FIELD OF THE INVENTION
[0001] The present invention is concerned with organic detergent builders which are both
hypochlorite resistant and biodegradable for use in automatic dishwashing detergent
liquids. Specifically, select ether carboxylates are used to prepare zero- or low-phosphate
based detergent compositions.
BACKGROUND OF THE INVENTION
[0002] Liquid detergents for automatic dishwashers have been commercialized since the mid-1980s
and have overcome many problems encountered with powder detergents. In particular
powder detergents lose solubility on aging, cake in the dispenser cup and generate
fine particles upon dispensing.
[0003] Efforts have also been made since the late 1960s to replace the high levels of phosphate
builders in both powder and liquid detergent products with non-phosphate ingredients
which fulfill builder functions without causing environmental damage. Builders in
automatic dishwashing products function to provide alkalinity, sequester hardness
ions and disperse soils so as to prevent redeposition on clean dishware surfaces.
[0004] Unfortunately, many organic or environmentally friendly builders are hypochlorite
sensitive and thus unstable in the presence of a chlorine bleaching agent, especially
in liquid detergent compositions.
[0005] In U.S. 4,933,101 (Procter & Gamble) numerous polycarboxylates are disclosed as suitable
for combination with a chlorine source to prepare detergent compositions. However,
this patent exemplifies only powdered compositions and states that builders such as
citrate have particularly good dishwashing performance. Citrate is not, however, stable
in the presence of free hypochlorite and breaks down in a liquid detergent composition.
[0006] Ether carboxylate compounds are disclosed in U.S. 4,689,167 (P&G) and 4,687,592 as
useful detergent builders. The patents, however, are silent on the hypochlorite resistance
of these organic builders in liquid detergent compositions, as well as their biodegradability.
Surprisingly, particular ether carboxylates have been discovered to both possess chlorine
bleach stability while being readily biodegradable and useful for providing a zero-
or low-phosphate liquid detergent composition. Ether carboxylates possess ether linkages
which resemble the ether linkages present in ethoxylated nonionic surfactants. Ethoxylated
nonionic surfactants, such as the Neodol® series owned by Shell Inc., are notoriously
unstable in the presence of chlorine bleach.
[0007] It has also been observed that ether carboxylates, such as ethylene glycol disuccinate
(EGDS) and propylene glycol disuccinate (PGDS), are chlorine stable but are not biodegradable.
The present invention not only pertains to particular ether carboxylate molecules
which possess surprisingly good chlorine bleach resistance, even at high temperatures,
but which are also readily biodegradable.
SUMMARY OF THE INVENTION
[0008] It is therefore an object of the present invention to provide an automatic dishwashing
liquid composition which includes a non-phosphate based builder which is not only
readily biodegradable but is surprisingly chlorine bleach resistant.
The object of the present invention is accomplished by providing an automatic dishwashing
liquid composition comprising about 3 to about 30% by weight of an ether carboxylate
builder selected from a group of compounds known as oxydisuccinates;
a chlorine donor source providing from about 0.2 to about 1.5% available chlorine;
about 0.1 to about 6% of a thickening agent;
about 3 to about 30% of an inorganic builder; and
optionally about 0.5 to about 15% of an anti-scalant agent and about 0.5 to about
4.0% of a low foaming surfactant.
[0009] Other optional ingredients such as colorants, dyes, pigments, perfumes anti-tarnish
agents, soil suspending agents, hydrotropes and mixtures thereof are also included.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Ether Carboxylate Builders
[0010] The aqueous compositions of the invention contain from about 3 to about 30%, preferably
from about 5 to about 20% of an ether carboxylate compound or mixtures thereof selected
from compounds known as oxydisuccinates.
[0011] A preferred oxydisuccinate within the scope of the invention includes 2,2'-oxodisuccinate.
[0012] The oxydisuccinates of the invention are made by any of the conventional means known
in the art.
