Note: Descriptions are shown in the official language in which they were submitted.
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
PERFUME COMPOSITIONS
10
Field of the invention
The present invention relates to perfume compositions, in particular to
laundry
and cleaning compositions incorporating such perfume compositions together
with a bleaching system.
Background of the invention
Most consumers have come to expect scented detergent products and to expect
that fabrics and other items which have been laundered with these products
also
have a pleasing fragrance. Further, perfumes by their ability to provide an
olfactory aesthetic benefit can serve as a signal of cleanliness.
Therefore, it is desirable and commercially beneficial to add perfume
materials to
such products. Perfume additives make laundry compositions more aesthetically
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
2
pleasing to the consumer, and in some cases the perfume imparts a pleasant
fragrance to fabrics treated therewith. However, the amount of perfume carry-
over from an aqueous laundry bath onto fabrics is often marginal. Indeed, a
problem encountered with perfumes is their volatility and many perfume
ingredients can be destroyed or damaged in the presence of cleaning
ingredients, especially alkali and bleaching system.
Bleaching systems like the peroxyacid, and more particularly the preformed
peroxyacid, are known in the art as effective soil removal agents.
The Applicants have now found that the problem of perfume oxidation may be
particularly troublesome with a bleaching system like the peroxyacid, and more
particularly the preformed peroxyacid.
Still, it has also been found that another problem with the formulation of
perfumed laundry and cleaning composition incorporating a bleaching system is
the tendency of the bleach, in particular with the peroxyacid, and more
particularly with the preformed peroxyacid, to show a loss of their activity
in the
presence of perfume ingredients.
One solution to this problem is encapsulation of the perfume. This increases
the
expense and complexity of the formulation and does not always provide
sufficient
protection.
2s Another solution is to use fully saturated perfume as taught by EP-
0,299,561.
Indeed, saturated perfumes have long been known and extensively used in the
perfumery art. One of the reason for their extensive use is their good
performance in term of stability and odor performance. However,
notwithstanding
the advance in the art represented by the above disclosure, there is still a
need
3o for further perfume compositions that would provide stabilised perfume in a
bleach containing environment.
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
3
Another solution to this problem is the reduction in the level of the bleach
system.
Whilst reducing the level of the bleach system employed in the wash tends to
ameliorate these problems, this is accompanied by a marked negative effect on
the soil removal ability.
The detergent formulator thus faces the challenge of formulating a product
which
maximises soil/stain removal, whilst avoiding degradation of the perfume
components and/or loss of the activity of the bleaching system.
The Applicants have now surprisingly found that the provision of specific
classes
of perfume raw materials fulfills such a need.
It is therefore an object of the present invention to provide compositions
suitable
for use in laundry washing methods which produces an excellent perfume
fragrance on fabrics as well as an excellent bleaching profile in the wash
liquor
and in the product during storage, in particular where such a bleaching system
is
a preformed peroxyacid.
It is a further object of the invention to provide compositions suitable for
use in
laundry washing methods which produce effective soil removal.
It is also an object of the present invention to provide a perfumed
composition as
well as laundry composition thereof containing a bleaching system, wherein the
perfume is stable in the presence of a bleaching system whilst not being
detrimental to the performance of either the perfume or the bleaching system.
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
4
mmarv of the invention
There is provided a perfume composition comprising perfume ingredients which
have a bleach stability index of at least 80%, and/or an odour character of
value
A or B with an odour intensity of at least 6, and selected from the classes of
unsaturated perfume ingredients of ester, ether, alcohol, aldehyde, ketone,
nitrite, lactone, schiff-bases, terpenes and derivatives thereof, cyclic
alkene,
cyclic oxide, oxime, and mixtures thereof, wherein the amount of unsaturated
materials represents at least 40% by weight of the perfume composition.
In another aspect of the invention, a laundry and cleaning composition
comprising a bleaching system and a perfume composition comprising perfume
ingredients which have a bleach stability index (BSI) of at least 80% and/or
an
~5 odour character of value A or B with an odour intensity of at least 6, and
selected
from the classes of unsaturated perfume ingredients of ester, ether, alcohol,
aldehyde, ketone, nitrite, lactone, schiff-bases, terpenes and derivatives
thereof,
cyclic alkene, cyclic oxide, oxime, and mixtures thereof.
