 2000-08-31
depending on machine type. If the user forgets to fill
up the tank, then glasses, in particular, acquire
unsightly lime spots and deposits. In the prior art,
therefore, there exist a number of proposals for
integrating a rinse aid into the machine dishwashing
detergent.
For instance, European Patent Application
EP-A-0 851 024 (Unilever) describes two-layer
detergent tablets whose first layer comprises peroxy
bleach, builder and enzyme while the second layer
comprises acidifiers, a continuous medium having a
melting point of between 55 and 70°C and scale
inhibitors. It is intended that the high-melting
continuous medium will effect retarded release of the
acids) and scale inhibitors) to produce a rinse aid
effect. This document makes no mention of powder-form
machine dishwashing compositions or rinse aid systems
comprising surfactant.
The prior German Patent Application DE 198 51 426.3
(Henkel KGaA) describes a process for producing
multiphase detergent tablets which comprises
compressing a particulate premix into tablets which
have a depression, which is subsequently filled with a
separately prepared melt comprising a meltable
substance and one or more active substances suspended
or dispersed therein. The teaching of this document is
also tied to the tablet commercial form.
The melt suspensions or melt emulsions disclosed in
the last-mentioned document, however, especially when
surfactants are incorporated as an active substance,
have a long-term stability which is in need of
improvement. After the emulsion has cooled, the
2

CA 02317182 2000-08-31
meltable substances are supposed to enclose the active
substance and protect it against premature release. If
the emulsion is not sufficiently stable, it undergoes
partial separation in the melted state prior to
dosing, leading to dosing inaccuracies. Slightly more
stable emulsions can be dosed but undergo partial
separation prior to solidification, so that the active
substance is released early on in the cleaning
operation.
It is an object of the present invention to provide
mixtures which possess long-term stability, which have
no propensity to separate in the course of dosing and
cooling and which, accordingly, give effective and
stable detergent components. It ought to be possible
to forego the addition of stabilizers. With particular
preference, the intention is to provide a single-phase
formulation which is no longer able to show any
propensity to separate. These long-term stable
mixtures and the detergent components prepared from
them ought to make it possible to utilize all known
advantages of the controlled release of ingredients,
especially a rinse aid effect, both for powder-form
detergents and for detergent tablets.
It has now been found that separation-stable melts may
be prepared from meltable substances having melting
points above 30°C, surfactants) and, optionally,
further ingredients such as emulsifiers, dyes and
fragrances, etc., if these mixtures contain at least
10~ by weight of fatty substance(s). Depending on the
nature of the surfactants and further active
substances and auxiliaries used, they may also be
prepared in single-phase form.
3

CA 02317182 2000-08-31
The melting point of such mixtures may be tailored to
the desired value by the nature and amount of the
individual ingredients, in particular by way of the
melting points and amounts of meltable substances)
and fatty substance(s). Above the melting point, the
mixtures are stable toward separation; below the
melting point there exist solidified mixtures in any
desired shape, which in the context of the present
specification are referred to as detergent components.
The present invention provides a detergent component
comprising
a) from 10 to 90~ by weight of surfactant(s),
b) from 10 to 90~ by weight of fatty
substance(s),
c) from 0 to 70~ by weight of meltable
substances) having a melting point of more
than 30°C, and
d) from 0 to 15~ by weight of further active
substances and/or auxiliaries.
In the context of the present application, the term
"detergent component" denotes solidified mixtures of
the ingredients a) to d), irrespective of their shape.
"Detergent components" in the sense of the present
application therefore include, for example, flakes,
prills, pellets, tablet regions, tablets per se, etc.
Preferred detergent components comprise as ingredient
a) from 15 to 80, preferably from 20 to 70, with
particular preference from 25 to 60, and in particular
from 30 to 50~ by weight of surfactant(s). All
surfactants from the groups of the anionic, nonionic,
cationic, and amphoteric surfactants may be used,
preferred detergent components comprising as
4

CA 02317182 2000-08-31
ingredient a) anionic and/or nonionic surfactant(s),
preferably nonionic surfactant(s).
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 Clz-la monoolefins
having 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-is alkanes, for example, by
sulfochlorination or sulfoxidation with subsequent
hydrolysis or neutralization, respectively. Likewise
suitable, in addition, are the esters of a-sulfo fatty
acids (ester sulfonates), e.g., the a-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.
5

CA 02317182 2000-08-31
Preferred alk(en)yl sulfates are the alkali metal
salts, and especially the sodium salts, of the
sulfuric monoesters of Clz-C18 fatty alcohols, examples
being those of coconut fatty alcohol, tallow fatty
alcohol, lauryl, myristyl, cetyl or stearyl alcohol,
or of Clo-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-Cis alkyl sulfates and Clz-Cls alkyl sulfates,
and also C14-Cls alkyl sulfates, are preferred. In
addition, 2,3-alkyl sulfates, which may be 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 C7_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-le 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.
6

CA 02317182 2000-08-31
Preferred sulfosuccinates comprise C$_18 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 having
preferably 8 to 18 carbon atoms in the alk(en)yl
chain, or salts thereof.
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.
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
7

CA 02317182 2000-08-31
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-14 alcohols containing 3 EO or
4 EO, C9_11 alcohol containing 7 EO, C13-is alcohols
containing 3 EO, 5 E0, 7 EO or 8 E0, Clz-la alcohols
containing 3 EO, 5 EO or 7 EO, and mixtures thereof,
such as 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 (narrow 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.
As further nonionic surfactants, furthermore, use may
also be made of alkyl glycosides of the general
formula RO(G)X, where R is a primary straight-chain or
methyl-branched aliphatic radical, especially an
aliphatic radical methyl-branched in position 2,
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
oligomerization, x, which indicates the distribution
of monoglycosides and oligoglycosides, is any desired
8

CA 02317182 2000-08-31
number between 1 and 10; preferably, x is from 1.2 to
1.4.
A further class of nonionic surfactants used with
preference, which are 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 having 1 to 4 carbon atoms in the
alkyl chain, especially fatty acid methyl esters.
Nonionic surfactants of the amine oxide type, examples
being N-cocoalkyl-N,N-dimethylamine oxide and
N-tallowalkyl-N,N-dihydroxyethylamine oxide, and of
the fatty acid alkanolamide type, may 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] (r) ,
where RCO is an aliphatic acyl radical having 6 to 22
carbon atoms, R1 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 carbon atoms and from 3 to 10 hydroxyl
groups. The polyhydroxy fatty acid amides are known
substances which are customarily obtainable by
9

CA 02317182 2000-08-31
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 _a_R2
R-CO-N-[Z] (II) ,
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 Rz is a linear,
branched or cyclic alkyl radical or an aryl radical or
an oxyalkyl radical having 1 to 8 carbon atoms,
preference being given to C1_4 alkyl radicals or phenyl
radicals, and [Z] is a linear polyhydroxyalkyl radical
whose alkyl chain is substituted by at least two
hydroxyl 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 be converted to
the desired polyhydroxy fatty acid amides by reaction
with fatty acid methyl esters in the presence of an
alkoxide as catalyst.

CA 02317182 2000-08-31
Preferred surfactants used are low-foaming nonionic
surfactants. With particular preference, the detergent
components of the invention for machine dishwashing
comprise nonionic surfactants, especially nonionic
surfactants from the group of the alkoxylated
alcohols. 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, Cia-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, Cla-ie alcohols containing 3 EO, 5 EO or 7
EO, and mixtures thereof, such as mixtures of Cla-i4
alcohol containing 3 EO and Cla-is alcohol containing
5 EO. The stated degrees of ethoxylation represent
statistical mean value, which for a specific product
may be an integer or a fraction. Preferred alcohol
ethoxylates have a narrowed homolog distribution
(narrow 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.
11

CA 02317182 2000-08-31
Especially preferred detergent components of the
invention are those that comprise a nonionic
surfactant having a melting point above room
temperature. Accordingly, preferred detergent
components comprise as ingredient a) nonionic
surfactants) having a melting point above 20°C,
preferably above 25°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
(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
12

CA 02317182 2000-08-31
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 (Cls-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" (see
above) are particularly preferred.
Accordingly, particularly preferred detergent
components of the invention comprise as ingredient a)
ethoxylated nonionic surfactant (s) obtained from Cs_zo
monohydroxyalkanols or Cs_zo alkylphenols or Cls-zo fatty
alcohols and 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 25~ 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. The alcohol or alkylphenol moiety of such
nonionic surfactant molecules in this case makes up
13

CA 02317182 2000-08-31
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 molar mass of
such nonionic surfactants. Preferred detergent
components comprise as ingredient a) 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 the company Olin Chemicals.
Further preferred detergent components of the
invention comprise as ingredient a) nonionic
surfactants of the formula
R10 [CHzCH (CH3) O] X [CHZCH20] y [CH2CH (OH) R2]
14

CA 02317182 2000-08-31
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
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 [CH2CH (R3) O] X [CH2] kCH (OH) [CH2] ~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 RZ 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

CA 02317182 2000-08-31
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 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 - 1, thereby simplifying the above
formula to
R10 [CHZCH (R3) O] XCHZCH (OH) CH20Rz .
In the last-mentioned formula, Rl, R2 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 R2 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 detergent components of the invention
comprising as ingredient a) endgroup-capped poly(oxy-
alkylated) nonionic surfactants of the formula
R10 [CH2CH (R3) 0] 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
16

CA 02317182 2000-08-31
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] XCHzCH (OH) CHZORZ
where x is from 1 to 30, preferably from 1 to 20, and
in particular from 6 to 18.
As ingredient b), the detergent components of the
invention comprise one or more fatty substances, with
preferred detergent components comprising as
ingredient b) from 12.5 to 85, preferably from 15 to
80, with particular preference from 17.5 to 75, and in
particular from 20 to 70~ by weight of fatty
substance ( s ) .
In the context of this specification, fatty substances
b) are substances which at standard temperature (20°C)
are liquid to solid and come from the group of the
fatty alcohols, fatty acids and fatty acid
derivatives, especially the fatty acid esters.
Reaction products of fatty alcohols with alkylene
oxides, and the salts of fatty acids, are included for
the purposes of the present specification among the
surfactants (see above) and are not fatty substances
in the sense of the invention. Fatty substances which
may be used with preference in accordance with the
invention are fatty alcohols and fatty alcohol
mixtures, fatty acids and fatty acid mixtures, fatty
acid esters with alkanols and/or diols and/or polyols,
fatty acid amides, fatty amines, etc.
17

CA 02317182 2000-08-31
Preferred detergent components comprise as ingredient
b) one or more substances from the groups of the fatty
alcohols, fatty acids, and fatty esters.
Fatty alcohols used are, for example, the alcohols
obtainable from natural fats and oils: 1-hexanol
(caproyl alcohol), 1-heptanol (enanthyl alcohol),
1-octanol (capryl alcohol), 1-nonanol (pelargonyl
alcohol), 1-decanol (capric alcohol), 1-undecanol,
10-undecen-1-ol, 1-dodecanol (lauryl alcohol), 1-tri-
decanol, 1-tetradecanol (myristyl alcohol), 1-
pentadecanol, 1-hexadecanol (cetyl alcohol), 1-
heptadecanol, 1-octadecanol (stearyl alcohol), 9-cis-
octadecen-1-of (oleyl alcohol), 9-trans-octadecen-1-of
(elaidyl alcohol), 9-cis-octadecene-1,12-diol
(ricinolyl alcohol), all-cis-9,12-octadecadien-1-of
(linoleyl alcohol), all-cis-9,12,15-octadecatrien-1-of
(linolenyl alcohol), 1-nonadecanol, 1-eicosanol
(arachidyl alcohol), 9-cis-eicosen-1-of (gadoleyl
alcohol), 5,8,11,14-eicosatetraen-1-ol, 1-
heneicosanol, 1-docosanol (behenyl alcohol), 13-cis-
docosen-1-of (erucyl alcohol), 13-trans-docosen-1-of
(brassidyl alcohol), and mixtures of these alcohols.
In accordance with the invention, guerbet alcohols and
oxo alcohols, for example, C13-is oxo alcohols or
mixtures of Clz-1g alcohols with Cla-14 alcohols can also
be used without problems as fatty substances. However,
it is of course also possible to use alcohol mixtures,
for example those such as the Cls-la alcohols prepared
by Ziegler ethylene polymerization. Specific examples
of alcohols which may be used as component b) are the
alcohols already mentioned above and also lauryl
alcohol, palmityl alcohol and stearyl alcohol, and
mixtures thereof.
18

CA 02317182 2000-08-31
Particularly preferred detergent components of the
invention comprise as ingredient b) one or more Clo-so
fatty alcohols, preferably Cla-a4 fatty alcohols, with
particular preference 1-hexadecanol, 1-octadecanol,
9-cis-octadecen-1-ol, all-cis-9,12-octadecadien-1-ol,
all-cis-9,12,15-octadecatrien-1-ol, 1-docosanol, and
mixtures thereof.
As ingredient b) it is also possible to use fatty
acids. Industrially, these are obtained primarily from
natural fats and oils by hydrolysis. Whereas the
alkaline saponification, conducted as long ago as the
19th century, led directly to the alkali metal salts
(soaps), nowadays only water is used industrially to
cleave the fats into glycerol and the free fatty
acids. Examples of processes employed industrially are
cleavage in an autoclave or continuous high-pressure
cleavage. Carboxylic acids which may be used as fatty
substances in the context of the present invention
are, for example, hexanoic acid (caproic acid),
heptanoic acid (enanthic acid), octanoic acid
(caprylic acid), nonanoic acid (pelargonic acid),
decanoic acid (capric acid), undecanoic acid etc.
Preference is given in the context of the present
invention to the use of fatty acids such as dodecanoic
acid (lauric acid), tetradecanoic acid (myristic
acid), hexadecanoic acid (palmitic acid), octadecanoic
acid (stearic acid), eicosanoic acid (arachidic acid),
docosanoic acid (behenic acid), tetracosanoic acid
(lignoceric acid), hexacosanoic acid (cerotic acid),
triacontanoic acid (melissic acid) and also the
unsaturated species 9c-hexadecenoic acid (palmitoleic
acid), 6c-octadecenoic acid (petroselinic acid), 6t-
octadecenoic acid (petroselaidic acid), 9c-
octadecenoic acid (oleic acid), 9t-octadecenoic acid
19

