Note: Descriptions are shown in the official language in which they were submitted.
1~1~534
Background of the Invention
It has long been known that detergent formulations in paste
or liquid form offer advantages to the consumer which
conventional granular or powder-form detergent compositions
cannot o~fer. The most important of these advantages is
that such paste or liquid compositions may be sold in con-
centrated form, so that the consumer may use a smaller,
more manageable amount of the composition for each wash
load and does not have to contend with the storage of large
volumes of the composition when it is not in use.
A wide variety of such types of detergent
;..;:
. ,
compositions has been disclosed for use in the laundering
of soiled fabrics. For example, French Patent 1,602,442,
Henkel & Cie, GmbH, issued December 31, 1970, relates to
a laundry detergent composition having a paste form, while
German Patent 2,226,925, Kao Soap Company, I.td., discloses
laundry detergent compositions in gel form, and Canadian
Patent 1,020,039,
''
;
.
',`
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'
:
5~
Collins et al, issued November 1, lg77, relates to laundry
detergent compositions in liquid form. Since laundry
detergent compositlons are usually mixed directly with the
wash water the first time in the washing cycle that the
- automatic washing machine is filled up, the use of such
paste or liquid detergent compositions does not present
any dispensing problem when used in a conventional
automatic clothes washing machine.
However, because of the nature of the washing
process and the structure of certain types of automatic
dishwashers, problems may be encountered when automatic
dishwasher detergent compositions are formulated in a
paste or liquid form. In double dispensing cup type
automatic dishwashers, the detergent composition to be
used in the washing process is loaded into an automatlc
dispenser in the machine prior to the start of the washing
cycle. Once the washing cycle is started, the dirty
tableware is subjected to a rinse step, prior to the
introduction of the detergent into the washing system.
After the water rinse is completed, the detergent dispen-
ser cup opens, the detergent composition is released into
the washing system, and the tableware is washed in an
aqueous solution of the detergent composition.
Because the detergent dispensers in dishwashers are
generally not constructed to be water-tight, the use of a
liquid detergent composition in such a dispenser would
- result in the detergent composition running out of the dis-
` penser during the rinse cycle, leaving no detergent present
when the dispenser cup opens at the start of the wash
cycle. As a result of its higher viscosity, a paste deter-
gent composition would not be subject to this problem and,
hence, would be suitable for use in this type of automatic
~; - 2 -
~'
P~
dishwasher. Consequently, paste-form detergent composi-
tions for use in automatic dishwashers have been disclosed.
For example, U.S. Patent 4,123,395, Maguire et al, issued
October 31, 1978; U.S. Patent 4,101,457, Place et al,
issued July 18, 1978, Canadian Patent 1,073,381, Maguire
et al, issued March 11, 1980; U.S. Patent 4,090,973,
. Maguire et al, issued May 29, 1978, and German Patent
2,038,103, ~enkel & Cie, GmbH, issued February 10, 1972,
; all disclose such paste-form detergent compositions.
, 10 Although the higher viscosity of the paste composi-
tions does eliminate the composition leakage problem which
may be present when liquid detergent compositions are used
in automatic dishwashers, such compositions tend to dis-
pense out of the dispenser cup very slowly during the wash
cycle and, hence, are slow to become solubilized in the
aqueous wash solution. The fact that the full amount of
` the detergent composition, placed in the dishwashing
machine, takes a longer time to get into the washing
solution, decreases the overall effectiveness of the
washing process.
It is therefore an object of this invention to form-
ulate paste-form detergent composition articles for use in
automatic dishwashers, which give effective cleaning of
tableware and cookware together with efficient release from
the detergent dispenser and effective solubilization into
the aqueous washing solution.
; It is a further object of this invention to formu-
late paste-form detergent composition articles for use in
automatic dishwashers which provide ease of handling and
dispensing for the user.
- 3 -
'',
.' i~
."' ` . ~
.'
-
:
- It is a still further object of this invention to produce
,,
-:~ paste-form detergent composition articles which minimize the
.,.. ,:'.
hygiene and safety problems which may accompany the use of
. ~ .
concentrated detergent compositions.
It is also an object of this invention to provide a
method for cleaning tableware and cookware-in an automatic
dishwasher utilizing the paste-form detergent composition
- articles of the present invention.
Summary of the Invention
In accordance with the present invention there is provided
, ~ ~
i~' an article for cleaning tableware and cookware in an automatic
dishwasher, consisting essentially of a packet made up of
a water-soluble material in film form, enclosing within it
a paste-form, automatic dishwasher-compatible detergent
composition.
It has been found that by including these paste-form
detergent compositions in packets made of a water-soluble
material, which may be added directly to the detergent dispenser
.
of the automatic dishwasher, the dispensing and solubilization
~ ~ .
` 20 problems can be eliminated, while still retaining the benefits
i which the paste-form compositions offer. In addition, the
~;'.. ~ ,
;` use of the detergent compositions in such packets provides
;~ easy handling of the compositions for the consumer and minimizes
~,,
user contact with any alkaline or enzyme ingredients which
- 25 the compositions may contain.
The water-soluble packet is preferably made from poly-
vinyl alcohol, polyethylene oxide, or methyl cellulose. It is
also preferred that the detergent compositions contained in the
- '
:
-- 4
.',',.", ~ ,
.:
-- ~ -
','' :, ,
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packet comprise an etho~ylated or propoxylated nonionic
surface-activ~ agent. The detergent composition may also
contain additional components which are often found in detergent
compositions for use in automatic dishwashers, such as organic
and inorganic detergent builder ingredients, alkali materials,
sequestering agents, china protecting agents, hydrotropes,
corrosion inhibitors, drainage promoting ingredients, dyes, and
perfumes. Preferred detergent compositions for use in the articles
of the present invention contain suds suppressing components
and/or high alkaline activity, amylolytic or proteolytic
enzymes.