2o Detailed description of the invention
Perfume composition
One essential feature of the perfume composition invention is that the
25 unsaturated perfume ingredient have a bleach stability index (BSI) of at
least
80% and/or an odour character of value A or B with an odour intensity of at
least
6.
By bleach stability index (BSI) of at least 80%, it is meant that the
composition
3o incorporating each of the tested perfume ingredient in a bleach containing
matrix
does not exhibit more than 20% Av0 loss after 2 weeks at 40°C,
preferably not
more than 15%, more preferably not more than 10%, and most preferably not
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
more than 5%. For this test, the pure perfume chemicals to be tested were
diluted at 0.2% via a solubiliser, namely C10-C18 sodium alkyl sulfate
condensed
with an average of three moles of ethylene oxide (AE3S), then incorporated in
a
finished product and then subjected to the accelerated aging test. The
accelerated aging test is set up as follows:
to 20g of each of the finished product incorporating the perfume ingredient
was taken and placed in an oven for 2 weeks at 40°C. The aged samples
were
compared versus freshly made perfumed product (The reference) by measuring
the Av0 before storage from the reference and after storage from the aged
product and expressing the difference in Av0 as % loss. The unperfumed
finished product formulation for testing is as follows:
Composition % by weight
PAP 3
Carbopol ETD 2691 0.3
Xanthan gum 0.2
Alkyl 3 ethoxy sulphate 2
HEDP 0.1
water to balance to
100%
pH 3.8
The definition of the abbreviated terms are given hereafter before the
examples.
15 The loss of available oxygen (Av0) of a bleach-containing composition over
time
can be measured with the iodometric titration method in which the bleach is
reduced by excess potassium iodide and the iodine formed is determined by
titration with sodium thiosulphate. This method is well known in the art and
is
reported for example in A Bleachers Handbook by and available from Interox.
2o Alternatively peracid concentration can also be measured using a
chromatography method described in the literature for peracids (F. Di Furia et
al.,
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
6
Gas-liquid Chromatography Method for Determination of Peracids, Analyst, Vol
113, May 1988, p 793-795).
Still another essential feature of the invention is that the perfume
ingredients also
exhibit a good impact and aging character profile. By good character impact
and
aging, it is meant that each of the unsaturated perfume ingredients have an
odour character of value A or B and an odour intensity of at least 6 as per
defined in the test below:
Odor Intensity Index method
By Odor Intensity Index, it meant that the pure perfume chemicals to be tested
were diluted at 0.2% via a solubiliser, namely C10-C1g sodium alkyl sulfate
condensed with an average of three moles of ethylene oxide (AE3S), then
incorporated in a finished product and stored for 24hours at room temperature.
15 This percentage is more representative of usage levels. The unperfumed
finished
product formulation is as above for the BSI test.
After the above mentioned 24 hours storage at room temperature, each of the
product containing the perfume ingredient and the unperfumed product were
2o then presented to the expert panellist for odor evaluation in plastic cups.
Expert
panellists are assessors trained for at least six months in odor grading and
whose gradings are checked for accuracy and reproducibility versus a reference
on an on-going basis. For each perfume ingredient, the panellist was presented
two products: one reference (unperfumed product) and the sample. The panellist
25 was asked to rank both sample products on the 2-9 odor intensity scale, 2-4
being no perfume detected with only base odor, 9 being very strong odor
present
with no base odor. The scale is as follows:
ODOR INTENSITY SCALE
Grade Description
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
7
9 Very strong perfume impactNo base odor
8 Strong perfume impact No base odor
7 Moderate perfume impact Slight base odor
6 Weak perfume impact Moderate base
odor
5 Very weak perfume impact Strong base odor
2-4 No perfume perceptible Only base odor
In addition, the panellist was asked to rank both smelling strips on the A-D
odor
~5 character scale, A being no change in odor character, D being unpleasant
odor
character. The scale is as follows:
ODOR CHARACTER CHANGE SCALE
Grade Description
A No change in odor character
B Slight change / perfume character still recognizable
C Significant change / perfume character no longer
recognizable
D Unpleasant odor character
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
8
Of the assessed perfume ingredients, only those which were assessed with an
odor character change of value A or B and an odour intensity of at least 6
were
kept, and further submitted to the accelerated aging test described
hereinafter:
15 to 20g of the finished product incorporating the perfume ingredient was
taken
and placed in an oven for 2 weeks at 40°C. The aged samples were
compared
versus a reference comprising 15 to 20g of finished product incorporating the
same perfume ingredient but stored at room temperature for 2 weeks.
