Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
WO 94125563 PCT/EP94/01330
2162246
PROCESS FOR CONSOLIDATING PARTICULATE SOLIDS AND
CLEANING PRODUCTS THEREFROM
BACKGROUND OF THE INVENTION
Field of the Invention
The invention relates to a process for consolidating beds of particulate
solids that include some water into unitary porous solids. The invention
also relates to various useful cleaning products, especially to textile,
dishwashing, and surface care cleaning products in porous solid form,
which can be made by the process. Still another aspect of the invention
relates to using the novel solid detergents, cleaners, soaps and surface
care products.
A product according to this invention is a "macrosolid", i.e., it is a
unitary solid three dimensional object that is (i) capable, at a minimum,
of reta i n i ng a def i n i to shape and s i ze under the i of 1 uence of the
norma 1
ambient gravitational field at the surface of the earth and of being moved
as a unit by forces exerted at only one end or edge thereof and (ii)
sufficiently large to include within itself at least one hypothetical cube
having a length of 2.5 millimeters (hereinafter often abbreviated "mm") on
each edge. Preferably, with increasing preference in the order given, a
macrosolid product according to the invention is sufficiently large to
include within a single product a hypothetical cube having a length of 5,
6.5, 8.2, 10.0, 12.1, or 13.0 nm on each edge. A macrosolid thus con-
trasts with a conventional granular or powdered sol id material , in which
each unitary particle is normally no more than 2.2 mm in at least one of
its three principal geometric dimensions. (Granular or powdered solid
cleaners are often preferred for domestic use, where the amount of clea-
ning power required often is highly variable from one use of the cleaner
to the next. However, granular or powdered cleaners require the perform-
ance of a separate volume or mass measuring step in order to give re-
producible results and efficient use of the cleaner. Therefore, under in-
dustrial or other conditions where the amount of cleaning power needed
from one use of a cleaner to the next is fairly constant, and/or the value
of time saved is more economically important than the possible waste of
small amounts of cleaner, macrosolid cleaners are generally preferred,
because a worker can quickly select and use some small integral number,
WO 94125563 216 2 2 ~ 5 PCT/EP94/01330
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usually one, of the macrosolid cleaners for each instance of use, without
the need for any more time-consuming measurement step.)
The units of the macrosolid cleaner according to this invention are com-
monly called "tablets" or "blocks", and these terms are used herein for
convenience in description but are not to be understood in and of them-
selves to imply anything about the content, strength, or application of
the particular formulation. Smaller macrosolids on the order of 10 to 50
grams in mass are generally referred to as "tablets" because such rela-
tively small macrosolids often are cylinders with a height Substantially
less than the diameter, while larger macrosolids with masses on the order
of 100 grams (hereinafter often abbreviated "g") to several kilograms
(hereinafter often abbreviated "kg") are generally referred to as
"blocks". Unless explicitly further qualified, however, neither "tablet"
or "block" should be understood herein as having any quantitative implica-
tions.
Discussion of Related Art
Acidic to strongly alkaline cleaners and detergents find wide application
in the form of powders, granulates, tablets, pastes, and blocks. Tablets
and blocks in the prior art have generally been made by pressing of
powdered solids or of paste-like slurries of such solids, or by molding of
molten constituents or of slurries of partially solid constituents in some
liquid that readily fills a mold. Many prior art processes for the
production of solid cleaning products or molded cleaners, for example,
require heating and mixing of the raw materials and/or aqueous solutions
in order to insure homogeneity in the final product. In addition, thicke-
ning, pouring, and cooling of the heated mixtures either alone or with the
use of molds or forms may also be required.
Most conventional prior art techniques for the production of tablets or
molded cleaners suffer from the disadvantage that they require the ad-
dition of certain additional auxiliaries, such as tabletting aids, which
must be added to the cleaning-effective raw materials. These aids are
required in order to stabilize the active ingredients to form a slurry or
paste mixture for further processing such as melting, pouring or being
pressed into the final desired product form. Such auxiliaries add no
cleaning power or other desired properties to the final product, but yet
are often required to enable raw materials to be conveniently pumped or
~aVO 94!25563 216 2 2 4 5 ~T~~4I01330
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otherwise conveyed within a process, or to facilitate heat transfer where
raw materials exhibit different degrees of heat stability. The use of
such auxiliaries may also contribute to delivery and dissolving problems.
The use of tabietting aids also is disadvantageous because it increases
both raw materials and manufacturing costs.
SUMMARY OF THE INVENTION
The development of a process that did not involve increased pressures, or
heating, pumping, pouring, cooling of melts, and the Pike, with the
attendant required steps could potentially streamline the manufacturing
process of solid detergents and cleaners. Moreover, a savings of raw
materials could also be realized if the addition of components that are
required solely for handling or heat stabilization purposes were ~o longer
required. Newer methods have been sought to overcome these disadvantages.
Currently, there is also a desire for higher performance products, which
implies the use of lesser quantities of auxiliaries and therefore greater
quantities of active components in smaller volumes. This gives rise to
what is perceived as a "stronger" product. The result is the tendency to-
wards more concentrated raw materials mixtures which, during the course of
manufacture, may exist as fluids and/or molten streams, with attendant
handling and processing concerns. It would therefore be advantageous to
develop a process for the manufacture of detergent or cleaner products
that demonstrated the required efficacy and featured ease and greater con-
venience in raw material handling and processing. _
The present invention seeks to provide a process
for the formation of solid tablet or block cleaning products directly from
powder or granular raw material mixtures.
The present invention also seeks to provide a process for the
formation of solid tablet or block cleaning products directly from pow-
dered or granular raw material mixtures, which does not require the
application of high pressures usually required to obtain press-form
macrosolids, or the bulk melting of raw material mixtures, and which
accommodates certain useful constituent materials that may be impractical
to use in a melt process because of temperature sensitivity or related
considerations.
WO 94/25563 216 2 2 4 6 PCTIEP9410133U '
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In another aspect the present invention seeks to provide an
alternate process and associated formulations for the production of
macrosolid detergents or cleaners in which the need for non-active ingre-
dients such as ballast, fillers, tabletting aids, and the like is elimina-
ted or at least reduced.
DESCRIPTION OF THE INVENTION
Other than in the operating examples, or where otherwise explicitly indi-
cated, all numbers expressing quantities of ingredients or reaction
conditions used herein are to be understood as modified in all instances
by the term "about" in describing the broadest scope of the invention.
Practice within the numerical limits given, however, is generally pre-
ferred.
Also, unless there is an explicit statement to the contrary, the descrip-
tion below of groups of chemical materials as suitable or preferred for a
particular ingredient according to the invention implies that mixtures of
two or more of the individual group members are equally as suitable or
preferred as the individual members of the group used alone. Furthermore,
the specification of chemical materials in ionic form should be understood
as implying the presence of some counterions as necessary for electrical
neutrality of the total composition. in general, such counter ions should
first be selected to the extent possible from the ionic materials speci-
fied as part of the invention; any remaining counterions needed may
generally be selected freely, except for avoiding any counterions that are
detrimental to the objects of the invention. Also, unless otherwise speci-
fied, figures expressed in terms of "percentu or ":" are to be understood
as percent by weight.
DETAILED SUMMARY OF THE INVENTION
It has surprisingly been discovered that high frequency electromagnetic
energy in the subinfrared range may be utilized for the rapid formation of
macrosolids from a volume of more to less tightly packed powder or
granular raw material(s), when at least part of these raw materials are
WO 94/25563 PCT/EP94/01330
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hydrated, and that this process may be used to produce particularly Nseful
acidic to strongly alkaline cleaners in macrosolid form. An important
feature of the invention is that reusable molds or "receptacle molds" can
be employed to enable the formation of tablets or block macrosolids with
excellent reliability and reproducibility. An advantage of the technique
is that it eliminates the need for forming intermediate bulk molten or
fluid phases and also eliminates the alternative need for high pressure
compression in order to generate the final macrosolid product form. A
further advantage of the invention is that certain components, which
heretofore could not practically be included in tablets produced by the
prior art technique of forming tablets under pressure, may be incorporated
directly into the macrosolids formed.
In this description, the term "cleaneru or "cleaning composition" includes
any substance that can readi ly be used to clean a hard surface or a tex-
tile, and thus includes compositions otherwise known as detergents,
cleaners, all-purpose cleaners, scouring cleaners, pre-soak, and pre-wash
products, whether formulated for domestic, institutional, or industrial
application or for manual or automatic laundry washing and dishwashing,
ware-washing, surface washing, floor care, hard surface cleaning, or the
like in any shape.
The term "hydrated" as used herein is to be understood as qualified impli-
citly, if not explicitly, to mean °hydrated at particular conditions of
temperature, pressure, and relative humidity of the atmosphere to which
exposed or with which in equilibrium", and if these conditions are not
specified explicitly, they are to be understood as those of the ambient
atmosphere in a space within which the temperature is maintained within
the normal range for human comfort, i.e., 18 - 30 ° C, and the relative
humidity is between 5 and 95 %, and further as implying that at least one
of the following characterizations of the material is true: (i) The mater-
ial is a solid including stoichiometrically well characterized water of
hydration or (ii) the material is liquid and/or solid with a definite mea-
surable mass and, if the temperature of the material is raised by a suffi-
cient amount above the reference temperature at which the material is hy-
drated, and/or if the pressure and/or relative humidity of the gaseous
atmosphere to which the material is exposed is lowered by a sufficient
WO 94/25563 PCT/EP94/01330
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amount from that with reference to which the material is hydrated, the
mass of water vapor in the atmosphere to which the material is exposed
will be increased and the mass of the solid and/or liquid formerly hydra-
ted material will decrease by an amount that is not more than 120 %, or
preferably, with increasing preference in the order given, not more than
115, 109, 106, 103 or 101, % of the amount by which the mass of the water
vapor in the gaseous atmosphere to which the formerly hydrated material is
exposed has increased. A combination of an initially anhydrous salt and
liquid water which is temporarily absorbed by the salt, or' even liquid
water itself, can thus be a "hydrated" material as required for certain
embodiments of this invention, but generally at least some solid hydrated
material is preferred.
Normally, the above specified transfer of mass from the solid and/or
liquid hydrated material to a water vapor containing gaseous phase, in
order for the material to be useful in this invention, must occur to a
measurable extent within 24 hours, or, with increasing preference in the
order given, will occur within 8, 5, 2, 1, 0.5, 0.2, 0.09, or 0.005, hours
after a change including at least one of the following conditions: The
temperature is raised by 50° C; the pressure is reduced by 100
millibars;
and/or the relative humidity is reduced by 20 %.
Microwaves, as described in the co-pending '728 application, have frequen-
cies above 300 megahertz (hereinafter often abbreviated as "MHz"), and are
generally regarded as having frequencies in the range of 300 to 300,000
MHz. Microwaves belong to the broader range of electromagnetic radiation
herein referred to as "subinfrared electromagnetic radiation" or "SER",
which have frequencies ranging from 3 to 300,000 MHz. The part of this
portion of the electromagnetic spectrum not occupied by microwaves is
known as the "radio wave [or 'frequency'] range", and has frequencies in
the range of 3 to 300 MHz. Microwaves are therefore very small wavelength
subinfrared waves. According to the present invention, it is possible to
use SER of either range, microwave or radio wave, to form the macrosolids
further described below.
The term "microwave treatment [or 'irradiation']" or "treatment by [or
'irradiation with'] microwaves" as used herein refers to the exposure of a
''VO 94/25563 2 16 2 2 4 6 PCTIEP94/01330
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raw material or mixture thereof to electromagnetic energy of the microwave
region. The term "SER treatment [or 'irradiation']" or "treatment by [or
'irradiation with'] SER" as used herein refers to the exposure of a raw
material or mixture thereof to electromagnetic fields of frequencies from
3 to 300,000 MHz. The words "exposure" or "treatment" in connection with
"SER" or "SER energy" are also to be understood to be generally synonymous
within this context. Where it is necessary to further distinguish between
lower frequency subinfrared electromagnetic energy (i.e., radio waves or
"RW" energy, which is generally understood to mean about 3' to about 300
MHz), and higher frequency subinfrared electromagnetic energy (microwave
range energy or "MW" energy, which is generally understood to mean about
300 to about 300,000 MHz), appropriate distinction will be made within the
text.
Although the permitted radio frequencies vary from country to country, the
most common frequencies for industrial, scientific and medical use ("ISM
bands" ) for radio frequency include 13.56 and 27.12 MHz, whi le those for
microwave frequency are 896 MHz and 2450 MHz.
For almost all non-conductive or dielectric chemical compounds that are
stable at normal ambient temperatures of 18 - 30 °C, SER is
nonionizing,
but it can cause motion of some atoms in a material with respect to other
atoms in the material by migration of ions, rotation of molecules with
dipole moments, or polarization of molecules within the high frequency
electromagnetic field. Exposure to SER does not cause permanent changes
in chemical bonding in such material.
The terms "particles", "particulate matter", and "powder(s)" imply, unless
explicitly stated to the contrary, that the material so described is in
the solid phase. A "bed" of particulate matter means a collection of
particles that, by virtue of mutual physical support among the particles,
and, optionally, between some of the particles and at least part of the
wall or walls of a container for the bed and/or a solid insert within the
bed, has a gross shape that does not change and a size that does not de-
crease by motion of the some of the constituent particles with respect to
others of the constituent particles under the influence of the ambient
WO 94/25563 216 2 2 ~ 6 pCT~~4/0133P
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gravitational force at the surface of the earth, in the absence of any
localized vibration of the bed.
In addition to the solid particles in the bed, there may also be some
liquid raw material in the bed, so long as the volume of liquid relative
to the volume of solid in the bed is not so large as to excessively
faci 1 itate the motion of the sol id particles in the bed with respect to
one another, so as to cause the bed to fail to satisfy the conditions of
having a gross shape and size unchanging under the influence°of gravity
as
specified above.
The container in which a particle bed is present may be as simple as a
flat sheet on which a bed of particles rests, although ordinarily it will
also have walls that offer some lateral support to the particle bed. The
bottom and walls if any of the container may be of any material adequate
to support the particle bed, i.e., not sufficiently porous that the
particles can pass through the it under the influence of gravity and the
pressure of overlying parts of the particle bed.
The material chosen for the container used according to the present inven-
tion may be any SER-compatible and SER-penetrable material and, in those
processes where higher temperatures are achieved, preferably is a material
that is capable of withstanding temperatures up to, e.g., 160° C. For
processes starting from raw material beds containing NaOH in concentra-
tions greater than 75 %, polystyrene or polyethylene molds preferably are
not used because of the danger of melting them. The material chosen for
the container or mold should also be one which can be formed into and
maintain the desired shape throughout repeated use, if such is desired.
Suitable reusable container materials include glass, polyethylene, poly-
propylene, plastic, ceramics, or composites thereof, or any other SER-com-
patible material at the particular temperatures achieved, depending upon
formulation of the starting raw materials. In those instances where the
raw material mixture contains corrosive components, it is preferable to
use a container made of material resistant to the corrosive effect of the
contents. Plastic films, including water soluble films, may be effective-
ly used as one time containers, which can be sealed after formation of the
WO 94125563 ~~ PCT/EP94101330
_g_
macrosolid product within them and serve as a shipping and dispensing
container for the product.
