Note: Descriptions are shown in the official language in which they were submitted.
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AUTOMATIC DISIiWASHING COMPOSITIONS COMPRYSJNG DIACYL
PEROX[DE BLEACH AND BLOOIKING PERFUME
TECHNICAL FIELD
The present invention relates to automatic dishwashing detergent compositions
comprising a diacyl peroxide bleaching agent and a blooming perfume
composition
containing blooming perfume ingredients and delayed blooming perfume
ingredients.
Preferred methods for cleaning dishware are included.
BACKGROUND OF TBE nWENTION
Builders, surfactants, alkalinity, and bleaching chemicals traditionally have
been.
used in automatic dishwashing detergent (ADD) compositions to promote soil
removal
from dishes, soil antiredeposition and anti-spotting benefits. However, strong
alkalis like
sodium hydroxide and bleaches such as hypochlorite can be damaging to, or
leave a film
upon, glasses, dishware or silverware. Accordingly, milder ADD compositions
have
been developed that make use of a source of hydrogen peroxide. Diacyl peroxide
bleaching agents are particularly effective at removing stains, especially
carotenoid, from
plastic dishware. However, such bleaching agents have strong base odors that
can be
difficult to mask or cover up with perfume compositions. This is especially
true in liquid,
gel and paste compositions where the bleaching agents can more readily degrade
or react
with other ingredients in the composition and introduce off odors.
Plastic dishware also tends to pickup residual food malodors or other malodors
from the dishwashing process. It is desirable to formulate perfume
compositions for
ADD products that can cover up or mask such malodors and give the impression
that
washed items, particularly plastic dishware, are fresh and clean at the end of
the washing
cycle when the consumer removes them from the machine. However, the perfume
smell
should not linger significantly or adhere noticeably to the washed items.
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Patent 6,143,707, Trinh et al, issued November 7, 2000, discloses automatic
dishwashing detergent compositions comprising blooming perfume compositions
containing blooming perfume ingredients, and optionally, delayed blooming
perfume
ingredients, and non-blooming perfume ingredients. The compositions can also
contain
bleaching agents, including diacyl peroxides.
U.S. Patent 5,089,162, Rapisarda et al, issued February 18, 1992, discloses
cleaning compositions containing bleach-stable yellow colorant and either a
chlorine
bleach or an oxygen bleach. The compositions may be automatic dishwashing
detergents,
and preferably have a lemon-like scent. Various perfume ingredients and
perfume
compositions are disclosed.
ST.JMMARY OF THE INVENTION
It has now been discovered that automatic dishwashing detergent compositions
comprising a blooming perfume composition and an effective amount of a diacyl
peroxide bleaching agent can be formulated to provide cleaning and stain
removal (e.g.,
carotenoid stain removal) benefits, while also providing a positive scent
signal to
consumers during use.
Taken broadly, the present invention encompasses automatic dishwashing
detergent compositions comprising, by weight:
(a) from about 0.01% to about 5% of a blooming perfume composition
comprising from about 15% to about 60% of blooming perfume ingredients having
a
boiling point of less than about 260 C and a ClogP of at least about 3, and
from about
15% to about 70% of delayed blooming perfume ingredients having a boiling
point of
less than about 260 C and a ClogP of less than about 3, wherein the weight
ratio of
blooming perfume ingredients to delayed blooming perfume ingredients is from
about
0.25 to about 1.5 and said blooming perfume composition comprises at least
about 40%
by weight of blooming perfume ingredients and delayed blooming perfume
ingredients;
and
(b) an effective amount of diacyl peroxide bleaching agent.
The 'above blooming perfume composition provides superior perfume effects in
that it masks the base odors from the diacyl peroxide bleaching agent in the
composition,
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while providing a pleasant fragrance in the area surrounding the automatic
dishwashing
machine during and after use: The perfume composition covers up or masks
residual food
malodors and/or other malodors from the dishwashing process, including on
washed
items such as plastic dishware that tend to pick up such malodors. The perfume
composition thus gives the impression that the washed items are fresh and
clean at the
end of the washing cycle when the items are removed from the machine. The
ingredients
of the perfume composition are also selected to minimize residual odor on
washed items,
particularly plastic items.
The present invention also encompasses cleaning methods; more particularly, a
method of washing dishware in a domestic automatic dishwashing appliance,
comprising
treating soiled dishware in an automatic dishwasher with an aqueous bath
comprising the
composition as provided above.
All parts, percentages and ratios used herein are expressed as percent weight
unless otherwise specified.
DETAIL.ED DESCRTP'lTON OF 1BE INVENTION
Automatic dishwashing compositions of the present invention comprise a
blooming perfume composition and an effective amount of diacyl peroxide
bleaching
agent, as described in more detail below.
Amounts of the essential ingredients can vary within wide ranges, however
preferred automatic dishwashing detergent compositions herein (which have a 1%
aqueous solution pH of from about 2 to about 12, more preferably from about 3
to about
11) comprise from about 0.01% to about 5%, preferably from about 0.03% to
about 3%,
and more preferably from about 0.05% to about 2%, of a blooming perfume
composition.
Preferred compositions herein are in the form of liquids, gels or pastes and
contain
from about 40% to about 99%, preferably from about 60% to about 99%, more
preferably
from about 80% to about 99%, of water. Because of the reactivity of bleaching
agents in
such compositions, and the potential for generation of off odors, the benefits
provided by
the present blooming perfume composition containing base masking perfume
ingredients
are generally greater in such compositions.
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By "effective amount" herein is meant an amount, which is sufficient, under
whatever comparative test conditions are employed, to enhance cleaning of a
soiled
surface. In automatic dishwashing, the soiled surface may be, for example, a
plastic
container with tomato stains or dishes soiled with simple starches or more
complex food
soils. The test conditions will vary, depending on the type of washing
appliance used and
the habits of the user. Of course, the performance of bleaches will be
affected by such
considerations, and the levels used in fully formulated detergent and cleaning
compositions can be appropriately adjusted.
Blooming Perfume Composition
Blooming perfume compositions, as disclosed herein, can be formulated into
automatic dishwashing detergent compositions and provide significantly better
noticeability to the consumer than non-blooming perfume compositions not
containing a
substantial amount of blooming perfume ingredients. Additionally, residual
perfume is
not desirable on many surfaces, including dishes, glasses and cutlery,
especially those
made of plastic, rubber and silicone.
A blooming perfume ingredient is characterized by its boiling point (B.P.) and
its
octanol/water partition coefficient (P). The octanol/water partition
coefficient of a
perfume ingredient is the ratio between its equilibrium concentrations in
octanol and in
water. The preferred perfume ingredients of this invention have a B.P.,
determined at the
normal, standard pressure of about 760 mm Hg, of ab-out 260 C or lower,
preferably less
than about 255 C; and more preferably less than about 250 C, and an
octanol/water
partition coefficient P of about 1,000 or higher. Since the partition
coefficients of the
preferred perfume ingredients of this invention have high values, they are
more
conveniently given in the form of their logarithm to the base 10, logP. Thus
the preferred
perfume ingredients of this invention have logP at 25 C of about 3 or higher.
Boiling points of many perfume compounds can be found in the following
sources:
Properties of Organic Compounds Database CD-ROM Ver. 5.0
CRC Press,
Boca Raton, Florida;
Flavor and Fragrance - 1995,
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Aldrich Chemical Co.,
Milwaukee, Wisconsin;
STN database/on-line,
Design Institute of for Physical Property Data,
American Institute of Chemical Engineers;
STN database/on-line,
Beilstein Handbook of Organic Chemistry,
Beilstein Information Systems; and
Perfume and Flavor Chemicals,
Steffen Arctander,
Vol. I, II - 1969.
When unreported, the 760 mm boiling points of perfume ingredients can be
estimated. The following computer programs are useful for estimating these
boiling
points:
MPBPVP Version 1.25 1994-96 Meylan
Syracuse Research Corporation (SRC)
Syracuse, New York; and
ZPARC,
ChemLogic, Inc.,
Cambridge, Massachusetts.
The logP of many perfume ingredients has been reported; for example, the
Pomona92 database, available from Daylight Chemical Information Systems, Inc.
(Daylight CIS), Irvine, California, contains many, along with citations to the
original
literature. However, the logP values are most conveniently calculated by the
Pamona
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Med Chem/Daylight "CLOGP" program, Version 4.42 available from Biobyte
Corporation, Claremont, California This program also lists experimental logP
values
when they are avaiIable in the Pomona92 database. The "calculated logP"
(C1ogP) is
determined by the fragment approach of Hansch and Leo (cf., A. Leo, in
Comprehensive
Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J. B. Taylor and C. A.