CA 02317182 2000-08-31
(elaidic acid), 9c,12c-octadecadienoic acid (linoleic
acid), 9t,12t-octadecadienoic acid (linolaidic acid),
and 9c,12c,15c-octadecatrienoic acid (linolenic acid).
Also possible for use, of course, are tridecanoic
acid, pentadecanoic acid, margaric acid, nonadecanoic
acid, erucic acid, eleostearic acid, and arachidonic
acid. For reasons of cost it is preferred to use not
the pure species but rather technical-grade mixtures
of the individual acids as obtainable from fat
cleavage. Such mixtures are, for example, coconut oil
fatty acid (approximately 6% by weight C8, 6% by
weight Clo, 48% by weight C12, 18% by weight C14, 10% by
weight C16, 2% by weight Cls, 8% by weight C18~, 1% by
weight C18~~) , palm kernel oil fatty acid (approximately
4% by weight Ce, 5% by weight Clo, 50% by weight Cla,
15% by weight C14, 7% by weight C16, 2% by weight Cla.
15% by weight C18,, 1% by weight C18") , tallow fatty
acid (approximately 3% by weight C14, 26% by weight
6, 2% by weight C16, , 2% by weight Cl~, 17% by weight
C18, 44% by weight C18~, 3% by weight C18", 1% by weight
C18~~ ~ ) , hardened tallow fatty acid (approximately 2% by
weight C14, 28% by weight C16, 2% by weight Cl~, 63% by
weight C18, 1% by weight Cle, ) , technical-grade oleic
acid (approximately 1% by weight C12, 3% by weight C14,
5% by weight C16, 6% by weight C16, , 1% by weight C1~,
2% by weight Cle, 70% by weight Cla, , 10% by weight Cla~~,
0.5% by weight Cle,~~) , technical-grade palmitic/stearic
acid (approximately 1% by weight C12, 2% by weight C14,
45% by weight C16, 2% by weight Cl~, 47% by weight C18,
1% by weight C18~), and soybean oil fatty acid
(approximately 2% by weight C14, 15% by weight C16, 5%
by weight C18, 25% by weight Cle,, 45% by weight Cl8", 7%
by weight C18~~ ~ ) .

CA 02317182 2000-08-31
As fatty acid esters, use may be made of the esters of
fatty acids with alkanols, diols or polyols, fatty
acid polyol esters being preferred. Suitable fatty
acid polyol esters include monoesters and diesters of
fatty acids with certain polyols. The fatty acids that
are esterified with the polyols are preferably
saturated or unsaturated fatty acids of 12 to 18
carbon atoms, examples being lauric acid, myristic
acid, palmitic acid, and stearic acid, preference
being given to the use of the fatty acid mixtures
obtained industrially, for example, the acid mixtures
derived from coconut oil, palm kernel oil or tallow
fat. In particular, acids or mixture of acids having
16 to 18 carbon atoms, such as tallow fatty acid, for
example, are suitable for esterification with the
polyhydric alcohols. In the context of the present
invention, suitable polyols for esterification with
the aforementioned fatty acids include sorbitol,
trimethylolpropane, neopentyl glycol, ethylene glycol,
polyethylene glycols, glycerol, and polyglycerols.
Preferred embodiments of the present invention provide
for the polyol esterified with fatty acids) to be
glycerol. Accordingly, preference is given to
detergent components of the invention comprising as
ingredient b) one or more fatty substances from the
group consisting of fatty alcohols and fatty acid
glycerides. Particularly preferred detergent
components comprise as component b) a fatty substance
from the group consisting of the fatty alcohols and
fatty acid monoglycerides. Examples of such fatty
substances used with preference are glyceryl
monostearate and glyceryl monopalmitate.
21

CA 02317182 2000-08-31
As their third ingredient, the detergent components of
the invention comprise one or more meltable substances
having a melting point above 30°C, preferred detergent
components being those comprising as ingredient c)
from 0 to 65, preferably from 0 to 60, with particular
preference from 0 to 55, and in particular from 0 to
50~ by weight of meltable substance(s).
The meltable substances used in the detergent
components of the invention are subject to a variety
of requirements, relating on the one hand to the
melting behavior or, respectively, solidification
behavior but on the other hand also to the material
properties of the melt in the solidified state, i.e.,
in the detergent components of the invention. Since
the detergent component is to be durably protected
against ambient influences in transit or storage, the
meltable substance must possess a high stability with
respect, for example, to impacts occurring in the
course of packaging or transport. The meltable
substance should, therefore, have either at least
partially elastic or at least plastic properties, in
order to react by elastic or plastic deformation to
any impact that does occur, and not to become crushed.
The meltable substance should have a melting range
(solidification range) situated within a temperature
range in which other ingredients of the detergent
components of the invention are not exposed to any
excessive thermal load. On the other hand, however,
the melting range must be sufficiently high still to
offer effective protection for the active substances
at least at slightly elevated temperature. In
accordance with the invention, the meltable substances
have a melting point above 30°C, preference being
22

CA 02317182 2000-08-31
given to detergent components comprising only meltable
substances having melting points above 40°C,
preferably above 45°C, and in particular above 50°C.
Particularly preferred detergent components comprise
as ingredient c) one or more substances having a
melting range between 30 and 100°C, preferably between
40 and 80°C, and in particular between 50 and 75°C.
It has proven advantageous for the meltable substance
not to exhibit a sharply defined melting point, as
encountered commonly with pure, crystalline
substances, but instead to have a melting range which
covers, in some cases, several degrees Celsius.
The meltable substance preferably has a melting range
which lies between about 52.5°C and about 80°C. In the
present case that means that the melting range occurs
within the stated temperature interval, and does not
denote the width of the melting range. The width of
the melting range is preferably at least 1°C, more
preferably from about 2 to about 3°C.
The abovementioned properties are in general possessed
by what are called waxes. The term "waxes" is applied
to a range of natural or synthetic substances which
melt without decomposition, generally at above 50°C,
and are of comparatively low viscosity, without
stringing, at just a little above the melting point.
They have a highly temperature-dependent consistency
and solubility.
According to their origin, the waxes are divided into
three groups: the natural waxes, chemically modified
waxes, and the synthetic waxes.
23

CA 02317182 2000-08-31
The natural waxes include, for example, plant waxes
such as candelilla wax, carnauba wax, ,Tapan wax,
esparto grass wax, cork wax, guaruma wax, rice germ
oil wax, sugar cane wax, ouricury wax, or montan wax,
animal waxes such as beeswax, shellac wax, spermaceti,
lanolin (wool wax), or uropygial grease, mineral waxes
such as ceresin or ozokerite (earth wax), or
petrochemical waxes such as petrolatum, paraffin waxes
or microcrystalline waxes.
The chemically modified waxes include, for example,
hard waxes such as montan ester waxes, sassol waxes,
or hydrogenated jojoba waxes.
By synthetic waxes are meant, in general, polyalkylene
waxes or polyalkylene glycol waxes. As ingredient c)
it is also possible to use compounds from other
classes of substance which meet the stated
requirements in terms of softening point. Examples of
synthetic compounds which have proven suitable are
higher esters of phthalic acid, especially
dicyclohexyl phthalate, which is available
commercially under the name Unimoll~ 66 (Bayer AG).
Also suitable are synthetically prepared waxes from
lower carboxylic acids and fatty alcohols, an example
being dimyristyl tartrate, which is available under
the name Cosmacol~ ETLP (Condea).
Preferably, the ingredient c) present in the detergent
components of the invention comprises a paraffin wax
fraction. That means that at least 10~ by weight of
the total meltable substances present, preferably
more, consist of paraffin wax. Particularly suitable
are paraffin wax contents (based on the total meltable
substance) of approximately 12.5 by weight,
24

CA 02317182 2000-08-31
approximately 15~ by weight or approximately 20~ by
weight, even higher proportions, of, for example, more
than 30~ by weight may be particularly preferred. In
one particular embodiment of the invention, the total
amount of the meltable substance used consists
exclusively of paraffin wax.
Relative to the other, natural waxes mentioned,
paraffin waxes have the advantage in the context of
the present invention that in an alkaline detergent
environment there is no hydrolysis of the waxes (as is
to be expected, for example, with the wax esters),
since paraffin wax contains no hydrolyzable groups.
Paraffin waxes consist primarily of alkanes, with
small fractions of isoalkanes and cycloalkanes. The
paraffin for use in accordance with the invention
preferably contains essentially no constituents having
a melting point above 70°C, with particular preference
above 60°C. Below this melting temperature, in the
detergent liquor, fractions of high-melting alkanes in
the paraffin may leave unwanted wax residues on the
surfaces to be cleaned or on the ware to be cleaned.
Wax residues of this kind lead in general to an
unattractive appearance of the cleaned surface and
should therefore be avoided.
Preferred detergent components comprise as ingredient
c) at least one paraffin wax having a melting range of
from 30°C to 65°C.
Preferably, the amount of alkanes, isoalkanes and
cycloalkanes which are solid at ambient temperature
(generally from about 10 to about 30°C) in the
paraffin wax used is as high as possible. The larger

CA 02317182 2000-08-31
the amount of solid wax constituents in a wax at room
temperature, the more useful that wax is in the
context of the present invention. As the proportion of
solid wax constituents increases, there is an increase
in the resistance of the detergent component to
impacts or friction against other surfaces, resulting
in a longer-lasting protection of the active
substances. High proportions of oils or liquid wax
constituents may cause weakening as a result of which
pores are opened and the active substances are exposed
to the ambient influences mentioned at the outset.
In addition to paraffin, the meltable substance may
further comprise one or more of the abovementioned
waxes or waxlike substances. Preferably, the mixture
forming the meltable substance should be such that the
detergent component is at least substantially water-
insoluble. At a temperature of about 30°C, the
solubility in water should not exceed about 10 mg/1
and preferably should be below 5 mg/1.
In any case, however, the material should preferably
have as low a solubility in water as possible, even in
water at elevated temperature, in order as far as
possible to avoid temperature-independent release of
the active substances.
The principle described above is used for the delayed
release of ingredients at a particular point in time
in the cleaning operation and can be employed with
particular advantage if washing is carried out in the
main wash cycle at a relatively low temperature (for
example, 55°C), so that the active substance is not
released from the rinse aid particles until the rinse
cycle at higher temperatures (approximately 70°C).
26

CA 02317182 2000-08-31
The abovementioned principle may, however, also be
inverted, such that the active substance or substances
is or are released from the material not in a retarded
manner but, rather, in an accelerated manner. This may
be simply achieved by using as meltable substances not
dissolution retardants but instead dissolution
accelerants, so that the solidified melt dissolves not
slowly but quickly instead. In contrast to the
dissolution retardants described above, whose
solubility in water is poor, preferred dissolution
accelerants are readily soluble in water. The water-
solubility of the dissolution accelerants may be
increased considerably still further by means of
certain additives, for example, by incorporation of
readily soluble salts or effervescent systems.
Dissolution-accelerated meltable substances of this
kind (with or without additions of further solubility
improvers) lead to rapid release of the enclosed
active substances at the beginning of the cleaning
operation.
Suitable dissolution accelerants, i.e. meltable
substances for the accelerated release of the active
substances from the detergent components, are in
particular the abovementioned synthetic waxes from the
group of polyethylene glycols and polypropylene
glycols, so that preferred detergent components
comprise as ingredient c) at least one substance from
the group of the polyethylene glycols (PEGS) and/or
polypropylene glycols (PPGs).
Polyethylene glycols (abbreviation PEGS) which can be
used in accordance with the invention are polymers of
ethylene glycol which satisfy the general formula III
27

CA 02317182 2000-08-31
H- (O-CHZ-CH2)n-OH (III)
in which n is able to adopt values between 1 (ethylene
glycol) and over 100,000. Critical in assessing
whether a polyethylene glycol may be used in
accordance with the invention is the aggregate state
of the PEG, i.e., the melting point of the PEG must be
above 50°C, so that the monomer (ethylene glycol) and
the lower oligomers where n - 2 to approximately 16
are not suitable for use, since they have a melting
point below 50°C. The polyethylene glycols with higher
molecular masses are polymolecular - that is, they
consist of collectives of macromolecules having
different molecular masses. For polyethylene glycols
there exist various nomenclatures, which can lead to
confusion. It is common in the art to state the
average relative molecular weight after the letters
"PEG", so that "PEG 200" characterizes a polyethylene
glycol having a relative molecular mass of from about
190 to about 210. In accordance with this
nomenclature, the industrially customary polyethylene
glycols PEG 1550, PEG 3000, PEG 4000, and PEG 6000 may
be used with preference in the context of the present
invention.
For cosmetic ingredients a different nomenclature is
used, where the abbreviation PEG is provided with a
hyphen and the hyphen is followed directly by a number
which corresponds to the number n in the
abovementioned formula III. According to this
nomenclature (known as the INCI nomenclature, CTFA
International Cosmetic Ingredient Dictionary and
Handbook, 5th Edition, The Cosmetic, Toiletry and
Fragrance Association, Washington, 1997), for example,
PEG-32, PEG-40, PEG-55, PEG-60, PEG-75, PEG-100,
28