A proc`ess for cleaning soiled tableware and cookware
in an automatic dishwasher, utilizing the detergent articles
of the present invention is also taught herein.
Detailed Description of the Invention
The detergent articles of the present invention consist
,~ , .
essentially of a pac~et made of a water-soluble or water-
dispersible film enclosing within it a paste-form detergent
composition, which will not dissolve said film, formulated for
'I
use in an automatic dishwasher. The components of the articles
of this in~ention will be discussed in detail hereinafter.
The detergent compositions used in the articles of
the present invention are in the form of a paste, and are
suitable for use in an automatic dishwasher. These paste-
form detergent compositions generally have viscositiesof about 5,000 centipoise, but which can range up to several
hundred million centipoise. As used herein, the term "paste" is
intended to encompass paste, gel, and viscous liquid detergent
_ 5 _
. . .
34
compositions having a minimum viscosity of at least about
1000 centipoise, preferably at least about 2,000 centipoise.
' The detergent compositions must exhibit certain
- performance characteristics to make them suitable for use
in an automatic dishwasher. The compositions should be
formulated so as to be relatively low sudsing in use. If a
composition tends to form excessive amounts of suds during
the dishwashing process, the mechanical operation of the
dishwashing machine can be impaired due to a lowering of
the pressure at which the washing liquid is forced against
the hard surfaces to be washed. This condition can be met
by the proper selection of the composition's surfactant
system or by the inclusion of a suds-regulating agent in
the detergent composition. The composition should also be
effective in the removal of various classes of food soils,
particularly proteinaceous, greasy, and fatty soils. The
detergent composition must also be sufficiently water-
soluble or water-dispersible at the 110F to 150F dish-
washer water temperatures, so as to assure a sufficient
amount of the composition in the washing system during the
~- dishwasher cycle. Finally, the detergent compositions
should have a pH, in use, of from about 8~5 to 11.5,
preferably from about 9 to 11, and most preferably from
about 9.5 to 10.5.
A large variety of detergent compositions for use
in automatic dishwashers may be formulated as pastes.
Examples of such compositions are disclosed in the above
mentioned U.S. Patents 4,123,395; 4,101,457 and 4,090,973
and Canadian patent 1,073l381.
; 30
~''
2f~39L
In addition, other automatic dishwasher detergent formula-
tions, which are usually made in granular or powder form,
may also be formulated as pastes, as long as any incompat-
ible components are not included. Examples of such
compositions are disclosed in Canadian Patent 966,751,
benson et al, issued April 29, 1975, Canadian Patent
Application Serial No. 218,740, Lagasse et al, filed
January 27, 1975; U.S. Patent 3,598,743, Coates, issued
August 10, 1971; U.S. Patent 3,544,473, Kitchen et al,
issued December 1, 1970; and U.S. Patent 3,630,923, Simmons
et al, issued December 28, 1971.
The detergent compositions used in the articles of
the present invention may contain water-soluble anionic or
nonionic surface-active agents. Anionic surfactants may be
used in conjunction with a suds-suppressing agent, so as to
control the sudsing characteristics of the entire composi-
tion. Anionic surfactants known ln the detergency arts may
be used in the compositions herein. Examples of such sur-
factants are listed in U.S. Patent 3,717,630, Booth, issued
February 20, 1973, and U.S. Patent 3,332,880, Kessler et al,
issued July 25, 1967. A preferred type of anionic surfact-
ant is disclosed in U.S. Patent 3,941,710, Gilbert et al,
issued March 2, 1976.
Preferred compositions for use in the articles
of the present invention contain a nonionic surface~
active agent, particularly an alkoxylated nonionic
surface-active agent, wherein the alkoxy moiety is
ethylene oxide, propylene oxide, or mixtures thereof.
The surface-active component should comprise
C
534
at least about 0.5% by weight of the detergent composition.
However, by choosing an appropriate nonionic surfactant
system, along with small quantities of materials such as
solubilizers, thickeners, and the like, stable paste-form
compositions containing up to about 55% of the nonionic
surfactant system may be prepared. Preferred detergent
compositions contain from about 1 to about 40% of the
nonionic surfactant, most preferably from about 3 to
about 30%.
Most commonly, nonionic surfactants are compounds
produced by the condensation of an alkylene oxide,
especially ethylene oxide (hydrophilic in nature) with
an organic hydrophobic compound, which is usually ali-
phatic or alkyl aromatic in nature. ~he length of the
hydrophilic polyoxyalkylene moiety which is condensed
with any particular hydrophobic compound can be readily
adjusted to yield a water-soluble compound having the
desired degree of balance between hydrophilic and hydro-
phobic properties. A typical listing of classes and
species of such nonionic surfactants useful herein
appears in U.S. Patent 3,664,961.