Ramsden, Eds., p. 295, Pergamon Press, 1990.) The
fragment approach is based on the chemical structure of each perfume
ingredient, and
takes into account the numbers and types of atoms, the atom connectivity, and
chemical
bonding. The ClogP values, which are the most reliable and widely used
estimates for
this physicochemical property, are preferably used instead of the experimental
logP
values in the selection of perfume ingredients which are useful in the present
invention.
Thus, when a perfume composition which is composed of ingredients having a
B.P. of about 260 C or lower and a ClogP, or an experimental logP, of about 3
or higher,
is used in an automatic dishwashing detergent composition, the perfume is very
effusive
and very noticeable when the product is used
Table 1 gives some non-limiting examples of blooming perfume ingredients,
useful in automatic dishwashing detergent compositions of the present
invention. The
blooming perfume compositions of the present invention contain at least 2
different
bloon-iing perfume ingredients, preferably at least 3 different blooming
perfume
ingredients, more preferably at least 4 different blooming perfume
ingredients, and even
more preferably at least 5 or more different blooming perfume ingredients.
Furthermore,
the blooming perfume compositions of the present invention contain from about
15 to
about 60% of blooming perfume ingredients, preferably from about 20 to about
50% of
blooming perfume ingredients, more preferably from about 25 to about 40% of
blooming
perfume ingredients. The bloozning perfume compositions herein preferably
should not
contain any single blooniing ingredient at a level that would provide, by
weight, more
than about 2% of that ingredient to the total dishwashing composition, more
preferably
not more than about 1.5%, and even more preferably not more than about 0.5%,
of the
dishwashing composition.
The perfume composition itself preferably should not contain more than 60% of
any single perfume ingredient.
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Most common perfume ingredients, which are derived from natural sources, are
composed of a multitude of components. For example, orange terpenes contain
about
90% to about 95% d-limonene, but also contain many other minor ingredients.
When
each such material is used in the fomiulation of blooming perfume compositions
of the
present invention, it is counted as one ingredient, for the purpose of
defining the
invention. Synthetic reproductions of such natural perfume ingredients are
also
comprised of a multitude of components and are counted as one ingredient for
the
purpose of defining the invention.
The blooming perfume composition of the present invention also contain from
about 15% to about 70%, preferably from about 20% to about 50%, more
preferably from
about 25% to about 40%, by weight, of delayed blooming" perfume ingredients.
The
delayed blooming perfume ingredients of this invention have a B.P., measured
at the
normal, standard pressure, of about 260 C or lower, preferably less than about
255 C;
and more preferably less than about 250 C, and a logP or ClogP of less than
about 3.
Thus, when a perfume composition is composed of some preferred blooming
ingredients
and some delayed blooming ingredients, the perfume effect is longer lasting
when the
product is used. Table 2 gives some non-limiting examples of delayed blooming
perfume
ingredients useful in automatic dishwashing detergent compositions of the
present
invention. Delayed blooming perfume ingredients are used primarily in
applications
where the water will evaporate, thus liberating the perfume.
Plastic dishware items are difficult to get fully dry in an automatic
dishwashing
machine. Due to the hydrophobic nature of plastic surfaces, water tends to
collect in tiny
droplets which evaporate less readily from the surface than does the thin
water film
formed on less hydrophobic surfaces such as ceramics. This slower drying of
plastic
surfaces is used to advantage in the present compositions where, because of
the high
concentration of delayed blooming ingredients, there will be a constant
release of
perfume materials from the perfume dispersed in the tiny water droplets on
plastic
dishware surfaces. This will occur over a longer period than for conventional
blooming
perfumes due to the relatively high level of delayed blooming perfume
ingredients in the
present compositions. Thus, plastic items removed from the dishwasher even a
considerable time after the cycle has finished will give the impression of
being clean and
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fresh, and any malodors will be maslced. A major advantage of this approach is
that the
delayed blooming perfume ingredients are not very residual to the plastic
since they are
not very hydrophobic. The delayed bloomirig perfume ingredients will thus
eventually
evaporate with the water droplets, leaving no taint on the plastic dishware.
The weight ratio of blooming perfume ingredients to delayed blooming perfume
ingredients in the present compositions should be from about 0.25 to about
1.5, preferably
from about 0.5 to about 1.35, more preferably from about 0.75 to about 1.2.
The
blooming perfume compositions also contain at least about 40 wt.% of the
combined
blooming perfume ingredients and delayed blooming perfume ingredients,
preferably at
least about 50 wt.% of the combined perfume ingredients, more preferably at
least about
55 wt.% of the combined perfume ingredients, and even more preferably at least
about 60
wt.% of the combined perfume ingredients. The blooming perfume compositions of
the
present invention contain at least 2 different delayed blooming perfume
ingredients,
preferably at least 3 different delayed blooming perfume ingredients, and more
preferably
at least 4 or more different delayed blooming perfume ingredients.
In the perfume art, some auxiliary materials having no odor, or a low odor,
are
used, e.g., as solvents, diluents, extenders or fixatives. Non-limiting
examples of these
materials are ethyl alcohol, carbitol, dipropylene glycol, diethyl phthalate,
triethyl citrate,
isopropyl myristate, and benzyl benzoate. These materials are used for, e.g.,
solubilize or
diluting some solid or viscous perfume ingredients to, e.g., improve handling
and/or
formulating. These materials are useful in the blooming perfume compositions,
but are
not counted in the calculation of the limits for the definition/formulation of
the blooming
perfume compositions of the present invention.
Non-blooming perfume ingredients are those having a B.P. of more than about
260 C. Table 3 gives some non-limiting examples of non-blooming perfume
ingredients
that have a ClogP of less than about 3. In certain automatic dishwashing
detergent
compositions, some non-blooming perfume ingredients can be used in small
amounts,
e.g., to improve overall perfume odor.
The blooming perfume compositions of present invention preferably also
comprise from about 1% to about 30%, preferably from about 2% to about 30%,
more
preferably from about 3% to about 25%, of non-blooming perfume ingredients
having a
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B.P. of more than about 260 C and having a ClogP of at least about 3. These
ingredients
are particularly effective at maslcing base odors from the diacyl peroxide-
bleaching agent.
When used at the low levels herein, an improved blooming perfume composition
is
obtained that betters masks base odors while still minimizing residual perfume
on dishes
and tableware. Table 4 provides some non-limiting examples of such base
masking
perfume ingredients.
In the following tables, measured boiling points are taken from the above-
mentioned sources.
Estimated boiling points are an average of those determined by the above-
mentioned computer programs.
The predicted ClogP at 25 C was determined by the following computer program:
Panoma MedChem/Daylight ClogP V. 4.42
Table 1
Examples of BloomingLPerfume Ingredients
Ingredient C1ogP Boiling Pt. Boiling Pt.
(Pred.) (Meas.) (Pred.)
Allo-ocimene 4.36 195
Allyl cyclohexanepropionate 3.94 252
Allyl heptanoate 3.40 209
trans-Anethole 3.31 232
Benzyl butyrate 3.02 240
Camphene 4.18 160
Cadinene 7.27 252
Carvacrol 3.40 238
cis-3-Hexenyl tiglate 3.80 225
Citronellol 3.25 223
Citronellyl acetate 4.20 234
Citronellyl nitrile 3.09 226
Citronellyl propionate 4.73 257
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Cyclohexylethyl acetate 3.36 222
Decyl Aldehyde (Capraldehyde) 4.01 208
Delta Damascone 3.62 256
Dihydromyrcenol 3.03 192
Dihydromyrcenyl acetate 3.98 221
3,7-Dimethyl-l-octanol 3.74 205
Diphenyloxide 4.24 259
Fenchyl Acetate
(1,3,3-Trimethyl-2-norbomanyl acetate) 3.53 234
Geranyl acetate 3.72 233
Geranyl formate 3.27 231
Geranyl nitrile 3.25 228
cis-3-Hexenyl isobutyrate 3.27 204
Hexyl Neopentanoate 4.06 213
Hexyl tiglate 4.28 221
alpha-Ionone 3.71 237
lonone Beta 3.77 239
Isobornyl acetate 3.53 238
Isobutyl benzoate 3.57 242
Isononyl acetate 4.28 220
Isononyl alcohol
(3,5,5-Trimethyl-l-hexanol) 3.08 194
Isopulegyl acetate 3.70 243
Lauraldehyde 5.07 250
Linalyl acetate 3.50 230
Lorysia 4.06 236
D-limonene 4.35 177
Lymolene 3.03 198
(-)-L-Menthyl acetate 4.18 227
Methyl Chavicol (Estragole) 3.13 216
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Methyl n-nonyl acetaldehyde 4.85 247
Methyl octyl acetaldehyde 4.32 224
beta-Myrcene 4.33 165
Neryl acetate 3.72 236
Nonyl acetate 4.41 229
Nonaldehyde 3.48 191
Para-Cymene 4.07 173
alpha-Pinene 4.18 156
beta-Pinene 4.18 166
alpha-Terpinene 4.41 175
gamma-Terpinene 4.35 183
Terpineolene 4.35 172
Alpha-Terpinyl acetate 3.58 220
Tetrahydrolinalool 3.52 202
Tetrahydromyrcenol 3.52 195
Undecavertol 3.69 235
2-Undecenal 4.22 235
Verdox (o-t-Butylcyclohexyl acetate) 4.06 239
Vertenex (4-tert.Butylcyclohexyl acetate) 4.06 237
Table 2
Examples of "Delayed Blooming" Perfume Ingredients
ClogP Boiling Pt. Boiling Pt.