After the two weeks of accelerated aging testing, the samples were evaluated
for
odor character change and odor intensity as per above mentioned method.
Preferred unsaturated perfume ingredients are those which still have an odor
character of value A or B and an odour intensity of at least 6 after the
accelerated aging test.
Still another essential feature of the perfume composition invention as is is
that,
the perfume composition contains an amount of unsaturated perfume ingredient
of at least 40%, preferably 50%, and more preferably of at least 70% by weight
of
the perfume composition.
When the perfume is used in a bleaching composition, the perfume composition
will preferably contain an amount of unsaturated perfume ingredient of greater
than 20%, preferably of at least 50%, and most preferably of at least 70% by
weight of the perfume composition.
The classes of unsaturated perfume ingredient are selected from ester, ether,
alcohol, aldehyde, ketone, nitrite, lactone, schiff-bases, terpenes and
derivatives
thereof, cyclic alkene, cyclic oxide, oxime, and mixtures thereof.
3o Preferred perfume ingredients are those which fulfill all of the
requirement of BSI,
character intensity and aging performance from the above mentioned class.
Some non-limiting examples are as follows:
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
9
i)-Class of ester:
Preferred esters are compound of the classes selected from alicyclic ester,
aliphatic ester, cyclic ester, aromatic ester, and mixtures thereof.
A suitable alicyclic ester compound for use herein is ethyl 2,6,6-trimethyl-
1,3-
cyclohexdiene-1-carboxylate (Ethyl safranate as supplied by Quest).
Suitable aliphatic ester compounds for use herein are selected from cis-beta-
gamma-hexenyl acetate (Cis 3 hexenyl acetate as supplied by Mitsui), 2-
methylbuten-2-ol-4-acetate (Prenyl acetate as supplied by IFF); glycolic acid,
2-
pentyloxy:allyl ester, methyl-2-nonenoate (Beauvertate as supplied by Quest),
cis-beta-gamma-Hexenyl salicylate, 4-methyl-pentan-2-of 2-butenoate
(Frutinat.exp as supplied by H&R), hexyl 2-butenoate (Hexyl crotonate as
supplied by H&R), acetyl diisoamylene (koavone as supplied by IFF), 3-
methylene-7-methyl-1-octen-7-yl acetate (Myrcenyl acetate crude as supplied by
~5 Quest), methyl 2-nonenoate, citronellyl acetate, isobutyl angelate, and
mixtures
thereof.
Suitable cyclic ester compounds are selected from tricyclo decenyl acetate
(Flor
acetate as supplied by IFF), tricyclo decenyl propionate (Frutene as supplied
by
IFF), 7-Acetyl, 1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphtalene (iso
E
2o super as supplied by IFF), ethyl 2-ethyl-6,6-dimethyl-2-
cyclohexenecarboxylate &
Ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate (givescone as supplied by
Givaudan-Roure), allyl cyclohexyloxy acetate (isoananat 660567 as supplied by
H&R), 4(3)-(4-Methyl-3-pentenyl)-3-cyclohexenyl-methyl acetate, 2-cyclopentyl-
cyclopentyl 2-butenoate, datilat from H&R, and mixtures thereof.
ii)-Class of ether
Preferred ethers are compounds of the classes selected from alicyclic ether,
cyclic ether, aromatic ether, and mixtures thereof.
Suitable alicyclic ether compounds for use herein are selected from 6-Butyl-
3,6
3o dihydro-2,4-dimethyl-2-hydro-pyran (Gyrane), 3, 6-dihydro-4, 6-dimethyl-2
phenyl-2hydro-pyran (Pelargene), and mixtures thereof.
A suitable cyclic ether compounds is 9-(Methyloxy)tricyclo[5,2,1,02~6)dec-3-
ene.