CA 02317182 2000-08-31
PEG-150, and PEG-180 may be used with preference in
accordance with the invention.
Polyethylene glycols are available commercially, for
example, under the trade names Carbowax~ PEG 540
(Union Carbide), Emkapol~ 6000 (ICI Americas),
Lipoxol~ 3000 MED (HTJLS America), Polyglycol~ E-3350
(Dow Chemical), Lutrol~ E4000 (BASF), and the
corresponding trade names with higher numbers.
Polypropylene glycols (abbreviation PPGs) which may be
used in accordance with the invention are polymers of
propylene glycol which satisfy the general formula IV
H-(O-CH-CHZ)"-OH (I~
CHI
in which n may adopt values of between 1 (propylene
glycol) and approximately 1000. As with the above-
described PEGS, critical to the evaluation of whether
a polypropylene glycol may be used in accordance with
the invention is the aggregate state of the PPG, i.e.,
the melting point of the PPG must be above 50°C, so
that the monomer (propylene glycol) and the lower
oligomers where n - 2 to approximately 15 are not
suitable for use since they have a melting point below
30°C.
In addition to the PEGS and PPGs which may be used
with preference as dissolution-accelerated meltable
substances, it is of course also possible to use other
substances provided their solubility in water is
sufficiently high and their melting point is above
30°C.
29

CA 02317182 2000-08-31
The detergent components of the invention may
preferably comprise as ingredient d) further active
substances and/or auxiliaries from the groups of the
dyes, fragrances, antisettling agents, suspension
agents, antifloating agents, thixotropic agents, and
dispersing auxiliaries in amounts of from 0 to 10~ by
weight, preferably from 0.25 to 7.5~ by weight, with
particular preference from 0.5 to 5~ by weight, and in
particular from 0.75 to 2.5~ by weight. While
fragrances and dyes, as customary ingredients of
detergents, are described later on below, the
ingredients specific to the detergent components of
the invention are described in the following text.
At unusually low temperatures, for example, at
temperatures below 0°C, the detergent component of the
invention may be crushed on impact or friction.. In
order to improve the stability at such low
temperatures, additives may be admixed, if desired, to
the meltable substances. Appropriate additives must be
completely miscible with the melted wax, must not
significantly alter the melting range of the meltable
substances, must improve the elasticity of the
detergent component at low temperatures, must not
generally increase the permeability of the detergent
component to water or moisture, and must not increase
the viscosity of the melt to such an extent that
processing is hindered or even made impossible.
Suitable additives which lower the brittleness of a
material consisting essentially of paraffin at low
temperatures are, for example, EVA copolymers,
hydrogenated resin acid methyl esters, polyethylene or
copolymers of ethyl acrylate and 2-ethylhexyl
acrylate.

CA 02317182 2000-08-31
It may also be of advantage to add further additives
to the meltable substance in order, for example, to
prevent premature separation within the mixture. The
antisettling agents which may be used for this
purpose, also referred to as suspension agents, are
known from the prior art, for example from the
manufacture of paints and printing inks. In order to
avoid sedimentation phenomena and concentration
gradients at the transition from the plastic
solidification range to the solid state, examples of
appropriate substances include surface-active
substances, solvent-dispersed waxes, montmorillonites,
organically modified bentonites, (hydrogenated) castor
oil derivatives, soya lecithin, ethylcellulose, low
molecular mass polyamides, metal stearates, calcium
soaps, or hydrophobicized silicas. Further substances
having said effects originate from the groups of the
antifloating agents and the thixotropic agents and may
be designated chemically as silicone oils (dimethyl-
polysiloxanes, methylphenylpolysiloxanes, polyether-
modified methylalkylpolysiloxanes), oligomeric titan-
ates and silanes, polyamines, salts of long-chain
polyamines and polycarboxylic acids, amine/amide-
functional polyesters, and amine/amide-functional
polyacrylates.
Additives from said classes of substance are available
commercially in great diversity. Examples of
commercial products which may be used as additives
with advantage in the context of the process of the
invention are Aerosil~ 200 (pyrogenic silica,
Degussa), Bentone~ SD-1, SD-2, 34, 52 and 57
(bentonite, Rheox), Bentone~ SD-3, 27 and 38
(hectorite, Rheox), Tixogel~ EZ 100 or VP-A
31

CA 02317182 2000-08-31
(organically modified smectite, Sudchemie), Tixogel~
VG, VP and VZ (QAV-loaded montmorillonite, Sudchemie),
Disperbyk~ 161 (block copolymer, Byk-Chemie),
Borchigeri ND (sulfo-free ion exchanger, Borchers),
Ser-Ad~ FA 601 (Servo), Solsperse~ (aromatic
ethoxylate, ICI), Surfynol~ grades (Air Products),
Tamol~ and Triton~ grades (Rohm&Haas), Texaphor 963,
3241 and 3250 (polymers, Henkel), Rilanit~ grades
(Henkel), Thixcin~ E and R (castor oil derivatives,
Rheox), Thixatrol~ ST and GST (castor oil derivatives,
Rheox), Thixatrol~ SR, SR 100, TSR and TSR 100
(polyamide polymers, Rheox), Thixatrol~ 289 (polyester
polymer, Rheox), and the various M-P-A~ grades X,
60-X, 1078-X, 2000-X, and 60-MS (organic compounds,
Rheox) .
Said auxiliaries may be used in varying amounts in the
detergent components of the invention, depending on
the active substance and material used. Customary use
concentrations for the abovementioned antisettling,
antifloating, thixotropic and dispersing agents are
within the range from 0.5 to 8.0~ by weight,
preferably between 1.0 and 5.0~ by weight, and with
particular preference between 1.5 and 3.0~ by weight,
based in each case on the total amount of meltable
substance and active substances.
Particularly preferred emulsifiers in the context of
the present invention are polyglycerol esters,
especially esters of fatty acids with polyglycerols.
These preferred polyglycerol esters can be described
by the general formula V
32

CA 02317182 2000-08-31
R'
HO-[CH2-CH-CH2-O]~ H (V),
in which R1 in each glycerol unit independently of one
another is H or a fatty acyl radical having 8 to
22 carbon atoms, preferably having 12 to 18 carbon
atoms, and n is a number between 2 and 15, preferably
between 3 and 10.
These polyglycerol esters are known and commercially
available in particular with the degrees of
polymerization n = 2, 3, 4, 6 and 10. Since substances
of the stated type also find broad application in
cosmetic formulations, a considerable number of these
substances are also classified in the
INCI nomenclature (CTFA International Cosmetic
Ingredient Dictionary and Handbook, 5th edition, The
Cosmetic, Toiletry and Fragrance Association,
Washington, 1997). This standard work of cosmetology
includes, for example, information under the headings
POLYGLYCERYL-3 BEESWAX, POLYGLYCERYL-3 CETYL ETHER,
POLYGLYCERYL-4 COCOATE, POLYGLYCERYL-10 DECALINOLEATE,
POLYGLYCERYL-10 DECAOLEATE, POLYGLYCERYL-10
DECASTEARATE, POLYGLYCERYL-2 DIISOSTEARATE,
POLYGLYCERYL-3 DIISOSTEARATE, POLYGLYCERYL-10
DIISOSTEARATE, POLYGLYCERYL-2 DIOLEATE, POLYGLYCERYL-3
DIOLEATE, POLYGLYCERYL-6 DIOLEATE, POLYGLYCERYL-10
DIOLEATE, POLYGLYCERYL-3 DISTEARATE, POLYGLYCERYL-6
DISTEARATE, POLYGLYCERYL-10 DISTEARATE,
POLYGLYCERYL-10 HEPTAOLEATE, POLYGLYCERYL-12 HYDROXY-
STEARATE, POLYGLYCERYL-10 HEPTASTEARATE,
POLYGLYCERYL-6 HEXAOLEATE, POLYGLYCERYL-2 ISOSTEARATE,
POLYGLYCERYL-4 ISOSTEARATE, POLYGLYCERYL-6
33

CA 02317182 2000-08-31
ISOSTEARATE, POLYGLYCERYL-10 LAURATE, POLYGLYCERYL
METHACRYLATE, POLYGLYCERYL-10 MYRISTATE,
POLYGLYCERYL-2 OLEATE, POLYGLYCERYL-3 OLEATE,
POLYGLYCERYL-4 OLEATE, POLYGLYCERYL-6 OLEATE,
POLYGLYCERYL-8 OLEATE, POLYGLYCERYL-10 OLEATE,
POLYGLYCERYL-6 PENTAOLEATE, POLYGLYCERYL-10
PENTAOLEATE, POLYGLYCERYL-6 PENTASTEARATE, POLY-
GLYCERYL-10 PENTASTEARATE, POLYGLYCERYL-2 SESQUI-
ISOSTEARATE, POLYGLYCERYL-2 SESQUIOLEATE, POLY-
GLYCERYL-2 STEAR.ATE, POLYGLYCERYL-3 STEARATE, POLY-
GLYCERYL-4 STEARATE, POLYGLYCERYL-8 STEARATE, POLY-
GLYCERYL-10 STEARATE, POLYGLYCERYL-2 TETRAISOSTEARATE,
POLYGLYCERYL-10 TETRAOLEATE, POLYGLYCERYL-2 TETRA-
STEARATE, POLYGLYCERYL-2 TRIISOSTEARATE, POLY-
GLYCERYL-10 TRIOLEATE, POLYGLYCERYL-6 TRISTEARATE. The
commercially available products from various
manufacturers, which are classified in said work under
the above headings, may be used with advantage as
emulsifiers.
A further group of emulsifiers which may be used in
the rinse aid particles of the invention are
substituted silicones which carry side chains that
have been reacted with ethylene oxide and/or propylene
oxide. Such polyoxyalkylenesiloxanes may be described
by the general formula VI
R' R' R'
H3C-Si-O-[Si-O]"-Si-CH; ( V 1),
R' R' R'
in which each radical R1 independently of one another
is -CH3 or a polyoxyethylene or polyoxypropylene group
34

CA 02317182 2000-08-31
- [CH (Rz) -CH2-0] XH, R2 is -H or -CH3, x is a number
between 1 and 100, preferably between 2 and 20, and in
particular below 10, and n indicates the degree of
polymerization of the silicone.
Optionally, said polyoxyalkylenesiloxanes may also be
etherified or esterified on the free OH groups of the
polyoxyethylene and/or polyoxypropylene side chains.
The unetherified and unesterified polymer of dimethyl-
siloxane with polyoxyethylene and/or polyoxypropylene
is referred to in the INCI nomenclature as DIMETHICONE
COPOLYOL and is available commercially under the trade
names Abil~ B (Goldschmidt), Alkasil~ (Rhone-Poulenc),
Silwet~ (Union Carbide) or Belsil~ DMC 6031.
The acetic-acid-esterified DIMETHICONE COPOLYOL
ACETATE (for example, Belsil~ DMC 6032, -33 and -35,
Wacker) and DIMETHICONE COPOLYOL BUTYL ETHER (e. g.,
KF352A, Shin Etsu) are likewise suitable for use as
emulsifiers in the context of the present invention.
In the case of the emulsifiers, as already with the
meltable substances and the other ingredients, they
may be used over a widely varying range. Normally,
emulsifiers of the abovementioned type make up from 1
to 25~ by weight, preferably from 2 to 20~ by weight,
and in particular from 5 to 10~ by weight, of the
weight of the detergent component.
As already mentioned earlier on above, the physical
and chemical properties of the detergent components of
the invention may be varied through a suitable choice
of the ingredients a) to d). If, for example, only
ingredients that are liquid at the melting temperature
of the mixture are used, then it is easy to prepare

CA 02317182 2000-08-31
single-phase mixtures, which are notable for
particular storage stability even in the molten state.
The addition of solids, such as color pigments or
substances having higher melting points, for example,
leads automatically to two-phase mixtures, which,
however, likewise exhibit excellent storage stability
and an extremely low propensity to separate.
Independently of the composition of the detergent
components of the invention, preference is given to
detergent components having a melting point of between
50 and 80°C, preferably between 52.5 and 75°C, and in
particular between 55 and 65°C.
At room temperature, the detergent components of the
invention are solidified mixtures of the
abovementioned ingredients, which may take on any
external form whatsoever. It is also possible to apply
the mixtures in melt form to support materials and so
provide support-based detergent components which
consist at room temperature of support materials) and
a melt solidified on said support materials. Suitable
support materials are all solids which do not soften
at the temperature of the melt and which, furthermore,
have a sufficiently great absorption capacity for the
melt. Particularly preferred support materials are
builders, which are described in detail later on
below.
The present invention additionally provides a process
for preparing particulate detergent components, which
comprises applying a melt comprising
a) from 10 to 90~ by weight of surfactant(s),
b) from 10 to 90~ by weight of fatty
substance(s),
36

CA 02317182 2000-08-31
c) from 0 to 70~ by weight of meltable
substances) having a melting point above
30°C, and
d) from 0 to 15~ by weight of further active
substances and/or auxiliaries
to one or more support materials and shaping the
mixture.
In this process variant, first of all a melt is
prepared, which may include further active substances
and auxiliaries. This melt is applied to a support
material and shaped as a mixture with said support
material.
With the abovementioned preparation process for the
rinse aid particles of the invention, preferred
process variants are those wherein the meltable
substance accounts for from 25 to 85~ by weight,
preferably from 30 to 70~ by weight, and in particular
from 40 to 50~ by weight of the melt.
The application of the melt to the support material
may be conducted in all customary mixing equipment.
The shaping step for the mixture of melt and support
material is likewise not subject to any technical
restriction, so that here as well the skilled worker
is able to select from the processes customary to him
or her. In the course of experiments conducted by the
applicant, processes which have proven preferable are
those wherein the shaping takes place by granulating,
compacting, pelletizing, extruding, or tableting.
The process of the invention embraces the application
of melts comprising the ingredients a) to d) to
support materials. In principle, melt and support
37