The "bulk volume" of a bed of particulate matter or of a porous solid
means the volume of the smal lest pore- and interstitial space-free sol id
that could be formed by filling all the pores and interstitial spaces of
the bed or porous solid, and the "pore volume" of a particle bed or porous
solid means the total volume required to fill all the pores and intersti-
tial spaces of the bed or porous solid to form such a smallest pore- and
interstitial space-free solid. The "density" of a bed of particulate
matter or of a porous sol id means the ratio of the mass of the total of
solid and liquid phases contained within the bed or porous solid to the
bulk volume of the bed or porous solid.
In one major embodiment, a process according to this invention comprises
steps of
(A) providing a container with walls penetrable by SER and having within
the container a bed of particles of raw material, at least part of
said raw material being a hydrated material; and
(B) irradiating the bed of particles provided in step (A) for a sufficient
time with SER of sufficient energy to cause the
temperature of at least part of said raw material to rise, and subse-
quently discontinuing the irradiation of raw material and cooling, so
as to transform the bed of particles into a macrosolid within said
container, said macrosolid having a bulk volume not greater than 1.20
times, or with increasing preference in the order given, not more than
1.15, 1.11, 1.08, 1.05, 1.03, 1.01, or 1.00 times, the bulk volume of
the particle bed from which it was formed.
It is known that exposure to electromagnetic energy in the microwave range
will cause water molecules to experience an increase in rotational energy,
which may subsequently be imparted to neighboring molecules or ions in the
form of heat. Similarly, electromagnetic energy in the radio wave range
will cause the dipoles within molecules of a susceptible material to try
to orient or align themselves with the electromagnetic field, thus gaining
energy. Because this field typically reverses in excess of 10 million
times a second (or in other words has a frequency of more than 10 MHz),
WO 94125563 PCTIEP9410133('
~16~~,~r6 - to _
internal friction takes place among the molecules, which can subsequently
be imparted to neighboring molecules or ions in the form of heat. Par-
ticle beds processed according to this invention in fact usually become
heated while being irradiated with SER.
The phenomenon of using SER is also known as dielectric heating, which is
distinct from conventional heating. Conventional heating has to be applied
externally and penetrates into a material by conduction. Dielectric
heating, on the other hand, produces heating directly within the material,
because all the molecules of the material are simultaneously exposed to
high frequency electromagnetic fields. Therefore, the "cooling" described
as part of step (B) above normally begins as soon as SER irradiation is
discontinued, and does not normally imply the use of any special cooling
machinery, although such could be used if desired.
For each material, there is a quantitative susceptibility to the heating
effects of high frequency electromagnetic energy, which can be measured as
a function of frequency, and generally varies considerably depending on
the frequency. Every material or material mixture therefore normally has
an optimum frequency at which it is most receptive to SER energy. Theore-
tically, this optimum frequency is the one that should be selected for SER
irradiation.
The amount of energy that a material absorbs at subinfrared electromagnet-
ic frequencies is known as its dielectric loss factor, a", which is the
product of the dielectric constant, e, and loss tangent, tan d. At the
molecular level, the loss tangent can be considered as an indication of
the average "friction" effect contributed by each polarized component, and
is measured as the tangent of the phase angle between the field in the
material and the applied field. Water has a very high loss factor, and is
therefore particularly receptive to dielectric treatment with SER energy.
By way of comparison, the dielectric loss factor for water (0.1 molal
NaCI) is 18 at 3,000 MHz, in the microwave range, but it is 100 at 10 MHz
(in the radio wave range). Most remaining raw materials) of the present
invention generally have much lower loss factors, and therefore will be
relatively little affected by SER irradiation. This provides a useful
limiting mechanism in many situations.
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Scanning electron microscopy ("SEM") studies of macrosolids formed accord-
ing to this invention, particularly those exposed to microwave irradia-
tion, show a "bridgework" structure, in which the originally individual
particles have been joined by sufficiently thick °bridges" to join the
former particle bed into a unitary macrosolid. The macrosolid thus formed
can simultaneously be described both as "hard" and "porous", due to the
presence of interstitial spaces as part of this bridgework structure.
While applicants do not wish to be bound by any particular theory, they
believe that the heat induced in the particle bed during irradiation, per-
haps accompanied by volatilization of some of the water initially present,
causes a localized sintering of hydrated species alone and/or accompanied
by a concomitant temporary dissolution of other species present in the raw
material to form abridges" between the initially separate particles in
substantially single point contact. This bridged-type structure may
account for the surprising strength and structural integrity of the
macrosolids formed during most processes according to the invention.
The application of a process according to this invention to certain kinds
of particle beds produces porous macrosolids with unique combinations of
properties that are valuable in many applications. Accordingly, another
major embodiment of this invention is a macrosolid article having the
following characteristics:
(A) at least one of the following two conditions is satisfied:
(i) at least 30 %, more preferably at least 50 %, or still more pref-
erably at least 60 %, of the mass of the macrosolid article con-
sists of material selected from the group consisting of alkali
metal and alkaline earth metal sulfates (including hydrogen sul-
fates), carbonates (including acid carbonates, also called bicarbo-
nates), silicates, optionally hydrated, the silicates preferably
having a molar ratio of metal oxide to silicon dioxide in the range
from 1.0:1.0 to 1.0:2.5 (thus including metasilicates, disilicates,
and crystalline layered silicates), zeolites, phosphates (including
condensed phosphates such as pyrophosphates and tripolyphosphates),
hydroxides, borates, and citrates, with the alkali metal salts
generally being preferred;
(ii) at least 5 %, or with increasing preference in the order given, at
WO 94/25563 PCT/EP94101330
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least 10, 20, 30, 40, 50, 60, 70, 80, or 90 %, but not more than 98
consists of material selected from the group consisting of
materials satisfying both the following two conditions: (ii.l) the
material is solid at 25° C and (ii.2) a solution of 10 % of the
material in water, or a saturated solution of the material in water
if its solubility is less than 10 %, has a pH at 25° C of not more
than 4, or with increasing preference in the order given, of not
more than 3.5, 3.0, 2.5, 2.0, 1.5, 1.0, 0.5, or 0.1; and if as much
as 10 % of the mass of the macrosolid is made up~ of strongly
alkaline materials, no more than 10 % and preferably no more than 5
of the mass of the macrosol i d i s made up of strong ly ac i d mate-
rials; and if as much as 10 % of the mass of the macrosolid is made
up of strongly acid materials, no more than 10 % and preferably no
more than 5 % of the mass of the macrosolid is made up of strongly
alkaline materials, a material being defined for this purpose as
"strongly alkaline" if a 0.1 N solution of the material in water at
25° C has a pH value of at least 12.0 and being defined as "strong-
ly acid" for this purpose if a 0.1 N solution of the material in
water at 25° C has a pH value of not more than 2.0;
(B) at least half of the mass of the macrosolid consists of chemical
species that are solid at 25° C and are soluble or homogeneously
dispersible in water at 25° C to form solutions containing at least
grams per liter of the dissolved or dispersed solid chemical
species; and
(C) upon immersion at 55° C in a volume of water that is at least ten
times the bulk volume of the macrosolid, the macrosolid dissolves,
disintegrates, or both dissolves and disintegrates, so that no part
of the macrosolid remains in any single undissolved particle having
a largest dimension greater than 2.2 mtn, within a time after
immersion that is not greater than 0.050 minutes, or with increa-
sing preference in the order given, not greater than 0.042, 0.036,
0.031, 0.027, 0.020, or 0.010 minutes, per cubic centimeter of bulk
volume of the macrosolid.
Although, as noted above, both strong acids and strong bases can be
included within the materials of a macrosolid according to this invention,
caution should be exercised during the manufacture of such macrosolids,
WO 94125563 ~~~ PCT/EP94/01330
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because, as a result of conversion of formerly solid acidic and alkaline
materials in the raw materials into partly molten or dissolved phases
during manufacture according to this invention, exothermic neutralization
reaction between materials thus freed to react with each other can cause
unwanted temperature irregularities during the SER processing. A signifi-
cant advantage of a process according to the present invention is that
additional pre-treatment processing steps, such as pre-heating the raw ma-
terial mixtures, fluidizing mixtures, pumping heated fluids, or conti-
nuously sweeping streams of hot air through the microwave or radio wave
treatment chamber, are not required, although it might sometimes be
advantageous. An advantage of the macrosolid tablets and blocks formed ac-
cording to the present invention is that a dissolving or pre-use step is
not required. The macrosolid tablet or block may be introduced directly
into the cleaning space in which the product is ultimately used, especial-
ly in the areas of industrial and household cleaning, and particularly
with respect to laundry and dishwasher applications.
As used herein, the term "cleaning space" is intended to encompass any
space in which there is contact between a solid surface, including a
textile, and a liquid, liquid slurry, or paste cleaning composition with
the result that some soil material, the presence of which is undesired on
the solid surface, is transferred to the cleaning composition. Thus, the
cleaning space may be the tub or interior space of a clothes or dish-
washing machine, a spray zone of an industrial bottle washing machine, a
sink for manual dishwashing, a floor or wall and the space immediately
surrounding the part of it to be cleaned, the exterior surface of a solid
object and the space immediately surrounding the part of the exterior
surface to be cleaned, and the like. In many cases, the cleaning composi-
tion is supplied to the cleaning area from a reservoir, which may be a
stock tank in a washing machine, a spray bottle, a mop bucket, or the
1 ike.
Still another embodiment of the invention is the use of macrosolid clean-
ing products as described above in cleaning any of the wide variety of
materials noted above. In particular, many of the macrosolid cleaner
embodiments of the invention are well suited for use in a dispensing
device and method of use as described in Figures 4 and 6 - 9 and in the
CA 02162246 2004-06-21
-14-
text from column 9 line 47 through column 16 line 31 of U. S. Reissue
Patent 32,763 of October 11, 1988 to Fernholz et al., In particular,
the terms "cast block" and the like in U.S. Re. 32,763 are to be
understood as replaced by "macrosolid cleaner" according to this
invention as described above, or a solid cleaner modified by
imbibition of additional material into a porous macrosolid cleaner
according to this invention as described below.
The porous macrosolids produced according to the invention are also
valuable in another application area. Many cleaners currently on the
market exist in liquid form as concentrates or so-called cleaner
"enhancers" which may contain alcohol or other organic solvents. When
combined with water in a use situation, a number of such cleaners
suffer from such undesirable phenomenon as phase separation and
salting- or settling-out in solution. Other cleaners incorporate
supplemental additives or require formulations with high water
content in order to keep materials in solution during storage,
transportation, etc. One disadvantage in such instances is that it is
costly to transport and provide additional packaging materials for
the larger required product volumes.
Certain attendant disadvantages of existing cleaner products may be
overcome by combining active components just prior to the dissolution
and use of a solid cleaner, such that there is insufficient
opportunity for components to phase separate or fall out of solution.
The macrosolids of the present invention are particularly adaptable to
such an application because, as described briefly above, some of the
macrosolid tablets or blocks formed according to the SER process of
the current invention exhibit remarkably rapid dissolution, or a
combination of dissolution and mechanical disintegration upon exposure
to water. Accordingly, another major embodiment of this invention is a
two-component or dual-pack article comprising, preferably consisting
essentially of, or more preferably consisting of:
(A) a macrosolid according to the invention as described above; and
(B) a liquid component, which may optionally contain dissolved solid
'~'O 94/25563 PCT/EP94/01330
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substances.
In one preferred embodiment of the invention, a macrosolid and a liquid
component are individually added, or combined and then added, to an appro-
priate amount of water to produce the desired cleaning solution for a
particular cleaning application just prior to use. As used herein, the
term "just prior to use" is meant to indicate that after the macrosolid
component and liquid component have been combined with water in prepara-
tion for use, the resulting cleaner is preferably used withih a time that
is not greater than 480 minutes, or with increasing preference in the
order given, not greater than 240, 120, 60, 30, 15, 5, 1, 0.50, 0.25,
0.10, 0.05, 0.025 or 0.01 minutes of the time at which the macrosolid
component and the liquid component are first combined with water.
A particular advantage of the dual-pack product according to the present
invention is that it permits the incorporation of certain liquids and
dissolved solid substances into a liquid phase of a cleaning formulation,
which for practical purposes cannot readily be incorporated into the solid
component. By way of illustration, such substances might include liquid
waxes or silicones, which are desirable in cleaners in the floor care
area, for example.
Description of Preferred Embodiments
Typical hydrated materials suitable for use in a process according to this
invention include materials that contain water of crystallization or
hydration, i.e., water molecules, present in a solid in definite stoichio-
metric ratio to another chemical constituent of the solid, which can be
expelled in whole or in some stoichiometricatly well defined part by
raising the temperature of the solid and/or lowering the amount of water
vapor in the gaseous atmosphere to which the solid is exposed past a
specific threshold value; and materials, such as the alkali metal hydrox-
ides, that, without necessarily having any definite stoichiometric hy-
drates, may contain "free" water molecules) in some more general associ-
ation with the solid in continuously variable amounts down to near zero.
Particular hydrated compounds useful in the practice of this invention in-
clude alkali metal hydroxides, such as sodium hydroxide and potassium
WO 94/25563 216 2 2 4 6 pCT/EP94101330
- 16 -
hydroxide; sulfates, such as magnesium and sodium sulfate; silicates, such
as sodium metasilicate; phosphates, such as sodium tripolyphosphate or
trisodium phosphate; carbonates, such as sodium or potassium carbonate;
bicarbonates, such as sodium or potassium bicarbonate; and borates, such
as sodium borate; etc.
A particularly preferred group of stoichiometrically well characterized
hydrated materials useful in this invention includes sodium metasilicate
pentahydrate (Na2Si03 - 5H20), sodium carbonate decahydrate (Na2C03 '
1OH20), sodium tetraborate tetrahydrate (borax, Na2B407 - 1OH20), (and)
sodium tripolyphosphate hexahydrate (Na5P3010 ' 6H20), trisodium citrat
dihydrate, sodium sulfate decahydrate and disodium hydrogen phosphate
dodecahydrate.
In some applications of the invention, it is preferred to include in the
raw material in the particle bed at least 4 ~s by volume, or with increa-
sing preference in the order given, at least 6, 10, 16, or 25 ~s by volume,
but not more than 35 ~ by volume, of solid material that melts at the
temperature actually reached during irradiation according to processes of
the invention. This readily melted material may or may not be hydrated,
but often is hydrated. For example, it has been observed that borax,
and sodium hydroxide monohydrate all melt readily under microwave
irradiation.
Another type of material that may be either hydrated or unhydrated and is
often advantageously included in the raw material for a process according
to this invention is the type known as crystalline layered silicates. Such
materials are described in U. S. Patent 4,820,439. The entire disclosure
of this patent, to the extent not inconsistent with any explicit statement
herein, is hereby incorporated herein by reference. In brief, crystalline
layered silicates consist essentially only of sodium, silicon, oxygen,
and, optionally hydrogen and are capable of acting as both alkalinizing
agents and builders in cleaning formulations. For certain products accor-
ding to the invention, at least 1 %, or with increasing preference in the
order given, at least 5, 10, 15, 20, 24, 28, 32, 35, 45, or 50 ~ of the
mass of the macrosolid article, but not more than 90 ~c of the mass of the
macrosolid article, consists of material selected from the group consist-
WO 94/25563 PCTIEP94/01330
ing of crystalline layered silicates. A particularly preferred crystalline
layered silicate is the one described in the noted patent as "Na-SKS-6"
and commercially available under the same designation from Hoechst.