Preferred nonionic surface-active agents include al-
koxylated nonionic surfactants wherein the alkoxy moiety
is selected from the group consisting of ethylene oxide,
propylene oxide, and mixtures thereof. Ethylene oxide
represents the preferred condensation partner. The al-
kylene oxide moiety is condensed with a nonionic-based
material according to techniques known in the art. All
alkoxylated nonionic detergents which are normally known
to be suitable for use in detergent technology can be
used herein. Examples of such components include:
-- 8
(1) The condensation product of one mole of a saturated
or unsaturated, straight or branched chain carboxylic acid
having from about 10 to about 18 carbon atoms with from about
5 to about 50 moles of ethylene oxide. The acid moiety can
consist of mixtures of acids in the above-delineated carbon
atoms range or it can consist of an acid having a specific
number of carbon atoms within this range. The condensation
product of one mole of coconut fatty acid having the approxi-
mate carbon chain length distribution of 2~ C10, 66% C12,
10 23% C14, and 9~ C16 with 35 moles of ethylene oxide is a
specific example of a nonionic containing a mixture of different
chain lengths fatty acid moieties. Other specific examples
of nonionics of-this type are: the condensation prodllct of
one mole of palmitic acid with 40 moles of ethylene oxide;
the condensation product of one mole of myristic acid with
35 moles of ethylene oxide; the condensation product of one
mole of oleic acid with 5 moles of ethylene oxide; and the
; condensation product of one mole of stearic acid with 30
moles of ethylene oxide.
(2) The condensation products of one mole of a saturated
or unsaturated, straight or branched chain alcohol having
from about 10 to about 24 carbon atoms with from about 5
to about 50 moles of ethylene oxide. The alcohol moiety can
consist of mixtures of alcohols in the above-delineated
carhon atom range or it can consist of an alcohol having a
specific number of carbon atoms within this range. The
condensation product of one mole of coconut alcohol having
the approximate chain length distribution of 2~ C10,
66% C12, 23% C14, and 9~ C16 with 45 moles of ethylene
g _
oxide is a specific example of a nonionic containing
a mixture of d~fferent chain length alcohol moieties.
Other specific examples of nonionics of this type
; are the condensation products of one mole of tallow alcohol
with 9 and 20 moles of ethylene oxide respectively; the
condensation products of one mole of lauryl alcohol with 35
moles of ethylene oxide; the condensation products of one
mole of myristyl alcohol with 30 moles of ethylene oxide;
and the condensation products of one mole of oleyl alcohol
with 40 moles of ethylene oxide.
(3) Polyethylene glycols having a molecular weight
of from aboùt 400 to about 30,000. For example, Dow
Chemical ~ompany'manufactures these nonionics in molecular
weights of 20,000, 9500, 7500, 4500, 3400, and 1450, all
of whicn are waxlike solids which melt between 110F and
200F.
(4) The condensation products of one mole of alkyl
phenol wherein the alkyl chain contains from about 8 to
about 18 carbon atoms with from about 4 to about 50 moles
of ethylene oxide. Specific examples of these nonionics
are the condensation products of one mole of decyl phenol
,.
with 40 moles of ethylene oxide; the condensation products
of one mole of dodecyl phenol with 35 moles of ethylene
oxide; the condensation products of one-mole of tetradecyl
phenol with 35 moles of ethylene oxide; and the condensation
products of one mole of hexadecyl phenol with 30 moles of
ethylene oxide.
(5) The ethoxylated surfactants disclosed in U.S.
r ~ Patent Application Serial Number 557,217, filed March 10,
~3~ 1975, inventor Jerome H. Collins~ in~r~or~tod---her~in by
-- 10 --
34
C rcfere*=~7 consisting essentially of a mixture of compounds
having at least two levels of ethylene oxide addition and
having the formula: Rl - R2 -O(CH2CE~2O) H, wherein Rl
is a linear alkyl residue and R2 has the formula -CHR3CH2-
wnerein R3 is seiected from the group consisting of hydrogenand mixtures thereof with not more than 40~ by weight of
lower alkyl, wherein Rl and R2 together form an alkyl residue
having a mean chain length in the range of 8-15 carbon atoms,
at least 65% by weight of said residue having a chain length
within + 1 carbon atom of the mean, wherein 3.5<n<5.5,
provided that the total amount of components in which n = 0
is not greater than 5~ by weight and the total amount o~
component~ in which n = 2-7 inclusive is not less than 63%
by weight, and the hydrophilic-lipophilic balance (HLB)
of said ethoxyl2te material is in .the rarge.f-om 9.5~ 5,
said surfactant composition being otherwise free of nonionic
- surfactants having an HLB outside of said range.
. Low-foaming alkoxylated nonionic.surfactants are preferred
for use in the detergent compositions, although nonionics which
do not exhibit low-foaming properties can be used without
departing from the spirit of this invention, as long as they
are used in conjunction with a suds-regulating agent so as to
control the foaming characteristics of the detergent composition
as a whole. Examples of nonionic low-foaming surface-active
components include: the condensation products of benzyl chloride
and an ethoxylated alkyl phenol wherein the alkyl group has from
about 6 to about 12 carbon atoms and wherein from about 12 to
about 20 ethylene oxide molecules have been condensed per mole
of alkyl phenol; polyetheresters of the formula
(ClC6H4) 2CHC02 (CH2-CE~2-0) XR
wherein x is an integer from 4 to 20 and R is a lower
alkyl group containing not more than 4 carbon atoms, for
example a component having the formula
(ClC6H4)2cHcO2(cH2cH2o)lS 3;
the polyalkoxylation products of alkyl phenol, for example,
the polyglycol alkyl phenol ethers containing an alkyl
group having at least 6 and, normally, from about 8 to
about 20 carbon atoms and having a molar ratio of ethylene
oxide to condensate of about 7.5; 9.0; 11.5; 20.5; and 30.
The alkyl group can, for example, be represented by diiso-
butylene; di-amyl; polymerized propylene; iso-octyl; and
nonyl.