Ingredient (Pred.) (Meas.) (Pred.)
Allyl Amyl Glycolate 2.38 218
Allyl caproate 2.87 186
Amyl acetate (n-Pentyl acetate) 2.30 147
Amyl Propionate 2.83 169
p-Anisaldehyde 1.78 249
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Anisic Aldehyde 1.78 220
Anisole 2.06 154
Benzaldehyde (Benzenecarboxaldehyde) 1.50 179
Benzyl acetate 1.96 211
Benzylacetone 1.74 234
Benzyl alcohol 1.10 205
Benzyl formate 1.50 203
Benzyl propionate 2.49 221
beta-gamma-Hexenol (2-Hexen-l-ol) 1.40 164
(+)-Camphor 2.18 207
(+)-Carvone 2.01 231
L-Carvone 2.01 230
Cinnamic alcohol 1.41 258
Cinnamyl formate 1.91 252
cis-Jasmone 2.64 253
cis-3-Hexenyl acetate 2.34 175
Citral (Neral) 2.95 208
Cumic alcohol 2.53 249
Cuminaldehyde 2.92 235
Cyclal (2,4-Dimethyl-3-
cyclohexene-l-carboxaldehyde) 2.36 203
Dimethyl benzyl carbinol 1.89 215
Dimethyl benzyl carbinyl acetate 2.84 248
Ethyl acetate 0.71 77
Ethyl acetoacetate 0.33 181
Ethyl amyl ketone 2.44 167
Ethyl benzoate 2.64 215
Ethyl butanoate 1.77 121
Ethyl Butyrate 1.77 124
Ethyl-2-methyl butryrate 2.08 131
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Ethyl-2-methyl pentanoate 2.69 159
3-Nonanone (Ethyl hexyl ketone) 2.97 187
Ethyl Maltol 0.68 248
Ethyl phenylacetate 2.35 228
Eucalyptol 2.76 176
Eugenol 2.40 253
Fenchyl alcohol 2.58 199
Flor Acetate (Tricyclodecenyl acetate) 2.36 233
Frutene (Tricyclodecenyl propionate) 2.89 250
gamma-Nonalactone 2.77 243
trans-Geraniol 2.77 230
cis-3-Hexen-l-ol / Leaf Alcohol 1.40 156
Hexyl acetate 2.83 171
Hexyl formate 2.38 155
Hydratopic alcohol 1.58 233
Hydroxycitronellal 1.54 241
Indole (2,3-Benzopyrrole) 2.13 254
Isoamyl alcohol 1.22 131
Isopropyl phenylacetate 2.66 237
Isopulegol 2.75 231
Isoquinoline (Benzopyridine) 1.82 243
Ligustral (2,4-Dimethyl-3-
Cyclohexene-l-carboxaldehyde) 2.36 204
Linalool 2.55 193
Linalool oxide 1.45 223
Menthone 2.83 214
4-Methylacetophenone 2.08 226
Methyl pentyl ketone 1.91 151
Methyl anthranilate 2.02 256
Methyl benzoate 2.11 199
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Methyl Phenyl Carbinyl Acetate
(alpha-Methylbenzyl acetate) 2.27 216
Methyl Eugenol (Eugenyl methyl ether) 2.67 254
Methyl Heptenone
(6-Methyl-5-hepten-2-one) 1.82 173
Methyl Heptine Carbonate 218
(Methyl 2-octynoate) 2.57
Methyl Heptyl ketone 2.97 195
Methyl Hexyl ketone 2.44 173
Methyl pamplemousse (1,1-dimethoxy- 2.70 194
2,2,5-trimethyl-4-hexene)
Methyl salicylate 2.45 223
Dimethyl anthranilate 2.16 255
Nerol 2.77 225
delta-Nonalactone 2.80 226
gamma-Octalactone 2.24 256
2-Octanol 2.72 180
Octyl Aldehyde (Caprylic aldehyde) 2.95 167
p-Cresol 1.97 202
p-Cresyl methyl ether 2.56 175
Acetanisole 1.80 258
2-Phenoxyethanol 1.19 245
Phenylacetaldehyde 1.78 195
2-Phenylethyl acetate 2.13 235
Phenylethyl alcohol 1.18 218
Phenyl Ethyl dimethyl Carbinol
(Benzyl-tert-butanol) 2.42 257
Prenyl acetate 1.68 150
Propyl butanoate 2.30 143
(+)-Pulegone 2.50 224
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Rose oxide (Methyl Iso Butenyl Tetrahydro
Pyran) 2.90 197
Safrole 2.57 235
Stemone (5-Methyl-3-heptanone-oxime) 2.64 205
4-Terpinenol 2.75 211
Alpha Terpineol 2.75 222
Trip1a1(2,4-Dimethyl-3-
Cyclohexene-l-carboxaldehyde) 2.36 204
Veratrole (1,2-Dimethoxybenzene) 1.60 206
Violiff 2.77 238
Viridine (Phenylacetaldehyde
dimethyl acetal) 1.29 220
Table 3
Examples of "Non-Bloominiz" Perfume Ingredients
Having ClogP of Less Than About 3
C1ogP Boiling Pt. Boiling Pt.
Ingredient (Pred.) (Meas.) (Pred.)
Coumarin 1.41 302
Ethyl methylphenylglycidate 2.71 274
Ethyl Vanillin 1.80 285
Isoeugenol 2.58 266
Methyl cinnamate 2.47 262
Methyl dihydro jasmonate 2.42 314
Methyl beta-naphthyl ketone 2.76 302
Para Hydroxy Phenyl Butanone
(Raspberry ketone) 1.07 301
Phenoxy ethyl isobutyrate 2.92 277
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Vanillin 1.28 285
Table 4
Examples of "Base Masking" Perfume Ingredients
ClogP Boiling Pt. Boiling Pt.
Ingredient (Pred.) (Meas.) (Pred.)