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
iii)-Class of alcohol
Preferred alcohols are compounds of the classes selected from primary
alcohols,
tertiary alcohols, aromatic alcohols, cyclic alcohols, and mixtures thereof.
s Suitable primary alcohol compounds are selected from beta gamma hexenol,
3,7-dimethyl-6-octen-1-of (citronellol), cis-3-hexenol, 9-Decen-1-of (rosalva
as
supplied by IFF), geraniol, and mixtures thereof.
Suitable tertiary alcohol compounds are selected from 2,6-dimethyl-7-octen-2-
of
(Dihydro myrcenol as supplied by IFF), 3,7-Dimethyl-1,6-octadien-3-of
(Linalool
1o as supplied by BASF), 4-Methyl-3-decen-5-of (undecavertol as supplied by
Givaudan-Roure), amyl vinyl carbinol from IFF, and mixtures thereof.
Suitable aromatic alcohol compounds are selected from 3-Phenyl-2-propen-1-ol,
2-Methyl-4-phenyl-1-pentanol, and mixtures thereof.
Suitable cyclic alcohol compounds are selected from 2-Ethyl-4-(2,2,3-trimethyl-
3
cyclopenten-1-yl)-2-buten-1-of (Sanjinol as supplied by IFF) , 4,7-Methano-1 H
inden-5-ol, 3a,4,5,6,7,7a-Hexahydro-2(or 3), 4-dimethyl, dimethyl cyclohexene
methanol (Floralol as supplied by IFF), 5-(2,2,3-Trimethyl-3-cyclopentenyl)-3
methylpentan-2-of (Sandalore as supplied by Givaudan-Roure), 1-Para-Menthen
4-0l, terpineol, ambrinol L20 from Takasago, and mixtures thereof.
iv)-Class of aldehyde
Preferred aldehydes are compounds of the classes selected from aliphatic
aldehyde, cyclic aldehydes, aliphatic primary aldehyde, aromatic aldehydes,
tertiary aldehydes, and mixtures thereof.
A suitable aliphatic aldehyde for use herein is 3,7-Dimethyl-6-octen-1-al
(Citronellal as supplied by Reynaud).
Suitable cyclic aldehydes for use herein are selected from 2-Methl-4(2,6,6-
trimethyl-1-cyclohexenyl-)2-butenal (Boronal as supplied by H&R), 1-Methyl-4-
(4-
methylpentyl)-3-cyclohexenecarbaldehyde, and mixtures thereof.
v)-Class of ketone
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
11
Preferred ketones are compounds of the classes selected from aliphatic
ketones,
aromatic ketones, cyclic ketones, macrocyclic ketones, and mixtures thereof.
A suitable aliphatic ketone for use herein is 2,7-Dimethyloct-5-en-4-one 50%
in
Iso Propyl Myristate (isotagetone 50 as supplied by BBA).
A suitable aromatic ketone for use herein is Hexahydro Tetramethyl
Methanonaphtalenone.
Suitable cyclic ketones for use herein are selected from 4-Penten-1-one,1-(5,5-
dimethyl-1-cyclohexen-1-yl)- (Neobutenone 10% as supplied by Firmenich), 5,8-
Methano-2H-1-benzopyran, 6-ethylideneoctahydro-, 2-Buten-1-one, 1-(2,6,6-
trimethyl-2-cyclohexen-1-yl)- (alpha-damascone as supplied by Firmenich) ,
Diethyl dimethylcyclohex-2-en-1-one (Two isomers), 2-Buten-1-one, 1-(2,6,6-
trimethyl-1-cyclohexen-1-yl)-, 2,5,10-Trimethyl-2,5,9-cyclododecatrien-1-yl
methyl
ketone & isomers (trimofix o as supplied by IFF), Methyl cedr-8-enyl ketone
(Vertofix coeur as supplied by IFF), and mixtures thereof.
A suitable macrocyclic ketone for use herein is Oxacyclohexadecen-2-one
(habanolide 100% as supplied by Firmenich).
vi)-Class of nitrites
Preferred nitrites are compounds of the classes selected from aliphatic
nitrite,
2o aromatic nitrite, cyclic nitrite, and mixtures thereof.
Suitable aliphatic nitrites are selected from 3,7-dimethyl-2,6-
octadienenitrile,
3,12-tridecadiene nitrite, iris nitrite, ozonil, teamonyl, and mixtures
thereof.