CA 02317182 2000-08-31
materials) may be present in varying amounts in the
resultant rinse aid particles. In preferred processes,
the mixture shaped comprises from 5 to 50~ by weight,
preferably from 10 to 45~ by weight, with particular
preference from 15 to 40~ by weight, and in particular
from 20 to 35~ by weight of a melt comprising the
ingredients a) to d), and from 50 to 95~ by weight,
preferably from 55 to 90~ by weight, with particular
preference from 60 to 85~ by weight, and in particular
from 65 to 80~ by weight, of support material(s).
Regarding the ingredients which are used in the
process of the invention and are processed to the
support material-based detergent components of the
invention, the comments made earlier on above apply
analogously.
The detergent components of the invention may also be
formulated without support material, so that they
consist solely of the ingredients a) to d). In this
case, for the preparation of particulate detergent
components of the invention, prilling, pelletizing and
flaking by means of cooling rolls have proven
particularly suitable.
The present invention therefore additionally provides,
in a first embodiment, a process for preparing prilled
detergent components, which comprises spraying a melt
comprising
a) from 10 to 90~ by weight of surfactant(s),
b) from 10 to 90~ by weight of fatty
substance (s) ,
c) from 0 to 70~ by weight of meltable sub
stance s) having a melting point above 30°C,
and
38

CA 02317182 2000-08-31
d) from 0 to 15~ by weight of further active
substances and/or auxiliaries
into a cold gas stream.
The process of the invention, which is referred to for
short as prilling, comprises the production of
granular elements from meltable substances, the melt
comprising the ingredients a) to d) being sprayed in
defined droplet size at the top of a tower,
solidifying in free fall, and being obtained as prill
granules at the base of the tower.
As the cold gas stream it is possible in very general
terms to use all gases, the temperature of the gas
being below the melting temperature of the melt. In
order to avoid long falling sections, use is
frequently made of cooled gases, for example,
supercooled air or even liquid nitrogen, which is
injected through a nozzle into the spray towers.
The particle size of the resulting prills may be
varied by way of the choice of droplet size, with
particle sizes which are easy to realize technically
lying within the range from 0.5 to 2 mm, preferably
around 1 mm.
An alternative process for prilling is pelletizing. A
further embodiment of the present invention therefore
envisages a process for preparing pelletized detergent
components, which comprises metering a melt comprising
a) from 10 to 90~ by weight of surfactant(s),
b) from 10 to 90~ by weight of fatty
substance(s),
39

CA 02317182 2000-08-31
c) from 0 to 70~ by weight of meltable sub-
stance s) having a melting point above 30°C,
and
d) from 0 to 15~ by weight of further active
substances and/or auxiliaries
onto cooled pelletizing plates.
Pelletizing comprises the metering of the melt
comprising the respective ingredients onto a (cooled)
belt or onto rotating, inclined plates which have a
temperature below the melting temperature of the melt
and are preferably cooled to below room temperature.
Here again, process variants may be practiced in which
the pelletizing plates are supercooled. In this case,
however, measures must be taken to counter the con-
densation of atmospheric moisture.
Pelletizing produces relatively large particles, which
in standard industrial processes have sizes of between
2 and 10 mm, preferably between 3 and 6 mm.
As an even more cost-effective variant for producing
particulate detergent components of the stated
composition from melts, the use of cooling rolls is
appropriate. A further subject of the present
invention is therefore a process for preparing
particulate detergent components, which comprises
applying a melt comprising
a) from 10 to 90~ by weight of surfactant(s),
b) from 10 to 90~ by weight of fatty
substance(s),
c) from 0 to 70~ by weight of meltable sub-
stances) having a melting point above 30°C,
and

CA 02317182 2000-08-31
d) from 0 to 15~ by weight of further active
substances and/or auxiliaries
by spraying or otherwise to a cooling roll, scraping
off the solidified melt, and comminuting the scrapings
if necessary.
The use of cooling rolls permits ready establishment
of the desired particle size range, which in this
process of the invention may also be below 1 mm, for
example from 200 to 700 ~.m.
Of course, it is also possible in accordance with the
invention to compress the particulate compositions to
a tablet or a region thereof . This tablet may then be
dosed by the user, for example; alternatively, it may
be added to compositions which are in powder form.
Another possibility is to use the particulate
compositions, especially the prills, pellets or
products from the cooling roll, as a tabletable premix
and to use this in the preparation of multiphase
tablets. Here, compressing then gives, for example,
multilayer tablets of which one layer has the
composition of a conventional detergent tablet, the
other layer the composition of the detergent component
of the invention, which displays its advantageous
nature in this commercial form as well.
Multiphase tablets may also be prepared by producing
tablets having cavities, for example, depressions or
continuous holes, and then filling these cavities with
other tablets. In the present case, it has been found
appropriate for the "base tablet", i.e., the tablet
having a cavity, to possess the composition of a
detergent tablet while the tablet present in the
cavity is a tablet which has been pressed from prills,
41

CA 02317182 2000-08-31
pellets or flakes. The adhesion of the two tablets to
one another may be achieved by adhesive bonding of the
two tablets; alternatively, it is possible to press
the tablets onto or into one another. Also possible is
plugging, where adhesion is brought about by the
geometric design of cavity and filling.
A preferred preparation process is, for example, the
preparation of the tablets by separate preparation
(compressing) of a base tablet a) and a core tablet
b), which is preferably pressed from prills of the
detergent components of the invention, followed by the
joining and the final compression of both parts.
The preparation of tablets from particulate detergent
components of the invention may take place in
accordance with common tableting procedures. These are
described in detail later on below.
The tablets may be produced in predetermined three-
dimensional forms and predetermined sizes. Suitable
three-dimensional forms are virtually any practicable
designs, i.e., for example, bar, rod or ingot form,
cubes, blocks and corresponding three-dimensional
elements having planar side faces, and in particular
cylindrical designs with a circular or oval cross
section. This latter design covers forms ranging from
tablets through to compact cylinders having a height-
to-diameter ratio of more than 1.
The produced tablet may take on any geometric form
whatsoever, with particular preference being given to
concave, convex, biconcave, biconvex, cubic,
tetragonal, orthorhombic, cylindrical, spherical,
cylinder-segmentlike, discoid, tetrahedral, dodeca-
42

CA 02317182 2000-08-31
hedral, octahedral, conical, pyramidal, ellipsoid,
pentagonal, heptagonal and octagonal-prismatic, and
rhombohedral forms. It is also possible to realize
completely irregular outlines such as arrow or animal
forms, trees, clouds, etc. If the produced tablet has
corners and edges, these are preferably rounded off.
As an additional visual differentiation, an embodiment
having rounded corners and beveled (chamfered) edges
is preferred.
The detergent components of the invention may be given
directly to the consumer, who then doses them into the
detergent additionally as required. On the basis of
this additional dosing step, however, apart from the
solid supply form and the addition in the same dosing
draw, the advantages relative to liquid rinse aids
would be minimized. It is therefore preferred to admix
the detergent components of the invention to
particulate machine dishwashing compositions or to
incorporate them into tablets.
The present invention therefore additionally provides
for the use of particulate detergent components
comprising
a) from 10 to 90~ by weight of surfactant(s),
b) from 10 to 90~ by weight of fatty
substance ( s ) ,
c) from 0 to 70~ by weight of meltable sub
stance s) having a melting point above 30°C,
and
d) from 0 to 15~ by weight of further active
substances and/or auxiliaries
in detergents for machine dishwashing.
43

CA 02317182 2000-08-31
These machine dishwashing compositions (MDWCs) may be
liquid or solid, with the solid commercial form being
accorded by far the greatest significance. Solid
machine dishwashing compositions may be supplied to
the consumer as "powder" or as tablets, it being
possible to incorporate the detergent components of
the present invention in both commercial forms.
The present invention further provides a particulate
machine dishwashing composition, comprising builders
and also, optionally, further detergent ingredients,
said composition comprising particulate detergent
components comprising, based on their weight,
a) from 10 to 90~ by weight of surfactant(s),
b) from 10 to 90~ by weight of fatty
substance (s) ,
c) from 0 to 70~ by weight of meltable sub-
stance s) having a melting point above 30°C,
and
d) from 0 to 15~ by weight of further active
substances and/or auxiliaries.
The ingredients of the machine dishwashing
compositions are described hereinbelow. In some cases,
they may also be present as ingredient d) or support
materials in the detergent components of the
invention.
The most important ingredients of machine dishwashing
compositions are builders. The machine dishwashing
detergents of the invention may comprise all of the
builders commonly used in detergents, i.e., in
particular, zeolites, silicates, carbonates, organic
cobuilders, and - where there are no ecological
prejudices against their use - the phosphates as well.
44

CA 02317182 2000-08-31
The builders mentioned below are all suitable as
support materials for the detergent components of the
invention, as set out earlier on above.
Suitable crystalline, layered sodium silicates possess
the general formula NaMSiXOzX+lyH2~, 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
of the formula indicated are those in which M is
sodium and x adopts the value 2 or 3. In particular,
both (3- and b-sodium disilicates NazSizO5~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 possible 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 yield at best one or more maxima of the
scattered X-radiation, having a width of several
degree units of the diffraction angle. However, good
builder properties may result, even particularly good

CA 02317182 2000-08-31
builder properties, if the silicate particles in
electron diffraction experiments yield vague or even
sharp diffraction maxima. The interpretation of this
is that the products 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.
The finely crystalline, synthetic zeolite used,
containing bound water, is preferably zeolite A
and/or P. A particularly preferred zeolite P is
Zeolite MAP~ (commercial product from Crosfield). Also
suitable, however, are zeolite X and also mixtures of
A, X and/or P. Another 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) K2O~A12O3~ (2-2 . 5) Si02~ (3 . 5-5. 5) HzO.
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.
46

CA 02317182 2000-08-31
Of course, the widely known phosphates may also be
used as builder substances provided such a use is not
to be avoided on ecological grounds. Among the large
number of commercially available phosphates, the
alkali metal phosphates, with particular preference
being given to pentasodium and pentapotassium
triphosphate (sodium and potassium tripolyphosphate,
respectively), possess the greatest importance in the
detergents industry.
Alkali metal phosphates is the collective term for the
alkali metal (especially sodium and potassium) salts
of the various phosphoric acids, among which
metaphosphoric acids (HP03)n and orthophosphoric acid
H3P04, in addition to higher-molecular-mass
representatives, may be distinguished. The phosphates
combine a number of advantages: they act as alkali
carriers, prevent limescale deposits on machine
components, and lime encrustations on fabrics, and
additionally contribute to cleaning performance.
Sodium dihydrogen phosphate, NaH2P04, exists as the
dehydrate (density 1.91 g cm-3, melting point 60°) and
as the monohydrate (density 2.04 g cm-3). Both salts
are white powders of very ready solubility in water
which lose the water of crystallization on heating and
undergo conversion at 200°C into the weakly acidic
diphosphate (disodium dihydrogen diphosphate,
Na2H2Pz0~) and at a higher temperature into sodium
trimetaphosphate (Na3P309) and Maddrell's salt (see
below). NaH2P04 reacts acidically; it is formed if
phosphoric acid is adjusted to a pH of 4.5 using
sodium hydroxide solution and the slurry is sprayed.
Potassium dihydrogen phosphate (primary or monobasic
47

CA 02317182 2000-08-31
potassium phosphate, potassium biphosphate, PDP),
KH2PO4, is a white salt with a density of 2.33 g cm-3,
has a melting point of 253° [decomposition with
formation of potassium polyphosphate (KP03)X], and is
readily soluble in water.
Disodium hydrogen phosphate (secondary sodium
phosphate), Na2HP04, is a colorless, crystalline salt
which is very readily soluble in water. It exists in
anhydrous form and with 2 mol (density 2.066 g cm-3,
water loss at 95°), 7 mol (density 1.68 g cm-3, melting
point 48° with loss of 5 Hz0), and 12 mol (density
1.52 g cm-3, melting point 35° with loss of 5 Hz0) of
water, becomes anhydrous at 100°, and if heated more
intensely undergoes transition to the diphosphate
Na4P20~ . Disodium hydrogen phosphate is prepared by
neutralizing phosphoric acid with sodium carbonate
solution using phenolphthalein as indicator.
Dipotassium hydrogen phosphate (secondary or dibasic
potassium phosphate), K2HP04, is an amorphous white
salt which is readily soluble in water.
Trisodium phosphate, tertiary sodium phosphate, Na3P04,
exists as colorless crystals which as the
dodecahydrate have a density of 1.62 g cm-3 and a
melting point of 73-76°C (decomposition), as the
decahydrate (corresponding to 19-20~s P205) have a
melting point of 100°C, and in anhydrous form
(corresponding to 39-40~ P205) have a density of 2.536
g cm-3. Trisodium phosphate is readily soluble in
water, with an alkaline reaction, and is prepared by
evaporative concentration of a solution of precisely
1 mol of disodium phosphate and 1 mol of NaOH.
Tripotassium phosphate (tertiary or tribasic potassium
phosphate), K3POQ, is a white, deliquescent, granular
48