Modified SCAS Test
[0013] A semi-continuous activated sludge test (SCAS) for determining the biodegradability
of nonionic, linear detergent components was devised by the American Society for Testing
and Materials (ASTM) D 2667, p 386-389. This test modified to determine the biodegradability
of organic test materials, which at the concentration used in the test:
(1) are soluble in water (at least 20 mg dissolved organic carbon/liter);
(2) have negligible vapor pressure;
(3) are not inhibitory to bacteria;
(4) do not significantly adsorb on glass surfaces; and
(5) are not lost by foaming from the test solution.
[0014] Therefore, the "modified SCAS test" has been found suitable by the Organization for
Economic Cooperation and Development (OECD) for determining the inherent biodegradability
of organic chemicals under aerobic conditions and is disclosed in the
OECD Guideline for Testing of Biodegradability Chemicals, Test 302A (May 12, 1981), herein incorporated by reference.
[0015] Test chemicals giving a result of greater than 70 percent loss of degradation of
carbon (DOC) within 28 days in this test are regarded as biodegradable. The use of
a compound specific analytical technique on ¹⁴C-labelled test substance is another
measure of biodegradability.
[0016] The modified SCAS test method is an adaptation of the Soap and Detergent Association
semi-continuous activated sludge (SCAS) procedure for assessing the primary biodegradation
of alkyl benzene sulphonate. The method involves exposure of the chemical to relatively
high concentrations of micro-organisms over a long time period (possibly several months).
The viability of the micro-organisms is maintained over this period by daily addition
of a settled sewage feed.
[0017] Because of the long detention period (36 hours) and the intermittent addition of
nutrients the test does not simulate those conditions experienced in a sewage treatment
plant. The results obtained with the test substance indicate that it has a high biodegradation
potential, and for this reason it is most useful as a test of inherent biodegradability.
[0018] Since the conditions provided by the test are highly favorable to the selection and/or
adaptation of microorganisms capable of degrading the test compound, the procedure
may also be used to produce acclimatized inocula for use in other tests. The test
is applicable to water soluble, non-volatile, organic chemicals that are not inhibitory
to bacteria at the test concentration.
Methodology
[0019] Activated sludge from a sewage treatment plant is placed in an aeration (SCAS) unit.
The test compound and settled domestic sewage are added, and the mixture is aerated
for 23 hours. The aeration is then stopped, the sludge allowed to settle and the supernatant
liquor is removed. The sludge remaining in the aeration chamber is then mixed with
a further aliquot of test compound and sewage and the cycle is repeated.
[0020] Biodegradation is established by determination of the dissolved organic carbon content
of the supernatant liquor. This value is compared with that found for the liquor obtained
from a control tube dosed with settled sewage only.
DESCRIPTION OF THE TEST PROCEDURE
Preparations
[0021] The aeration units are cleaned and fixed in a suitable support. The air inlet tubes
are connected to the supply manifold. A small laboratory scale air compressor is used
to aerate the units, and the air is presaturated with water to reduce evaporation
losses from the units.
[0022] A sample of mixed liquor from an activated sludge plant treating predominantly domestic
sewage is obtained. Approximately 150 ml of the mixed liquor are required for each
aeration unit.
[0023] The organic carbon analyzer is calibrated using potassium hydrogen phthalate.
[0024] Stock solutions of the test compounds are prepared: the concentration normally required
is 400 mg/litre as organic carbon which gives a test compound concentration of 20
mg/litre carbon at the start of each aeration cycle if no biodegradation is occurring.
[0025] The organic carbon content of the stock solutions is measured.
Test conditions
[0026] A high concentration of aerobic micro-organisms is used, and the effective detention
period is 36 hours. The carbonaceous material in the sewage feed is oxidized extensively
within 8 hours of the start of each aeration cycle. Thereafter, the sludge respires
endogenously for the remainder of the aeration period, during which time the only
available substrate is the test compound unless this is also readily metabolized.