Additional examples of effective low-foaming nonionics
include: the polyalkylene glycol condensates disclosed
in U.S. Patent 3,048,548, having alternating hydrophilic
oxyethylene chains and hydrophobic oxypropylene chains
wherein the weight of the terminal hydrophobic chains, the
- weight of the middle hydrophobic unit and the weight of
the linking hydrophilic units each represent about 1/3
of the condensate; the de-foaming nonionic surfactants
disclosed in U~S. Patent 3,382,17~, having the general
formula Z[(OR)nOH]z wherein Z is alkoxylatable
material, R is a radical derived from an alkylene
oxide which can be ethylene and propylene and n is
an integer from, for example, 10 to 2000 or more and
z is an integer determined by the number of reactive
oxyalkylatable groups. Z can be represented by nor~al
- 12 -
,.,~
biodegradable alcohols such as, for example, those
obtained by reduction of fatty acids derived from coconut
oil, palm kernel oil, tallow and also those obtained from
petroleum such as, for example, the mixtures of C10
to C18 straight-chain primary alcohols; the nonionic
surface-active agents of U.S. Patent 3,549,539 being a
mixture of nonylphenol-5-EO or the condensation product
of a random Cl1 to C15 secondary alcohol and ethylene
oxide having an HLB value between 11.5 and 13.5; and a
polyethylene oxide/polypropylene oxide condensate that
consists of between 5 and 25% polyethylene oxide and 95
and 75% polypropylene oxide and has a molecular weight
between 1500 and 2700; the conjugated polyoxyalkylene
; compounds described in U.S. Patent 2,677,700, corres-
: ponding to the formula:
Y(C3H6O)n(c2H4o)m
wherein Y is the residue of organic compounds having
from about 1 to 6 carbon atoms and at least one reactive
hydrogen atom, n has an average value of at least about
6.4, as determined by hydroxyl number and m has a value
such that the oxyethylene portion constitutes about 10
to 90 weight percent of the molecule; the conjugated poly-
oxyalkylene compounds described in U.S. Patent 2,674,619,
incorporated herein by reference, having the formula:
Y[ (C3H60)n(C2H40)mH]X
- 13 -
534
wherein Y is the residue of organic compounds having from
about 2 to 6 carbon atoms and containing x reactive hydrogen
atoms in which x has a value of at least about 2, n has a
value such that the molecular weight of the polyoxypropylene
hydrophobic base is at least a~out 900 and m has a value such
that the oxyethylene content of the molecule is from about
10 to 90 weight percent. Compounds falling within the
scope of the definition for Y include, for example, pro~ylene
glycol, glycerine, pentaerythritol, trimethylolpropane,
ethylenediamine and the like. The oxypropylene chains
optionally, but advantageously, contain small amounts of
~ ethylene oxide and the oxyethylene chains also optionally,
but advantageously, contain s~all amo~l~nts of propylene
oxide.
lS Additional conjugated polyoxyalkylene surface-active
agents which are advantageously used in the compositions
of this invention correspond to the formula:
.
P[(c3H6o)n(c2H4o)mH]x
' ' ' :
wherein P is the residue of organic compounds having
from about 8 to 18 carbon atoms and containing x reactive
hydrogen atoms in which x has a value of 1 or 2, n has a
value such that the molecular weight of the polyoxypropylene
portion is at least about 58 and m has a value such that the
oxyethylene content of the molecule is from about 10 to 90
- 25 weight percent and the formula:
. ,.~, . . .. ..
. . '. '
'' ~
~f~
P[(c2H4o)n(c3H6o)mH]x
wherein P is the residue of an organic compound having from
about 8 to 18 carbon atoms and containing x reactive
hydrogen atoms in which x has a value of 1 or 2, n has a
value such that the molecular weight of the polyoxyethylene
portion is at least about 44 and m has a value such that
the oxypropylene content of the molecule is from about 10
to 90 weight percent. In either case the oxypropylene
chains may contain optionally, but advantageously, small
amounts of ethylene oxide and the oxyethylene chains may
contain also optionally, but advantageously, small amounts
of propylene oxide.
Preferred nonionic surfactants for use in the present
invention include the mono- and polyalkoxy-substituted
surfactants having the terminal hydroxyl of the alkoxy group
acylated by certain monobasic acids ("capped" surfactants),
; described in U.S. Patent 4,088,598, Williams, issued May 9,
1978.
Highly preferred alkoxylated nonionics for use
herein include the condensation product of one mole of
tallow alcohol with from about 6 to about 20 moles,
especially 9 moles, of ethylene oxide; the alkoxylate
commercially available under the trademark P~URADOT
HA-433~ Wyandotte Chemical Corp., which has a molecular
weight in the range from 3700-4200 and contains about 3
monostearyl acid phosphate suds suppressor;
- 15 -
,~i
and also the condensation product of C14_15 alcohol wi
5 to 17 moles particularly 7-9 moles, of ethylene oxide.
An example of such a surfactant is commercially available
as NEODOL 45-7, available from Shell Chemical Corp.,
which is the condensation product of C14 15 alcohol with
7 moles of ethylene oxide per molecule of alcohol.
The compositions for use in the articles of this in-
vention may also comprise a suds-regulating agent for the
purpose of controlling the sudsing of the composition
during use. Excessive sudsing can have the effect of
decreasing the efficiency of the dishwashing machine and,
hence should be avoided. The final selection of the suds-
suppressing agent depends, at least in part, upon the qual-
itative and quantitative characteristics of the particular
surface-active agent which is utilized in the detergent
composition. Suds-regulating agents are particularly use-
ful in automatic dishwashing detergent compositions since
some types of food residues, especially proteinaceous food
residues, exhibit suds-boosting properties.