CA 02317182 2000-08-31
powder of density 2.56 g cm-3, has a melting point of
1340°, and is readily soluble in water with an
alkaline reaction. It is produced, for example, when
Thomas slag is heated with charcoal and potassium
sulfate. Despite the relatively high price, the more
readily soluble and therefore highly active potassium
phosphates are frequently preferred in the detergents
industry over the corresponding sodium compounds.
Tetrasodium diphosphate (sodium pyrophosphate),
Na4P207, exists in anhydrous form (density 2.534 g cm-3,
melting point 988°, 880° also reported) and as the
decahydrate (density 1.815-1.836 g cm-3, melting point
94° with loss of water). Both substances are colorless
crystals which dissolve in water with an alkaline
reaction. Na4P207 is formed when disodium phosphate is
heated to > 200° or by reacting phosphoric acid with
sodium carbonate in stoichiometric ratio and
dewatering the solution by spraying. The decahydrate
complexes heavy metal salts and water hardeners and
therefore reduces the hardness of the water. Potassium
diphosphate (potassium pyrophosphate), K4P20~, exists
in the form of the trihydrate and is a colorless,
hygroscopic powder of density 2.33 g cm-3 which is
soluble in water, the pH of the 1~ strength solution
at 25° being 10.4.
Condensation of NaH2P04 or of KH2P04 gives rise to
higher-molecular-mass sodium and potassium phosphates,
among which it is possible to distinguish cyclic
representatives, the sodium and potassium metaphos-
phates, and catenated types, the sodium and potassium
polyphosphates. For the latter in particular a large
number of names are in use: fused or calcined
phosphates, Graham's salt, Kurrol's and Maddrell's
49

CA 02317182 2000-08-31
salt. All higher sodium and potassium phosphates are
referred to collectively as condensed phosphates.
The industrially important pentasodium triphosphate,
Na5P301o (sodium tripolyphosphate), is a
nonhygroscopic, white, water-soluble salt which is
anhydrous or crystallizes with 6 H20 and has the
general formula Na0- [P (O) (ONa) -O] n-Na where n - 3 .
About 17 g of the anhydrous salt dissolve in 100 g of
water at room temperature, about 20 g at 60°, around
32 g at 100°; after heating the solution at 100°C for
two hours, about 8~ orthophosphate and 15~s diphosphate
are produced by hydrolysis. For the preparation of
pentasodium triphosphate, phosphoric acid is reacted
with sodium carbonate solution or sodium hydroxide
solution in stoichiometric ratio and the solution is
dewatered by spraying. In a similar way to Graham's
salt and sodium diphosphate, pentasodium triphosphate
dissolves numerous insoluble metal compounds
(including lime soaps, etc). Pentapotassium
triphosphate, KSP301o (potassium tripolyphosphate), is
commercialized, for example, in the form of a 50~
strength by weight solution (> 23~ P205, 25~ K20) . The
potassium polyphosphates find broad application in the
detergents industry. There also exist sodium potassium
tripolyphosphates, which may likewise be used for the
purposes of the present invention. These are formed,
for example, when sodium trimetaphosphate is
hydrolyzed with KOH:
(NaP03) 3 + 2 KOH ~ Na3KzP301o + H20
They can be used in accordance with the invention in
precisely the same way as sodium tripolyphosphate,
potassium tripolyphosphate, or mixtures of these two;

CA 02317182 2000-08-31
mixtures of sodium tripolyphosphate and sodium
potassium tripolyphosphate, or mixtures of potassium
tripolyphosphate and sodium potassium
tripolyphosphate, or mixtures of sodium
tripolyphosphate and potassium tripolyphosphate and
sodium potassium tripolyphospate, may also be used in
accordance with the invention.
Organic cobuilders which may be used in the machine
dishwashing compositions of the invention are, in
particular, polycarboxylates/polycarboxylic acids,
polymeric polycarboxylates, aspartic acid,
polyacetals, dextrins, further organic cobuilders (see
below), and phosphonates. These classes of substance
are described below.
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 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
51

CA 02317182 2000-08-31
detergents. 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 poly-
carboxylates, for the purposes of this document, 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 this document.
Suitable polymers are, in particular, polyacrylates,
which preferably have a molecular mass of from 2000 to
20,000 g/mol. Owing to their superior solubility,
preference in this group may be given in turn to the
short-chain polyacrylates, which have molecular masses
of from 2000 to 10,000 g/mol, and with particular
preference from 3000 to 5000 g/mol.
52

CA 02317182 2000-08-31
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 of acrylic acid
and from 50 to 10~ by weight of malefic acid. Their
relative molecular mass, based on free acids, is
generally from 2000 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 compositions is
preferably from 0.5 to 20~ 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
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 comprising, as monomers,
salts of acrylic acid and of malefic acid, and also
vinyl alcohol or vinyl alcohol derivatives, or those
comprising, as monomers, salts of acrylic acid and of
2-alkylallylsulfonic acid, and also sugar derivatives.
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
53

CA 02317182 2000-08-31
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 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. 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 maltodextrins having a DE
of between 3 and 20 and dried glucose syrups having a
54

CA 02317182 2000-08-31
DE of between 20 and 37, and also so-called yellow
dextrins and white dextrins having higher molecular
masses, in the range from 2000 to 30,000 g/mol.
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. 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) 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. Suitable use amounts in
formulations containing zeolite and/or silicate are
from 3 to 15~ by weight.
Examples of further useful organic cobuilders are
acetylated hydroxy carboxylic acids and their salts,
which may also, if desired, 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.
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

CA 02317182 2000-08-31
salt giving an alkaline (pH 9) reaction. Suitable
aminoalkanephosphonates are preferably
ethylenediaminetetramethylenephosphonate (EDTMP),
diethylenetriaminepentamethylenephosphonate (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 compositions also contain bleach, it may be
preferred to use aminoalkanephosphonates, expecially
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.
Preferred particulate machine dishwashing compositions
of the invention comprise builders in amounts of from
20 to 80~ by weight, preferably from 25 to 75~ by
weight, and in particular from 30 to 70~s by weight,
based in each case on the weight of the composition.
Important ingredients of detergents in addition to the
builders are, in particular, substances from the
groups of the surfactants, bleaches, bleach
activators, enzymes, polymers, fragrances, and dyes.
Important representatives from the aforementioned
classes of substance are described below, reference
being made to the remarks earlier on above in respect
of the description of the surfactants.
56

CA 02317182 2000-08-31
Preferred particulate machine dishwashing compositions
further comprise one or more substances from the
groups of the bleaches, bleach activators, bleaching
catalysts, surfactants, corrosion inhibitors,
polymers, dyes, fragrances, pH modifiers, complexing
agents, and enzymes.
Among the compounds used as bleaches which yield H202
in water, particular importance is possessed by sodium
percarbonate. Examples of further bleaches which may
be used are sodium perborate tetrahydrate and sodium
perborate monohydrate, peroxy pyrophosphates, citrate
perhydrates, and also H2O2-donating peracidic salts or
peracids, such as perbenzoates, peroxophthalates,
diperazelaic acid, phthaloimino peracid, or
diperdodecanedioic acid.
"Sodium percarbonate" is a term used unspecifically
for sodium carbonate peroxohydrates, which strictly
speaking are not "percarbonates" (i.e., salts of
percarbonic acid) but rather hydrogen peroxide adducts
onto sodium carbonate. The commercial product has the
average composition 2 Na2C03~3 HzOz and is thus not a
peroxycarbonate. Sodium percarbonate forms a white,
water-soluble powder of density 2.14 g cm-3 which
breaks down readily into sodium carbonate and oxygen
having a bleaching or oxidizing action.
Sodium carbonate peroxohydrate was first obtained in
1899 by precipitation with ethanol from a solution of
sodium carbonate in hydrogen peroxide, but was
mistakenly regarded as a peroxycarbonate. Only in 1909
was the compound recognized as the hydrogen peroxide
addition compound; nevertheless, the historical name
(sodium percarbonate) has persisted in the art.
57

CA 02317182 2000-08-31
Industrially, sodium percarbonate is produced
predominantly by precipitation from aqueous solution
(known as the wet process). In this process, aqueous
solutions of sodium carbonate and hydrogen peroxide
are combined and the sodium percarbonate is
precipitated by means of salting agents (predominantly
sodium chloride), crystallizing aids (for example
polyphosphates, polyacrylates), and stabilizers (for
example, Mgz+ ions). The precipitated salt, which still
contains from 5 to 12~ by weight of the mother liquor,
is subsequently centrifuged and dried in fluidized-bed
driers at 90°C. The bulk density of the finished
product may vary between 800 and 1200 g/1 according to
the production process. Generally, the percarbonate is
stabilized by an additional coating. Coating
processes, and substances used for the coating, are
amply described in the patent literature.
Fundamentally, it is possible in accordance with the
invention to use all commercially customary
percarbonate types, as supplied, for example, by the
companies Solvay Interox, Degussa, Kemira or Akzo.
Detergents of the invention may also comprise bleaches
from the group of organic bleaches. 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 as
alkylperoxybenzoic acids, but peroxy-a-naphthoic acid
and magnesium monoperphthalate, (b) aliphatic or
substituted aliphatic peroxy acids, such as
peroxylauric acid, peroxystearic acid, s-phthalimido-
58

CA 02317182 2000-08-31
peroxy caproic acid [phthaloiminoperoxyhexanoic acid
(PAP)], o-carboxybenzamidoperoxycaproic acid, N-
nonenylamidoperadipic acid and N-nonenylamido-
persuccinates, and (c) aliphatic and araliphatic
peroxy dicarboxylic acids, such as 1,12-diperoxy
decanedicarboxylic acid, 1,9-diperoxyazelaic acid,
diperoxysebacic acid, diperoxybrassylic acid, the
diperoxyphthalic acids, 2-decyldiperoxybutane-1,4
dioic acid and N,N-terephthaloyldi(6-aminopercaproic
acid) may also be used.
Bleaches in the detergents of the invention for
machine dishwashing may also be substances which
release chlorine or bromine. Among the 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 (DICA) and/or salts
thereof with cations such as potassium and sodium.
Hydantoin compounds, such as 1,3-dichloro-5,5-
dimethylhydantoin, are likewise suitable.
In order to achieve a "post-bleaching" effect, the
abovementioned bleaches may also be introduced into
the machine dishwashing compositions of the invention
in part by way of the detergent components of the
invention, where they represent the ingredient d).
Bleach activators, which boost the action of the
bleaches, are, for example, compounds containing one
or more N-acyl and/or O-acyl groups, such as
substances from the class of the anhydrides, esters,
imides and acylated imidazoles or oximes. Examples are
tetraacetylethylenediamine TAED, tetraacetylmethylene-
59

CA 02317182 2000-08-31
diamine TAMD, and tetraacetylhexylenediamine TAHD, and
also pentaacetylglucose PAG, 1,5-diacetyl-2,2-
dioxohexahydro-1,3,5-triazine DADHT, and isatoic
anhydride ISA.
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-acyl groups of the stated number of carbon
atoms, and/or substituted or unsubstituted benzoyl
groups. Preference is given to polyacylated
alkylenediamines, especially
tetraacetylethylenediamine (TAED), acylated triazine
derivatives, especially 1,5-diacetyl-2,4-dioxohexa-
hydro-1,3,5-triazine (DADHT), acylated glycolurils,
especially tetraacetylglycoluril (TAGU), N-acylimides,
especially N-nonanoylsuccinimide (NOSI), acylated
phenolsulfonates, especially n-nonanoyl- or
isononanoyloxybenzenesulfonate (n- or iso-NOBS),
carboxylic anhydrides, especially phthalic anhydride,
acylated polyhydric alcohols, especially triacetin,
ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydro-
furan, N-methylmorpholiniumacetonitrile methyl sulfate
(MMA), and the enol esters known from German Patent
Applications DE 196 16 693 and DE 196 16 767, and also
acetylated sorbitol and mannitol and/or mixtures
thereof (SORMAN), acylated sugar derivatives,
especially pentaacetylglucose (PAG), pentaacetyl-
fructose, tetraacetylxylose and octaacetyllactose, and
acetylated, optionally N-alkylated glucamine and
gluconolactone, and/or N-acylated lactams, for
example, N-benzoylcaprolactam. Hydrophilically
substituted acylacetals and acyllactams are likewise

CA 02317182 2000-08-31
used with preference. Combinations of conventional
bleach activators may also be used.
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 machine
dishwashing detergents. 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-ammine
complexes.
Preference is given to the use of bleach activators
from the group of polyacylated alkylenediamines,
especially tetraacetylethylenediamine (TAED), N-acyl
imides, especially N-nonanoylsuccinimide (NOSI),
acylated phenolsulfonates, especially n-nonanoyl- or
isononanoyloxybenzenesulfonate (n- or iso-NOBS), N-
methylmorpholiniumacetonitrile methyl sulfate (MMA),
preferably in amounts of up to 10~ by weight, in
particular from 0.1~ by weight to 8~ by weight, more
particularly from 2 to 8~ by weight, and with
particular preference from 2 to 6~ by weight, based on
the overall composition.
Bleach-boosting transition metal complexes, especially
those with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti
and/or Ru, preferably selected from the group of
manganese and/or cobalt salts and/or complexes, with
particular preference from cobalt ammine complexes,
cobalt acetate complexes, cobalt carbonyl complexes,
the chlorides of cobalt or manganese, and manganese
61

CA 02317182 2000-08-31
sulfate, are used in customary amounts, preferably in
an amount of up to 5~ by weight, in particular from
0.0025 by weight to l~s by weight, and with particular
preference from 0.01 by weight to 0.25 by weight,
based in each case on the overall composition. In
specific cases, however, it is also possible to use a
greater amount of bleach activator.
Suitable enzymes in the detergents of the invention
include in particular those from the classes of the
hydrolases such as the proteases, esterases, lipases
or lipolytic enzymes, amylases, glycosyl hydrolases,
and mixtures of said enzymes. All of these hydrolases
contribute to removing stains, such as proteinaceous,
fatty or starchy marks. For bleaching, it is also
possible to use oxidoreductases. Especially suitable
enzymatic active substances are those obtained from
bacterial strains or fungi such as Bacillus subtilis,
Bacillus licheniformis, Streptomyces griseus, Coprinus
cinereus and Humicola insolens, and also from
genetically modified variants thereof. 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 lipolytic enzymes,
or of protease, amylase and lipase or lipolytic
enzymes, or protease, lipase or lipolytic enzymes, but
especially protease and/or lipase-containing mixtures
or mixtures with lipolytic enzymes. Examples of such
lipolytic enzymes are the known cutinases. Peroxidases
or oxidases have also proven suitable in some cases.
The suitable amylases include, in particular, alpha-
amylases, iso-amylases, pullulanases, and pectinases.
62