These features, combined with daily reinoculation of the test when domestic sewage
is used as the medium, provide highly favorable conditions for both acclimatization
and biodegradation.
Performance of the Test
[0027] A sample of mixed liquor from a suitable activated sludge plant is obtained and aerated
during transportation to the laboratory. Each aeration unit is filled with 150 ml
of mixed liquor and the aeration is started. After 23 hours, aeration is stopped,
and the sludge is allowed to settle for 45 minutes. The tap is opened and 100 ml of
the supernatant liquor withdrawn. A sample of settled domestic sewage is obtained
immediately before use, and 100 ml are added to the sludge remaining in each aeration
unit. Aeration is started anew. At this stage no test materials are added, and the
units are fed daily with domestic sewage only until a clear supernatant liquor is
obtained on settling. This usually takes up to two weeks, by which time the dissolved
organic carbon in the supernatant liquor at the end of each aeration cycle should
be less than 12 mg/litre.
[0028] At the end of this period the individual settled sludges are mixed, and 50 ml of
the resulting composite sludge are added to each unit.
[0029] 100 ml of settled sewage are added to the control units and 95 ml plus 5 ml of the
appropriate test compound stock solution (400 mg/l) to the test units. Aeration is
started again and continued for 23 hours. The sludge is then allowed to settle for
45 minutes and the supernatant drawn off and analyzed for dissolved organic carbon
content.
[0030] The above fill and draw procedure is repeated daily throughout the test.
[0031] Before settling it may be necessary to clean the walls of the units to prevent the
accumulation of solids above the level of the liquid. A separate scraper or brush
is used for each unit to prevent cross contamination.
[0032] Ideally, the dissolved organic carbon in the supernatant liquors is determined daily,
although less frequent analysis is permissible. Before analysis the liquors are filtered
through washed 0.45 µm membrane filters and certifuged. Temperature of the sample
must not exceed 40°C while it is in the centrifuge.
[0033] The length of the test for compounds, showing little or no biodegradation is indeterminate,
but experience suggests that this should be at least 12 weeks.
Treatment of the Results
[0034] The dissolved organic carbon results in the supernatant liquors of the test units
and the control units are plotted against time. As biodegradation is achieved the
level found in the test will approach that found in the control. Once the difference
between the two levels is found to be constant over 3 consecutive measurements, 3
further measurements are made and the percentage biodegradation of the test compound
is calculated by the following equation:

where
O
T = concentration of test compound as organic carbon added to the settled sewage at
the start of the aeration period.
O
t = concentration of dissolved organic carbon found in the supernatant liquor of the
test at the end of the aeration period.
O
c = concentration of dissolved organic carbon found in the supernatant liquor of the
control.
[0035] The level of biodegradation is therefore the percentage elimination of organic carbon.
[0036] If from the outset there is no difference between the control and the test, or the
difference between the two remains constant at a level less than would be expected
if no degradation had taken place, further tests are necessary to distinguish between
biodegradation and adsorption. This may be done by using the supernatant liquors as
a source of inoculum for tests such as the Sturm or the Closed Bottle Tests (OECD
Test Guidelines 301 B and 301 D).
Bleaches
[0037] A wide variety of bleaching agents may be employed for use with these automatic detergent
liquid compositions. Both halogen and peroxygen type bleaches are encompassed by this
invention.
[0038] Among the suitable halogen donor bleaches are heterocyclic N-bromo and N-chloro imides
such as trichlorocyanuric, tribromocyanuric, dibromo and dichlorocyanuric acids, and
salts thereof with water solubilizing cations such as potassium and sodium. An example
of the hydrated dichlorocyanuric acid is Clearon® CDB56, a product manufactured by
the Olin Corp.. Such bleaching agents may be employed in admixtures comprising two
or more distinct chlorine donors. An example of a commercial mixed system is one available
from the Monsanto Chemical Company under the trademark designation "ACL-66" (ACL signifying
"available chlorine" and the numerical designation "66", indicating the parts per
pound of available chlorine) which comprises a mixture of potassium dichloroisocyanurate
(4 parts) and trichloroisocyanurate acid (1 part).