Suds-regulating components are normally used in an
amount of from about 0.001% to about 5%, preferably from
about 0.05% to about 3~, and especially from about 0.1
to about 1%. Suds-suppressing agents known in the art
to be suitable for use in the detergent context are use-
ful in the compositions herein.
Preferred suds-suppressing additives are described
in U.S. Patent 3,933,672, Bartolotta et al, issued
January 20, 1976, relating to silicone suds-controlling
agents. The silicone material can be represented b~
alkylated polysiloxane materials such as silica
aerogels and xerogels, and hydrophobic silicas of
- 16 -
~~3~
various types. The silicone material may be described as
a siloxane ha~ing the formula:
j R ~
~S10~
R' x
wherein x is from about 20 to about 2,000 and R and R' are
each alkyl or aryl groups, especially methyl, ethyl, propyl,
but~l, and phenyl. The polydimeth~l siloxanes (R and R' are
methyl) having a molecular weight within the range of from
about 200 to 200,000, and higher, are all useful as suds
controlling agents. Additional suitable silicone materials,
10 wherein .he side chdin groups are R and R' are alkyl, aryl,
or mixed alkyl and aryl hydrocarbyl groups, exhibit useful
suds controlling properties. Examples of such ingredients
include diethyl-, dipropyl-, dibutyl-, metyl and ethyl-,
phen~lmethyl polysiloxanes and the like. Additional useful
15 silicone suds controlling agents can be represented by a
mixture of an alkylated siloxane, as referred to above, and
solid silica~ Such mixtures are prepared by affixing the
silicone to the surface of the solid silica. A preFerred
silicone suds controlling agent is represented by a hydro-
phobic silanated ~most preferably trimethylsilanated) silicahaving a particle size in the range of from about 10 milli-
microns to 20 millimicrons in a specific surface area above
- about 50 square meters per gram, intimately admi~ed with dimethyl
silicone fluid having a molecular weight in the range of from
about 500 to about 200,000 at a ~Jeight ratio of silicone to
- 17 -
silanated silica of from about 19:1 to about 1:2. The
silicone suds suppressing agent is advantageously release-
ably ineorporated in a water-soluble or water-dispersible,
substantially nonsurface-active detergent-impermeable
- carrier.
Partieularly useful suds-suppressors are the self-
emulsified silicone suds-suppressors described in Canadian
Patent Applieation Serial No. 263,320, Gault et al, filed
October 13, 1976. An example of such a compound is DB-544,
whieh is a mixture of siliea, an alkoxylated siloxane, and
a siloxane/glycol copolymer, and is eommereially available
from Dow Corninq.
Mieroerystalline waxes having a melting point in the
range of from 35C to 115C and a saponifieation value less
than 100, represent an additional example of a preferred
suds regulating eomponent for use in the subject composi-
tions. The microcrystalline waxes are substantially
water-insoluble, but are water-dispersible in the presence
of organie surfaetants. Preferred mieroerystalline waxes
have a melting point of from about 65C to 100C, a molee-
ular weight in the range of 400 to 1000, and a penetration
value of at least 6, measured at 77F by ASTM-D1321. Suit-
able examples of the above waxes inelude: microcrystalline
and oxidized mierocrystalline petrolatum waxes; Fischer-
Tropsch and oxidized Fiseher-Tropseh waxes; ozokerite;
eeresin; montan wax; beeswax; candelilla; and carnauba wax.
Alkyl phosphate esters represent an additional
preferred suds suppressant for use herein. These preferred
phosphate esters are predominantly monostearyl acid phos-
phate which, in addition thereto, ean eontain di- and
tristearyl phosphates and monooleyl phosphates, which can
contain di and trioleyl phosphates.
- 18 -
.~ .
34
The alkyl phosphate esters frequently contain some
trialkyl phosphate. Accordingly, a preferred phosphate
ester can contain, in addition to the monoalkyl ester,
e.g., monostearyl phosphate, up to about 50 mole percent
of dialkyl phosphate and up to about 5 mole percent of
trialkyl phosphate.
The dishwasher-compatible detergent compositions use-
ful in the present invention may also contain an enzyme
component. The enzymes aid and augment the removal of
soils from the objects to be cleaned. This enzymatic
action may result from a series of individual chemical
reactions, such as hydrolysis, oxidation and substitution
reactions.
Because the detergent compositions useful herein
have a relatively high in-use pH, the enzymes which are
most useful in the detergent compositions are those which
exhibit a high degree of enzymatic activity in highly
alkaline systems. Thus, the preferred enzymes are high
alkaline activity proteases, high alkaline activity
20 amylases, and mixtures thereof. Preferred proteolytic
enzymes are those which exhibit a proteolytic activity
of 80 to 100% of maximum activity when measured at pH
12 using the Anson Hemoglobin method carried out in the
presence of urea. Examples of this type of proteolytic
enzyme are described in British Patent Specification
1,361,686, and correspond to bacterium strains which have
been deposited at the National Collection of Industrial
Bacteria (NCIB), Torry Research Station, Aberdeen,
Scotland, and are produced by the bacterium strains
numbered NCIB 10317, NCIB 10147, NCIB 10313, and NCIB
10315. Another preferred proteolytic enzyme is that
- 19 -
3~
cultivated from the microorganism Bacillus Firmus strain
NRS 783, as described in U.S. Patent 3,827,938, Aunstrup
et al, issued August 6, 1974. This
- l9a -
strain of Bacillus Firmus may be obtained from the U.S.