Crystalline layered silicates generally improve the mechanical strength
and resistance to mechanical damage of macrosolids according to the
invention that contain them and also improve the rate at which such macro-
solids dissolve and/or disintegrate upon contact with liquid water. Be-
cause of the first improvement noted, larger amounts of other materials
which have useful cleaning properties, but tend to lower the mechanical
strength of macrosolids containing them, can be incorporated into macro-
solids according to this invention than would be practical in the absence
of the crystalline layered silicates. Such desirable constituents of
macrosolids according to the invention as abrasives, and, especially,
surfactants, fall into this class of materials that can be more practi-
cally incorporated into macrosolids according to the invention when
accompanied by crystalline layered silicates.
A process according to the invention utilizes as one of its inputs a plur-
ality, usually a large plurality, of relatively. small particles, which may
be called powder, granules, grills, or some similar term, to make a
relatively large unitary solid. In most examples of practical interest,
the relatively small particles used are sufficiently small that it is
impractical to count and characterize each of them individually. There-
fore, all specifications herein that refer to quantitative geometrical
characteristics of individual raw material particles are to be understood
as satisfied by consideration of a sufficient number of individual par-
ticles as to give statistical assurance at the 90 % confidence level or
higher that the average of the specified geometrical characteristic for
the entire particle distribution is within 10 % of the value specified.
For the purposes of this description, the "largest dimension" of any uni-
tary solid body means the largest distance possible between two hypothet-
ical parallel planes both of which are touched by the solid body, while
the "smallest dimension" of the unitary solid body is the distance between
the closest of all possible pairs of two hypothetical parallel planes
between which the solid body can fit. Preferably, with increasing prefe-
rence in the order given, the ratio between the largest dimension and the
WO 94/25563 ~ PCT/EP94/0133P
~~,6
- 18 -
smallest dimension of the particles utilized as raw material in a process
according to this invention is not greater than 10:1, 5:1, 2.0:1.0,
1.8:1.0, 1.55:1.00, 1.42:1.00, 1.33:1.00, 1.25:1.00, 1.18:1.00, 1.11:1.00,
or 1.06:1.00.
Also, independently, with increasing preference in the order given, the
ratio of the smallest dimension of the macrosolid made by a process
according to this invention to the smallest dimension of the raw material
particles used to make it is at least 5:1, 10:1.0, 30:1.0 , 120:1.00, or
600:1.00. This condition shall be considered to be satisfied if satisfied
for the smallest dimension of the raw material particles used as deter-
mined by a statistical analysis as described above, or alternatively if
satisfied by an "alternative smallest dimension" defined by the maximum
size of the openings in a screen, cloth mesh, or like structure that has
openings of a known maximum size and through which all the particles in
the particle bed have been passed. Independently, it is preferred that the
average size of the raw material particles used fall within the range from
1 mm to 2 mm, more preferably from 0.10 to 1.2 mm, or still more prefer-
ably from 0.10 to 0.5 mm. Independently, it is preferred that the maximum
particle size of the solids used in the raw material not be, with increa-
sing preference in the order given, greater than 1.0, 0.84, 0.71, 0.60,
0.50, 0.42, 0.35, 0.30, 0.25, 0.21, 0.18, 0.15, 0.13, 0.10, 0.088, 0.074,
or 0.063 mm.
Also, independently, with increasing preference in the order given, it is
preferred that at least 60, 70, 80, 87, 92, 97, or 99 % of the volume of
the bed of particles utilized in a process according to this invention be
solid rather than liquid at the temperature of the bed before beginning
irradiation with SER; and, independently, that the pore volume of the
particle bed utilized in a process according to the invention fall within
the range of from 1 to 50, 3 to 45, 5 to 40, 7 to 35, 10 to 30, 13 to 28,
15 to 26, or 17 to 25, % of the bulk volume of the particle bed. In-
dependently, it is also preferred that the pore volume of the macrosolid
formed at the end of process step (B) as defined above in a process
according to the invention fall within the range of from 1 to 50, 3 to 45,
to 40, 7 to 35, 10 to 30, 13 to 28, 15 to 26, or 17 to 25, % of the bulk
volume of the macrosolid.
'VO 94/25563 ~~ PCTIEP94I01330
- 19
Further, in at least one major embodiment of the invention, it is prefer-
red that, with increasing preference in the order given, at least 35, 50,
60, 65, 76, 82, 87, 91, or 94 % of the mass of the raw material in the
particle bed utilized in a process according to this invention or present
in a macrosolid according to this invention is selected from the group
consisting of alkali metal and alkaline earth metal sulfates (including
hydrogen sulfates), carbonates, hydrogen carbonates, silicates, optionally
hydrated, having a molar ratio of metal oxide to silicon dioxide in the
range from 1.0:1.0 to 2.5:1.0 for alkali metals and in the range from
0.5:1.0 to 1.25:1.0 for alkaline earth metals (thus including metasili-
cates, disilicates, and crystalline layered silicates), phosphates (inclu-
ding condensed phosphates such as pyrophosphates and tripolyphosphates),
hydroxides, borates, and citrates. For most purposes, the alkali metal
salts, particularly the sodium and potassium salts, are preferred over the
alkaline earth metal salts. Stoichiometric water of hydration and revers-
ibly bound water in solid phases are both to be considered as part of the
salt or hydroxide to which they are bound in determining what fraction of
the raw material particle mass is selected from this group of preferred
constituents.
In many embodiments of the invention, it has been found that the most de-
sirable products are achieved when the content of water in the raw mate-
rial particle bed is in the range from 1 to 25 %, or more preferably from
2 to 20 %, of the total mass. In determining the percentage of water in
the total mass, any water of hydration present in the solids forming the
raw material particle bed is counted as water, as are any liquid water
present in the bed and any additional water that would be expelled as
vapor from the initially solid part of the bed upon heating the bed to
100° C, or to the maximum temperature actually reached within the
particle
bed during any part of the process, if such maximum temperature is known
or controlled and is lower than 100° C. (This value can be determined
by
measuring the expulsion of water vapor from a sample of the same raw
material or raw material mixture, with the same particle size for each
chemically distinct constituent, as forms the raw material particle bed
used in the process according to the invention.) Alternatively, the water
content can be measured by a modified Karl Fischer titration method.
WO 94/25563 PCTIEP94/0133Q
2.162246 - 20 -
The SER technique of the present invention may successfully be applied to
a variety of cleaning formulations such as detergents or ware-washing,
pre-washes, dishwasher detergents, carpet cleaners, floor care products,
and general rinse/wash or all-purpose cleaners, and the like, for textiles
or hard surfaces. An advantage of this technique is that the desired
cleaner or detergent product may normally be obtained promptly upon the
conclusion of the SER treatment.
The temperature of the particle bed at the beginning of SER treatment in a
process according to this invention may be varied within wide limits, but
for convenience and economy generally is preferred to be within the range
of 15 to 50, more preferably from 20 to 35, still more preferably from 20
to 25, ° C. In addition, particularly when the raw materials used in
the
process include such chemicals as the alkali metal hydroxides with very
high heats of solution in water, it is often advantageous in a process
according to the invention to control the temperature during step (B) of
the process by means of a device that discontinues or reduces the power of
the subinfrared electromagnetic irradiation when a preset temperature of a
suitable probe, which is electronically connected to the controls for gen-
eration of the SER radiation source used in the process and is physically
located in close proximity to, preferably within 1 mm of, at least a part
of the initial particle bed, is exceeded. Such preferences can not be
stated on a general basis, as they depend on the particular materials
processed, but guidelines can be obtained from the examples below.
If more than one chemical species makes up the solid raw material of the
particle bed used in a process according to the invention, all the solid
components are preferably mixed with one another to form a substantially
homogeneous particle bed which is exposed to SER. Methods for such mixing
will be generally known to those skilled in the art. For example, hand or
mechanical stirrers and/or shakers may be used, the roughly mixed raw
materials may be passed through a grinder or other comminution device, or
the like.
The duration of exposure of the raw material mixture to SER according to
the process of the current invention will depend upon a number of factors,
the most important of which are discussed here. These include: the power
VO 94125563 216 2 2 4 6 PCT/EP94/01330
- 21 -
of the SER source; the initial temperature of the raw materials in the
particle bed; the water content of the raw material; the temperature-sen-
sitivity, if any, of the raw materials; the shape or configuration of the
container used; and the bulk of the material contained therein. When tem-
perature-insensitive materials are used, however, it is the time duration
required to achieve a sufficient temperature - that is, the temperature at
which the material is transformed from a bed of discrete particles into a
unitary solid, or into a material that will constitute a unitary solid
when cooled to a normal ambient temperature - that will usually govern the
duration of exposure of the raw material mixture to SER. The time of
irradiation normally is preferably within the range of 5 seconds (herein-
after often abbreviated "sec") to 30 minutes (hereinafter often abbrevia-
ted "min"), or more preferably from 30 sec to 20 min.
For example, exposure to microwave radiation in a MLS-1200 T device
(Buchi) operating at 2450 MHz and 250 Watts for times from 2 to 4 minutes
has been found to be sufficient to form 30 g tablets from raw materials
that were stable to temperatures of up to 140 - 160 °C, while 250 g
blocks
at the same power level needed at least 12 minutes. On the other hand, 30
g tablets can be formed in 15 seconds with the same microwave radiator at
1000 watts power. With a Hotpoint Model RE600002.92KW microwave generator
rated and used at 240 watts of power output, samples on the order of 400 g
in size needed approximately 8 minutes, while 1 - 2 kg blocks may require
20 minutes or more. Slightly longer times are needed if more
temperature-sensitive raw materials are included in the particle bed.
I t i s a 1 so wi th i n the teach i ng of the present i nvent i on to use
more than
one power setting for different time periods, or to "pulse" a sample with
SER radiation for short intervals, interrupted by other short intervals in
which power is discontinued. "Pulsing" of this type has been found to be
particularly advantageous when strongly acidic macrosolids are desired as
the output of a process according to the invention. Prolonged SER-irradia-
tion of highly acidic particle beds tends to result in oxidative decom-
position of the particle bed and a consequently weak macrosolid, or often
failure to form a macrosolid at all, but short pulses interrupted by
periods without irradiation often overcome this problem. In such circums-
tances, the time for a continuous interval of irradiation preferably is,
WO 94/25563 PCT/EP94/0133~
W62246
- 22 -
with increasing preference in the order given, not greater than 120, 85,
60, 45, 30, 20, 15, 10, 8, 7, 6, or 4 sec, and each such continuous
interval of irradiation is independently preferably followed by an
interval of at least equal length in which irradiation is not applied to
the particle bed. Generally, the accumulated time of actual irradiation
when using the pulsing technique is approximately the same as for contin-
uous irradiation in a single interval to form a macrosolid from other
materials, but the time will obviously be adjusted as necessary by those
skilled in the art. Any acid that is solid at the temperature of the
particle bed can be successfully incorporated by this technique. Examples
include citric, malefic, oxalic, and sulfamic acids, with the latter
especially preferred for making strong acid cleaners, with a pH value of
as low as about 1 for a solution containing 1 % by weight of the cleaner,
that are especially useful for removing difficult to remove soils such as
cement residues.
Measurements of the dielectric parameters made by means of a Hewlett-Pack-
ard HP85070M Dielectric Probe Measurement System have demonstrated that
radio wave irradiation is suitable for a number of raw material mixtures
as shown in Table 1. In all three cases, the dielectric loss factor, e, in
the radio wave range is higher than in the microwave range, suggesting
that the time required to form macrosolids of a particular composition via
radio wave irradiation according to the present invention should be less
than the amount of time required for formation of macrosolids via micro-
wave radiation. With increasing preference in the order given, the time
required with radio wave irradiation will be no more than 2.0, 1.75, 1.5,
1.25, 1.0, 0.75, 0.25 or 0.01 times the amount of time required for forma-
tion of macrosolids via microwave radiation.
WO 94/25563
16 2 2 4 6 ~T~~4/01330
- 23 -
Table
Frequency Dependence of Dielectric Loss-Factors, E, for
Three Ray Material Compositions Measured at Roan Temperature
Dielectric Loss-Factor, E
200 MHz (Radio 2,000 MHz (Micro-
Composition Wave Range) wave Range) '
Composition 1 "' 13.5 "' 2.5
(PerclinTM Supra)
Composition 2 "' 1 "' 0.5
(SekumaticTM PR)
Composition 3 ~ 1 "' 0.5
(ImiTM-powder)
Macrosolid tablets and blocks according to the present invention prefer-
ably contain at least 0.1 percent, but more preferably at least 2 % of
water up to 15, or more preferably up to 11, % of water, the difference,
if any, in water content before and after the subinfrared electromagnetic
irradiation being believed to be due to the evolution of some water which
usually accompanies the process. More preferably, the macrosolid products
of some processes of the present invention contain from 0.5 to 10 percent
of water, and still more preferably from 2 to 6 % of water. The amount of
water present in the macrosolid product may be determined by a conven-
tional modified Karl Fischer titration, which may be carried out as de-
scribed in the indented paragraphs immediately following below. This
method determines the amount of water volatilized from the sample by
heating to 200 °C, including any water which is generated as a result
of
any possible decomposition reaction that occurs, (e. g., the decomposition
of perborate). The method is accurate to abaut 0.1 % of water content.
WO 94/25563 PCT/EP9410133~"
2.1622 9~6 - 24 -
Principle of the Method: Water is volatilized from the sample material to
be tested by heating to 200 °C in a special drying oven. The water
vapor
released is transferred in a dry nitrogen stream into an connected auto-
matic Karl Fischer titrator and therein is titrated.
Apparatus; The apparatus consists of a special drying oven (MetrohmTM E
613) and an automatic Karl Fischer Titrator (e.g., MetrohmTM E 452). The
outlet from the oven is connected by a glass tube with an inlet capillary
tube in the titration container of the titrator.
Nitrogen suoplv: Conventional compressed nitrogen in a steel tank is
used. The pressure is reduced with the help of a pressure reducing valve
to about 2.5 kilopascals/cm2. The outlet from the tank valve is connected
via a hose, made of polyethylene and reinforced with glass fibers, to a
gas flow meter, equipped with a control valve; after the gas flow meter,
an empty safety washing bottle is placed in series, followed by a gas
washing bottle containing concentrated sulfuric acid.
The washing bottle is connected to a tubing tee, from which one branch
leads to a safety pressure-relief valve, e.g., a washing bottle highly ov-
erfilled with sulfuric acid, prior to which again an empty safety bottle
should be inserted in a serial connection.
From the other branch leading from the tee, a connection with the drying
oven is made via a glass tube, which is perfectly fitted and which is pro-
vided at the end with a spherical ground glass joint. No silicone hose or
polyethylene hose may be used in place of the glass tube, as otherwise at
high air humidity water will diffuse into it and cause an erroneously high
value for water.
Dryin4 oven: The drying oven can be in essence used as delivered; how-
ever, the gas inlet and the gas outlet on the internal attachment piece
should be provided with a spherical joint.
Connection between the dryinQ oven and the Karl-Fischer-titrator: The
connection between the drying oven and the titrator consists of a glass
tube provided with spherical joints, the internal diameter of the tube
being 1.5 - 2 mm and the glass tube being attached to an inlet capillary
tube of internal diameter of 1.5 mm, also provided also with a spherical
NO 94125563 216 2 2 4 6 PCTIEP94101330
- 25 -
joint. These parts are preferably manufactured specifically for this pur-
pose and are adjusted to fit the spatial conditions and/or the titration
container. The interconnecting tube may be omitted, if the spatial place-
ment of the apparatus permits it. The connecting passageway between the
oven and the titrator preferably is provided with a heating device, such
as a strip heater or the like, which allows heating up to 80 - 100 ° C,
because the water can otherwise condense out in this zone.