[0039] Other N-bromo and N-chloro imides may also be used such as N-brominated and N-chlorinated
succinimide, malonimide, phthalimide and naphthalimide. Other compounds include the
hydantoins, such as 1, 3-dibromo and 1,3-dichloro-5,5-dimethylhydantoin, N-monochloro-C,
C-dimetylhydantoin methylene bis(N-bromo-C,C-dimethylhydantoin); 1,3-dibromo and 1,3-dichloro
5-methyl-5-n-amylhydantoin, and the like. Further useful hypohalite liberating agents
comprise tribromomelamine and trichloromelamine.
[0040] Dry, particulate, water-soluble anhydrous inorganic salts are likewise suitable for
use herein such as lithium, sodium or calcium hypochlorite and hypobromite.
[0041] Preferred chlorinating agents include potassium and sodium dichloroisocyanurate dihydrate,
chlorinated trisodium phosphate and calcium hypochlorite. Particularly preferred are
sodium or potassium dichloroisocyanurate dihydrate. Preferred concentrations of all
of these materials should be such that they provide about 0.2 to about 1.5% available
chlorine. Hypohalite liberating compounds may generally be employed in automatic dishwashing
detergents at a level of from 0.5 to 5% by weight, preferably from 0.5 to 3%.
[0042] Suitable chlorine-releasing agents are also disclosed in the ACS monograph entitled
"Chlorine - Its Manufacture, Properties and Uses" by Sconce, published by Reinhold
in 1962.
[0043] Chlorine bleach sources of the present invention may be encapsulated by the processes
disclosed in EP-A-0,510,761.
[0044] It may be appreciated that the oxygen bleaches which may be included in the compositions
of the invention are alkali metal and ammonium salts of inorganic peroxygen compounds
such as perborates, percarbonates, persulfates, dipersulfates and the like. Generally
the inorganic oxygen compound will be used in conjunction with an activator such as
TAED (tetraacetyl ethylene diamine), sodium nonyl oxybenzene sulfonate or choline
sulfophenyl carbonate or a catalyst such as manganese or other transition metal, as
is well known in the bleaching art (see e.g., U.S. 5,041,232; 5,045,223; and 5,047,163,
Batal et al. describing organic catalysts). Insoluble organic peroxides such as diperoxydodecanedioic
acid (DPDA), phthalimidoperoxycaprionic acid (PAP) or lauroyl peroxide, or benzoyl
peroxide, may also be used. Many others known in the art may also be used. Generally,
the peroxygen compounds are present at a level of from 0.5 to 20% by weight, 0.005
to 5% catalyst and/or 0.5 to 3% activator.
Surfactants
[0045] If encapsulated chlorine bleach is used in the present invention, a wide variety
of alkoxylates may be used. Particularly preferred are the defoaming nonionics such
as those given in U.S. Patent No. 4,973,419.
[0046] It may also be appreciated that low-foaming bleach resistant surfactants may also
be included in the liquid detergent formulas of the present invention, as are known
in the art. The preferred range of a surfactant useful in the invention is about 0.5
to about 4.0%.
Inorganic Builders
[0047] Inorganic builders in an amount of from about 3 to about 30%, preferably 3 to 10%,
may also be present in the formula as water hardness sequestering agents or builders.
[0048] Use of the sequestrant, in excess of its solubility limit within the formula requires
that the solid be present as fine particles which are suspended by the structuring
system. The presence of solids will affect the viscosity of the liquid and may modify
the range of the structurants needed to deliver the proper rheology. Inorganic builders
which may be used are sodium and potassium salts of polyphosphate, orthophosphate,
carbonate, bicarbonate, sesquicarbonate and borate.