Department of Agriculture, Agricultural Research Service,
Peoria, Illinois, as strain NRRL B 1107. Preferred
commercially available protecolytic enzymes for use in
these detergen~ compositions, are available under the
tradenames SP-72 (Experase~ and SP-88, produced and
marketed by Novo Industri A/S, Copenhagen, Denmark.
Preferred amylolytic enzymes are those which exhibit
an amylolytic activity of greater than 50% of maximum
activity when measured at pH 8 by the SKB method at 37C.
Commercially available examples of such amylolytic
enzymes include Monsanto~ DA-10, available from Monsanto;
Rapidase~, available from Societe Rapidase, France;
Milezyme~, available from Miles Laboratories, Elkhart,
Indiana; and Ban~, available from Novo Industri A/S,
Denmark. Particularly preferred amylolytic enzymes are
those described in British Patent Specification 1,296,839,
cultivated from the strains of Bacillus Lichenformis NCIB
. _
8061, NCIB 8059; ATCC (America type culture collection)
20 6334; ATCC 6598; ATCC 11945; ATCC 8480; AT~C 9945A. A
particularly preferred, commercially available amylolytic
enzyme, is produced and distributed under the tradename
SP-95 (Termamy ~ , by Novo Industri A/S, Copenhagen,
Denmark.
In a particularly preferred embodiment, the enzyme
component consists of a mixture,of the preferred proteo-
lytic and preferred amylolytic enzymes, disclosed above, in
a ratio of from about 4:1 to 1:4 by weight, preferably from
about 2:1 to about 1:2, and most preferably in a ratio of
about 1:1. The preferred proteolytic, amylolytic and enzyme
mixture components discussed above are disclosed and defined
in U.S. Patent 4,090,973, Maguire et al, issued May 29, 1978.
- 20 -
C
The enzyme component is included in the detergentcompositions in an amount effective to provide beneficial
cleaning properties in an automatic dishwasher context. It
is preferred that the enzymes be used in an amount such that
the final cleaning composition has an amylolytic activity of
at least 150 kilo Novo units per kilogram and/or a proteo-
lytic activity of at least 6.0 Anson units per kilogram.
This corresponds roughly to detergent compositions comprising
from about 0.001% to about 5% by weight, of the enzyme
component, utilizing generally available commercial enzyme
preparations. Most preferably, this corresponds to detergent
compositions comprising from about 0.1% to about 1.5% by
weight of the enzyme component. The enzymes used in the
detergent compositions may, for stability reasons, be
encapsulated with a nonionic surface-active material, as
described in U.S. Patent 4,090,973.
In addition to the components described hereinbefore,
the detergent compositions used in the articles of the
present invention can contain additional ingredients which
are known to be suitble for use in automatic dishwashing
compositions, in the art-established levels for their known
functions. Organic and inorganic detergent builder ingred-
ients, alkali materials, sequestering agents, china-protecting
agents, reducing agents, hydrotropes, corrosion inhibitors,
soil-suspending ingredients, drainage promoting ingredients,
enzyme-stabilizing aids, dyes, perfumes, fillers, crystal
modifiers and the like represent examples of functional
classes of additional automatic dishwashing composition
additives.
.
S;34
Suitable inorganic builders include polyphosphates, for
example, tripolyphosphate, pyrophosphate, or metaphosphate,
carbonates, bicarbonates, and alkali silicates. Particu-
larly preferred are the sodium and potassium salts of the
aforementioned inorganic builders. Examples of water-
soluble organic builder components include the alkali metal
salts of polyacetates, carboxylates, polycarboXylates, and
polyhydroxysulfonates. Additional examples include sodium
citrate, sodium oxydisuccinate, and sodium mellitate. Normally
;~
these builder ingredients can be used in amounts of up to 60~,
preferably in the range of from about 1~ to 50~ by weight.
In o;rder to provide satisfactory pasty compositions,
up to about 60~ of a solvent, solubilizing material, or
suspending agent may be included. Examples of preferred
components of this type include polyethyiene glycol having a
~` molecular weight of about 400, triethanolamine, methyl esters,
' C C12 13 alcohols commercially available as NEODO ~ 3 alcohols
from Shell Chemical Corp., and mixtures thereof. Water
may be used in this context and forms the continuous phase of
: .
20~ a concentrated dispersion, however, preferred compositions for
use herein are essentially anhydrous. In many cases, it is
desirable to include a viscosity control agent or a thixotropic
agent to provide a suitable product form. For example, aqueous
solutions or dispersions may be thickened or made thixotropic
by the use of conventional agents such as methylcellulose,
carboxymethylcellulose, starch, polyvinylpyrrolidone, gelatin,
colloidal silica, natural or synthetic clay materials and the like.
To make the detergent articles of the present invention,
a dishwasher-compatible detergent composition, such as those
described above, is enclosed in a packet made up of a water-soluble
- 22 -
34
material in film form. As used herein, the term "water-soluble
film" is intended to include those films which are water-
dispersible, as well as those which are water-soluble. Each
packet may contain a premeasured amount of the detergent
composition suitable for a single washing load in an automatic
dishwasher, or a convenient fraction of such an amount. It -
is preferred that the packets contain from about 2 to 50 grams,
most preferably from about 5 to about 20 grams, of the detergent
composition. In addition, the packet should be of a convenient
size so as to fit, either folded or unfolded, into the detergent
dispenser cup of an automatic dishwasher.