Karl Fischer Titrator: A Karl Fischer titrator consists of 3 subunits,
the titration container with a stirring device, the control' and measuring
electronics, and a dispenser, e.g., Metrohm DosimatTM E 655. The cover of
the titration container is provided with 5 passages, From among them, the
first opening is used for the reading electrode, the inlet capillary tube
is led into the second opening, the third is provided with a rubber
stopper with a hole dri l led through, into which a thin polyethylene hose
of internal diameter of about 1 - 2 mm is inserted deep enough that it
reaches into the titration container up to about 3 centimeters (herein
often abbreviated "cm") above its bottom. The other end of the hose leads
to a waste container for solvents. The inlet for the Karl Fischer reagent
is connected with the fourth opening, and the fifth opening is provided
with a ground joint stopcock. All passages must be sufficiently tightly
fitting to avoid penetration by water vapor in the air.
The performance of water determination: The drying oven is preheated to
200° C, and the heating of the connecting pipe between the oven and the
titrator is also begun. The nitrogen feed is opened and controlled so that
about 60 ml/min of nitrogen gas flow through the equipment, and the ground
joint stopcock located in the cover of the titration container is also op-
ened. Fifty ml of methanol is introduced into the titration container, the
titrator is switched on and the methanol is titrated. A one-component Karl
Fischer reagent is used as the titration agent, the pyridine-free Hydranal
CompositeTM of Riedel de Haen Company having proved satisfactory. When the
equipment is completely sealed, the blank consumption after the methanol
titration must be below 0.4 ml/h.
The titrator is set to switch off after 30 seconds of operation. With the
help of a 50 ml syringe, 50 ml of water is added to the methanol previous-
ly titrated and the titration is started again. The coefficient "Fu of the
reagent solution is calculated from the equation:
WO 94/25563 PCTIEP94101330
21.6224 - 26 -
F =
to
consumption reading
This factor determination should be repeated at least three times, then an
average from the obtained values should be calculated.
If the titration container after the completion of the titration is more
3
than 2/3 full, the stopcock in the cover is closed. The overpressure,
building up subsequently, will propel the liquid through the polyethylene
hose into the solvent waste container, until the liquid level reaches the
lower edge of the PE hose, then the stopcock in the cover is opened again.
Water determination in detergents and cleaning agents: The sample of which
the water content is to be determined is placed in a small steel boat
(about 6 cm in length x 1.5 cm height x 1 cm width). If no small steel
boat is available, a small boat of comparable measurements can be shaped
from a strip of aluminum foi 1 of 0.5 mm thickness. Into the boat, 300 -
500 mg of the substance to be analyzed is weighed. For liquid alkaline
samples a glazed porcelain boat should be substituted.
The small boat is introduced into the oven heated to 200° C, the
titrator
is pre-set for 30 sec operation and the titration is started. During this
process it should be carefully assured that the methanol used had already
been titrated.
Depending on the substance, the titration is completed after 10 to 20
minutes, the titrator automatically switches itself off, and the value is
recorded.
The water content of the substance is calculated as follows:
ml consumption ~ F - a ~ 100
H20 =
E
where a = the theoretical titer of the Karl Fischer reagent, F = coeffi-
cient of Karl-Fischer-reagent, and E = sample mass in mg.
_ 2162246
'NO 94/25563 PCT/EP94/01330
- 27 -
Reproducibility: The standard deviation for this determination, from 6
replications on one sample with a mean value of 20.5 % water, is 1.1 %.
relative.
The invention includes within its scope the formation of macrosolid tab-
lets or blocks which are formed from a mixture of raw materials containing
all or nearly all of the necessary components for a cleaner formulation.
In general, the ingredients and the relative proportions in which they are
used in macrosolid cleaners according to this invention are substantially
the same as those intended to be used for the same purposes ~in other solid
cleaners of the prior art. The cleaner formulations suited to the present
invention include all-purpose cleaners, detergents, industrial or institu-
tional cleaners, ware-washing cleaners and automatic detergents for
textile or hard-surface cleaning purposes. In one embodiment of the
invention, it is possible to form macrosolid cleaner or macrosolid de-
tergent tablets or blocks directly from raw material mixtures in dispo-
sable packaging, which constitutes the container during processing.
Water-soluble films may be used for the disposable packaging, as discussed
further below. The macrosolid tablets or blocks of the present invention
may further comprise one part of a multiple-part cleaning combination.
In yet another embodiment of the invention, it is possible to after-treat
tablets, blocks, or molded macrosolids in which a particular component,
such as a microwave-sensitive substance such as an enzyme, or a surface
coating designed to impart certain properties, such as slower dissolution,
for example, is excluded from the raw material mixture prior to treatment.
The SER technique permits the use of these substances by incorporating
them into the porous product from the end of step (B) in a process accor-
ding to the invention as defined above, due to the porous structure in the
SER macrosolid thus formed. Accordingly, substances such as those common-
ly used for coatings on cleaner blocks to protect against skin contact
(i.e., materials such as poly{alkylene}s, especially poly{ethylene};
poly{alkylene glycol}s, especially poly{ethylene glycol}; fatty acids;
fatty acid amides; paraffin waxes; sorbitol; carbohydrates such as su-
crose; and nonionic surfactants) can be successfully incorporated into the
initial macrosolid product by dipping macrosolid blocks or tablets into
appropriate liquid compositions and then drying some or all of the
WO 94/25563 PCTIEP94101330
~,162~~6
liquid constituents into a solid contained within the pores of the ini-
tially produced macrosolid.
Other conventional techniques such as spraying or otherwise applying the
component onto the SER macrosolid are also possible due to the open space
structure of the SER-formed products. On the other hand, if only a surface
protective coating is desired, imbibition of the coating material into the
pores and interstitial spaces of the macrosolid cleaners produced accor-
ding to this invention may be minimized by coating with a relatively
viscous coating material. Providing protection against unwanted contact
with the skin of users of the macrosolid products of this invention, as
with similar conventional products of the prior art, is important for
safety when the cleaners are strongly alkaline in composition.
In this respect, the SER technique of the current invention presents a
distinct advantage in the formation of macrosolid products over several
prior art techniques. For example, in the formation of tablets by prior
art techniques that involve elevated pressure, the structure of the
resulting solid product is such that the solid cannot readily absorb
additional materials once the tablet has been formed. Where an after-
treatment or incorporation of a SER-sensitive or heat-sensitive material
is desired, the open structure of the SER produced macrosolids permits
incorporation of substances through permeation of these interstices. In
this way, a broader range of products in macrosolid form, including prod-
ucts with most or all of the pores present in the initially formed macro-
solid filled with some solid material, may be achieved with the SER
process of the current invention than is possible with conventional
techniques.
In addition to the preferred materials already described above, other ma-
terials that are suitable and useful for at least some applications as
part of the raw material particle bed for a process according to this
invention include the usual nonionic, anionic, cationic and zwitterionic
surfactants and mixtures thereof. The surfactant or surfactants chosen
for use as constituents of the particle bed in accordance with the present
invention in general comprise no more than 40 %, and preferably no more
than 25 %, more preferably no more than 15 % of the total raw material
WO 94/25563 216 2 2 4 6 pCT~pg4101330
- 29 -
mixture, unless the latter includes substantial amounts of crystalline
layer silicates, in which case the amount of surfactant may be increased
to as much as 60 %. However, if desired, as it is for certain products
according to the invention, additional surfactant can be added by imbi-
bition into the pores and interstitial spaces of the initially produced
macrosolid product according to this invention.
Silicates that are useful in the process of the present invention include
alkali metal metasilicates, where the alkali metal is preferably sodium.
Preferred sodium metasilicates include the anhydrous form as well as
sodium metasi 1 icate ~ 5 H20. Si 1 icates may preferably be present accor-
ding to the present invention in amounts from 0 to 90 %, more preferably 1
to 90 %. Hydrated forms of sodium silicate, particularly sodium silicate ~
H20, were found to aid in the SER solidifying process when used in rang-
es of at least 1 percent but less than 50 percent, and preferably between
1 to 30 percent. Also, as already noted above, crystalline layer silicates
are often highly preferred and advantageous constituents of the particle
beds to be consolidated according to this invention.
Phosphates that may be used in the SER process of the present invention
include alkali metal tripolyphosphates, hydrogen phosphates and pyrophos-
phates, either in anhydrous or hydrated forms or a combination thereof.
The preferred alkali metal is sodium. Preferred sodium phosphates include
anhydrous sodium tripolyphosphate ("STPP"), STPP ~ 6 H20, and trisodium
phosphate (TSP) ~ 10 H20. Phosphates may preferably be used in amounts of
up to 80 %, more preferably 5 to 80 %. Borates that may be used in the SER
process of the present invention include alkali metal borates, either in
the hydrous or anhydrous forms or a combination thereof. The alkali metal
is preferably sodium. Preferred sodium borates include sodium borate ~ 10
H20 (borax). Borates may preferably be present in amounts of up to 20 %,
and thus are preferably used in combination with at least one other raw
material.
Carbonates and bicarbonates that may be used in the SER process of the
present invention include alkali metal carbonates and alkali metal bi-
carbonates, either in the hydrous or anhydrous forms, or a combination
thereof. The alkali metal is preferably sodium or potassium. Preferred
WO 94/25563 PCT/EP94101330
~~.s~~~~ - 3~ -
sodium carbonates include anhydrous sodium carbonate and sodium carbonate
~ 10 H20. Mixtures of sodium carbonate and amorphous sodium silicate sold
under the denomination Nabion 15 by Rhone-Poulenc. The preferred bicarbo-
nate is anhydrous, and sodium is the preferred alkali metal. Suitably
hydrated carbonates may preferably be used in amounts of up to 100 %, more
preferably 1 to 100 %, of the total raw materials mixture. Bicarbonates,
which are also known as hydrogen carbonates or acid carbonates, may
preferably be used in amounts of up to 40 %, more preferably 2 to 40 %,
and are thus preferably used in combination with at least One other raw
material. Where bicarbonates are used in formulations for promoting
hyg i ene , they are pref erab 1 y used i n amounts of up to 20 %. Where b i
car-
bonates are used for dishwasher formulations, they are preferably used in
amounts from 5 to 40 %. In certain cases, it is preferable to avoid using
bicarbonates in the same raw material mixture as either carbonates or
citrates.
Alkali metal hydroxides may preferably be present in amounts of up to 80
percent, and more preferably from 2 to 70 percent. Preferred hydroxides
include sodium and potassium hydroxide. For applications in the kitchen
hygiene area, or wherever tablets with high alkali content are especially
desired, the process of the present invention offers several advantages
over prior art techniques. The manufacture of solids containing high
alkali content is not practical using pressing techniques of the prior
art , for examp 1 e, due to mo i sture accumu 1 at ion wh i ch occurs on the
pres-
sing apparatus during the process. This is particularly bothersome where
formulations containing both sodium hydroxide and perborate are desired,
to the extent that the manufacture of pressed tablets containing such com-
positions is believed never to have been practical. Furthermore, it is not
possible to mechanically press tablets with high alkali content when there
is greater than 80 % moisture present in the air. The microwave process of
the present invention is not affected by either of these conditions, and
macrosolid tablets that are not only high in alkali content, but that also
contain perborate, have successfully been obtained.
Sulfates that may be used in the SER process of the present invention in-
clude alkali metal sulfates and alkaline earth sulfates (in both cases
including hydrogen sulfates), although calcium sulfate is only rarely used
WO 94/25563 2 ~ 6 2 2 4 6 PCT/EP94/01330
- 31 -
because of its low solubility. Alkali metal sulfates are preferably used
in the non-hydrated form; alkaline earth sulfates are preferably used in
the hydrated form. Sodium is the preferred alkali metal for alkali metal
sulfates, and magnesium is the preferred alkaline earth metal for alkaline
earth sulfates. When an alkaline earth sulfate is used in the hydrated
form, the preferred alkaline earth sulfate is MgS04 ~ 7 H20. Alkali or al-
kaline earth sulfates may preferably be used in amounts of up to 80 % of
the raw material, but more preferably are used in amounts of 1 to 30 %.
Citrates that may be used in the SER process of the present invention in-
clude hydrated and non-hydrated alkali metal citrates, and sodium is the
preferred alkali metal. Especially preferred citrates are the mono-, di-,
and pentahydrates of trisodium citrate. Alkali metal citrates may prefer-
ably be present in amounts of up to 95 percent, more preferably 1 to 95 %,
of the total solid raw material, and are especially preferably used in
amounts of 30 to 50 % for general cleaning formulations. With respect to
some formulations for use in the dishwashing area, citrates are more pref-
erably used in amounts of 80 to 90 % of the total solid raw material.
Nonionic surfactants that may effectively be used in the SER process of
the present invention include those commonly used solid cleaners of
similar chemical composition in the prior art, such as alkylpoly- and
-oligoglucosides, N-acylglucamides, alkyl-, arylalkyl-, alkylaryl-, and
aryl-polyoxyalkylenes, esters and amides of polyoxyalkylated alcohols,
preferably ethoxylated fatty alcohols and ethoxylated alkyl phenols. In
some particular applications, the most preferred ethoxylated fatty alcohol
is tallow alcohol condensed with an average of 14 moles of ethylene oxide
per mole of tallow alcohol (this alcohol-ether is hereinafter often
abbreviated "TA 14") and the preferred ethoxylated alkyl phenols are
nonylphenol ethoxylates such as NPE 9.5 (with an average of 9.5 molecules
of EO per molecule of nonyl phenol). Nonionic surfactants may preferably
be present in amounts of up to 40 percent, and more preferably in amounts
of 1 to 25 %, in the absence of crystalline layer silicates, but may be
present in amounts of up to 60 % in the presence of the latter.
Anionic surfactants that may be used in the practice of the present inven-
tion include alkane sulfonates, oc olefin sulfonates, fatty acid sulfo-
WO 94125563 PCT/EP94101330
21~'~2~6 - 32 -
nates, fatty alkyl sulfates, fatty alkyl ether sulfates, sulfosuccin.ates,
fatty alkyl ether carboxylates, isethionates, taurides, sarcosides, fatty
acid sulfates, sulfonamidocarboxylates, salts of partial organic esters of
sulfuric and phosphoric acids, salts of sulfated esters and amides of
carboxylic acids, with a preferred group including fatty alkyl sulfates,
fatty alkyl ether sulfates, MersolatTM 95, and linear alkylbenzene sulpho-
nates. Anionic surfactants may preferably be present in amounts up to 40
percent, and more preferably from 0.5 to 25 %, in the absence of crystal-
1 i ne 1 aver s i 1 i Gates , but may be present i n amounts of up to 60 % i n
the
presence of the latter.
Cationic and zwitterionic surfactants may preferably be present in amounts
of up to 25 %, and more preferably from 1 to 15 % of the total raw mate-
rial mixture. Typical raw materials of this type, all of which are sui-
table for use in this invention, include amine oxides, amidazolinocarboxy-
lates, betaines, and aminocarboxylic acids for zwitterionic surfactants;
and primary, secondary, tertiary, and quaternary ammonium salts, such as
alkanolammonium, imidazolinium, quinolinium and isoquinolinium salts, and
thiazolinium salts as well as the more common fatty ammonium salts, along
with sulfonium and tropylium salts, for cationic surfactants.