[0049] Water-insoluble aluminosilicate ion-exchange materials may be used as alternative
builders (e.g. GB 1,473,201 and 1,473,202 - Henkel). These are crystalline or amorphous
materials of general formula
(Cat
2/nO)
x. Al₂O₃(SiO₂)
y. zH₂O
wherein Cat is a cation having a valency n that is exchangeable with Calcium (e.g.
Na+ or K+);x is a number from 0.7 to 1.5; y is a number from 1.3-4; and z is such
that the bound water content is from 1% to 28% by weight. Preferred is the commercially
available product Zeolite type A.
Na₂O Al₂O₃ 2SiO₂ 4.5H₂O
Silicates
[0050] Of the alkaline metal silicates, sodium silicate having a ratio of SiO₂:Na₂O of from
about 1.0 to about 3.3, preferably from about 2 to about 3.2 is useful for the present
invention. The liquid silicate form is preferred. Solid silicates may also be used
either alone or in combination with liquid silicates.
Thickeners and Stabilizers
[0051] Thickeners for use in the compositions according to the invention are disclosed in
U.S. Patent No. 4,836,948 (Corring) herein incorporated by reference. Particularly
preferred thickeners are the cross-linked polymers having molecular weights ranging
from about 500,000 to about ten million, preferably between 500,000 and 4,000,000.
Examples of commercially available cross linked polymers are the Carbopol® resins
manufactured by the B.F. Goodrich Chemical Company. These materials include Carbopol
941® (m.w. 1,250,000) Carbopol 934® (m.w. 3,000,000), Carbopol 940® (m.w. 4,000,000)
and Carbopol 617® (m.w. 4,000,000). Analogs provided by other manufacturers would
also be useful. The chlorine bleach may be encapsulated, thus polymers such as those
disclosed in U.S. Patent No. 4,260,528 (Fox et al.) may also be used.
[0052] The thickening polymer is present in the compositions in a range of 0 to about 3.0
by wt./ and preferably about 0.4% to about 1.5% by wt.
[0053] Co-structurants or stabilizers may also be used in combination with the thickeners.
Examples of such preferred co-structurants and stabilizers include (1) alumina described
in U.S. Patent No. 4,836,948, (2) alkali metal silico aluminate described in U.S.
Patent No. 4,941,988, (3) polyvalent metal soaps, described in U.S. Patent No. 4,752,409
and (4) a synthetic hectorite clay such as Laponite® XLS supplied by Waverly Mineral
Products Co., subsidiary of Laporte, Inc..
[0054] Preferred co-structurants include alumina and the hectorite clays. The co-structurants
may be used in a range of from about .005 to 1%; preferably about .01 to about .5%;
and especially preferred about .01 to about .1%.
Scale Inhibitors and Anti-Scalants
[0055] An anti-scalant agent inhibits the development of the microscopic nuclei to the critical
size and then the agent redisperses to act on other nuclei. Anti-scalant agents are
also useful in broader applications such as in industrial boilers, water purification,
evaporators, etc.
[0056] Any conventional anti-scalant (sometimes described as dispersant) which is used to
prevent the deposition of sparingly soluble salt scale, such as CaCO₃ in water systems
is considered within the scope of this invention.
[0057] Anti-scalant agents are available in either powder or solution form, generally solution
form is available, and may be provided as acids, partially neutralized acids or otherwise
contain a free acid. Examples of suitable phosphorus containing scale inhibitors include
methylene phosphonates, methylene phosphonic acid, and other phosphates and phosphonates
listed in McCutcheon's
Functional Materials, North America Edition, Volume 2, McCutcheon Division Publishing, Glen Rock, New
Jersey (1991).
[0058] Preferred methylene phosphonates include pentasodium amino tris, hexamethylene diamine
tetra, hexapotassium, octasodium diethylene triamine penta.
[0059] Particularly preferred methylene phosphonic acids include diethylene triamine penta
acid. Especially preferred is hydroxy ethylene diphosphonic acid in aqueous solution
supplied as Arquest® 710 by Aquaness Chemicals or as Dequest® 2010 by Monsanto. The
same diphosphonic acid is available in powder form as Dequest® 2016D by Monsanto or
amino tri (methylene phosphonic acid) sold as Arquest® 709 by Aquaness Chemicals.