A film suitable for use in making packets of the foregoing
type must be rapidly and completely soluble or dispersible
in hot water ranging in temperature from about llO to about
150F, particularly about 120F. It must be strong, tough,
flexible, shock-resistant and nontacky during storage at
, both high and low temperatures and humidity. Very importantly,
these properties must be retained by the film while it is in
contact with the alkaline detergent compositions used in the
present invention. In choosing a film, it is important
that the one chosen is compatible with the components of the
; detergent composition to be contained in the article. This ~
; compatibility is particularly important in terms of the solvent,
described above, used in the detergent composition. For example,
where the detergent composition contains water as its solvent,
the film chosen must be one which will readily solubilize in
the 110-150F dishwasher water, but which will not be solubilized,
during storage, by the water in the composition. The film used
- 23 -
2~3~
to make the packets should have a thickness of from about
0.5 to 5 mils, preferably from about 1 to 3 mils, and most
preferably about 1.5 mils.
It is, furthermore, very desirable that the water-
soluble film be readily self-sealable, especially by heat,
heat and water, or ultrasonic sealing methods. The sealed
portions should dissolve well, along with the remainder of
the packets. Preferably, the film should seal completely
and permanently at a relatively low temperature and in a
short period of time.
Examples of materials useful in making the packets
of the present invention include modified starches,
methyl and hydroxy propylmethylcellulose derivatives,
hydroxyethyl cellulose, carboxymethylcellulose, poly-
vinyl alcohols, such as those described in U.S. Patent
3,413,229, Bianco et al, issued November 26, 1968; U.S.
Patent 3,277,009, Freifeld et al, issued October 4, 1966;
and U.S. Patent 3,300,546, Baechtold, issued January 24,
1967, polyvinylpyrrolidone, and ethylene oxide polymers.
These materials are discussed in detail in Water Soluble
Resins, Davidson and Sittig, Van Nostrand Reinhold Co.,
1968. Preferred materials for making the packets include
polyvinyl alcohol, polyethylene oxide, and methylcellulose.
The detergent articles of the present invention are
utilized by placing them inside of an automatic dishwasher
prior to the start of the dishwashing cycle, in the place
of ordinary dishwasher detergent compositions. It is pre-
ferred that the detergent articles are placed inside the
detergent dispenser cup of the automatic dishwasher.
- 24 -
34
The following nonlimiting examples illustrate the articles
and methods of the present invention.
EXAMPLE I
A paste-form detergent composition suitable for use in
automatic dishwashers, having the components set forth below,
was formulated using conventional methods. The composition
had a vis~osity of about 500,000 centipoise.
Component ~ by weight
-
Sodium tripolyphosphate 24.1
P205 10.6
` Silicate solids (4:1 ratio
by weight o 2.4r:2.0r) 17.0
sio2 11. 9
Water 8.5
Neodol 45_71 4.2
Triethanolamine 19.0
Dye 1.0
Perfume 0.2
SAG lOQ 0,7
SP-883 (in polyethylene
glycol 6000 prills)1.2
Termamyl (in polyethylene
glycol 6QOO prills)1.6
:~., , , -: . . ..
534
Condensation product of one mole of C14 15 alcohol with 7
moles of ethylene oxide.
2A polydimethylsiloxane silica suds suppressor, commercially
available from Dow Corning.
A proteolytic enzyme, commercially available from Novo
-~ Industri A/S, Copenhagen, Denmark, which exhibits an activity
of greater than 80% of its maximum activity when measured at
pH 12 using the Anson hemoglobin method in the presence of urea.
An amylolytic enzyme, commercially available from Novo
Industri A/S, Copenhagen, Denmark, which exhibits an activity
of greater than 50~ of its maximum activity when measured at
pH 8 by the SKB method at 37C.
Article A was made by heat-sealing about 12 grams of the
; above composition in a 5cm. square packet made out of a medium
hydrolysis polyvinyl alcohol film, commercially available from
Monosol, having a thickness of about 1.5 mils. Article B was
made by heat-sealing about 12 grams of the above composition
in a Scm. square packet made out of Edisol-M, a methyl cellulose
film, having a thickness of about 1.5 mils, commercially avail-
able from Polymer Films, Inc.
Bach of the above articles was placed in the detergent
dispenser cup of a Frigidaire automatic dishwasher, and the
amount of time which it took for the article and the enclosed
composition to completely dissolve in the washing solution during
the washing cycle, after the dispenser cup opened, was determined.
Each composition was tested in water temperatures of 130F and
140F, with a water hardness of 15 grains/gallon. As a control,
the same tests were carried out using 12 gram portions of the
,~
'
- 26 -
.
i -- ~
34
.
above paste composition, which were placed directly into the
detergent dispenser cup of the dishwasher. The results
obtained are summarlzed in the table below.
Article Dissolution Time (seconds) __ -
Water Temperature 130F 140F
.
A 30 30
~ 30 45
Control 90 90
.
The data above indicate that the inclusion of the paste-
form detergent compositions in the water-soluble packets,
increased the rates at which the paste compositions were dis-
pensed out of the dishwasher dispenser cup and were dissolved
into the aqueous washing solution, during the automatic dish-
washer cleaning cycle.
; 15 Substantially similar results are obtained when the
nonionic surfactant of Example I is substitutea with the
condensation product of tallow alcohol with about 9 moles of
ethylene oxide (TAE9), or an ethylene oxide/propylene oxide
condensate of trimethylol propane (commercially available
r~ from Wyandotte as Plurado ~HA-433), or with a similar surfactant
substituted with a substantially identical alkoxylate containing,
instead o~ the tri~methylol propane radical, an alkalol selected
from the group consisting of propylene glycol, glycerine,
pentaerythritol, and ethylenediamine.
;
- 27 -
___
L25i~
Similar results are also obtained where the water-soluble
film used to make the packets is polyethylene oxide, hydroxy-
ethylcellulose, carboxymethylcellulose or a hydroxy propyl-
methylcellulose derivative.