Optionally, the raw material mixture of the current invention may also
contain additives and auxiliaries. Additives preferably are present in
amounts not greater than 60 %, more preferably not greater than 40 %, or
still more preferably in amounts of 0.5 to 15 %. Examples of suitable
additives include, but are not necessarily limited to: active oxygen
sources and oxidizing materials; activators for active oxygen sources;
active chlorine sources and chlorinecontaining materials; enzymes; seques-
trants; fillers and builders; abrasives; turbidity promoters; dispersants
and dispersing agents; corrosion inhibitors; and disinfectants.
Auxiliaries may preferably be present in amounts of up to 10 %, and are
more preferably used in amounts of 0.1 to 2 %. Examples of auxiliaries in-
clude, but are not necessarily limited to: perfumes; optical brighteners;
dyes and pigments; defoamers and foam inhibitors; solubilizers; anti-re-
deposition agents, and dye transfer inhibitors.
216 2 2 4 6 pCT~p94/01330
WO 94125563
- 33 -
With respect to additives that may be used in the current invention,
chlorine and oxygen sources may be effectively used either coated or
uncoated, and may be added directly to the raw material mixture in either
form. Alternately, these materials may be incorporated into the SER-
formed product subsequent to initial macrosolid formation. Another
advantage of the present invention, therefore, is that unlike prior art
techniques for casting or molding solid detergents, the SER process of the
present invention does not require that chlorine-containing components be
included as a preformed plug, cartridge, or core.
Typical chlorine sources that may be effectively used according to the
present invention include chloroisocyanurates such as di- or tri-chloro-
isocyanurates, and polychloroisocyanuric acids. Two examples of the latter
include CDB-56TM (available from Olin) and ACL-90T~'i (available from
Monsanto). In the present invention, chlorine sources may preferably be
present in amounts of up to 30 percent, and more preferably from 1 to 5
percent. It has been found that raw material mixtures that incorporate
chlorine sources tend to exhibit temperature sensitivity during the
microwave process, and where such materials are used, temperature controls
should be preferably implemented such that the raw material mixture does
not exceed a particular temperature. In the case of chlorine source mater-
ials, it was determined that temperatures should preferably be kept under
approximately 383 °K (110 °C).
Active oxygen sources are typically used in powder or granular detergent
formulations, but their use in uncoated form in the present process
generally is not preferred, although both coated and uncoated forms have
successfully been used in the present invention, with careful temperature
control. If the raw material mixture achieves too high a temperature
during certain SER treatments, uncoated oxygen sources or oxidizing
sources such as sodium perborate or sodium percarbonate have been observed
to decompose, accompanied by the evolution of gas, which caused foaming in
the sample being irradiated. Accordingly, temperatures for raw material
mixtures containing oxygen sources should preferably be kept under
approximately 343 °K (70 °C) during microwave processing
according to this
invention. Short pulsed intervals of irradiation interrupted by intervals
PCT/EP94/01331!
WO 94/25563
- 34 -
without irradiation may be effectively used for such temperature control,
as already noted.
Coated oxygen sources, however, have surprisingly been found to demon-
strate good compatibi 1 ity with the SER technique, and tablets and blocks
containing coated perborate or coated percarbonate have successfully been
produced directly from pre-mixtures containing these raw materials. Coated
forms of oxygen sources are especially preferred in applications where
strongly alkaline formulations are desired. The use of 'these coated
compounds as an active oxygen source in the process of the present inven-
tion is therefore preferred. Perborates, percarbonates, or other conven-
tional oxygen sources may preferably be present in amounts up to 30
percent, and more preferably from about 5 to about 25 percent. Perborates
preferably used have the general formula MB03 ~ yH20, where M is an alkali
metal, most preferably sodium, and y is a number from 1 to 4.
In addition to the active oxygen sources themselves, it is often advan-
tageous to include in the particle bed to be consolidated according to
this invention and/or in the macrosolids produced according to this
invention one or more materials from the class known in the cleaner art as
"activators" or "bleach precursors". Suitable such materials include
pentaacetyl glucose ("PAG"), 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-tri-
azine ("DADHT"), and N,N,N',N'-tetraacetyl ethylene diamine ("TAED"), with
the latter preferred. Amounts of these activator materials are preferably
from 1 - 10 % in particle beds or macrosolids that also contain active
oxygen sources.
Also belonging to the category of additives in the current invention are
enzymes. Where enzymes are used directly in the raw material mixture of
the invention in solid form, they preferably feature a coating or encapsu-
lation. Uncoated enzymes that are commercially available in fluid form may
also be used. Alternately, enzyme solutions may also be incorporated into
the macrosolid SER tablet or block at a point in the process subsequent to
SER treatment. This incorporation is possible in the present invention
because of pores and/or interstitial spaces which are formed in the
macrosolids during exposure to SER radiation. These internal spaces permit
the adsorption of enzymes, or any other material, directly into the
WO 94125563 PCTIEP94/01330
2162246
-35-
macrosolid tablet or block. According to one embodiment of the present in-
vention, where the final product contains enzymes, they may preferably be
either amylases or proteases. If desired, the enzymes may be conventional-
ly coated, as with sulfate coatings, to protect them from adverse inter-
actions with other constituents of the raw materials used. Enzymes may
preferably be present in amounts up to 10 percent, and more preferably
from 0.1 to 5 percent.
The technique of the present invention represents a distinct advantage
over melt-block processes for the production of enzyme containing deter-
gent formulations of the prior art. Since the SER process of the current
invention may be implemented for short durations - minutes or even se-
conds, depending upon composition and size as discussed above - enzymes
such as lipases, cellulases, proteases, and amylases may be directly in-
corporated into the macrosolids produced by this technique.
As indicated above, other conventional detergent or cleaner components may
also be used as additives to the raw materials mixtures according to the
SER process of the invention in addition to active oxygen sources, activa-
tors for these active oxygen sources, chlorine sources, and enzymes. These
substances include: sequestrants; fillers and builders; abrasives; tur-
bidity promoters, dispersants and dispersing agents; corrosion inhibitors;
heavy metal scavengers; waxes; and disinfecting substances.
Examples of builders are phosphonates and polycarboxylates (i.e., alkali
metal salts of homo- or co-polymers of acrylic acids), which may prefer-
ably be present in amounts of up to 30 percent, and are more preferably
used in amounts of 1 to 15 percent; crystalline layer silicates, which may
be used in amounts up to 90 %; and zeolites which may be used in amounts
up to 60 %, preferably in amounts of 10 to 40 %.
Abrasives that may preferably be used according to the present invention
include such substances as marble, quartz, and alumina powders, preferably
of the polishing grit or particle size, and they preferably are present in
amounts not greater than 60 %, or more preferably not greater than 40 %.
In one particular embodiment of the present invention, it is possible to
include abrasives of varying size directly into the raw material particle
WO 94!25563 PCT/EP94/01330
21fi2246 - 36 _
bed prior to SER treatment, based on the application desired for the .final
product. The incorporation of abrasives directly into the particle bed
therefore constitutes an advantage over milk-type scouring products (also
called scouring creams) of the prior art. Prior art products often have
sedimentation problems due to the presence of scouring powders and granu-
lar solids in the milk liquor, which settle with time. In order to over-
come these problems, prior art scouring creams often require the use of
suspension agents, which subsequently introduces a second problem. That
is, the use of a second, surfactant-containing cleaning product is often
required in order to wash away the scouring powder and granules after use
of the first scouring cream. This may further introduce rinsing problems.
The SER technique of the present invention avoids both problems, as scour-
ing powders and granular solids of different sizes may be incorporated,
along with a surfactant, directly into a raw material pre-mix formulation.
Not on ly does th i s reduce the number of steps that may be requ i red i n a
particular cleaning operation, it also reduces the number of items and
therefore attendant packaging materials required.
Turbidity promoters include preferred styrene-vinylpyrrolidone copolymers
in addition to other usual turbidity promoters. Dispersants include, among
known dispersants, especially naphthalene sulfonic acid condensation
products. Preferred corrosion inhibitors include such materials as tech-
nical 2-buten-1,4-diols (available from Colus). Preferred heavy metal
scavengers include phosphonates, nitrilotriacetic acid ("NTA"), and
ethylene diamine tetraacetic acid ("EDTA"). Waxes preferably are present,
if at all, in amounts not greater than 5 percent, and more preferably in
amounts from about 0.1 to 2 percent. Disinfectants include the normal
disinfecting substances that would be known by one familiar with the
cleaning arts, and may be used in conventional amounts.
Perfumes, optical brighteners, dyes and pigments may preferably be used in
amounts of up to 3 percent, and more preferably from 0.001 to 1 percent.
Where foam inhibitors or defoamers are used, they may be mixed directly
with the raw materials of the particle bed. One advantage over prior art
techniques of casting or molding solid detergents is that according to the
SER process of the present invention, it is not necessary to include the
'NO 94125563 1 ~ 16 2 2 4 5 PCT/EP94/01330
- 37 -
foam inhibitor component as a preformed plug or core, as has been, taught
in some prior art.
Dedusters and defoamers such as paraffin oil and silicone oil respective-
ly, for example, may be present in amounts of up to 5 percent, and are
preferably present in amounts of 0.1 to 3 percent. Anti-redeposition
agents may be present in amounts of up to 5 percent, and are preferably
present in amounts of 0.1 to 3 percent. The preferred anti-redeposition
agent is carboxymethyl cellulose (CMC). The preferred so~lubilizers are
alkyl carbonic acids, cumene sulfonates, and toluene sulfonates, although
other solubilizers known to those familiar with the cleaner arts are also
suitable. Dye transfer inhibitors may also be used in amounts of up to 5
percent, and are preferably present in amounts of 0.1 to 3 percent. The
preferred dye transfer inhibitor is poly~(vinyl pyrrolidone} ("PVP").
When the particle bed to be irradiated according to the invention contains
materials likely to emit gas at elevated temperatures, such as enzymes,
active oxygen sources, activators for active oxygen sources, or sodium
bicarbonate, irradiation under reduced pressure may be advantageous.
In certain embodiments of the present invention, a separate liquid phase
component can be used in combination with a macrosolid component produced
by the SER process of the invention, resulting in a two component or
"dual-pack" product system. Generally, in the liquid phase component of
such dual-packs, the ingredients which are used according to this inven-
tion are substantially the same as those intended to be used for the same
purposes in other liquid cleaners of the prior art. The proportions can be
varied therefrom, however, as it may not be necessary to include water, or
at least the same amount of water as is required in prior art liquid
compositions, as water will be introduced to the liquid component and
macrosolid just prior to use. Moreover, another feature of such a dual-
pack embodiment is that it is possible to manufacture more concentrated
products than is possible in the prior art, without having to compromise
final product quality.
In certain preferred embodiments, the liquids used in the dual-pack embod-
iment are selected from the group consisting of known nitrogen-containing
WO 94/25563 PCT/EP9410133Q
-3s-
solvents such as ammonium hydroxide or ethanolamines, propylene glycol
ethers and glycol ether solvents such as Propasol solvent B (Union
Carbide), monophenyl glycols such as phenoxy ethanol, and salts of cumene
sulfonates, toluene and xylene sulfonates, with the sodium salt generally
being the preferred constituent, such as sodium cumene-sulfonate (40
aqueous solution). In general, all the usual water-dispersible materials
and solubilizing agents, such as alcohols, can also be used.
It is also anticipated that for certain applications, it may be desirable
to include certain dissolved solids in the liquid component of the dual-
pack embodiment according to the present invention. Such may be the case,
for example, if a material is not amenable to treatment by SER and there-
fore cannot be incorporated into a macrosolid produced according to the
process of the invention, or for reasons of convenience or handling, it is
more advantageous to include such material in the liquid component phase
of the dual-pack product. Examples of such materials include low-boiling
alcohols, ethanolamines and perfumes with low boiling points that can be
evaporated off during treatment by SER. In other instances, it may be
desirable both to dissolve certain solids in the liquid component and also
to include them in the macrosolid component of the dual-pack product. One
example of such a material is potassium hydroxide. In yet additional em-
bodiments of the invention, it is possible to combine a macrosolid cleaner
with different dual-pack fluid components, or to use a particular dual-
pack fluid component with different macrosoiid cleaners in order to
achieve a desired result. These and other variations will be apparent to
those skilled in the pertinent art.
The maximum temperature that is acceptable for the SER process of the
present invention will be below the decomposition temperature of any tem-
perature-sensitive materials, such as oxidizing materials or chlorine-con-
taining materials, that are present in the raw material processed.
In contrast to the press-forming of detergent tablets, it has been found
that the SER process of the present invention can be used to produce
macrosolid products of virtually unlimited size. It will be appreciated by
those knowledgeable in the relevant field, however, that certain practical
constraints exist. The power of the SER source, the size of the SER
WO 94/25563 PCT/EP94/01330
- '~~~~s
chamber, and the internal temperature that can be attained in a sample
within a convenient and economically practical amount of time are all
factors that determine the optimal size particle bed to be used. For
example, it has been successfully demonstrated that raw material samples
ranging from 10 grams to several thousand grams can be conveniently and
reproducibly exposed to microwave radiation for times as short as one to
two minutes up to approximately twenty minutes in order to yield tablets
or block macrosolids according to the process of the present invention
without external application of pressure, although preformirig of the raw
material mixture by application of low pressure might also be possible.
The descriptions and examples contained below contain further guides for
successfully practicing the SER method of the present invention.
It has also been found that the shape of the container used to hold the
particulate starting raw materials can be optimized in order to enable
production of the most advantageously stable macrosolid tablet or block
formed. The container used is generally open at the top to permit the
escape of volatilized water that is generated from the sample during SER
treatment. Where the open end or open portion of a container has an area
"A", the ratio of the square root of A to the depth "D" of the particle
bed, i.e., the maximum distance, in a direction perpendicular to the plane
of the area "A", that is within the particle bed, is preferably within the
range from 1: 2 to 10:1, or more pref erab ly from 1:1 to 5:1. Th i s range of
ratios permits formation of macrosolid blocks as well as "flatter" disc-
shaped macrosolids that are surprisingly strong and exhibit good integral
strength, without compromising physical strength, so that the product can
be conveniently handled without being readily broken or producing much
powder.
V i rtua 11 y any conf i gurat i on may be used f or a conta i ner i n order
to pro-
duce a macrosolid tablet or block according to the present invention. A
variety of particular forms may be desired, for instance, based upon
different machine applications. The dimensional constraints for the tablet
or block will depend upon the path that water molecules must travel in
order to escape from the bulk raw material mixture as part of the SER
process, and the length of time that exposure to SER is needed before
exceeding the temperature stability of any of the raw materials. Where a
WO 94125563 ~ PCTlEP94/01330
'~~.6 ~ _ao_
particular cleaner tablet or block shape is desired that does not meek the
above optimal dimension criteria, such shape is still possible, providing
that there are suff i c i ent open i ngs made i n the s i des or at the per i
phery
of the container to permit the evolution of water molecules from the bulk
of the raw material mixture during SER treatment.
The method of the invention is readily adapted for use on a continuous
basis, wherein a plurality of initial particle beds in a plurality of
containers is continuously introduced, by a conventional conveyor for
example, into a SER heating zone and the resultant macrosolid product is
continuously removed from said zone, or from an intermediate cooling zone,
in macrosolid form. Not only is it possible to employ reusable containers
with the process of the present invention, but actual shipping or handling
containers can also be used as the containers during the SER processing in
order to streamline the production and packaging processes.