Suitable aromatic nitrites are selected from 5-Phenyl-3-methyl-penten-2-acid-
nitrite, 2-Benzyl-2-methyl-3-butenenitril, and mixtures thereof.
A suitable cyclic nitrite for use herein is a mixture of 3-(4,7,7-
Trimethylcicyclo(4.1.0)hept-3-ylidene)-propanenitrile and 3-(4,7,7-
Trimethylcicyclo(4.1.0)hept-3-ylidene)-propenenitrile (rose nitrite as
supplied by
PFW).
so vii)-Class of lactones
A suitable lactone is 1,2-benzopyrone (coumarin as supplied by Rhodia).
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
12
viii)-Class of Schiff-Bases
Suitable Schiff-bases for use herein are selected from Methyl 2-((-1-(2, 4-
dimethyl-3-cyclohexenyl)methylidene)amino)-1-benzenecarboxylate (ligantraal as
supplied by Quest), Methyl 2-((-2-methylpentylidene)amino)-1-
benzenecarboxylate (mevantraal (q) as supplied by Quest), and mixtures
thereof.
ix)-Class of terpene and derivatives thereof
Suitable terpenes for use herein are selected from Dimethyl-2-Methylene
Bicyclo(3,1,1) Heptane (6,6-) (beta pinene as supplied by IFF), Para-Mentha
1,4{8)-diene (terpinolene as supplied by BBA), and mixtures thereof.
Still other unsaturated perfume ingredients for use herein which fulfill the
BSI
requirement of at least 80% include the following perfume ingredients: geranyl
nitrite from BASF, hexyl cinnamic aldehyde from COURTAULDS, maceal from
QUEST, methyl cedrylone from BORDAS, rhuboflor from FIRMENICH, allyl amyl
glycolate from I.F.F., azarbre from QUEST, calyxol from QUEST, cinnamic
alcohol from H & R, citrowanil b from FRAGR. RES., diantheme from H & R,
dimethyl-cyclormol from I.F.F., ionone alpha from I.F.F., ionone beta from GIV-
ROURE, iso jasmone from GIV-ROURE, iso longifolanone from QUEST, lyral
2o from I.F.F., mandaril 600 135 from H & R, myraldyl acetate from GIV-ROURE,
neofolione from GIV-ROURE, pamplefleur from I.F.F., paxamber from I.F.F,
prenyl salicylate from FRAGR. RES, pyroprunat from H & R, stemone from GIV-
ROURE, terpinenol from DRAGOCO, undecylenic aldehyde from GIV-ROURE,
verdalia a from I.F.F., vernaldehyde from GIV-ROURE, ambretone from
TAKASAGO, bergamal from I.F.F., bergoxane from PFW, cantryl from
DRAGOCO, citrathal s tw from QUEST, decave from I.F.F., dihydro jasmone
from QUEST, fleuroxene extra from QUEST, florasantol .exp from TAKASAGO,
galbanolene super from FIRMENICH, gardocyclene from QUEST, iso butavan
from QUEST, linalyl acetate from GIV-ROURE, from I.F.F., malusate from
so B.B.A., melafleur from I.F.F., octenyl acetate from I.F.F., prismantol from
I.F.F.,
prismylate from I.F.F., profarnesal from H & R, roseate from I.F.F., silwanol
from
FRAGR. RES., tetrameran from I.F.F., violiff from I.F.F., plinol special from
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
13
MILLENIUM, plinyl acetate from MILLENIUM, trans-2-hexenal from MILLENIUM,
trans-2-hexenol from MILLENIUM, karlenol from MILLENIUM, karlenyl acetate
from MILLENIUM, and mixtures thereof.
Of course, mixtures of the above ingredients are also encompassed within the
scope of the present invention.
Laundry and cleaning composition
In another aspect of the invention, the perfume composition of the invention
is
1o incorporated in a laundry and cleaning composition, in particular a
bleaching
composition comprising a bleaching system. Typical levels of incorporation of
the
perfume composition are of from 0.01 % to 10%, preferably from 0.05% to 5%,
and more preferably from 0.1 % to 3%, by weight of the laundry and cleaning
composition.
Laundry and cleaning compositions include compositions which are typically
used for laundering fabrics and cleaning hard surfaces such as dishware,
floors,
bathrooms, toilet, kitchen and other surfaces in need of a cleaning.