CA 02317182 2000-08-31
The enzymes may be adsorbed on carrier substances or
embedded in coating substances in order to protect
them against premature decomposition. The proportion
of the enzymes, enzyme mixtures or enzyme granules may
be, for example, from about 0.1 to 5~ by weight,
preferably from 0.5 to about 4.55 by weight.
Dyes and fragrances may be added to the machine
dishwashing compositions of the invention in order to
enhance the esthetic appeal of the products which are
formed and to provide the consumer with not only the
performance but also a visually and sensorially
"typical and unmistakable" product. As perfume oils
and/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,
phenoxyethyl isobutyrate, p-tert-butylcyclohexyl
acetate, linalyl acetate, dimethylbenzylcarbinyl
acetate, phenylethyl acetate, linalyl benzoate, benzyl
formate, ethyl methylphenylglycinate, allyl cyclo-
hexylpropionate, styrallyl propionate, and benzyl
salicylate. The ethers include, for example, benzyl
ethyl ether; the aldehydes include, for example, the
linear alkanals having 8-18 carbon atoms, citral,
citronellal, citronellyloxyacetaldehyde, cyclamen
aldehyde, hydroxycitronellal, lilial and bourgeonal;
the ketones include, for example, the ionones,
a-isomethylionone and methyl cedryl ketone; the
alcohols include anethole, citronellol, eugenol,
geraniol, linalool, phenylethyl alcohol, and
terpineol; the hydrocarbons include primarily the
terpenes such as limonene and pinene. Preference,
however, is given to the use of mixtures of different
63

CA 02317182 2000-08-31
odorants, which together produce an appealing
fragrance note. Such perfume oils may also contain
natural odorant mixtures, as obtainable from plant
sources, examples being pine oil, citrus oil, jasmine
oil, patchouli oil, rose oil or ylang-ylang oil.
Likewise suitable are clary sage oil, camomile 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.
The fragrances may be incorporated directly into the
detergent of the invention; alternatively, it may be
advantageous to apply the fragrances to carriers.
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. Incorporating the dyes as ingredient d)
into the detergent components of the invention is also
possible, and results in a fragrance sensation when
the machine is opened.
In order to enhance the esthetic appeal of the
compositions of the invention, they (or parts thereof)
may be colored with appropriate dyes. Preferred dyes,
whose selection presents no difficulty whatsoever to
the skilled worker, possess a high level of storage
stability and insensitivity to the other ingredients
of the compositions or to light and possess no
' pronounced affinity for the substrates to be treated
with the compositions, such as glass, ceramic, or
plasticware, so as not to stain them.
64

CA 02317182 2000-08-31
The detergents of the invention may include corrosion
inhibitors for protecting the ware or the machine,
with special importance in the field of machine
dishwashing being possessed, in particular, by silver
protectants. The known substances of the prior art may
be used. In general it is possible to use, in
particular, silver protectants selected from the group
consisting of triazoles, benzotriazoles,
bisbenzotriazoles, aminotriazoles,
alkylaminotriazoles, and transition metal salts or
transition metal complexes. Particular preference is
given to the use of benzotriazole and/or
alkylaminotriazole. Frequently encountered in cleaning
formulations, furthermore, are agents containing
active chlorine, which may significantly reduce
corrosion of the silver surface. In chlorine-free
cleaners, use is made in particular of oxygen-
containing and nitrogen-containing organic redox-
active compounds, such as divalent and trivalent
phenols, e.g. hydroquinone, pyrocatechol,
hydroxyhydroquinone, gallic acid, phloroglucinol,
pyrogallol, and derivatives of these classes of
compound. Inorganic compounds in the form of salts and
complexes, such as salts of the metals Mn, Ti, Zr, Hf,
V, Co and Ce, also find frequent application.
Preference is given in this context to the transition
metal salts selected from the group consisting of
manganese and/or cobalt salts and/or complexes, with
particular preference cobalt ammine complexes, cobalt
acetate complexes, cobalt carbonyl complexes, the
chlorides of cobalt or of manganese and manganese
sulfate. Similarly, zinc compounds may be used to
prevent corrosion on the ware.

CA 02317182 2000-08-31
The particulate machine dishwashing compositions of
the invention may comprise the\ detergent components of
the invention in varying amounts, the amount being
higher or lower depending on the composition of the
detergent components and on the desired success.
Preferred particulate machine dishwashing compositions
comprise the particulate detergent component in
amounts of from 0.5 to 30~ by weight, preferably from
1 to 25~ by weight, and in particular from 3 to 15~ by
weight, based in each case on overall composition.
In terms of their composition, the detergent
components of the invention may be designed so that
they dissolve to a minor extent, if at all, in the
main wash cycle (and also in optional prewash cycles).
This ensures that the surfactants are not released
until the rinse cycle, where they develop their
action. In addition to this chemical formulation, a
physical formulation may be necessary depending on the
type of dishwasher, so that the rinse aid particles
are not pumped off in the machine when the water is
changed and hence are no longer available for the
rinse cycle. Standard domestic dishwashers, upstream
of the detergent-liquor pump, which pumps the water or
cleaning solution from the machine after the
individual cleaning cycles, comprise a sieve insert,
intended to prevent clogging of the pump by food
residues. If the user cleans heavily soiled kitchen-
and tableware, then this sieve insert requires regular
cleaning, which is a simple operation owing to the
ease of access and removability. The detergent
components of the invention, then, are preferably
designed in terms of their size and shape such that
they do not pass through the sieve insert of the
dishwasher even after the cleaning cycle, i.e., after
66

CA 02317182 2000-08-31
exposure to agitation in the machine and to the
detergent solution. This ensures that detergent
components are present in the dishwasher in the rinse
cycle, these detergent components releasing the active
substances) under the action of the warmer water and
so bringing the desired rinse effect. Particulate
machine dishwashing compositions that are preferred in
the context of the present invention are those wherein
the particulate detergent component has particle sizes
of between 1 and 40 mm, preferably between 1.5 and 30
mm, and in particular between 2 and 20 mm.
In the dishwashing compositions of the invention, the
detergent components, having the sizes stated above,
may project from the matrix of the other particulate
ingredients; alternatively, the other particles may
likewise have sizes within the stated range, so that,
overall, a detergent is formulated that comprises
large detergent particles and detergent-component
particles. Especially if the detergent components of
the invention are colored, i.e., have red, blue,
green, or yellow color, for example, it is
advantageous for the appearance of the product, i.e.
of the overall detergent, if the detergent components
are visibly larger than the matrix comprising the
particles of the other ingredients of the detergent.
Here, preference is given to inventive particulate
machine dishwashing compositions which (without taking
into account the particulate detergent component) have
particle sizes if between 100 and 3000 ~,m, preferably
between 300 and 2500 ~,m, and in particular between 400
and 2000 Vim.
If the detergents of the invention are formulated as a
powder mixture, then - especially if there are large
67

CA 02317182 2000-08-31
differences between the size of detergent component
and detergent matrix - on the one hand partial
separation may occur when the pack is shaken, and on
the other hand dosing may be different in two
successive washing operations, since the user does not
always automatically dose equal quantities of the
detergent and detergent component. If it is desired
technically to use an identical quantity for each
washing operation, this can be realized by the
packaging - familiar to the skilled worker - of the
compositions of the invention in water-soluble film
bags. The present invention also provides a
particulate machine dishwashing composition wherein
one dose unit is welded in a water-soluble film bag.
By this means, the user need only insert a bag,
containing for example a detergent powder and a
plurality of visually distinctive detergent-component
particles, into the dosing drawer of his or her
dishwasher. This embodiment of the present invention
is therefore a visually attractive alternative to
conventional detergent tablets.
Since the user does not use only particulate
detergents for machine dishwashing, but would also
like to have recourse to tablets, these are further
provided by the present invention. For this purpose,
the melt comprising the ingredients a) to d) may be
formulated as a phase of a tablet, said phase
possessing, for example, the form of layer, corelike
insert, etc.
The present invention thus further provides a
multiphase detergent tablet for machine dishwashing,
comprising builders and also, optionally, further
68

CA 02317182 2000-08-31
detergent ingredients, wherein at least one phase
comprises
a) from 10 to 90~ by weight of surfactant(s),
b) from 10 to 90~ by weight of fatty
substance (s) ,
c) from 0 to 70~ by weight of meltable sub-
stance s) having a melting point above 30°C,
and
d) from 0 to 15~ by weight of further active
substances and/or auxiliaries.
In the context of the present invention, the
individual phases of the tablet may have different
three-dimensional forms. The simplest embodiment is
that of two-layer or multilayer tablets, each layer of
the tablet constituting one phase. In accordance with
the invention, however, it is also possible to prepare
multiphase tablets in which individual phases have the
form of inclusions into (an)other phase(s). In
addition to so-called "ring-core" tablets, possible
examples include laminated tablets or combinations of
the stated embodiments. Examples of multiphase tablets
can be found in the figures of EP-A-055 100 (Jeyes),
which describes toilet cleaning blocks. The most
widespread three-dimensional form in the art at
present for multiphase tablets is the two-layer or
multilayer tablet. In the context of the present
invention, therefore, it is preferred for the phases
of the tablet to have the form of layers and for the
tablet to have 2, 3 or 4 phases.
The tablets of the invention may take on any geometric
form whatsoever, with particular preference being
given to concave, convex, biconcave, biconvex, cubic,
tetragonal, orthorhombic, cylindrical, spherical,
69

CA 02317182 2000-08-31
cylinder-segmentlike, discoid, tetrahedral, dodeca-
hedral, octahedral, conical, pyramidal, ellipsoid,
pentagonal-, heptagonal- and octagonal-prismatic, and
rhombohedral forms. It is also possible to realize
completely irregular outlines such as arrow or animal
forms, trees, clouds, etc. If the tablets of the
invention have corners and edges, these are preferably
rounded off. As an additional visual differentiation,
an embodiment having rounded corners and beveled
(chamfered) edges is preferred.
Instead of the layer structure, it is also possible to
prepare tablets which comprise the detergent component
of the invention in the form of other phases. Here, it
has been found suitable to prepare base tablets which
have one or more cavities, and to insert the melt
comprising ingredients a) to d) of the detergent
component of the invention into the cavity and allow
it to solidify therein. This preparation process
produces preferred ~ multiphase detergent tablets
comprising a base tablet, which has a cavity, and a
part present at least partly in the cavity.
The cavity in the compressed part of such tablets of
the invention may have any form whatsoever. It may go
right through the tablet, i.e., have an opening on
different sides, for example, at the top and bottom
side, of the tablet; alternatively, it may be a cavity
which does not go through the entire tablet, and whose
opening is visible only on one tablet side. The form
of the cavity may also be chosen freely within wide
limits. For reasons of process economy, continuous
holes whose openings are located on opposite faces of
the tablets, and depressions having an opening at one
tablet side, have become established. In preferred

CA 02317182 2000-08-31
detergent tablets, the cavity has the form of a
continuous hole whose openings are located on two
opposite tablet surfaces. The form of a continuous
hole of this kind may be chosen freely, preference
being given to tablets wherein the continuous hole has
circular, ellipsoid, triangular, rectangular, square,
pentagonal, hexagonal, heptagonal or octagonal
horizontal sections. It is also possible to realize
completely irregular hole shapes, such as arrow or
animal forms, trees, clouds, etc. As with the tablets,
preference is given, in the case of angular holes, to
those having rounded corners and edges or having
rounded corners and chamfered edges.
The abovementioned geometric embodiments may be
combined with one another as desired. For instance, it
is just as possible to prepare tablets having a
rectangular or square outline and circular holes as it
is to prepare circular tablets having octagonal holes,
there being no limits on the diversity of possible
combinations. Particular preference is given in this
context to annular tablets, i.e., circular tablets
with a circular hole.
If the aforementioned principle of the hole open at
two opposite tablet sides is reduced to an opening,
depression tablets are obtained. Detergent tablets of
the invention wherein the cavity has the form of a
depression are likewise preferred. With this
embodiment, as with the "hole tablets", the tablets of
the invention may take on any geometric form
whatsoever, with particular preference being given to
concave, convex, biconcave, biconvex, cubic,
tetragonal, orthorhombic, cylindrical, spherical,
cylinder-segmentlike, discoid, tetrahedral,
71

CA 02317182 2000-08-31
dodecahedral, octahedral, conical, pyramidal,
ellipsoid, pentagonal-, heptagonal- and octagonal-
prismatic, and rhombohedral forms. It is also possible
to realize completely irregular outlines such as arrow
or animal forms, trees, clouds, etc. If the tablet has
corners and edges, these are preferably rounded off.
As additional visual differentiation, an embodiment
having rounded corners and beveled (chamfered) edges
is preferred.
The form of the depression may also be chosen freely,
preference being given to tablets in which at least
one depression may take on a concave, convex, cubic,
tetragonal, orthorhombic, cylindrical, spherical,
cylinder-segmentlike, discoid, tetrahedral, dodeca-
hedral, octahedral, conical, pyramidal, ellipsoid,
pentagonal-, heptagonal- and octagonal-prismatic, or
rhombohedral form. It is also possible to realize
completely irregular depression forms, such as arrow
or animal forms, trees, clouds, etc. As with the
tablets, depressions having rounded corners and edges
or having rounded corners and chamfered edges are
preferred.
In the case set out above, the part present at least
partially in the cavity consists solely of ingredients
a) to d) of the detergent components. It is, however,
also possible to introduce support material-based
detergent components into the cavity (cavities). For
reasons of process economy, however, preference is
given to multiphase detergent tablets wherein the part
present in the cavity comprises
a) from 10 to 90~ by weight of surfactant(s),
b) from 10 to 90~ by weight of fatty
substance(s),
72