In one embodiment of the present invention, a container of a watersoluble
film material is used. The container preferably retains an opening to
permit the evolution of water molecules from the raw materials during SER
treatment, and can be sealed in a subsequent step. In yet another embod-
iment of the present invention, the container is a light-weight packaging
or a thin polymertype material, which may be especially desirable for
dispensing purposes in connection with the use of larger block macro-
solids. In still another embodiment of the present invention, rigid or
flexible bags are used as containers.
In one embodiment of the invention when the container is a reusable one,
it is advantageous to use a container with walls that are capable of re-
versibly adsorbing and/or absorbing water. This promotes more rapid
solidification of the particle beds used in such containers. In a varia-
tion, several such containers on a continuous belt that circulates in and
out of the SER cavity, and optionally to another source of high tempera-
ture to drive out water from the container walls while the containers are
empty, are used.
The dimensions of the final tablet or block macrosolid that is produced
according to the present invention will, as indicated above, depend upon
"'CVO 94/25563 ~ ~ ~~ PCTIEP94/01330
- 41 -
the initial sample size and the shape of the receptacle mold or container
used. Thus, a sample of 30 g of raw material that was exposed to microwave
radiation in a 100 ml Petri dish gave rise to a tablet on the order of 5.4
cm in diameter by approximately 2.0 cm in height. A macrosolid cylindrical
block formed from a 250 g sample had dimensions of approximately 6 cm for
both diameter and height. The dimensions for a cylindrical block formed
from 1 k i l ogram of raw mater i a l s were approx imate ly ~ 16 cm i n d i
ameter by
4.5 cm. Dimensions f or other size tablets and blocks may be found in the
examples below.
The tablet or block macrosol id formed via the SER process may usual ly be
conveniently and readily removed from a reusable solidifying container by
merely inverting the container to dislodge the item thus produced. If de-
sired, a releasing agent such as a silicone spray may also be used to
pre-treat the mold before the raw material mixture is introduced in to the
mold.
As already briefly noted above, it has been surprisingly found that some
of the macrosolid tablets or blocks formed according to the SER process of
the current invention including conventional water soluble alkaline
cleaner materials and/or crystalline layer silicates exhibit remarkably
rapid dissolution, or a combination of dissolution and mechanical disinte-
gration, upon exposure to water. In comparison studies, microwave macro-
solids produced by the current invention exhibited dissolution rates that
were at least an order of magnitude faster than commercially available
solids. Thus, blocks on the order of hundreds of grams up to kilogram size
have been shown to disrupt and dissolve readily when dropped into a beaker
of water. One 400 g sample fell completely apart and was entirely flushed
out of the dispensing chamber into which it had been placed. The bottom of
the sink into which the material was dispensed had a build-up of un-
dissolved material from the block. The macrosolid block therefore allows
for easier handling than a powder and has similar - if not better -
dissolving characteristics. This further provides for less opportunity for
operator exposure to partially dissolved tablets or blocks. From the fore-
going, the fact that such SER-produced macrosolid blocks offer certain
conveniences in handling and shipping would therefore be appreciated by
PCT/EP94/01330
WO 94/25563
- 42 -
those knowledgeable in this field. Specific comparison data for relative
dissolution/disintegration rates are given in Table 2 below.
For additional handling convenience or modification of the block proper-
ties, it was discovered that a thin coating layer of poly{ethylene glycol}
(hereinafter often abbreviated "PEG") can be introduced into blocks
consolidated via the SER technique of the present invention. By way of
example, either the blocks were dipped into melted PEG after microwave
treatment, or PEG was added to '
Table 2
Relative Dissolution Rates of Commercially Available
Cleaner Tablets Compared to Microwave t~acrosolid Tablets
Prepared by a Process of This Invention
Sample Time for tablet to
Sample used/Use Mass completely dissolve
(min.)
Topmat TabsTM/industrial"' 5 (fresh tablet)
40
40 8 - 10 (older tablet)
TopmatTM Dos extra/ind.60 23 - 26
SomatTM Tabs/household 35 20 - 23
SomatTM Supra Tabs/h.hold25 13 - 15
CalgonitTM Tabs/household18 "' 2
HuyTM Tabs/household 20 8 - 10
Example 1.1 (below) 30 "' 0.2 (9 seconds)
Larger scale product,
with
the same materials as 230 "' 0.8 (50 seconds)
Example 1.1
Example 1.2 (below) 30 ~ 0.2 (14 seconds)
Example 1.6 (below) 30 "' 0.7 (40 seconds)
Example 1.11 (below) 30 0.3-0.4
(20-25 sec.)
Notes for Table 2
Dissolution rates were measured in 1 liter of stirred tap water at 55
°C.
The CalgonitTM Tabs contain special disintegrating promoting agents.
WO 94/25563 2 16 2 2 4 6
PCT/EP94/01330
- 43 -
the raw materials in powder or flake form prior to microwave treatmgnt. In
this manner, PEG of various molecular weights may be incorporated into
larger macrosolid blocks. In particular, PEG 900, 1450, 3350, 8000, and
20,000 (the numbers representing weight average molecular weights of the
PEG) all gave acceptable results via either of the above incorporation
techniques. It should also be recognized that, where desired, a combina-
tion of the dipping or incorporation techniques is also possible, and
would be consistent with the teaching of the present invention.
Macrosolid blocks that were dipped into PEG were exposed to the molten
substance for times that varied from approximately five to approximately
sixty seconds. One hundred gram samples were prepared that contained an
additional 10 to 36 g of PEG in the raw materials prior to microwave
treatment. Dispensing rates for PEG-treated blocks - either coated with
PEG or with PEG incorporated therein - were then compared. In general, PEG
coated blocks dispensed at a somewhat slower rate than analogous blocks
containing solidified PEG in the raw materials.
WO 94/25563 PCTIEP94I01330
44 - 2162246
Tvoical Methods of Making Products According to the Invention
While the following processes are described with reference to specific
components, it should be understood that other components and similar pro-
cesses can be used together with the SER process of the present invention
in order to produce cleaners or detergents in the form of tablet or block
macrosolids.
Typically, the starting raw materials for the desired cleaner or detergent
formulation are mixed or combined together at ambient temperatures to form
a pre-mix, which is introduced into a reusable mold or a receiving con-
tainer device. The minimum amount of solid raw material which is normally
used to form a macrosolid tablet or block according to the present inven-
tion is one half gram (0.5 g).
The small amount of water required for the process of the invention is us-
ually already present in the solid raw materials. Where this is not the
case, water may be added to the raw materials prior to SER treatment to
provide the water required, depending upon the desired formulation. Where
well-characterized hydrates are used, and the other raw materials are not
strongly hygroscopic, the water content may be calculated based on the
chemical formula and percent of the well-characterized hydrated raw
materials) used in the pre-mix.
As will be apparent to those knowledgeable in the field, in certain in-
stances it may be desirable to pre-heat one or more raw materials or
portions thereof prior to SER treatment. Furthermore, preformed cores or
plugs such as those described in U.S. Re. No. 32,763 (Fernholz, et al.)
can be introduced into the container for the raw material particle bed,
before or after the raw material mixture has been introduced into the
mold, but before it is exposed to SER radiation. Alternatively, it may
also be desirable to after-treat the macrosolid block or tablet thus
formed via a subsequent technique such as dipping, spraying or coating,
etc., as discussed above. Such after-treatment may be desirable where, for
instance, a particular desired component of the final product is not
stable to SER irradiation, or a particular characteristic enhancement or
deterrent is desired.
°WO 94/25563 ~ PCT/EP94/01330
_ 45 _
The stability and uniformity of the subinfrared electromagnetic radiation
in the SER chamber or at the point of treatment is an important factor for
the successful practical application of the process according to the
present invention. A non-uniform distribution of SER energy has been
observed to create localized hot spots in the raw materials which can lead
to uneven heating and temperature "runaway." Furthermore, a constant and
non-varying SER radiation intensity from one SER treatment to the next is
important, so that raw material formulations may be repeatedly and repro-
ducibly solidified by the technique.
The amount of time required to form a macrosolid tablet or block is de-
pendent on the sample weight, the size and shape of the container used,
and either penetration depth of SER or the path length required for loss
of volatilized water. In those instances where larger amounts of water may
be evolved during SER treatment, it may be desirable to sweep the treat-
ment chamber with air or an appropriate inert gas so as to prevent conden-
sation of undesired water within the chamber. With samples on the order of
30 g size, this was not necessary. However, even with the smaller 30 g
tablets, where production conditions require large numbers of samples to
be simultaneously treated, then, depending upon the size and configuration
of the chamber and container in which the samples are exposed to SER, the
use of a sweeping stream may be advantageous.
The present invention may be further appreciated by reference to the fol-
lowing specif is examples and comparisons. As wi 11 be readi ly apparent to
one skilled in the relevant art, these examples are illustrative of
various parameters of the present invention, but they in no way limit its
scope, except to the extent that any parameters shown in the examples may
be incorporated into the appended claims.
EXAMPLES GROUP 1
General Conditions for This Group
A Microwave Laboratory Systems Bilchi Model MLS 1200 T microwave generator
with 2450 MHz frequency microwaves was used at a power setting of 250
watts. The compounds specified below were anhydrous ( i .e. , free from any
stoichiometrically well characterized water of hydration) unless noted to
WO 94125563 PCT/EP94101330
- 46 -
the contrary. The compounds used were initially in granular or powdered
form from conventional commercial sources. These were mixed together and
then ground for about one minute in a conventional domestic coffee grinder
(Krups Type D6, 150 watts power rating) for homogenization and some size
reduction. The water contents of the starting raw materials were de-
termined by calculation from the known hydrated materials used in each ex-
ample.
Thirty grams of the ground raw material mix was put into place in a stand-
ard laboratory PyrexR glass Petri dish 5.4 cm in diameter 5y 2.0 cm in
height. The Petri dish was gently tapped and shaken by hand to facilitate
f i 11 ing it with the ground raw material mix. The top of the particle bed
in the Petri dish was levelled with a scraper, and a cylindrical block
about 2 mm smaller in diameter than the Petri dish was used to apply
gentle pressure of about 0.1 Newton to lightly compact the particle bed
before exposure to the microwave radiation for a period of 2 to 4 minutes,
except as noted. In some examples where noted below, an electronic con-
troller linked with a temperature probe kept inside the microwave cavity
in close proximity to the Petri dish containing the particle bed was used
to reduce microwave power as needed to maintain the probe temperature at
or below a preset level.
In each case a single macrosolid cleaner tablet with substantially the
same d imens i ons as the conta i ner i n wh i ch i t had been formed and ,
except
for Example 1.11, a mass of 30~3 grams was obtained. The product could be
removed from the container within a few seconds after discontinuing the
microwave radiation.
EXAMPLE 1.1
A thirty gram (30 g) cleaner tablet was prepared according to the inven-
tion using the following procedure. Approximately 60 parts of sodium meta-
silicate, 24 parts of sodium tripolyphosphate (STPP), and 16 parts of
sodium carbonate decahydrate were mixed together. The resulting mixture,
which had an initial water content of 10 %, was introduced into a contai-
ner which was then placed into a microwave compartment. The mixture was
exposed to microwave radiation for a few minutes, after which a macrosolid
- 216 2 2 4 6 PCT/EP94101330
~'O 94/25563
- 47 -
cleaner tablet measuring approximately 5 cm in diameter by 1.5 cm high was
obtained.
EXAMPLE 1.2
This sample was a variation of the formulation used in Example 1.1, in
that it included an uncoated chlorine source, and hydrated forms of sodium
silicate and sodium tripolyphosphate, but no sodium carbonate. The proce-
dure used was the same as that described for Example 1.1, except that a
temperature sensing probe spaced no more than 1 mm from the particle bed
container was utilized, and control of the microwave generator was imple-
mented such that the temperature was maintained below approximately
383° K
(110° C). Accordingly, 2 parts of dichloroiso-cyanurate 2H20, 47 parts
of
sodium metasilicate, 10 parts of sodium silicate_5H20, 40 parts of sodium
tripolyphosphate 6H20 and 1 part of paraffin oil were mixed together. The
mixture, which had an initial water content of 14 %, was exposed to
microwave radiation for a few minutes, after which a macrosolid 30 g
cleaner tablet measuring approximately 5 cm by 1.2 cm was obtained.
EXAMPLE 1.3
This example illustrates the difference in having NaOH replace the sodium
metasilicate of Example 1.1. In this instance, hydrous and anhydrous phos-
phates are also included. The procedure that was used was the same as de-
scribed in Example 1.1, except that an external temperature control was
implemented to prevent the temperature within the microwave chamber from
exceeding 383° K (110° C). Accordingly, 1 part of sodium
metasilicate,
14.5 parts of sodium tripolyphosphate, 14.5 parts of sodium tripolyphos-
phate ~6H20 ("STPP"), 10 parts of sodium carbonate ~ 1OH20, and 60 parts
of sod i um hydrox i de were m i xed together to g i ve a pre-mi x that conta
i ned
% water. This mixture was exposed to microwave radiation for a few
minutes, after which a macrosolid 30 g tablet measuring approximately 5 cm
by 1.2 cm was obtained. It should be noted that localized "hot spots" and
temperature runaway may be observed with other similar raw materials
mixes, especially those containing 65 % or more of NaOH, when they are ex-
posed to microwave radiation without any form of temperature control. Tem-
perature control, even with samples containing as much as 50 % NaOH, is
therefore recommended.
WO 94125563 PCT/EP94101330
2162246 - 48 -
EXAMPLE 1.4
The purpose for this example was to provide a formulation that included
sodium hydroxide with an available chlorine source. Example 1.4 therefore
represents a variation on Example 1.3 above. The procedure followed was
similar to that in Example 1.1. Accordingly, 57.7 parts of sodium
hydroxide, 1.9 parts of coated dichloroisocyanurate ,- 2H20, 1 part of
sodium silicate, 14 parts of sodium tripolyphosphate, 14 parts of sodium
tripolyphosphate ~ 6H20, 9.6 parts of sodium carbonate ~ 1OH20, 0.9 parts
of wax, and 0.9 parts of paraffin oil were mixed together. The mixture,
which contained approximately 10 % water, was exposed to microwave radia-
tion for a few minutes, after which a macrosolid 30 g tablet measuring
approximately 5 cm by 1.2 cm was obtained.
The chlorine contents of the products from Examples 2 and 4 were deter-
mined by titration, both before microwave treatment, and fourteen days
thereafter. The results obtained, which gave nearly the theoretical
values, are given in Table 3 below.
TABLE 3
Available Chlorine
(expressed as percent)
Untreated Fourteen Days
Example No. Product After Treatment
1.2 1.10 1.04
1.4 0.77 0.76
EXAMPLE 1.5
This example illustrates a cleaner formulation that contained an uncoated
perborate as an available oxygen source. The sample was prepared according
to the procedure described in Example 1.1. Accordingly, 6 parts of un-
coated sodium perborate ~ H20, 45 parts of sodium si 1 icate, 15 parts of
sodium silicate ~ 5H20, 28 parts of sodium tripolyphosphate, 3 parts of
sodium carbonate, and 3 parts of sodium carbonate ~ 1OH20 were mixed
'~'O 94/25563 ' 216 2 2 45 pCT~p94/01330
-49-
together, to give a pre-mix which contained approximately 9 o water.