(Ambrettolide)
Oxacycloheptadec-10-en-2-one 6.36 352
(Amyl benzoate) n-Pentyl benzoate 4.23 263
Isoamyl cinnamate 4.45 300
alpha-Amylcinnamaldehyde 4.32 289
alpha-Amylcinnamaldehyde
dimethyl acetal 4.03 320
(iso-Amyl Salicylate) isopentyl salicylate 4.43 277
(Aurantiol) Methyl
anthranilate/hydroxycitronellal Schiff base 4.22 413
Benzophenone 3.18 305
Benzyl salicylate 4.21 320
beta-Caryophyllene 6.45 263
Cedrol 4.53 274
Cedryl acetate 5.48 289
Cinnamyl cinnamate 4.64 387
Citrathal 3.93 262
Citronellyl isobutyrate 5.04 266
Clonal 4.90 267
Cyclohexyl salicylate 4.48 327
Cyclamen aldehyde . 3.46 271
Cyclabute 3.41 275
delta-Dodecalactone 4.39 279
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(Dihydro Isoj asmonate) Methyl 2-hexyl-3-
oxo-cyclopentanecarboxylate 3.09 314
Diphenylmethane 4.06 265
Ethylene brassylate 4.62 390
Ethyl undecylenate 4.99 261
Florhydral 3.55 277
Iso E Super 4.85 306
(Exaltolide) Pentadecanolide 6.29 338
(Galaxolide) 4,6,6,7,8,8-Hexamethyl-
1, 3,4,6,7, 8-hexahydro-c yclopenta(G)-2-
benzopyran 6.06 335
gamma-Methyl lonone
(alpha-Isomethylionone) 4.02 278
Geranyl isobutyrate 5.00 295
Habanolide 6.29 330
Hexadecanolide 6.85 352
cis-3-Hexenyl salicylate 4.61 323
alpha-Hexylcinnamaldehyde 4.85 334
n-Hexyl salicylate 5.09 318
Hexadecanolide 6.85 352
alpha---Irone 4.23 279
6-Isobutylquinoline 3.99 294
Lilial (p-tert.Butyl-alpha- 282
methyldihydrocinnamic aldehyde, PT 3.86
Bucinol)
Linalyl benzoate 5.42 325
(2-Methoxy Naphthalene) beta-Naphthyl
methyl ether 3.24 274
Nectaryl 4.43 317
Neobutenone 3.63 266
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10-Oxahexadecanolide 4.38 355
Patchouli alcohol 4.53 317
(Phantolide) 5-Acetyl-1,1,2,3,3,6-
hexamethylindan 5.69 333
Phenethyl benzoate 4.06 335
Phenethyl phenylacetate 3.77 350
Phenyl Hexanol (3-Methyl-5-phenyl-l-
pentanol) 3.17 296
Tonalid (7-Acetyl-1,1,3,4,4,6-
hexamethyltetralin) 6.25 344
delta-Undecalactone 3.86 262
ganimma-Undecalactone 3.83 286
Vertinert Acetate 5.47 332
Perfumes suitable for use in automatic dishwashing detergent compositions can
be
formulated from known fragxance ingredients, and for purposes of enhancing
environmental compatibility, the perfume is preferably substantially free of
halogenated
fragrance materials and nitromusks.
The compositions of this invention may contain an effective amount of various
moisture-activated encapsulqted perfume particles, as an optional ingredient.
These are
described in detail in U.S. Patent 6,143,707, Trinh et al.,
The encapsulated particles act as protective carriers and reduce the loss of
perfume prior to use. Such materials include, for example,
cyclodextrin/perfume
inclusion complexes, polysaccharide cellular matrix perfume microcapsules, and
the like.
Encapsulation of perfume rninimizes the diffusion and loss of the volatile
blooming
perfume ingredients. Perfume is released when the materials are wetted, to
provide a
pleasant odor signal in use. Especially preferred are cyclodextrin inclusion
complexes.
The optional water-activated protective perfume carriers allow the use of
lower
levels of perfume in the detergent compositions herein because of the reduced
loss of the
perfume during manufacturing and use. Due to the minimal loss of the volatile
ingredients in the blooming perfume compositions, perfume compositions that
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incorporate water activated protective perfume carrier can contain less
blooming perfume
ingredients than those used in the free, unencapsulated form. The encapsulated
and/or
complexed perfume compositions typically contain at least about 20%,
preferably at least
about 30%, and more preferably at least about 40%, blooming perfume
ingredients.
Optionally, but preferably, compositions that contain encapsulated and/or
complexed
perfume also comprise free perfume in order to provide consumers with a
positive scent
signal before the composition is used.
Bleaching Agent
The composition of the present invention generally contain from about 0.1% to
about 10%, preferably from about 0.3% to about 7%, more preferably from about
0.5% to
about 5%, and most preferably from about 0.7% to about 3%, of diacyl peroxide
of the
general formula:
RC(O)OO(O)CR
wherein each R, independently, is a hydrocarbyl group. Each R can be an alkyl,
aryl,
heterocyclic, imino, amino, or floro group. Preferably no more than one R is a
hydrocarbyl chain of longer than ten carbon atoms, more preferably at least
one has an
aromatic nucleus.
The preferred diacyl peroxides have a melting point greater than about 30 C,
preferably greater than about 50 C, most preferably above 70 C.
The diacyl peroxide should be present in the form of insoluble or relatively
insoluble particles having a particle size of from about 0.1 to about 30
microns,
preferably from about 0.5 to about 20 microns, more preferably from about 1 to
about 10
microns. Preferably, at least about 25%, more preferably at least about -50%,
even more
preferably at least about 75%, most preferably at least about 90%, of the
particles are
smaller than 10 microns, preferably smaller than 6 microns. Compositions
having larger
size diacyl peroxide particles are more difficult to stabilize in the
preferred liquid or gel
compositions of the invention, particularly during storage for longer periods
of time, and
often result in increased deposition and filming on dishware during use in
automatic
dishwashing machines. Diacyl peroxides within the above particle size range
have also
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been found to provide better stain removal from plastic dishware, while
minimizing
undesirable deposition and filming, than larger diacyl peroxide particles. The
preferred
diacyl peroxide particle size thus allows the formulator to obtain good stain
removal with
a low level of diacyl peroxide, which reduces deposition and filming.
Conversely, as
diacyl peroxide particle size increases, more diacyl peroxide is needed for
good. stain
removal, which increases deposition on surfaces encountered during the
dishwashing
process.
Examples of suitable diacyl peroxides include dibenzoyl peroxide, benzoyl
lauryl
peroxide, benzoyl succinyl peroxide, di-(2-methybenzoyl) peroxide, diphthaloyl
peroxide, and mixtures thereof. Preferably, the diacyl peroxide is selected
from
dibenzoyl peroxide, dicumyl peroxide, diphthaloyl peroxide, and mixtures
thereof. A
particulary prefen:ed diacyl peroxide is dibenzoyl peroxide.
Optional Ingredients
Preferred liquid or gel compositions of the present invention contain a
viscoelastic,
thixotropic thickening agent. The thickening agent is used at a level of from
about 0.1%
to about 5%, preferably from about 0.2% to about 3%, most preferably from
about 0.3%
to about 2%, by weight of the composition. The type and level of thickener
should be
selected to provide the desired product thickness and stability, while
minirn~~ing
undesired properties such as deposition and filming on plastic surfaces.
Preferably, the thickening agent is a polymer with a molecular weight of at
least
about 500,000, preferably from about 500,000 to 10,000,000. The polymeric
thickening
agent can be, but is not limited to, a cross-linked polycarboxylate polymer.
The cross-linked polycarboxylate polymer is preferably a carboxyvinyl polymer.
Such compounds are disclosed in U.S. Patent 2,798,053, Brown, issued on July
2, 1957.
Methods for making carboxyvinyl polymers are also
disclosed in Brown. Carboxyvinyl polymers are substantiaIIy insoluble in
liquid, volatile
organic hydrocarbons and are dimensionally stable on exposure to air.
Various carboxyvinyl polymers, homopolymers and copolyrners are commercially
available from B. F. Goodrich Company, New York, N.Y., under the trade name
Carbopol . These polymers are also known as carbomers or polyacrylic acids.
Carboxyvinyl polymers useful in formulations of the present invention include
Carbopol
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910 having a molecular weight of about 750,000, Carbopol 941 having a
molecular
weight of about 1,250,000, and Carbopols 934 and 940 having molecular weights
of
about 3,000,000 and 4,000,000, respectively. More preferred are the series of
Carbopols,
which use ethyl acetate and cyclohexane in the manufacturing process, for
example,
Carbopol 981, 984, 980, and 1382, and their easy-to-disperse equivalents such
as
Carbopol ETD2001, ETD2050 and ETD2020.
Preferred polycarboxylate polymers of the invention are non-linear, water-
dispersible, polyacrylic acid cross-linked with a polyalkenyl polyether and
having a
molecular weight of at lease 750,000, preferably from about 750,000 to about
4,000,000.
H'ighly preferred examples of these polycarboxylate polymers for use in the
present
invention are Sokalan PHC-25 , a polyacrylic acid available from BASF
Corporation,
the Carbopol series resins available from B. F. Goodrich, and the Polygel
series available
from 3-V Chemical Corporation. Mixtnres of polycarboxylate polymers as herein
described may also be used.
The polycarboxylate polymer-thickening agent can be used alone or with
inorganic
clays (e.g. aluminum silicate, bentonite, fumed silica). The preferred clay-
thickening
agent can be either naturally occuiling or synthetic. A preferred synthetic
clay is the one
disclosed in the U.S. Patent 3,843,598. . Naturally
occurring clays include some smectite and attapulgite clays as disclosed in
U.S. Patent
4,824,590.