CA 02317182 2000-08-31
c) from 0 to 70~ by weight of meltable sub-
stance s) having a melting point above 30°C,
and
d) from 0 to 15~ by weight of further active
substances and/or auxiliaries.
The size of the depression or continuous hole in
comparison to the total tablet is guided by the
desired end use of the tablets . Depending on with how
much further active substance the remaining void
volume is to be filled, and on whether a smaller or
larger amount of detergent component is to be present,
the size of the cavity may vary. Irrespective of the
end use, in preferred detergent tablets the volume
ratio of compressed part ("base tablet") to detergent
component is from 2:1 to 100:1, preferably from 3:1 to
80:1, with particular preference from 4:1 to 50:1, and
in particular from 5:1 to 30:1.
Besides the stated volume ratio, it is also possible
to state a mass ratio of the two parts, the two values
correlating to one another by way of the densities of
the base tablet and, respectively, of the detergent
component. Irrespective of the density of the
individual parts, preference is given to detergent
tablets of the invention wherein the weight ratio of
base tablet to detergent component is from 1:1 to
100:1, preferably from 2:1 to 80:1, with particular
preference from 3:1 to 50:1, and in particular from
4:1 to 30:1.
Analogous details may also be given for the surfaces
visible in each case of the base tablet and,
respectively, of the detergent component. Here,
preference is given to detergent tablets wherein the
73

CA 02317182 2000-08-31
outwardly visible surface area of the detergent
component accounts for from 1 to 25~, preferably from
2 to 20~, with particular preference from 3 to 15~,
and in particular from 4 to 10~, of the total surface
area of the tablet.
The detergent component and the base tablet are
preferably colored so as to be visually
distinguishable. In addition to visual
differentiation, performance advantages may be
obtained by virtue of different solubilities of the
different regions of the tablet. Detergent tablets in
which the detergent component dissolves more rapidly
than the base tablet are preferred in accordance with
the invention. By incorporating certain constituents,
on the one hand, it is possible to accelerate
specifically the solubility of the detergent
component; secondly, the release of certain
ingredients from the detergent component may lead to
advantages in the washing or cleaning process.
Preference is also given, of course, to detergent
tablets of the invention wherein the detergent
component dissolves later in the wash program than the
base tablet. Performance advantages from this retarded
release may be achieved, for example, by using a
slower-dissolving detergent component to release
active substances) only in later cycles. Thus in the
case of machine dishwashing, for example, it can be
ensured by means of slower-dissolving detergent
components that further active substances) is(are)
available in the rinse cycle. By means of additional
substances such as nonionic surfactants, acidifiers,
soil release polymers, etc., it is possible in this
way to enhance the rinse results. The incorporation of
74

CA 02317182 2000-08-31
perfume is also readily possible; by means of its
retarded release it is possible in the case of
dishwashers to eliminate the "alkali odor" when the
machine is opened, which is a frequent occurrence. In
relation to the detergent components of the invention,
the acidifier, soil release polymer, etc. ingredients
are in this case ingredients d).
In preferred embodiments of the present invention the
base tablet possesses a high specific weight. The
invention prefers detergent tablets wherein the base
tablet has a density of more than 1000 g dm-3,
preferably more than 1025 g dtri3, with particular
preference more than 1050 g dm-3, and in particular
more than 1100 g dm-3.
In order to facilitate the disintegration of highly
compacted tablets, it is possible to incorporate
disintegration aids, known as tablet disintegrants,
into the tablets in order to reduce the disintegration
times. Tablet disintegrants, or disintegration
accelerators, are understood in accordance with Rompp
(9th Edition, Vol. 6, p. 4440) and Voigt "Lehrbuch der
pharmazeutischen Technologie" [Textbook of
pharmaceutical technology] (6th Edition, 1987, pp.
182-184) to be auxiliaries which ensure the rapid
disintegration of tablets in water or gastric fluid
and the release of the drugs in absorbable form.
These substances increase in volume on ingress of
water, with on the one hand an increase in the
intrinsic volume (swelling) and on the other hand, by
way of the release of gases, the generation of a
pressure which causes the tablets to disintegrate into
smaller particles. Examples of established

CA 02317182 2000-08-31
disintegration aids are carbonate/citric acid systems,
with the use of other organic acids also being
possible. Examples of swelling disintegration aids are
synthetic polymers such as polyvinylpyrrolidone (PVP)
or natural polymers and/or modified natural substances
such as cellulose and starch and their derivatives,
alginates, or casein derivatives.
Preferred detergent tablets contain from 0.5 to 10~ by
weight, preferably from 3 to 7~ by weight, and in
particular from 4 to 6~ by weight, of one or more
disintegration aids, based in each case on the tablet
weight. If only the base tablet comprises
disintegration aids, then these figures are based only
on the weight of the base tablet. If disintegration
aids are incorporated into the detergent components of
the invention, they count as ingredient d).
Preferred disintegrants used in the context of the
present invention are cellulose-based disintegrants
and so preferred detergent tablets comprise a
cellulose-based disintegrant of this kind in amounts
from 0.5 to 10~ by weight, preferably from 3 to 7~ by
weight, and in particular from 4 to 6~ by weight. Pure
cellulose has the formal empirical composition
(CsH~o~s) n and, considered formally, is a (3-1, 4-
polyacetal of cellobiose, which itself is constructed
of two molecules of glucose. Suitable celluloses
consist of from about 500 to 5000 glucose units and,
accordingly, have average molecular masses of from
50,000 to 500,000. Cellulose-based disintegrants which
can be used also include, in the context of the
present invention, cellulose derivatives obtainable by
polymer-analogous reactions from cellulose. Such
chemically modified celluloses include, for example,
76

CA 02317182 2000-08-31
products of esterifications and etherifications in
which hydroxy hydrogen atoms have been substituted.
However, celluloses in which the hydroxy groups have
been replaced by functional groups not attached by an
oxygen atom may also be used as cellulose derivatives.
The group of the cellulose derivatives embraces, for
example, alkali metal celluloses,
carboxymethylcellulose (CMC), cellulose esters and
cellulose ethers and aminocelluloses. Said cellulose
derivatives are preferably not used alone as
cellulose-based disintegrants but instead are used in
a mixture with cellulose. The cellulose derivative
content of these mixtures is preferably less than 50~
by weight, with particular preference less than 20~ by
weight, based on the cellulose-based disintegrant. The
particularly preferred cellulose-based disintegrant
used is pure cellulose, free from cellulose
derivatives.
The cellulose used as disintegration aid is preferably
not used in finely divided form but instead is
converted into a coarser form, for example, by
granulation or compaction, before being admixed to the
premixes intended for compression. Detergent tablets
comprising disintegrants in granular or optionally
cogranulated form are described in German Patent
Applications DE 197 09 991 (Stefan Herzog) and
DE 197 10 254 (Henkel) and in International Patent
Application W098/40463 (Henkel). These documents also
provide further details on the production of
granulated, compacted or cogranulated cellulose
disintegrants. The particle sizes of such
disintegrants are usually above 200 Vim, preferably
between 300 and 1600 ~m to the extent of at least 90~
by weight, and in particular between 400 and 1200 ~m
77

CA 02317182 2000-08-31
to the extent of at least 90~ by weight. The
abovementioned, relatively coarse cellulose-based
disintegration aids, and those described in more
detail in the cited documents, are preferred for use
as disintegration aids in the context of the present
invention and are available commercially, for example,
under the designation Arbocel~ TF-30-HG from the
company Rettenmaier.
As a further cellulose-based disintegrant or as a
constituent of this component it is possible to use
microcrystalline cellulose. This microcrystalline
cellulose is obtained by partial hydrolysis of
celluloses under conditions which attack only the
amorphous regions (approximately 30~ of the total
cellulose mass) of the celluloses and break them up
completely but leave the crystalline regions
(approximately 70~) intact. Subsequent deaggregation
of the microfine celluloses resulting from the
hydrolysis yields the microcrystalline celluloses,
which have primary particle sizes of approximately 5
~m and can be compacted, for example, to granules
having an average particle size of 200 Vim.
Detergent tablets which are preferred in the context
of the present invention further comprise a
disintegration aid, preferably a cellulose-based
disintegration aid, preferably in granular,
cogranulated or compacted form, in amounts of from 0.5
to 10~ by weight, preferably from 3 to 7~ by weight,
and in particular from 4 to 6~ by weight, based in
each case on the tablet weight.
The detergent tablets of the invention may further
comprise, both in the base tablet and in the detergent
78

CA 02317182 2000-08-31
component, a gas-evolving effervescent system. Said
gas-evolving effervescent system may consist of a
single substance which on contact with water releases
a gas. Among these compounds mention may be made, in
particular, of magnesium peroxide, which on contact
with water releases oxygen. Normally, however, the
gas-releasing effervescent system consists in its turn
of at least two constituents which react with one
another and, in so doing, form gas. Although a
multitude of systems which release, for example,
nitrogen, oxygen or hydrogen are conceivable and
practicable here, the effervescent system used in the
detergent tablets of the invention will be selectable
on the basis of both economic and environmental
considerations. Preferred effervescent systems consist
of alkali metal carbonate and/or alkali metal hydrogen
carbonate and of an acidifier apt to release carbon
dioxide from the alkali metal salts in aqueous
solution.
Among the alkali metal carbonates and/or alkali metal
hydrogen carbonates, the sodium and potassium salts
are much preferred over the other salts on grounds of
cost. It is of course not mandatory to use the pure
alkali metal carbonates or alkali metal hydrogen
carbonates in question; rather, mixtures of different
carbonates and hydrogen carbonates may be preferred
from the standpoint of wash technology.
In preferred detergent tablets, the effervescent
system used comprises from 2 to 20~ by weight,
preferably from 3 to 15~ by weight, and in particular
from 5 to lOg by weight, of an alkali metal carbonate
or alkali metal hydrogen carbonate, and from 1 to 15,
preferably from 2 to 12, and in particular from 3 to
79

CA 02317182 2000-08-31
10~ by weight of an acidifier, based in each case on
the total tablet.
As examples of acidifiers which release carbon dioxide
from the alkali metal salts in aqueous solution it is
possible to use boric acid and also alkali metal
hydrogen sulfates, alkali metal dihydrogen phosphates,
and other inorganic salts. Preference is given,
however, to the use of organic acidifiers, with citric
acid being a particularly preferred acidifier.
However, it is also possible, in particular, to use
the other solid mono-, oligo- and polycarboxylic
acids. Preferred among this group, in turn, are
tartaric acid, succinic acid, malonic acid, adipic
acid, malefic acid, fumaric acid, oxalic acid, and
polyacrylic acid. Organic sulfonic acids such as
amidosulfonic acid may likewise be used. A
commercially available acidifier which is likewise
preferred for use in the context of the present
invention is Sokalan~ DCS (trademark of BASF), a
mixture of succinic acid (max. 31~ by weight),
glutaric acid (max. 50~ by weight), and adipic acid
(max. 33~ by weight).
In the context of the present invention, preference is
given to detergent tablets where the acidifier used in
the effervescent system comprises a substance from the
group of the organic di-, tri- and oligocarboxylic
acids, or mixtures thereof.
Following production, the particulate detergents
and/or detergent tablets of the invention, and the
novel detergent components per se, may be packed, the
use of certain packaging systems having proven
particularly useful. The present invention

CA 02317182 2000-08-31
additionally provides a combination comprising (a)
particulate detergents) and/or (a) detergent
tablets) of the invention and a packaging system
containing said detergent and/or said detergent
tablet(s), said packaging system having a moisture
vapor transmission rate of from 0.1 g/m2/day to less
than 20 g/m2/day if said packaging system is stored at
23°C and a relative equilibrium humidity of 85~.
The packaging system of the combination of detergent
component and/or detergent and/or detergent tablets)
and packaging system has, in accordance with the
invention, a moisture vapor transmission rate of from
0.1 g/m2/day to less than 20 g/mz/day when said
packaging system is stored at 23°C and a relative
equilibrium humidity of 85~. These temperature and
humidity conditions are the test conditions specified
in DIN Standard 53122, which allows minimal deviations
(23 ~ 1°C, 85 ~ 2~ relative humidity). The moisture
vapor transmission rate of a given packaging system or
material may be determined in accordance with further
standard methods and is also described, for example,
in ASTM Standard E-96-53T ("Test for measuring water
vapor transmission of materials in sheet form") and in
TAPPI Standard T464 m-45 ("Water vapor permeability of
sheet materials at high temperature and humidity").
The measurement principle of common techniques is
based on the water uptake of anhydrous calcium
chloride which is stored in a container in the
appropriate atmosphere, the container being closed at
the top face with the material to be tested. From the
surface area of the container closed with the material
to be tested (permeation area), the weight gain of the
calcium chloride, and the exposure time, the moisture
vapor transmission rate may be calculated as follows:
81