Controls were implemented such that the temperature was maintained below
approximately 383° K (110° C). Afterwards, a macrosolid 30 g
cleaner
tablet measuring approximately 5 cm by 1.2 cm was obtained.
EXAMPLE 1.5
The formulation in this example contained NaOH and a coated perborate as
an available oxygen source. The sample was prepared according to the pro-
cedure described in Example 1.1. Accordingly, 50 parts of sodium
hydroxide, 10 parts of sodium hydroxide ~ 1H20, 6 parts of coated sodium
perborate ~ H20, 1 part of sodium silicate ~ 5H20, 23 parts of sodium
tripolyphosphate, and 10 parts of sodium carbonate ~ 1OH20 were mixed
together. A macrosolid 30 g cleaner tablet measuring approximately 5 cm by
1.2 cm was obtained. Controls were again implemented so that the tempera-
ture was maintained below approximately 343° K (70° C) during
microwave
treatment.
EXAMPLE 1.7
This was similar to Example 1.6 above, except that the raw materials con-
tained less sodium hydroxide and more coated sodium perborate. The pro-
cedure followed was that as described in Example 1.1. Accordingly, 34
parts of sodium hydroxide, 8.5 parts of sodium hydroxide ~ 1H20, 21.3
parts of coated sodium perborate ~ H20, 1.1 parts of sodium silicate ~
5H20, 24.5 parts of sodium phosphate, and 10.6 parts of sodium carbonate
1OH20 were mixed together to give a premix which contained approximately
14 % water. The temperature was again maintained below approximately
343°
K (70° C) during the microwave treatment.
EXAMPLE 1.8
This example was also similar to Example 1.6 above, except that the avail-
able oxygen source was coated instead of uncoated percarbonate. The pro-
cedure followed was that as described in Example 1.1. Accordingly, 50
parts of sodium hydroxide, 10 parts of sodium hydroxide ~ 1H20, 6 parts of
sodium percarbonate ~ 2H20, 1 part of sodium silicate ~ 5H20, 23 parts of
sodium tripolyphosphate, and 10 parts of sodium carbonate ~ 1OH20 were
mixed together. The mixture contained approximately 13 % water. The
WO 94125563 PCT/EP94/01330
-50-
temperature was again maintained below approximately 343° K (70°
C) during
the microwave treatment.
The oxygen contents of the raw materials and products from Examples 5 - 8
were determined using standard titration techniques, both before and after
microwave treatment. The results obtained, which gave nearly the theore-
tical values before treatment, are shown in Table 4 below.
As may be seen from the data in Table 4, samples containing !coated oxygen
sources retained at least 48 % of the activity of the initial raw material
after microwave treatment. The biggest difference in available oxygen
content before and after microwave treatment was seen with Example 1.5,
where an uncoated oxygen source was used.
EXAMPLE 1.9
This example illustrates the incorporation of sodium sulfate, as well as
an anionic and a non-ionic surfactant, into a cleaner formulation. The
procedure fol-
''VO 94/25563 ~ PCT/EP94/01330
- 51
TABLE 4
Available Oxygen
(expressed as percent)
Before After Seven Days
ExampleMicrowave Microwave After
No. Treatment Treatment Treatment
1.5 0.9 (uncoated)< 0.1 not avail.
1.6 0.41 (coated) 0.40 0.42
1.7 1.51 (coated) 1.38 not avail.
1.8 0.75 (coated) 0.36 not avail.
lowed was similar to that as described in Example 1.1. Accordingly, 5
parts of sodium silicate, 37.5 parts of sodium carbonate, 29 parts of
sodium carbonate ~ 1OH20, 25 parts of sodium sulfate, 1 part of non-ionic
surfactant (TA 14) and 2.5 parts of anionic surfactant (MersolatTM 95)
were mixed together to give a pre-mix that contained approximately 18
water.
EXAMPLE 1.10
This example is similar to Example 1.9 above, except that less sodium sul-
fate and more of the anionic surfactant was used. The procedure followed
was that described in Example 1.1. Accordingly, 5 parts of sodium sili-
cate, 37.5 parts of sodium carbonate, 29 parts of sodium carbonate
1OH20, 22.5 parts of sodium sulfate, 1 part of non-ionic surfactant (TA
14TM) and 5 parts of anionic surfactant (MersolatTM 95) were mixed to-
gether to give a pre-mix that contained approximately 18 ~c of water.
The detergent contents of the raw materials and products of Examples 9 and
were determined both before and after microwave treatment. The results
obtained, which gave nearly the theoretical values, are shown in Table 5.
From these two examples, it may be seen that it is readily possible to
incorporate anionic and non-ionic surfactants into a raw material mixture
WO 94/25563 .~ PCT/EP94/01330
- 52 -
that is then exposed to microwave radiation to form a stable product that
maintains an effective detergent strength. It should be noted that the
surfactants may be used in virtually any form: pastes, liquids, solids,
powders, flakes or granules.
'VO 94/25563 ~ ~ ~ PCT/EP94/01330
- 53
TABLE 5 ;
Detergent Composition
(expressed as percent)
Non-ionic Anionic
Detergent Detergent
Before / After Before / After
Microwave Microwave
Example No. Treatment Treatment
1.9 0.99 / 0.96 1.83 / 1.83
1.10 0.99 / 0.96 3.90 / 3.85
EXAMPLE 1.11
Approximately 85.7 grams of sodium citrate ~ 2H20, 4.3 grams of sodium
sulfate ~ 1OH20, and 10 grams of DehyponT~'i LT 104 (fatty alcohol poly-
glycol ether, terminally blocked, nonionic surfactant, product of Henkel)
were mixed together and placed into the container which was introduced
into a microwave compartment. The mixture was exposed to microwave radia-
tion for 3 minutes, after which a macrosolid tablet measuring approximate-
ly 5 cm by 1.2 cm was obtained.
EXAMPLE 1.~2
Approximately 40.2 % of sodium sulfate, 34.5 % of sodium citrate dehy-
drate, 11.5 % of SOKALANTM CP5, 11.5 % of sodium carbonate decahydrate,
and 2.3 % of TAED, totalling 30 g in mass, are mixed together and placed
into the container as above. The mixture is exposed to microwave radiation
for 3 minutes, after which a microsolid tablet measuring approximately 5
cm by 1.2 cm is obtained.
EXAMPLE 1.13
Approximately 29 % of sodium tripolyphosphate, 1.0 % of sodium metasili
cate, 8.5 % of sodium carbonate decahydrate, 41 % of sodium hydroxide, 15
of sodium hydroxide monohydrate, 1 % of defoamer, and 4.5 % of coated
dichloroisocyanurate dehydrate, totalling 30 g mass, are mixed together
and placed into the container as above. The mixture is exposed to
WO 94/25563 21 b 2 2 4 6 pCT~p94101330
- 54 -
microwave radiation for 3 minutes, after which a microsolid tablet
measuring approximately 5 cm by 1.2 cm is obtained.
EXAMPLES 1.14 - 1.22
These examples were all performed in the same general manner as for the
preceding examples in this group, with a total of 30 grams of raw material
to produce a macrosolid tablet approximately 5 cm by 1.2 cm. The composi-
tions of the raw materials for each of these examples are shown in Table
6. It might be advantageous to irradiate temperature-sensitive raw mate-
rial mixtures (e. g. containing sodium perborate or sodium hydrogen
carbonate) in a reduced pressure environment (example No. 1.21, 1.22).
'VO 94/25563 216 2 2 ~ 6 PCT/EP94101330
- 55 -
N
N O O O O ~ O O O O O
~ ~
r1 P. n 00 N
N
O N ~ N ~'f O O O O O O
'
O
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01 u~ ~n tn
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O O O ~C~M M O N O O O
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N N N N N iI~Z N N 1-"(.~
tJ
WO 94/25563 PCT/EP94/01330
21 b2246
- 56 -
~n o N o a o
O O O O O O
N
N ~O O O O O O
.-r n
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ri
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-
WO 94/25563 PCT/EP94/01330
- 57 - ~1 ~2~2~ 6'
EXAMPLES 1.23 - 1.27
These examples were all performed in the same general manner as for the
other examples in this group, with a total of 30 grams of raw material to
produce a macrosolid tablet approximately 5 cm by 1.2 cm, except for one
important variation: The microwave radiation was pulsed, alternating for 5
sec intervals with and without radiation until a total of 45 sec of
radiation time had accumulated for the samples. The compositions of the
raw materials for each of these examples, all of which iACluded a sub-
stantial proportion of the strong acid sulfamic acid, are shown in Table
7.
TABLE 7
Component of Raw Percent
Material of
Component
in
Example
No.:
1.23 1.24 1.25 1.26 1.27
Na2S04 1OH20 5 5 5 5 0
Na2HP04 12H20 0 0 0 0 5
Na2S04 0 0 5 0 0
DehyphonTM LT 104 2 2 2 0 0
MERSOLATTM H95 0 0 0 3 0
Sulfamic acid 95 g3 88 g2 g5
EXAMPLES 1.28 - 1.41
These examples were all performed in the same general manner as for the
other examples in this group (except Examples 1.23 - 1.27), with a total
of 30 grams of raw material to produce a macrosolid tablet approximately 5
cm by 1.2 cm. All of these examples utilize a preferred crystalline
layered silicate material already briefly noted above, Na-SKS-6 commer-
cially supplied by Hoechst AG. The compositions of the raw materials for
each of these examples are shown in Table 8. Compositions 1.32, 1.33,
1.35, and 1.36 consist only of water (as water of hydration) and alkaline
cleaning agents. They can be used, for example, as water softening
WO 94/25563 PCTIEP94101330
- 58
compositions as part of a cleaner unit construction system ("Baukasten-
system")
EXAMPLES 1.42 - 1.47
These examples offer direct comparisons between macrosolids with crystal-
line layered silicates and those with anhydrous sodium metasilicate
instead of the crystalline layered silicate. All these examples were
performed in the same general manner as for the other examples in this
group (except Examples 1.23 - 1.27), with a total of 30 grams of raw
material to produce a macrosolid tablet approximately 5 cm by 1.2 cm. The
compositions of the raw materials for each of these examples are shown in
Table 9, along with some mechanical strength and disintegration rate
comparisons for the macrosolid products. The latter characteristics are
reported according to scales defined as follows:
disintegration rate mechanical strength
++ 1 g of macrosolid is dissolvedthe macrosolid cannot be
in 1 1 of stirred tap water broken in two parts by hand
at
55C (20C) in less than 6 sec.
(19 sec.)
+ 1 g of macrosolid is dissolvedthe macrosolid doesn't break
in 1 1 of stirred tap water when dropped on a tiled
at floor
55C (20C) in less than 10 from 2 m height but can
sec. be
(30 sec.) broken by hand
- 1 g of macrosolid is dissolvedthe macrosolid breaks in
two
in 1 1 of stirred tap water parts when dropped on a
at tiled
55C (20C) in a time between floor from 2 m height
and 60 sec. (30 sec. and
5 min.)
-- 1 g of macrosolid is dissolvedthe macrosolid breaks
in 1 1 of stirred tap water completely when dropped
at on
55C (20C) in more than 60 a tiled floor from 2 m height
sec.
(5 min. )
WO 94/25563 PCT/EP94/01330
_ 59 _
o ac o 0 0 0
O
O O ~ O O N O
Cp N
O ~ O O O O O
~
O
M
O O ~ O O N O
M
O O ~ O O N O
O
Z ~O 1d~ tn
M
M O ~ O O O O
M
d
E
b
X M
O M M v v O O
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~
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L
C~ Z Z Z Z Z Z d N
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H
WO 94125563 216 2 2 4 6 PCT/EP94/01330
- 60 -
0 0 0 0 0
rr
0
0 0 0 ~ o 0
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M b
O O O tt7O O L
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ed
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O O O N M O ~O
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47
N
d
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O O O O O O +1
M Vf
r
r
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O
d
ri
~
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r e6 N O
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L
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in O >> J
C .r O m n O O
t O
.r ~ Z 1-- ~ d
r
t0 ~ 1- J r .~ Q
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H
O 4d V ~ ~ ~t ~ W
L C d +~
t~ C IC H- 1- i- ~ ~ GJ
C7 t0 +~ d
CO O ~ 2 O d ~ C1 ..
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; = W
J t -r-u LJ e0 O O
0 .J O T
V U C9 ~ D 4. U Z
~ v1 U
Q
H
v0 94/25563 216 2 2 4 6 PCT/EP94/01330
- 61 -
TAB
Component of Raw Percent
l~laterial of
Component
in
Exa~le
Ho.:
1.42 1.43 1.44 1.45 1.4fi 1.47
Pentasodium tripoly-40 40 39.1 39.1 0 0
phosphate
Na2Si03 32 0 37.3 0 20 ~ 0
Na2Si03 5H20 15 15 16 16 0 0
Na-SKS-6 0 32 0 37.3 0 20
Na2C03 0 0 0 0 44.8 44.8
Na2C03 . 1OH20 8.5 8.5 7.6 7.6 30.2 30.2
Coated dichloroiso- 4 4 0 0 0 0
cyanurate dehydrate
DEHYPONTM LT 104 0.5 0.5 0 0 5 5
Mechanical strength + ++ + ++ - ++
rating
Disintegration rate + ++ + ++ + ++
rating
EXAMPLES 1.48 - 1.51
These examples offer direct comparisons between macrosolids with crystal-
line layered silicates and those with Zeolite A, waterglass, or anhydrous
sodium metasilicate instead of the crystalline layered silicate. All
these examples were performed in the same general manner as for the other
examples in this group (except Examples 1.23 - 1.27), with a total of 30
grams of raw material to produce a macrosolid tablet approximately 5 cm by
1.2 cm. The compositions of the raw materials for each of these examples
are shown in Table 10.
EXAMPLES 1.52 - 1.57
These examples all illustrate macrosolids that are particularly useful as
laundry or other textile cleaning products. They were all performed in the
same general manner as for the other examples in this group (except
WO 94/25563 216 2 2 4 b pCT~p94101330
- 62 -
Examples 1.23 - 1.27), with a total of 30 grams of raw material to produce
a macrosolid tablet approximately 5 cm by 1.2 cm. Compositions of the
particle bed used are shown in Table 11.
t
WO 94/25563 2 j 6 2 2 4 6 pCT/Epg4/01330
- 63 -
TABLE 10
Component of Raw Percent
Material of Component
in Example
Ro.:
1.48 1.49 1.50 1.51
Na2Si03 0 0 34.5 0
PORTILTM waterglass 0 34.5 0 ~0
Na-SKS-6 34.5 0 0 0
Na2C03 32.5 32.5 32.5 32.5
Na2C03 H20 33 33 33 33
Zeolite A 0 0 0 34.5
Mechanical strength rating+ ++ _ _-
Disintegration rate rating++ -- + +
EXAMPLES 1.58 - 1.
These examples all illustrate macrosolids that are particularly useful as
the cleaners for automatic dishwashing operations. They were all performed
in the same general manner as for the other examples in this group (except
Examples 1.23 - 1.27), with a total of 30 grams of raw material to produce
a macrosolid tablet approximately 5 cm by 1.2 cm. Compositions of the
particle bed used are shown in Table 12.
EXAMPLES 1.64 - 1.
These examples all illustrate macrosolids that contain both acids and
alkaline cleaning agents. They were all performed in the same general
manner as for the other examples in this group (except Examples 1.23 -
1.27), with a total of 30 grams of raw material to produce a macrosolid
tablet approximately 5 cm by 1.2 cm. Compositions of the particle bed used
are shown in Table 13.