Other types of thickeners, which can be used in this composition, include
natural
gums, such as xanthan gum, locust bean gum, guar gum, and the like. Semi-
synthetic
thickeners such as the cellulosic type thickeners: hydroxyethyl and
hydroxymethyl
cellulose (ETHOCEL and METHOCEL available from Dow Chemical) can also be
used. Mixtures of polymeric thickening agents, semi-synthetic, and natural
thickeners
herein described may also be used.
Preferred liquid or gel compositions of the present invention contain from
about
40% to about 99%, preferably from about 60% to about 99%, more preferably from
about
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80% to about 99%, and most preferably from about 90% to about 99%, by weight
of
water.
The compositions may also contain minor amounts of solvents in which the
diacyl
peroxide will not dissolve. Suitable solvents useful herein are glycerol,
dimethyl
siloxanes, sorbitol, and mixtures thereof. If present, such solvents represent
less than
about 20%, preferably less than about 10%, most preferably less than about 5%,
by
weight of the composition.
The compositions herein should not contain significant amounts of solvents
capable
of dissolving the diacyl peroxides herein. Examples of such solvernts are N-
alkyl
pyrrolidones, such as N-ethyl pyrrolidone, diacetone alcohol, alkyl ethers,
cyclic alkyl
ketones, and mixtures thereof. Amines, ethers and low molecular weight primary
and
secondary alcohols (about Ci-C6) also are preferably not present, since it is
believed that
they may iiitroduce stability problems. Preferably, the compositions herein
contain no
more than about 5% by weight of such solvents. More preferably, the
compositions
contain no more than about 2% by weight of such solvents. Most preferably,
they are
substantially free of such solvents.
Preferred liquid or gel compositions herein have a pH, measured at a
concentration
of 1% by weight in water, of from 2 to about 10, preferably from about 3 to
about 9, more
preferably from about 4 to about 8, and most preferably from about 5 to about
7. At
higher pHs, the diacyl peroxide particles are degraded and stain removal
performance is
reduced, particularly in the presence of agents that solubilize the diacyl
peroxide such as
surfactants.
The compositions may thus comprise a pH-adjusting component selected from
water-soluble alkaline inorganic salts and water-soluble organic or inorganic
builders.
Preferred pH-adjusting components are selected from the group consisting of:
sodium/potassium carbonate or sesquicarbonate; sodium/potassium silicate,
preferably
hydrous sodium silicate having Si02:Na20 ratio of from about 1.:1 to about
2:1;
sodium/potassium citrate; citric acid; sodium/potassium bicarbonate;
sodium/potassium
borate, preferably borax; and sodium/potassium hydroxide; and mixtures
thereof.
Alkali metal silicates also provide protection against corrosion of metals and
inhibit
corrosion of glasswares and chinawares, as described in EP 717,102, published
June 19,
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1996, However, the silicate type and level must be
selected such that the pH stays within the desired pH range.
The pH-adjusting system can be complemented (e.g., for improved sequestration
in
hard water) by other optional detergency builder salts selected from phosphate
or
nonphosphate detergency builders known in the art, which include the various
%yater-
soluble, alkali metal, ammonium or substituted ammonium borates,
hydcoxysulfonates,
polyacetates, and polycarboxylates. Preferred is the alkali metal, especially
sodium, salts
of such materials. Alternate water-soluble, non-phosphorus organic builders
can be used
for their sequestering properties. Examples of polyacetate and polycarboxylatc
builders
are the sodium, potassium, lithium, ammonium and substituted ammonium salts of
ethylenediamine tetraacetic acid, ethylenediamine disuccinic acid (especially
the S,S-
form); nitrilotriacetic . acid, tartrate monosuccinic acid, tarttate
disuccinic acid,
oxydisuccinic acid, carboxymethyloxysuccinic acid, and mellitic acid, and
sodium
benzene polycarboxylate salts. Water insoluble builder like zeolites can also
be used as
builders.
The compositions of the present invention may also contain various other
ingredients known for use in bleaching compositions, particularly compositions
for use in
automatic dishwashing machines. Generally, the compositions herein contain
from about
0.01% to about 20%, preferably from about 0.1% to about 15%, more preferably
from
about 0.5% to about 10%, by weight, of such optional ingredients.
Heavy metal ion sequestrants (chelants) are useful components herein. These
components may also have calcium and magnesium chelation capacity, but
prefereritially
bind heavy metal ions such as iron, manganese and copper. If present, the
heavy metal
ion sequestrant is preferably used at a level of from 0.005% to 5%, more
preferably from
0.05% to 1%, by weight of the composition.
Heavy metal ion sequestrants, which are acidic in nature, having for example
phosphonic acid or carboxylic acid functionalities, may be present either in
their acid
fornm or as a complex/salt with a suitable counter cation such as an alkali or
alkaline metal
ion, ammonium, or substituted ammonium ion, or any mixtures thereof.
Preferably any
salts/complexes are water-soluble. The molar ratio of said counter cation to
the heavy
metal ion sequestrant is preferably at least 1:1.
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Suitable heavy metal ion sequestrants for use herein include the organo
aminophosphonates, such as the amino alkylene poly (alkylene phosphonates) and
nitrilo
trimethylene phosphonates. Preferred organo aminophosphonates are diethylene
triamine
penta (methylene phosphonate) and hexamethylene diamine tetra (methylene
phosphonate).
Other suitable heavy metal ion sequestrants for use herein include
nitrilotriacetic
acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid,
ethylenetriamine pentacetic acid, or ethylenediamine disuccinic acid.
Especially
preferred is ethylenediamine-N,N'-disuccinic acid (EDDS), most preferably
present in the
form of its S,S isomer, which is preferred for its biodegradability profile.
Still other suitable heavy metal ion sequestrants for use herein are
iminodiacetic
acid derivatives such as 20-hydroxyethyl diacetic acid or glyceryl imino
diacetic acid.
A preferred chelant is an organo diphosphonic acid or one of its
salts/complexes.
The organo diphosphonic acid is preferably a C1-C4 diphosphonic acid, more
preferably
a C2 diphosphonic acid, such as ethylene diphosphonic acid, or most preferably
ethane 1-
hydroxy-1, 1-diphosphonic acid (HEDP).
The compositions of the present invention can additionally contain an
additional
amount of oxygen bleach or chlorine bleach.
The oxygen bleach should be sufficient to provide from 0.01% to about 8%,
preferably from about 0.1% to about 5.0%, more preferably from about 0.3% to
about
4.0%, most preferably from about 0.8% to about 3% of available oxygen (AvO) by
weight of the composition.
The peroxygen bleaching systems useful herein are those capable of yielding
hydrogen peroxide in an aqueous liquor. These compounds include, but are not
limited
to, hydrogen peroxide, the alkali metal peroxides, organic peroxide bleaching
compounds
such as urea peroxide and inorganic persalt bleaching compounds such as the
alkali metal
perborates, percarbonates, perphosphates, and the like. Mixtures of two or
more such
bleaching compounds can also be used.
Preferred peroxygen bleaching compounds include sodium perborate, commercially
available in the form of mono-, tri-, and tetra-hydrate, sodium pyrophosphate
peroxyhydrate, urea peroxyhydrate, sodium percarbonate, and sodium peroxide.
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Particularly preferred are sodium perborate tetrahydrate, sodium perborate
monohydrate
and sodium percarbonate. Percarbonate is especially preferred because of
environniental
issues associated with boron.
Suitable oxygen-type bleaches are further described in U.S. Patent No.
4,412,934
(Chung et al), issued November 1, 1983, and peroxyacid bleaches described in
Euro
. pean
Patent Application 033,259, Sagel et al, published September 13, 1989 can be
used.
The optional peroxygen bleach component may be formulated with an activator
(peracid precursor). The activator is present at levels of from about 0.01% to
about 5%,
preferably from about 0.1clo to about 4%, more preferably from about 0.5% to
about 2%,
by weight of the composition. Preferred activators are selected from the group
consisting
of benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-
chlorobenzoylcaprolactam,
benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS),
phenylbenzoate (PhBz), decanoyloxybenzenesulphonate (C10-OBS),
benzolyvalerolactam (BZVL), octanoyloxybenzenesulphonate (Cg-UBS),
perhydrolyzable esters and mixtures thereof, most preferably
benzoylcaprolactam and
benzolyvalerolactam. Preferred bleach activators are those described in U.S.
Patent
5,130,045, Mitchell et al, and 4,412,934, Chung et al, and in U. S. Patents
5,998,350 and
5686,401, and EP 699,230.
The mole ratio of peroxygen bleaching compound (as AvO) to bleach activator in
the present invention generally ranges from at least 1:1, preferably from
about 20:1 to
about 1:1, more preferably from about 10:1 to about 3:1.