Polymeric anti-scalants suitable for the invention include polymaleic acid and its
sodium salts (Belclene® 200 and 201) supplied by Ciba-Geigy a polycarboxylate polymer
series prepared from the copolymerization of acrylic and maleic acid sold under the
Sokalan® CP Series by BASF of and sodium polyacrylates and polyacrylic acid available
under the Sokalan PA Series supplied by BASF.
[0060] A polyacrylic acid and a sodium or ammonium polyacrylate are also suitable, such
as products produced by Alco Chemical Corp., Division of National Starch and Chemicals,
known as the Alcosperse® Series, Colloids sold by Rhone-Poulenc Corp. Good-rite® Series
supplied by B.F. Goodrich and Acusol® Series supplied by Rohm & Haas.
[0061] Particularly preferred anti-scalants include Colloid® 117/50; Colloid® 211, 223(D)
and 274; Good-rite® K-732, K-752, K-7058, K-G00N; Acusol® 445, and Alcosperse® 602N.
[0062] Additional anti-scalants suitable for the invention are described in Kirk-Othmer
Encyclopedia of Chemical Technology, 3rd Edition, Volume 7, John Wiley & Sons, NY (1979), describing anti-nucleation
agents or anti-scalants as dispersant materials.
[0063] A sulfonated styrene maleic anhydride copolymer is also a suitable anti-scalant for
the invention and may be obtained as Versa® TL 7 supplied by National Starch. Other
copolymers include Narlex® D-82 supplied by National Starch and sodium lignosulfonates
supplied under the trademark Orzans® by ITT Rayonier.
Optional Ingredients
[0064] Bleach stable colorants such as Direct Yellow 28 and others disclosed in GB patent
application No. 2,233,662 allowed August 9, 1991 may be used in the present invention.
Bleach sensitive dyes such as those described in U.S. Patent No. 4,464,281 may also
be used in embodiments containing oxygen or encapsulated bleach. Alternatively, pigments
such as Ultramarine Blue 5151 or Ultramarine Blue 17 may also be used. Greater latitude
in the selection of perfume ingredients is provided because destabilization by chlorine
is not a factor.
[0065] If additional defoaming is desired, silicones such as a polydimethyl siloxane with
6% hydrophobed silica supplied as Antifoam DB-100® by Dow Corning may be used. Minor
amounts of other ingredients such as anti-tarnish agents, soil suspending agents,
hydrotropes, etc. may also be included in the inventive formulations. The amount of
each optional additive is no greater than about 0.5% by weight.
[0066] The following examples will serve to distinguish this invention from the prior art,
and illustrate its embodiments more fully. Unless otherwise indicated, all parts,
percentages and proportions referred to are by weight.
Example I
[0067] The hypochlorite stability of the sequestrants was measured. A standard thiosulfate
titration for remaining hypochlorite was performed. pH 12 solutions containing 5%
sequestrant and hypochlorite bleach to deliver 1% AvCl₂ were prepared. The solutions
were stored in a 40°C oven to accelerate bleach decomposition. Results are tabulated
below. Structures are given in Table 2.
Table 1
| Species |
8-Day % AvCl₂ at 40°C |
| Oxydisuccinate (ODS)I |
96 (48% at 32 days) |
| Ethylene glycol disuccinates (EGDS)II |
97 |
| Propylene glycol disuccinate (PGDS)III |
98 |

[0068] It is noted from Tables 1 and 2 above, that none of the ether carboxylates (ODS,
EGDS or PGDS) decompose the available chlorine of the sample solutions. However, only
ODS is also biodegradable (see Example II).