D(M~LES AtOUP 2
WO 94/25563 PCT/EP94/01330
- 64 - 2162246
All the examples in this group were consolidated using a Hotpoint Model
RE60002.92KW microwave generator (serial number AT9789585) rated at 450
watts power output. The general conditions were otherwise the same as for
Group 1, except that the containers were of high density polyethylene and
the sizes of the containers were more varied, corresponding to the sizes
of the particle beds used, and that the raw materials were not ground, but
merely mixed together by hand, with no deliberate size reduction. The
particle sizes of the vari-
" WO 94/25563 216 2 2 4 6 PCT/EP94/01330
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TABLE 11
Component of Ray Percent
!laterial of
Conponent
in
Exaeple
No.:
1.52 1.53 1.54 1.55 1.56 1.57
C12-14 fatty acid soap 2 2 1.2 2 1.2 0
C12-alkylbenzene 10 10 8.9 13 9 7
su lfonate
C12-18 fatty alcohol+5 4.5 4.5 2.6 4 2.6 10
E01
SokalanTM CP52 6 6 8.2 5 8.75 0
Hydroxyethane-1,1- 0.2 0.2 0.2 0.2 0.2 0
diphosphonate
Na2C03 1OH20 14 14 21 20 21 23
Amorphous sodium 3.5 3.5 2.4 0.8 2.4 8
disilicate
Trisodium polyphosphate0 0 0 0 0 30
Zeolite A 35 0 32 6 0 0
Na-SKS-6 0 35 0 43 32 0
Lipase 0.5 0.5 0 0.5 1 1
Protease 0.95 0.95 1 1 1 1
Silicone oil 0.15 0.15 0.15 0.15 0.15 0
TAED 5.5 5.5 5.5 0 5.5 0
Optical brightener 0.2 0.2 0.2 0.2 0.2 0
Coated sodium perbora~e16 16 12 0 12 0
monohydrate
Na2S04 1.5 1.5 1.65 4.15 0 20
Footnotes for Table
11
This product is made
by condensing an average
of 5 moles of ethylene
oxide ("EO") per mole
of alcohol with a mixture
of fatty alcohols of
varying chain length
as noted.
2This is an acrylate-maleinate
copolymer available
commercially from
BASF.
WO 94/25563 PCTIEP94/01330
2.162246 _ ss -
ous raw materials were as shown immediately below. The sieve sizes (num-
bers) noted are U. S. Standard Sieves, described in American Society for
Testing and Materials ("ASTM") Standard E-11-61 as "Tyler equivalent
designations".
WO 94125563 ~~ PCT/EP94/01330
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TABLE 1
Component of Ray ~lateri Percent
a 1 of
Component
i
n
Exaople
No.:
1.58 1.59 1.60 1.61 1.62 1.63
Na2C03 0 27 0 19.5 0 0
NaHC03 15 0 31 0 31.6 0
Na2C03 1OH20 0 0 16 5 , 8 5.9
Amorphous sodium disilicate20 20 0 0 0 0
Na-SKS-6 0 0 0 20 0 0
Trisodium citrate dihydrate40 26 36 26 44.9 0
Pentasodium tripoly- 0 0 0 0 0 29.6
phosphate
Sodium metasilicate 0 0 0 0 0 45.7
Sodium metasilicate 0 0 0 0 0 17.5
pentahydrate
Coated dichloroisocyanurate0 0 0 0 0 1.3
SokalanTM CP5 10 10 0 0 0 0
DegapasTM 3104N1 0 0 0 12.5 0 0
Coated sodium perborate 7 10 10 10 10 0
monohydrate
DehydolTM LS22 1 1 1 1 1 0
APGTM 2253 1 1 1 1 0.8 0
TAED 3 3 3 3 1.9 0
Amylase 1.5 1 1 1 1 0
Protease 1.5 1 1 1 0.8 0
Footnotes for Table 11
lThis is an aqueous solution
containing 40 % solids
of an acrylate
polymer available commercially
from Degussa.
This is a fatty alcohol
ethoxylate available commercially
from Henkel
KGaA.
3This is a C8-10 fatty
alkylpolyglucoside available
commercially from
Henkel Corporation.
WO 94/25563 PCT/EP94/01330
~,~6~24~ - 68 -
TABLE 13
Component of Ray haterial Percent of
Component
in
Example ho.:
1.64 1.65
Trisodium citrate dihydrate 55 57
Sulfamic acid 30 10 '
Sodium carbonate decahydrate 5 13
Sodium carbonate 10 20
Sodium tetraborate tetrahydrate: 0.5 % maximum retained on sieve # 40; 80
% minimum through sieve # 100; 10 maximum through sieve # 200.
Trisodium phosphate dodecahydrate: 99.0 % minimum through sieve # 20; 10
% maximum through sieve # 100.
Tetrasodium pyrophosphate (anhydrous): 5.0 % maximum retained on sieve #
14; 25 % maximum through sieve # 100.
Sodium tripolyphosphate hexahydrate: 1.0 % maximum retained on sieve #
14; 15 % maximum retained on sieve # 20; 75.0 % minimum retained on sieve
# 60; 10.0 % maximum through sieve # 100.
Sodium tripolyphosphate granules (anhydrous): 0.5 % maximum retained on
sieve # 12; 12 % maximum retained on sieve # 20; 5 % maximum through sieve
# 200.
Sodium tripolyphosphate powder (anhydrous): 5 % maximum retained on sieve
# 60; 90 % minimum through sieve # 100.
Sodium metasilicate pentahydrate: 0.1 % maximum retained on sieve # 12;
8.0 % maximum retained on sieve # 20; 80 % minimum retained on sieve # 50;
% maximum through sieve # 50 but retained on sieve # 60; 5 % maximum
through sieve # 60 but retained on sieve # 100; 2 % maximum through sieve
# 100.
Sodium metasilicate (anhydrous): 2.0 % maximum retained on sieve # 18; 80
minimum retained on sieve # 60; 5.0 % maximum through sieve # 60 but
retained on sieve # 100; 2.0 % maximum through sieve # 100.
~O 94!25563 ~ PCTIEP94101330
- 69
Sodium hydroxide (anhydrous): 1.0 maximum retained on sieve # 12; 40.0 %
maximum retained on sieve # 20; 80 % minimum retained on sieve # 60; 5.0 %
maximum through sieve # 100.
Sodium carbonate (anhydrous): 0.5 maximum retained on sieve # 14; 10.0 %
maximum retained on sieve # 20; 75 % minimum retained on sieve # 100; 5.0
maximum through sieve # 200.
EXAMPLE 2.1
20 g of sodium metasilicate ~ 5H20, 50 g of sodium metasilicate, and 30 g
of sodium tripolyphosphate powder were mixed together to give a premix
which contained approximately 8.5 % water. The mixture was exposed to mi-
crowave irradiation for 2 min to give a macrosolid tablet.
EXAMPLE 2.2
20 g of sodium metasilicate ~ 5H20, 50 g of sodium metasilicate, and 30 g
of sodium tripolyphosphate granules were mixed together to give a premix
which contained approximately 8.5 % water. The mixture was exposed to
microwave irradiation for 2 min to give a macrosolid tablet.
EXAMPLE 2.3
20 g of sodium metasilicate ~ 5H20, 50 g of sodium metasilicate, and 30 g
of sodium carbonate, were mixed together to give a premix which contained
approximately 8.5 % water. The mixture was exposed to microwave irradia-
tion for 2 min to give a macrosolid tablet.
EXAMPLE 2.4
20 g of sodium metasilicate ~ 5 H20, 30 g of sodium metasilicate, 20 g of
sodium carbonate, and 30 g of sodium tripolyphopshate granules were mixed
together to give a premix which contained approximately 8.5 % water. The
mixture was exposed to microwave irradiation for 2 min to give a macro-
solid tablet.
EXAMPLE 2.5
g of sodium metasilicate ~ 5 H20, 55 g of sodium metasilicate, and 35 g
of sodium tripolyphosphate granules were mixed together to give a premix
which contained approximately 4.3 % water. The mixture was exposed to mi-
crowave irradiation for 2 min to give a macrosolid tablet.
WO 94/25563 2'~ 6 ~ ~, 4 ~ PCTIEP94101330
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EXAMPLE 2.6
20 g of sodium tetraborate ~ 5H20, 30 g of sodium metasilicate, 20 g of
sodium carbonate, and 30 g of sodium tripolyphosphate granules were mixed
together to give a premix which contained approximately 5.8 % water. The
mixture was exposed to microwave irradiation for 2.5 min to give a macro-
solid tablet.
EXAMPLE 2.7
20 g of sodium tetraborate ~ 5H20, 50 g of sodium metasilicate, and 30 g
of sodium tripolyphosphate granules were mixed together to give a premix
which contained approximately 5.8 % water. The mixture was exposed to
microwave irradiation for 1.5 min to give a macrosolid tablet.
EXAMPLE 2.8
g of sodium tetraborate ~ 5H20, 40 g of sodium metasilicate, 20 g of
sodium carbonate, and 30 g of sodium tripolyphosphate granules were mixed
together to give a premix which contained approximately 2.9 % water. The
mixture was exposed to microwave irradiation for 2 min to give a macro-
solid tablet.
EXAMPLE 2.9
10 g of sodium tetraborate ~ 5H20, 55 g of sodium metasilicate, and 35 g
of sodium tripolyphosphate granules were mixed together to give a premix
which contained approximately 2.9 % water. The mixture was exposed to mi-
crowave irradiation for 100 sec to give a macrosolid tablet.
EXAMPLE 2.10
10 g of trisodium phosphate ~ 12H20, 55 g of sodium metasilicate, and 35 g
of sodium tripolyphosphate granules were mixed together to give a premix
which contained approximately 5.2 % water. The mixture was exposed to mi-
crowave irradiation for 2 min to give a macrosolid tablet.
EXAMPLE 2.11
g of trisodium phosphate ~ 12H20, 30 g of sodium metasilicate, 20 g of
sodium carbonate, and 30 g of sodium tripolyphosphate granules were mixed
together to give a premix which contained approximately 10.4 % water. The
'WO 94/Z5563 216 2 2 4 b PCT/EP94/01330
- 71 -
mixture was exposed to microwave irradiation for 2 min to give a mapro-
solid tablet.
EXAMPLE 2.12
20 g of trisodium phosphate ~ 12H20, 50 g of sodium metasilicate, and 30 g
of sodium tripolyphosphate granules were mixed together to give a premix
which contained approximately 10.4 % water. The mixture was exposed to
microwave irradiation for 2 min to give a macrosolid tablet.
EXAMPLE 2.13
200 g of sodium metasilicate ~ 5 H20, 500 g of sodium metasilicate, and
300 g of sodium tripolyphosphate granules were mixed together to give a
premix which contained approximately 8.5 % water. The mixture was exposed
to microwave irradiation for 17 min to give a solid block containing 3.0 %
water.
EXAMPLE 2.14
200 g of sodium metasilicate ~ 5H20, 435 g of sodium metasilicate, 300 g
of sodium tripolyphosphate granules, 50 g of sodium carbonate, 10 g of
carboxymethylcellulose ("CMC") and 5 g of PVP were mixed together to give
a premix which contained approximately 8.5 % water. The mixture was
exposed to microwave irradiation for 18 min to give a solid block contai-
ning 3.0 % water. The block discolored somewhat during the microwave
irradiation, presumably due to decomposition of CMC and PVP. The block was
submerged in a liquid mixture of 20 % of polyethylene glycol) with an
average molecular weight of about 8000 ("PEG 8000") and 80 % of nonyl-
phenol ethoxylate having an average of 9.5 moles of ethylene oxide per
mole of nonylpheroi ("NPE 9.5") at 70° C until there was no further
visual
evidence of evolution of gas, which was assumed to be air being displaced
from the pores of the block. The block absorbed 319 g of solution, thus
adding 33 % to its former weight. This equals to having a block which
contains 21 % of NPE 9.5.
ExA6PLES GROUP 3
The following examples are consolidated using a radio wave radiation
source.
Examples 3.1 - 3.3
WO 94/25563 PCT/EP94/01330
6 -72-
General conditions are otherwise the same as for Group 1. The compositions
of the raw materials for each of these examples are shown in Table 14.
EXAMPLES GROUP 4
The following examples feature compositions for a solid component com-
prising a macrosolid cleaner tablet, and a liquid component, which
together form a two component or "dual-pack" product. The macrosolid
cleaner tablets are prepared using SER under conditions which are
otherwise generally the same as for Group 1. In each case, a~macrosolid
cleaner tablet is obtained with substantially the same dimensions as the
container in which it had been formed, and has a
TABLE 14
Component of Raw Percent
of Component
in
Example
No.:
3.1 3.2 3.3
Sodium metasilicate 1 40.9 5.5
Sodium metasilicate 5H20 0 11.8 0
Coated dichloroisocyanurate dehydrate3.5 0 0
Sodium tripolyphosphate 30 38.7
Sodium hydroxide 41 0 0
Sodium hydroxide H20 15 0 0
WUBTM 308 (defoamer) 1 1.1 0
Sodium carbonate 0 0 3.5
Sodium carbonate decahydrate 8.5 7.5 31.5
Sodium sulfate 0 0 27.7
MERSOLATTM95 0 0 2.7
TA 14 0 0 1.1
mass of 50~5 grams. The composition for the fluid component is given as
percent volume in a total of 260~26 ml.
WO 94/23563 216 2 2 4 6 PCT/EP94/01330
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Example 4.1
The first component of a dual-pack product according to the invention, a
fifty gram (50 g) macrosolid cleaner tablet, was prepared from approxi-
mately 58 parts of sodium metasilicate, 24 parts of .sodium tripoiyphos-
phate, 16 parts of sodium carbonate decahydrate and 2 parts of OehyponTM
LT 104 (non-ionic surfactant). The second dual-pack product component, an
accompanying liquid formulation totalling two hundred sixty milliliters
(260 ml), was prepared from 20 parts of monoethanolamine, 14.3 parts of
PropasolTM Solvent B, 14.3 parts of monophenyl glycol (technical grade)
and 51.4 parts of 40 % aqueous solution of sodium cumene sulfonate.
Example 4.2
The first component of a dual-pack product according to the invention, a
fifty gram (50 g) macrosolid cleaner tablet similar in composition to that
of Example 4.1, was prepared from approximately 56 parts of sodium meta-
silicate, 26 parts of sodium tripolyphosphate, 16 parts of sodium carbo-
nate decahydrate, 1_5 parts of DehyponTM LT 104 (non-ionic surfactant) and
0.5 parts GenapolTM OX 060 {non-ionic surfactant commercially available
from Hoechst). The second dual-pack product component, an accompanying
liquid formulation totalling two hundred sixty milliliters (260 mi) was
prepared as f or the liquid component from sample 4.2 above: 20 parts of
monoethanolamine, 14.3 parts of PropasolTM Solvent B, 14.3 parts of _
monophenyl glycol {technical grade) and 51.4 parts of 40 & sodium cumene
sulfonate in water solution.
The foregoing is considered to be illustrative only of the principles of the
invention.
Further, since numerous modifications and changes will occur to those skilled
in the
art, it is not desired to limit the invention to the exact construction and
operation
shown and described, and, accordingly, all suitable modifications and
equivalents may
be resorted to, falling within the scope of the invention.