The compositions of the present invention may also contain a bleach catalyst
material, such as disclosed in U.S. Patents 4,430,243; 5,246,621; 5,244,594;
4,246,612;
5,227,084; 5,194,416; 5,114,606; and 5,114,611.
Other bleach catalysts are described, for example, in European patent
application
publication no. 408,131 (cobalt complex catalysts), European patent
application
publication nos. 384,503 and 306,089 (rnetallo-porphyrin catalysts), U.S.
4,728,455
(manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent
application publication no. 224,952 (absorbed manganese on aluminosilicate
catalyst),
U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium
salt),
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U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (ferric complex
catalyst),
German Pat. Specification 2,054,019 (cobalt chelant catalyst), Canadian
866,191
(transition metal-containing salts), U.S. 4,430,243 (chelants with manganese
cations and
non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate
catalysts).
Compositions of the present invention can comprise detergent surfactants,
provided
the surfactant type and level are selected to maintain the desired diacyl
peroxide particle
size. Low foaming nonionic surfactants (LFNIs) are preferred, and can be
present in
amounts from 0.1% to about 15% by weight, preferably from about 0.25% to about
10%,
most preferably from about 0.5% to about 5%. LFNIs are most typically used to
provide
the improved water-sheeting action (especially from glass), which they confer
to the
product. They also encompass non-silicone, phosphate or nonphosphate polymeric
materials further illustrated hereinafter which are known to defoam food soils
encountered in automatic dishwashing.
Preferred LFNIs include nonionic alkoxylated surfactants, especially
ethoxylates
derived from primary alcohols, and blends thereof with more sophisticated
surfactants,
such as the polyoxypropylene/polyoxyethylene/ polyoxypropylene reverse block
polymers. The PO/EO/PO polymer-type surfactants are well known to have foam
suppressing or defoaming action, especially in relation to common food soil
ingredients
such as egg.
In a preferred embodiment, the LFNI is an ethoxylated surfactant derived from
the
reaction of a monohydroxy alcohol or alkylphenol containing from about 8 to
about 20
carbon atoms, excluding cyclic carbon atoms, with from about 6 to about 15
moles of
ethylene oxide per mole of alcohol or alkyl phenol on an average basis.
A particularly preferred LFNI is derived from a straight chain fatty alcohol
containing from about 16 to about 20 carbon atoms (C16-C20 alcohol),
preferably a C18
alcohol, condensed with an average of from about 6 to about 15 moles,
preferably from
about 7 to about 12 moles, and most preferably from about 7 to about 9 moles
of ethylene
oxide per mole of alcohol. Preferably the ethoxylated nonionic surfactant so
derived has
a narrow ethoxylate distribution relative to the average.
The LFNI can optionally contain propylene oxide in an amount up to about 15%
by
weight. Other preferred LFNI surfactants can be prepared by the processes
described in
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WO 02/064722 PCT/US02/04441
U.S. Patent 4,223,163, issued September 16, 1980, Builloty,
Preferred compositions herein containing the LFNI make use of ethoxylated
monohydroxy alcohol or alkyl phenol and additionally comprise a
polyoxyethylene,
polyoxypropylene block polymeric compound; the ethoxylated monohydroxy alcohol
or
alkyl phenol fraction of the LFNI comprising from about 20% to about 80%,
preferably
from about 309'o to about 70%, of the total LFNI.
Suitable block polyoxyethylene-polyoxypropylene polymeric compounds that meet
the requirements described herein before include those based on ethylene
glycol,
propylene glycol, glycerol, trimethylolpropane and ethylenediamine as
initiator reactive
hydrogen compound. Polymeric compounds made from a sequential ethoxylation and
propoxylation of initiator compounds with a single reactive hydrogen atom,
such as C12_
18 aliphatic alcohols, do not generally provide satisfactory suds control in
the instant
compositions. Certain of the block polymer surfactant compounds designated
PLURONIC and TETRONIC by the BASF-Wyandotte Corp., Wyandotte, Michigan,
are suitable in compositions of the invention.
A particularly preferred IENI contains from about 40% to about 70% of a
polyoxypropylene/polyoxyethylenelpolyoxypropylene block polymer blend
comprising
about 75%, by weight of the blend, of a reverse block co-polymer of
polyoxyethylene and
polyoxypropylene containing 17 moles of ethylene oxide and 44 moles of
propylene
oxide; and about 25%, by weight of the blend, of a block co-polymer of
polyoxyethylene
and polyoxypropylene initiated with trimethylolpropane and containing 99 moles
of
propylene oxide and 24 moles of ethylene oxide per mole of trimethylolpropane.
Suitable for use as LFNI in the compositions are those LFNI having relatively
low
cloud points and high hydrophilic-lipophilic balance (BLB). Cloud points of 1%
solutions in water are typically below about 32oC and preferably lower, e.g.,
OoC, for
optimum control of sudsing throughout a full range of water temperatures.
LFNIs, which may also be used, include a C18 alcohol polyethoxylate, having a
degree of ethoxylation of about 8, commercially available SLF18 from BASF, and
any
biodegradable LFNI having the cloud point properties discussed herein above.
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The compositions herein can additionally contain an anionic surfactant, in an
amount-from 0 to about 5%, preferably from about 0.1% to about 3%, more
preferably
from about 0.25%n to about 1%, by weight of the composition.
Suitable anionic surfactants include branched or linear alkyl sulfates and
sulfonates. These may contain from about 8 to about 20 carbon atoms. Other
anionic
surfactants include the alkyl benzene sulfonates containing from about 6 to
about 13
carbon atoms in the alkyl group, and mono- and/or dialkyl phenyl oxide mono-
and/or di-
sulfonates wherein the alkyl groups contain from about 6 to about 16 carbon
atoms. All
= of these anionic co-surfactants are used as stable salts, preferably sodium
and/or
potassium.
Preferred anionic surfactants include sulfobetaines, betaines, alkyl
(polyethoxy)
sulfates (AES) and alkyl (polyethoxy) carboxylates, which are usually high
sudsing.
Optional anionic surfactants are further illustrated in published Brifish
Patent Applicatipy'
No. 2,116,199A; U.S. Pat. No. 4,005,027, Hartman; U.S. Pat. No. 4,116,851,
Rupe et al;
and U.S. Pat. No. 4,116,849, Leikhim,
The preferred anionic surfactants of the invention in combination with the
other
components of the composition provide excellent cleaning and outstanding
performance
from the standpoints of residual spotting and filming. However, many of these
co-
= surfactants may also be high sudsing thereby requiring the addition of LFNI,
LFNI in
combination with alternate suds suppressors as further disclosed hereinafter,
or alternate
suds suppressors without conventional LFNI components.
The compositions of the invention can optionally contain an alkyl phosphate
ester
suds suppressor, a silicone suds suppressor, or combinations thereof. Levels
in general
are from 09'o to about 3%, preferably from about 0.001% to about 2%. Typical
levels
tend to be low, e.g., from about 0.01% to about 1% when a silicone suds
suppressor is
used. Preferred non-phosphate compositions oinit the phosphate ester component
entirely.
It is preferable to avoid the use of simple calcium-precipitating soaps as
antifoams
in the present compositions as they tend to deposit on the dishware. Indeed,
phosphate
esters are not entirely free of such problems and the formulator will
generally choose to
minimize the content of potentially depositing antifoams in the instant
compositions.
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Compositions herein may additionally contain a dispersant polymer. Dispersant
polymers are generally compatible with the diacyl peroxide (i.e. do not
solubilize the
diacyl peroxide) and typically are used at levels up to about 10%, preferably
from about
0.1% to about 6%, more preferably from about 0.2% to about 4% by weight of the
composition. Dispersant polymers are useful for improved filming performance
of the
present compositions, especially in higher pH embodiments, such as those in
which pH
exceeds about 9.5. Particularly preferred are polymers, which inhibit the
deposition of
calcium carbonate or magnesium silicate on dishware.
Dispersant polymers suitable for use herein are illustrated by the film-
forming
polymers described in U.S. Pat. No. 4,379,080 (Murphy), issued Apr. 5, 1983
Suitable polymers are preferably at least partially neutralized or alkali
metal,
ammonium or substituted ammoniurn (e.g., mono-, di- or .triethanolammonium)
salts of
polycarboxylic acids. The alkali metal, especially sodium salts are most
preferred. While
the molecular weight of the polymer can vary over a wide range, it preferably
is from
about 1000 to about 500,000, more preferably is from about 1000 to about
250,000, and
most preferably, from about 1000 to about 5,000.