Example II
[0069] The solutions of Example I were tested by the modified Semi-Continuous Activated
Sludge (SCAS) test described above to determine the biodegradability of the selected
ether carboxylate builders. Sludge samples containing each of the builders were placed
in 1,500 ml aeration units and tested as described by the OECD guidelines. The acclimatization
time for the builders resulting from the modified SCAS testing are given below:
| Species |
Modified SCAS Acclimatization Times |
DOC Percentages |
| ODS |
2-3 weeks |
>80% |
| EGDS |
7 weeks |
>80% |
| PGDS |
9 weeks |
>80% |
Examples III-VI
[0070] Compositions useful as liquid detergent compositions are listed below:
A composition including sodium tripolyphosphate as a builder is listed for comparison
purposes.
Examples 3-6 ADL Formulas
[0071]
| Component |
3 |
4 |
5 |
6 |
| Sodium Disilicate (2.0 ratio) |
15.0 |
15.0 |
15.0 |
15.0 |
| Carbopol 940a |
1.2 |
1.2 |
1.2 |
1.2 |
| CDB Wax Encapsulates (to give 1.0% AvCL) |
3.6 |
3.6 |
3.6 |
3.6 |
| SLF-18b |
2.0 |
2.0 |
2.0 |
2.0 |
| Chlorine Donor (to give 1% AvCl) |
-- |
-- |
-- |
-- |
| Alcosperse 602N (AA)c |
-- |
5.0 |
-- |
5.0 |
| Sokalan CP-7d (2:1 AA/MA) |
-- |
-- |
5.0 |
-- |
| STPP (Anhydrous) |
25.0 |
-- |
-- |
-- |
| ODS |
-- |
10.0 |
-- |
-- |
| EGDS |
-- |
-- |
10.0 |
-- |
| PGDS |
-- |
-- |
-- |
10.0 |
[0072] All components are listed in terms of active percentages and builder molecules are
presented as sodium salt levels.
a) a 4,000,000 MW cross-linked polymer supplied by B.F.Goodrich Chemical Co.
b) a low-foaming surfactant supplied by BASF.
c) anti-scalant supplied by National Starch.
d) copolymerization product of acrylic and maleic acid supplied by BASF.
Examples VII-X
[0073] One of the criteria used to judge the performance of a dishwasher detergent is glassware
appearance after washing. In this example, ten glass tumblers were placed in a Sears
Kenmore dishwasher. Forty grams of a 4:1 mixture of margarine and powdered milk were
placed in the dishwasher. 40 grams of each of the formulas shown below were added
to the dishwasher dispenser cups. After repeating the test through 4 wash cycles,
glasses were visually inspected and rated. They were rated numerically for spotting
and filming on a scale of 0 to 4 (0 = best; 4 = worst) for spotting, and 0 to 5 (0
= best; 5 = worst) for filming. Differences of about 0.5 in spotting, and 1.0 in filming
are considered significant compared to a 25% liquid STPP formula. Lipstick soiled
glasses were placed in the dishwasher as a builder sensitive monitor. Removal of fatty
acids of pigments in lipstick formulations are sensitive to both builders and surfactant.
[0074] The results are as follows:
| Example |
Formula |
Spotting |
Filming |
% Lipstick Remaining |
| 7 |
10% ODS |
0 |
1.4 |
Trace |
| 8 |
10% PDGS |
0 |
1.8 |
Trace |
| 9 |
10% EGDS |
0.2 |
2.0 |
Trace |
| 10 |
25% STPP |
0.3 |
0.9 |
Trace |
[0075] ODS was observed to have significantly better overall performance in preventing spotting,
filming and lipstick remaining on the dishware over both EGDS and STPP, the phosphate
based composition. Although ODS and PGDS had almost parity performance, PGDS is not
biodegradable according to the modified SCAS test.
Example XI
[0076] A liquid detergent composition including ODS may be prepared as described in Examples
III-VI except the chlorine source used is 1% hypochlorite to provide 1% available
chlorine and the surfactant, SLF-18, is omitted from the formula.