CA 02317182 2000-08-31
24 ~ 10,000 x
MVTR= A ~-[g/mz /24 h]
Y
where A is the area of the material to be tested in
cm2, x is the weight gain of the calcium chloride in
g, and y is the exposure time in h.
The relative equilibrium humidity, often referred to
as "relative atmospheric humidity", is 855 at 23°C
when the moisture vapor transmission rate is measured
in the context of the present invention. The ability
of air to accommodate water vapor increases with
temperature up to a particular maximum content, the
so-called saturation content, and is specified in
g/m3. For example, 1 m3 of air at 17° is saturated with
14.4 g of water vapor; at a temperature of 11°,
saturation is reached with just 10 g of water vapor.
The relative atmospheric humidity is the ratio,
expressed as a percentage, of the actual water vapor
content to the saturation content at the prevailing
temperature. If, for example, air at 17° contains
12 g/m3 water vapor, then the relative atmospheric
humidity (RH) - (12/14.4) 100 = 83~. If this air is
cooled, then saturation (100 RH) is reached at what
is known as the dew point (in the example: 14°), i.e.,
on further cooling a precipitate is formed in the form
of mist (dew). The humidity is determined
quantitatively using hygrometers and psychrometers.
The relative equilibrium humidity of 85~ at 23°C can
be established precisely, for example, in laboratory
chambers with humidity control, to +/-2~ RH depending
on the type of apparatus. In addition, constant and
well-defined relative atmospheric humidities are
82

CA 02317182 2000-08-31
formed in closed systems at a given temperature over
saturated solutions of certain salts, these humidities
deriving from the phase equilibrium between water
partial pressure, saturated solution, and sediment.
The combinations of the invention may of course in
turn be packaged in secondary packaging, examples
being cardboard packaging or trays, there being no
need to impose further requirements on the secondary
packaging. The secondary packaging, accordingly, is
possible but not necessary.
Packaging systems which are preferred in the context
of the present invention have a moisture vapor
transmission rate of from 0.5 g/mz/day to less than
15 g/m2/day.
Depending on the embodiment of the invention, the
packaging system of the combination of the invention
contains a defined amount of novel detergent
component, a defined amount of a particulate detergent
composition, or one or more detergent tablets. In
accordance with the invention it is preferred either
to design a tablet such that it comprises one
application unit of the detergent, and to package this
tablet individually, or to pack into one packaging
unit the number of tablets which totals one
application unit. In the case of an intended dose of
80 g of detergent, therefore, it is possible in
accordance with the invention to produce and package
individually one detergent tablet weighing 80 g, but
in accordance with the invention it is also possible
to package two detergent tablets each weighing 40 g
into one pack in order to arrive at a combination in
accordance with the invention. This principle can of
83

CA 02317182 2000-08-31
course be extended, so that, in accordance with the
invention, combinations may also comprise three, four,
five or even more detergent tablets in one packaging
unit. Of course, two or more tablets in a pack may
have different compositions. In this way it is
possible to separate certain components spatially from
one another in order, for example, to avoid stability
problems.
The packaging system of the combination of the
invention may consist of a very wide variety of
materials and may adopt any desired external forms.
For reasons of economy and of greater ease of
processing, however, preference is given to packaging
systems in which the packaging material has a low
weight, is easy to process, and is inexpensive. In
combinations which are preferred in accordance with
the invention, the packaging system consists of a bag
or pouch of single-layer or laminated paper and/or
polymer film.
The detergent tablets may be filled unsorted, i.e. as
a loose heap, into a pouch made of said materials. On
esthetic grounds and for the purpose of sorting the
combinations into secondary packaging, however, it is
preferred to fill the detergent tablets individually,
or sorted into groups of two or more, into bags or
pouches. For individual application units of the
detergent tablets which are located in a bag or pouch,
a term which has become established in the art is that
of the "flow pack". Flow packs of this kind may
optionally then - again, preferably sorted - be
packaged into outer packaging, which underscores the
compact commercial form of the tablet.
84

CA 02317182 2000-08-31
The single-layer or laminated paper or polymer film
bags or pouches preferred for use as packaging systems
may be designed in a very wide variety of ways: for
example, as inflated pouches without a center seam or
as pouches with a center seam which are sealed by
means of heat (heat sealing), adhesives, or adhesive
tapes. Single-layer pouch and bag materials include
the known papers, which may if appropriate be
impregnated, and also polymer films, which may if
appropriate be coextruded. Polymer films that can be
used as a packaging system in the context of the
present invention are specified, for example, in Hans
Domininghaus, "Die Kunststoffe and ihre
Eigenschaften", 3rd edition, VDI Verlag, Diisseldorf,
1988, page 193. Figure 111 shown therein also gives
indications of the water vapor permeability of the
materials mentioned.
Combinations which are particularly preferred in the
context of the present invention comprise as packaging
system a bag or pouch of single-layer or laminated
polymer film having a thickness of from 10 to 200 ~,m,
preferably from 20 to 100 Vim, and in particular from
to 50 ~,m.
Although it is possible in addition to the
abovementioned films and papers also to use wax-coated
papers in the form of cardboard packaging as a
packaging system for the detergent tablets, it is
preferred in the context of the present invention for
the packaging system not to comprise any cardboard
boxes made of wax-coated paper. In the context of the
present invention, the term "packaging system" always
relates to the primary packaging of the detergent
component, composition or tablets, i.e., to the

CA 02317182 2000-08-31
packaging whose inner face is in direct contact with
the detergent component, composition or tablet
surface. No requirements whatsoever are imposed on any
optional secondary packaging, so that all customary
materials and systems can be used in this case.
As already mentioned earlier on above, the detergent
components, detergent compositions, or detergent
tablets of the combination in accordance with the
invention comprise further ingredients of detergents,
in varying amounts, depending on their intended use.
Independently of the intended use of the compositions
or tablets, it is preferred in accordance with the
invention for the detergent compositions) or
tablets) to have a relative equilibrium humidity of
less than 30~ at 35°C.
The relative equilibrium humidity of the detergent
compositions or tablets may be determined in
accordance with common methods, the following
procedure having been chosen in the context of the
present investigations: a water-impermeable 1 liter
vessel with a lid which has a closable opening for the
introduction of samples was filled with a total of
300 g of detergent tablets and held at a constant 23°C
for 24 h in order to ensure a uniform temperature of
vessel and substance. The water vapor pressure in the
space above the tablets can then be determined using a
hygrometer (Hygrotest 6100, Testoterm Limited,
England). The water vapor pressure is then measured
every 10 minutes until two successive values show no
deviation (equilibrium humidity). The abovementioned
hygrometer permits direct display of the recorded
values in ~ relative humidity.
86

CA 02317182 2000-08-31
Likewise preferred are embodiments of the combination
in accordance with the invention wherein the packaging
system is of resealable configuration. Combinations
wherein the packaging system has a microperforation
may also be realized with preference in accordance
with the invention.
As mentioned earlier on above, detergent components,
detergent compositions or detergent tablets for
machine dishwashing may be prepared by the processes
of the invention. Accordingly, the present invention
additionally provides a method of cleaning kitchen-
and tableware in a dishwasher, which comprises placing
one or more particulate detergents and/or one or more
detergent tablets of the invention in the dispensing
compartment of the dishwasher and running a wash
program in the course of which the dispensing
compartment opens and the detergents) and/or
tablets) is or are dissolved.
With the cleaning method of the invention as well it
is possible to forego the dispensing compartment and
to place the detergent components and/or detergent
compositions or the tablets) of the invention, for
example, in the cutlery basket. Here again, of course,
the use of a dosing aid, for example, a basket insert
which is placed in the washing compartment, is
possible without problems. Accordingly, the present
invention further provides a method of cleaning
kitchen- and tableware in a dishwasher, which
comprises placing one or more particulate detergents
of the invention and/or one or more detergent tablets
of the invention, with or without a dosing aid, in the
washing compartment of the dishwasher and running a
87

CA 02317182 2000-08-31
wash program in the course of which the detergents)
and/or the tablets) is or are dissolved.
Examples
Melts whose composition is indicated in the table
below were prepared by dry-mixing the particulate
ingredients b) (fatty substance) and c) (meltable
substance), melting them and adding ingredient a)
(surfactant) and also, optionally, adding further
ingredients d).
Table l: Melts [~s by weight]
No. Ingred- Ingred- Ingredient Ingred- Me ting
cent a) ient b) c) ient d) point
Paraffin Cla-as Nonionic
57-60C fatty surfact- Dye [C]
alcohol ant*
I 0 39.5 60 0.5 58.0-62.5
2 0 49.5 50 0.5 58.5-62.5
3 0 59.5 40 0.5 60.0-64.0
4 0 69.5 30 0.5 61.5-64.0
5 49.5 20 30 0.5 55.0-60.5
6 39.5 20 40 0.5 55.0-60.0
7 29.5 20 50 0.5 55.0-60.0
8 39.5 30 30 0.5 57.0-59.5
9 29.5 30 40 0.5 57.0-59.0
10 19.5 30 50 0.5 55.0-58.0
11 29.5 40 30 0.5 57.0-58.5
12 19.5 40 40 0.5 57.0-59.5
13 9.5 40 50 0.5 57.0-60.0
14 19.5 50 30 0.5 58.0-61.5
15 9.5 50 40 0.5 59.0-62.0
88

CA 02317182 2000-08-31
* Poly Tergent SLF-18B-45: alcohol alkoxylate from
Olin Chemicals, softening point 25-45°C
Compositions 1 to 15 of the invention were readily
prillable, pelletizable, or shapable to particles
using cooling rolls. The prills had particle sizes of
between 800 and 1200 Vim, the pellets had sizes of
between 3 and 6 mm, and the particles obtained from
cooling roll treatment possessed an average size of
800 ~,m.
In addition, detergent tablets for machine dishwashing
were prepared which were filled with melts of
compositions 1 to 15 of the invention.
For this purpose, two-layer rectangular tablets were
produced by compressing two different premixes, these
tablets having a depression in the form of a semi-
ellipse. These tablets consisted of 75~ by weight
bottom phase and 25~ by weight top phase. The
composition (in ~ by weight, based on the respective
premix) of the two premixes and thus of the two
different phases of the depression tablets is shown in
the table below:
Premix 1 Premix 2
(bottom phase) (top phase)
Sodium carbonate 32.0 -
Sodium tripolyphosphate 52.0 91.4
Sodium perborate 10.0 -
Tetraacetylethylenediamine 2.5 -
Benzotriazole 1.0 -
C12 fatty alcohol 2.5 -
containing 3 EO
Dye 0.2
89

CA 02317182 2000-08-31
Enzymes 6.0
Perfume 0.4
Silicone oil 2.0
Compositions 1 to 15 of the invention were melted and
poured in a weight ratio of 96 to 4 (amounts in ~s by
weight, based on the tablets after filling) into the
depression tablets. The filled tablets were left to
cool at room temperature and then were packaged
individually.
In comparison with tablets similar in composition but
wherein the ingredients of compositions 1 to 15 of the
invention were added individually to the premix 1 and
compressed together with it, the filled depression
tablets exhibit markedly improved rinse performances.
All of the aforementioned tests were conducted in a
number of commercially customary dishwashers by a
number of individual testers, the tablets being placed
in the dispensing compartment of the machine and a
55°C program being run with the machine loaded. In
none of the tests were additional detergents or rinse
aids employed.
The fillings of the tablets do not dissolve in the
conventional 50/55°C main wash cycle. After the hotter
rinse cycle, there are no residues of compositions 1
to 15 in the dishwasher, i.e., the fillings of the
tablets dissolve without residue in the rinse cycle.

Representative Drawing

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Administrative Status

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Event History

Description Date
Inactive: IPC from MCD 2006-03-12
Inactive: IPC from MCD 2006-03-12
Application Not Reinstated by Deadline 2002-12-04
Inactive: Dead - No reply to Office letter 2002-12-04
Deemed Abandoned - Failure to Respond to Maintenance Fee Notice 2002-09-03
Inactive: Status info is complete as of Log entry date 2002-01-10
Inactive: Abandoned - No reply to Office letter 2001-12-04
Application Published (Open to Public Inspection) 2001-02-28
Inactive: Cover page published 2001-02-27
Amendment Received - Voluntary Amendment 2000-12-07
Inactive: IPC assigned 2000-10-04
Inactive: First IPC assigned 2000-10-04
Inactive: IPC assigned 2000-10-04
Inactive: IPC assigned 2000-10-04
Inactive: IPC assigned 2000-10-04
Inactive: Courtesy letter - Evidence 2000-09-26
Inactive: Filing certificate - No RFE (English) 2000-09-21
Filing Requirements Determined Compliant 2000-09-21
Inactive: Inventor deleted 2000-09-20
Inactive: Inventor deleted 2000-09-20
Inactive: Inventor deleted 2000-09-20
Inactive: Inventor deleted 2000-09-20
Inactive: Inventor deleted 2000-09-20
Inactive: Inventor deleted 2000-09-20
Inactive: Inventor deleted 2000-09-20
Inactive: Inventor deleted 2000-09-20
Application Received - Regular National 2000-09-19

Abandonment History

Abandonment Date Reason Reinstatement Date
2002-09-03

Fee History

Fee Type Anniversary Year Due Date Paid Date
Application fee - standard 2000-08-31
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN
Past Owners on Record
ARND KESSLER
BERND RICHTER
CHRISTIAN NITSCH
JUERGEN HAERER
MATTHIAS SUNDER
PETER SCHMIEDEL
ROLF BAYERSDOERFER
THOMAS HOLDERBAUM
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Description 2000-08-31 90 3,915
Cover Page 2001-02-26 1 26
Claims 2000-08-31 10 318
Abstract 2000-08-31 1 13
Filing Certificate (English) 2000-09-21 1 163
Request for evidence or missing transfer 2001-09-04 1 111
Courtesy - Abandonment Letter (Office letter) 2002-01-08 1 172
Reminder of maintenance fee due 2002-05-01 1 111
Courtesy - Abandonment Letter (Maintenance Fee) 2002-10-01 1 182
Correspondence 2000-09-21 1 15