Excellent performance is also obtained when the suds
suppressor, used above, is replaced by a silicone suds suppressor
selected from the group consisting of trimethyl-, diethyl-,
dipropyl-; dibutyl-, methylethyl-, and phenylmethylpolysiloxane
and mixtures thereof, in an amount ranging from about 0.1%
to about 0.5~. Similar results are also obtained by using
monostearyl acid phosphate suds suppressor, or a self-
emulsified silicone suds suppressor, such as DB-544, commercially
available from Dow Corning.
~esults substantially comparable to those above can also
be obtained when the suds suppressor is a microcrystalline
wax having a melting point from 65C to 100C, and which is
selected from petrolatum and oxidized petrolatum waxes,
Fischer-Tropsch and oxidized Fischer-Tropsch waxes, ozokerite,
ceresin, montan wax, beeswax, candelilla, and carnauba wax.
Substantially comparable results are obtained where the
builder used in the paste-form detergent composition above is
replaced by sodium or potassium pyrophosphate, metaphosphate,
bicarbonate; an alkali metal salt of a polyacetate, carboxylate,
polycarboxylate or a polyhydroxy sulfonate; sodium citrate,
sodium oxydisuccinate, or sodium mellitate.
- 28 -
5~
EXAMPLE II
.
A paste-form detergent composition for use in automatic
dishwashers, having a viscosity of about 500,000 centipoise,
and having the following composition is formulated: -
Component % by weight _-
Neodol 45-7 5.8
DB-544 0.8
Silicate solids (2.Or) 14.0
; Triethanolamine 27.0
Anhydrous sodium tripoly- 35.0
phosphate
sp_721 0.6
Milezyme2 0.6
Water and minorsbalance to 100
~ proteolytic enzyme available from Novo Industri A/S,
Copenhagen, Denmark, which exhibits an activity of greater than
80% of its maximum activity when measured at pH 12 using the Anson
hemoglobin method in the presence of ureaO
An amylolytic enzyme available from Miles Laboratories,
~lkhart, Indiana, which exhibits activity greater than 50% of
its maximum activity when measured at pH 8 by the SKB method at
37C
About 8 grams of this composition is placed in a water-
soluble packet made of polyvinyl alcohol film, having a
thickness of 2.5 mils. The packet is sealed by the heat and
water method. This detergent article exhibits good dispensing
and dissolution properties when used in an automatic dishwasher.
.
- 29 -
.
EXA~lPLE III
A paste-form detergent composition for use in automatic
dishwashers, having a viscosity of about 1,000,000 centipoise,
and having the following composition, is formulated:
Component % by weight
~ Ethylene oxide/propylene 25.0
: oxide condensate of --
trimethylol propane ~~
Sodium cumene sulfonate 10.0
Silicate solids (2.Or) 12.0
Triethanolamine 19.0
Anhydrous sodium tripoly- 25.0
phosphate
SP-88 . 0.8
Termamyl 0.4
Monostearyl acid phosphate 0.75
DB-544 0.25
Waters and minors balance to 100
About 15 grams of this composition is placed in a water-
soluble packet made of polyethylene oxide film, having a
thickness of 1.5 mils. The packet is sealed ultrasonicalIy.
The detergent article is placed in the detergent dispenser
cup of an automatic dishwasher, and dirty dishes and
tableware are washed with it. The dishes and tableware are
clean after the completion of the dishwasher cycle, and there
is no residue of the paste or the packe~ remaining in the
dispenser cup or on the inside of the dishwasher.
- 30 -
' ~
53~
EXAMPLE IV
A gel-form detergent composition for use in automatic
dishwashers, having the following composition, is formulated:
Component % by weight
TAEg 7 9
Silicate solids (2.Or) 32.0
Sodium tripolyphosphate 19.8
SP-88 0 4
Termamyl 0.8
Waters and minorsbalance to 100
About 12 grams of this composition is placed in a water-
soluble packet made of a medium hydrolysis polyvinyl alcohol
fi7m, commersially available from Monosol, having a thickness
of about 1.5 mils. The packet is heat-sealed. This detergent
article exhibits good cleaning, dispensing and solubilizing
properties when used in an automatic dishwasher.
- 31 -
534
EXAMPLE V
The following three paste-form detergent compositions
for use in automatic dishwashers, having the following compositions,
are formulated:
Component ~ by weight
A B C --
Neodol 45-7 7.2 7.2 7.2
Polyethyleneglycol 400 20.4 - -
Neodol 23 alcohol - 20.4
Mineral oil - - 20.4
Silicate solids (2.4x) 21.4 21.4 21.4
Silicate solids (2.Or) 4.36 4.36 4.36
Sodium tripolyphosphate 25.5 25.5 25.5
- Sodium carbonate -9.2 9:2 -9.2
Water 8.4 8.4 8.4
Dye 0-04 0.04 0-04
Perfume 0.3 0.3 0.3
Enzyme (SP-72 encapsu- 3.2 3.2 3.2
lated in polyethylene-
glycol 6000)
Each of the above paste-form deterge~t compositions
(about 10 grams of each) is sealed in water-soluble packets -
made of Edisol- ~ a methyl cellulose film, having a thickness
of about 1.5 mils, commercially available from Polymer Films,
Inc. The packets are heat-sea~ed. Each of these detergent
articles exhibits good cleaning, dispensing and solubil-
ization properties, when placed in the detergent dispenser
cup and used in an automatic dishwasher.
What is claimed is:
- 32 -