Other suitable dispersant polymers include those disclosed in U.S. Patent No.
3,308,067 issued March 7, 1967, to Diehl. Unsaturated
monomeric acids that can be polymerized to form suitable dispersant polymers
include
acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid,
aconitic acid,
mesaconic acid, citraconic acid and methylenemalonic acid. The presence of
monomeric
segments containing no carboxylate radicals such as methyl vinyl ether,
styrene, ethylene,
etc. Is suitable provided that such segments do not constitute more than about
50% by
weight of the dispersant polymer.
Copolymers of acrylamide and acrylate having a molecular weight of from about
3,000 to about 100,000, preferably from about 4,000 to about 20,000, and an
acrylamide
content of less than about 50%, preferably less than about 20%, by weight of
the
dispersant polymer can also be used. Most preferably, such dispersant polymer
has a
molecular weight of from about 4,000 to about 20,000 and an acrylamide content
of from
about 0% to about 15%, by weight of the polymer.
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Particularly preferred dispersant polymers are low molecular weight modified
polyacrylate copolymers. -Such copolymers contain as monomer units: a) from
about
90% to about 10%, preferably from about 80% to about 20% by weight acrylic
acid or its
salts and b) from about 10% to about 90%, preferably from about 20% to about
80% by
weight of a substituted acrylic monomer or its salt and have the general
formula: -
[(C(R2)C(Rl)(C(O)OR3)]- wherein the incomplete valencies inside the square
braces are
hydrogen and at least one of the substituents Rl, R2 or R3, preferably Rl or
R2, is a 1 to
4 carbon alkyl or hydroxyalkyl group, Rl or R2 can be a hydrogen and R3 can be
a
hydrogen or alkali metal salt. Most preferred is a substituted acrylic monomer
wherein
R1 is methyl, R2 is hydrogen and R3 is sodium.
The low molecular weight polyacrylate dispersant polymer preferably has a
molecular weight of less than about 15,000, preferably from about 500 to about
10,000,
most preferably from about 1,000 to about 5,000. The most preferred
polyacrylA,
copolymer for use herein has a molecular weight of 3500 and is the fully
neutralized form
of the polymer comprising about 70% by weight acrylic acid and about 30% by
weight
methacrylic acid.
Other suitable modified polyacrylate copolymers include the low molecular
weight
copolymers of unsaturated aliphatic carboxylic acids disclosed in U.S. Patents
4,530,766,
and 5,084,535,
Preferred polymers also include polyacrylates with an average molecular weight
of
from about 1,000 to about 10,000, and acrylate/maleate or acrylate/ fumarate
copolymers
with an average molecular weight of from about 2,000 to about 80,000 and a
ratio of
acrylate to maleate or fumarate segments of from about 30:1 to about 1:2.
Examples of
such copolymers based on a mixture of unsaturated mono- and dicarboxylate
monomers
are disclosed in European Patent Application No. 66,915, published December
15, 1982.
Other dispersant polymers useful herein include the polyethylene glycols and
polypropylene glycols having a molecular weight of from about 950 to about
30,000,
which can be obtained from the Dow Chemical Company of Midland, Michigan. Such
compounds for example, having a melting point within the range of from about
30 to
about 100 C can be obtained at molecular weights of 1450, 3400, 4500, 6000,
7400,
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9500, and 20,000. Such compounds are formed by the polymerization of ethylene
glycol
or propylene glycol with the requisite number of moles of ethylene or
propylene oxide to
provide the desired molecular weight and melting point. The polyethylene,
polypropylene and mixed glycols are referred to using the formula
HO(CH2CH2O)m(CH2CH(CH3)O)n(CH(CH3)CH2O)OH wherein m, n, and o are
integers satisfying the molecular weight and temperature requirements given
above.
The present compositions may also contain corrosion inhibitor. Such corrosion
inhibitors are preferred components of machine dishwashing compositions in
accord with
the invention, and are preferably incorporated at a level of from 0.05% to
10%, more
preferably frorn 0.1% to 5% by weight of the total composition. Suitable
corrosion
inhibitors include paraffin oil, typically a predominantly branched aliphatic
hydrocarbon
having a number of carbon atoms in the range of from 20 to 50. Preferred
paraffin oil is
selected from the predominantly branched C25-45 species with a ratio of cyclic
to
noncyclic hydrocarbons of about 32:68. A paraffin oil meeting these
characteristics is
sold by Wintershall, Salzbergen, Germany, under the trade name WINOG 70.
Other suitable corrosion inhibitor compounds include benzotriazole and any
derivatives thereof, mercaptans and diols, especially mercaptans with 4 to 20
carbon
atoms including lauryl mercaptan, thiophenol, thionapthol, thionalide and
thioanthranol. Also suitable are the C12-C20 fatty acids and hydroxy fatty
acids, or their
salts, especially aluminum tristearate. Phosphonated octa-decane and other
anti-oxidants
such as betahydroxytoluene (BHT) are also suitable.
Bleach-stable dyes (such as those disclosed in U.S. Patent 4,714,562, Roselle
et al, issued December 22, 1987) can also be added to the present compositions
in
appropriate amounts.
Method for Cleaning
The present invention also encompasses a method for cleaning dishware in an
automatic dishwashing machine, said method comprising contacting said dishware
with
an aqueous bath comprising the automatic dishwashing detergent composition
herein. In
a preferred embodiment, the method encompasses cleaning plastic dishware
surfaces
while minimizing deposition, comprising contacting said surfaces with an
aqueous wash
liquor comprising from about 10 ppm to about 300 ppm of the above diacyl
peroxide
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particles having a particle size of from about 0.1 to about 30 microns. The
wash liquor
preferably has a pH of from about 2 to about 11, preferably from about 2 to
about 10, for
good cleaning performance.
The diacyl peroxide particles in the wash liquor preferably have a particle
size
from about 0.5 to about 20 microns, more preferably from about 1 to about 10
microns,
for best stain removal, while minimizing filming due to deposition of larger
diacyl
peroxide particles. Filming can also increase if the diacyl peroxide particles
are
solubilized, or if the concentration of the diacyl peroxide in the wash liquor
exceeds
about 300 ppm. In a preferred embodiment, the aqueous wash liquor comprises
from
about 20 to about 250 ppm, more preferably from about 50 to about 200 ppm,
most
preferably from about 50 to about 150 ppm, of the diacyl peroxide particles.
For compositions herein intended for cleaning dishwashing machines, where
deposition of diacyl peroxide particles and filming are not noticeable to
consumers, it will
be appreciated that larger diacyl peroxides particles and higher levels
thereof may be
used, and the optional cleaning ingredients herein may be preferred.
The aqueous wash liquor is formed by dispersing the bleaching composition
herein
in a dishwashing machine. In a preferred embodiment, the bleaching composition
herein
is a thixotropic gel that is dispensed from the main wash dispensing cup of
the automatic
dishwashing machine. This provides adequate contact time for the diacyl
peroxide
particles to bleach and remove stains from plastic surfaces during the washing
process.
In contrast, dosing during the pre-wash may not allow enough active bleaching
species to
survive until the main wash for optimum performance. Alternatively, thicker
products
may be formulated that release an adequate amount of diacyl peroxide particles
during
the washing process, even when dispensed at the beginning of the process. For
example,
a thickened product can be dispensed from a tube or bottle onto the door
(including in an
open dispensing cup ) or bottom of the machine, or directly onto stained
dishware in the
machine. The dishwashing machine can then be operated, with or without a fully
formulated, automatic dishwashing detergent composition added to one or both
dispensing cups. The products of the present invention can also be dosed from
a device
placed inside the machine, so long as there is adequate contact time between
the diacyl
peroxide particles and the surfaces to be bleached. However, dosing of the
diacyl
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peroxide in the final rinse generally provides insufficient contact time for
optimum
bleaching performance.
Additionally, a package for the bleaching composition herein preferably is
substantially impermeable to water, carbon dioxide, and light. Plastic
bottles, including
refillable or recyclable types, as well as conventional barrier cartons or
boxes are
generally suitable. When ingredients are not highly compatible, e.g., mixtures
of silicates
and citric acid, it may further be desirable to coat at least one such
ingredient with a low-
foaming nonionic surfactant for protection. There are numerous waxy materials,
which
can readily be used to foim suitable coated particles of any such otherwise
incompatible
components.
The package preferably contains instructions on the use of the composition
herein
with the package containing the composition or with other forms of advertising
associated
with the sale or use of the composition. The instructions may be included in
any manner
typically used by consumer product manufacturing or supply companies. Examples
include providing instructions on a label attached to the container holding
the
composition; on a sheet either attached to the container or accompanying it
when
purchased; or in advertisements, demonstrations, and/or other written or oral
instructions
which may be connected to the purchase or use of the composition. The
instructions
should guide the user on the optimum methods for using the composition herein,
including preferred dosage levels to obtain the desired concentration of
diacyl peroxide in
the wash liquor, and the preferred contact time and wash liquor temperature
for optimum
performance. For preferred compositions herein, intended for use in bleaching
and
removing stains from plastic dishware, the instructions direct the user to
fill the main
wash dispensing cup of the automatic dishwashing machine and run the machine
without
adding their regular detergent. Other preferred compositions of the invention
can be
dispensed from the pre-wash dispensing cup, or as otherwise described above,
particularly if they contain sufficient thickener to provide for release of at
least a portion
of the diacyl peroxide in the main wash cycle. Such compositions are
preferably used in
conjunction with a regular automatic dishwashing detergent composition. Other
preferred compositions herein intended for use as a machine cleaning product
to de-stain
and clean plastic surfaces on the interior of an automatic dishwashing machine
preferably
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include instructions for use thereof. For example, the instructions may direct
the user to
fill the main wash dispensing cup with the product and run the machine empty.
The following examples illustrate the compositions of the present invention.
These
examples are not meant to limit or otherwise define the scope of the
invention. All parts,
percentages and ratios used herein are expressed as percent weight unless
otherwise
specified.
Perfume A and B are examples of preferred blooming perfume compositions of the
invention. The perfumes also contain preferred blooming, delayed blooming, and
base
masking perfume ingredients herein.
PERFUME A
Perfume Ingredients Wt. %
Blooming Ingredients
Citronellyl Acetate 1.00
Delta Damascone 0.15
Geranyl Nitrile 5.25
Ionone Beta 12.00
d-Limonene 3.65
Methyl Nonyl Acetaldehyde 2.00
Undecavertol 0.25
Verdox 0.30
Vertenex 8.95
(33.55%)
Delayed BloomingIngredients
Allyl Amyl Glycolate 1.30
Benzyl Acetone 1.00
Beta Gamma Hexenol 0.05
Cis-3-Hexenyl Acetate 0.20
Dimethyl Benzyl Carbinyl Acetate 2.50
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Ethyl Maltol 0.05
Ethyl-2-methyl Butyrate 0.30
Ethyl-2-methyl Pentanoate 0.25
Eucalyptol 0.63
Flor Acetate 2.25
Frutene 2.25
Geraniol 10.50
Ligustral 4.50
Methyl Iso Butenyl Tetrahydro Pyran 0.10
Methyl Phenyl Carbinyl Acetate 3.50
Stemone 0.30
Terpineol 1.00
(30.68%)
Base Maskin~Ingredients
Florhydral 0.25
Habanolide 100% 3.75
Alpha-Hexylcinnamaldehyde 10.55
Iso E Super 5.00
Lilial 2.50
Nectaryl 2.25
Gamma-Undecalactone 0.60
(24.90%)
Other Ingredients
Methyl Dihydro Jasmonate 9.87
Para Hydroxy Phenyl Butanone 0.60
Vanillin 0.40
(10.87%)
PERFUME B
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Perfume Ingredients Wt. %
Blooming Ingredients
Beta Pinene 1
Citronellyl Acetate 1
Decyl Aldehyde 1
Delta Damascone 0.3
Geranyl Nitrile 5
d-Limonene 15
Lorysia 5
Lymolene 6
Para Cymene 2
Terpineolene 2
Tetra Hydro Linalool 4
(42.3%)
Delayed Blooming In,gredients
Allyl Amyl Glycolate 4
Allyl Caproate 2
Ethyl-2-methyl Butyrate 0.5
Eucalyptol 3
Flor Acetate 5
Frutene 5
Geraniol 5
Ligustral 3
Linalool 5
Methyl Pamplemousse 7
Octyl Aldehyde 1
Phenyl Ethyl Alcohol 3
Prenyl Acetate 2
Violiff 1
(46.5%)
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Base Maslcing Ingredients
Citrathal 2
Clonal 0.1
Iso E Super 5
Florhydral 1
Nectaryl 1
Neobutenone 0.1
(9.2%)
Other Ingredients
Methyl Dihydro Jasmonate 2
EXAMPLE I
Stable, liquid compositions of the present invention are as follows:
% by weight of active material
INGREDIENTS A B c D E F G
Dibenzoyl Peroxide* 0.9 3.6 3.0 0.5 1.5 0.9 1.8
Carbopol 980 0.5 1.5 0.4 0.4 1.0 0.5 0.5
Sodium Hydroxide 0.07 0.3 0.1 -- -- 0.1 0.14
Nonionic surfactant
(SLF 18) -- -- -- 5.0
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Sodium Citrate - -- 10
- - - -
Na2CO3/K2CO3 -- - - 1.0 - - -
Sodium Silicate (2.4 ratio) - -- - - 1.0 Dispersant (Acuso1480N) - - - 4.0
- - -
Sorbitol - - -- -- -- 6.0 -
Perfume A or B 0.125 0.125 0.15 0.15 0.15 0.15 0.125
Water + preservative ** - ------ Balance to 100
pH (2% in water) 6.0 6.5 6.5
*1-10 micron size particles, available as OxyCare 50 (50% active) fxom ABCO
Industries.
**100 ppm NeoloneM-50 from Rohm & Hass, plus 0.15% Dantogard2000 from Lonza.
The above compositions are made by slowly adding the Carbopol thickener to
deionized water, allowing enough time for the Carbopol to become hydrated, and
-then
adding the benzoyl peroxide, perfume and other ingredients, except caustic, to
the
mixture. The sodium hydroxide, citrate, carbonate or silicate is then slowly
added to
neutralize the Carbopol and thicken the product, with any nonionic surfactant
added last.
The resulting thixotropic gels are paracularly useful for removing stains from
plastic
dishware, while minimizing deposition and filming on the dishware. Composition
A is
preferably squirted into the main wash dispensing cup of an automatic
dishwashing
machine, and used as a plastic cleaner in place of a regular automatic
dishwashing
detergent composition. Composition B is a thicker product that preferably is
placed in
the pre-wash dispensing cup and used with a regular automatic dishwashing
detergent
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composition. Composition G is preferably a machine cleaning product that is
squirted
into the main wash dispensing cup prior to the machine being run empty.
EXAMPLE II
Granular compositions of the present invention are as follows. All percentages
noted are by weight of the finished compositions, other than the perborate
(monohydrate)
component, which is listed as AvO.
Wei ng t%
Ingredients: A B C
Catalystl 0.008 0.004 --
SavinaseTM 12T -- 1.12 --
Protease D 0.9 -- --
DuramylTM 1.5 0.75 --
Sodium Tripolyphosphate (STPP) 31.0 30.0 33.2
Sodium Carbonate 20.0 30.5 29.0
Polymer3 4.0 -- --
Sodium Perborate (AvO) 2.2 0.7 --
Sodium dichlorocyanurate
dihydrate5 -- -- 2.5
Dibenzoyl Peroxide* 0.2 0.5 0.5
2 R Silicate (Si02) 8.0 3.5 8.5
Paraffin 0.5 0.5 --
Benzotriazole 0.3 0.15 --
PLURAFACTM4 2.0 0.75 2.6
Perfume A or B 0.10 0.15 0.2
Sodium Sulfate, Moisture-----------------------Balance-----------------------
1 Pentaammineacetatocobalt (III) nitrate; may be replaced by MnTACN.
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2 May be replaced by 0.45 Protease D.
3 Polyacrylate or Acusol480N or polyacrylate/polymethacrylate copolymers.
4 May be replaced by PolyTergent SLF-18.
Avg. C12 = 0.28 -2.8%.
5 * 1-10 micron size particles, available as Oxycare 50 (50% active) from
ABCO
Industries, preferably added as composite particles containing polyethylene
glycol as
described in U.S. Patent 5,763,378, Painter et al..
In Compositions A and B, the catalyst and enzymes are introduced into the
compositions as 200-2400 micron composite particles which are prepared by
spray
coating, fluidized bed granulation, marumarizing, prilling or flaking/grinding
operations.
If desired, the protease and amylase enzymes may be separately formed into
their
respective catalystlenzyme composite particles, for reasons of stability, and
these separate
composites added to the compositions.