Accordingly,
by laundry and cleaning compositions, these are to be understood to include
not
only detergent compositions which provide fabric cleaning benefits, but also
compositions such as hard surface cleaning which provide hard surface cleaning
benefit.
Preferred are those laundry compositions which incorporate a bleaching system.
Incorporation of the perfume in the laundry and cleaning compositions can
conveniently be carried out, if necessary, by conventional incorporation
means,
such as by spray-on for granular compositions or emulsification for liquid
compositions.
Bieachina s stem
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
14
The laundry and cleaning compositions of the invention comprises a bleaching
system. Preferably the bleaching system is selected from:
i)-a source of hydrogen peroxide in combination with an organic peroxyacid
bleach precursor compound;
ii)-a preformed organic peroxyacid,
iii)-a halogen bleach component;
iv)-persulfate salts; and
v)-mixtures thereof.
1o In a preferred embodiment of the invention, the bleaching system is capable
of
providing organic peroxyacid bleach to a wash solution.
In one preferred execution the bleaching system contains a hydrogen peroxide
or
a source thereof and an organic peroxyacid bleach precursor compound. The
production of the organic peroxyacid occurs by an in situ reaction of the
precursor with hydrogen peroxide or a source thereof. Preferred sources of
hydrogen peroxide include inorganic perhydrate bleaches. In an alternative
preferred execution a preformed organic peroxyacid is incorporated directly
into
the composition. Compositions containing mixtures of a hydrogen peroxide
2o source and organic peroxyacid precursor in combination with a preformed
organic peroxyacid are also envisaged.
i)-a source of hydrogen peroxide in combination with an organic peroxyacid
bleach precursor compound;
Inorganic perhydrate bleaches
Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These
salts are normally incorporated in the form of the alkali metal, preferably
sodium
salt at a level of from 1 % to 40% by weight, more preferably from 2% to 30%
by
3o weight and most preferably from 5% to 25% by weight of the compositions.
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
Examples of inorganic perhydrate salts include perborate, percarbonate,
perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts
are
normally the alkali metal salts. The inorganic perhydrate salt may be included
as
the crystalline solid without additional protection. For certain perhydrate
salts
5 however, the preferred executions of such granular compositions utilize a
coated
form of the material which provides better storage stability for the
perhydrate salt
in the granular product.
Suitable inorganic perhydrate salts include perborate bleaches, e.g., sodium
1o perborate (e.g., mono- or tetra-hydrate), sodium carbonate peroxyhydrate
and
equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea
peroxyhydrate, and sodium peroxide.
A preferred percarbonate bleach comprises dry particles having an average
15 particle size in the range from 500 micrometers to 1,000 micrometers, not
more
than 10% by weight of said particles being smaller than 200 micrometers and
not
more than 10% by weight of said particles being larger than 1,250 micrometers.
Optionally, the percarbonate can be coated with silicate, borate or water-
soluble
surfactants. Percarbonate is available from various commercial sources such as
2o FMC, Solvay and Tokai Denka.
Peroxygen bleaching agents, the perborates, the percarbonates, etc., are
combined with bleach activators, which lead to the in situ production in
aqueous
solution (i.e., during the washing process) of the peroxy acid corresponding
to
the bleach activator. Peroxyacid bleach precursor compounds are preferably
incorporated at a level of from 0.5% to 20% by weight, more preferably from 1
to 15% by weight, most preferably from 5% to 10% by weight of the cleaning
compositions.
3o Various non-limiting examples of activators are disclosed in U.S 4,915,854,
and
U.S 4,412,934. The nonanoyloxybenzene sulfonate (NOBS), 3,5,5-tri-methyl
hexanoyl oxybenzene sulfonate (ISONOBS), tetraacetyl ethylene diamine
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
16
(TAED), acetyl triethyl citrate (ATC) activators are typical, and mixtures
thereof
can also be used. See also U.S. 4,634,551 for other typical bleaches and
activators useful herein.
Highly preferred amido-derived bleach activators are those of the formulae:
R1 N(R5)C(O)R2C(O)L or R1 C(O)N(R5)R2C(O)L
wherein R1 is an alkyl group containing from 6 to 12 carbon atoms, R2 is an
alkylene containing from 1 to 6 carbon atoms, R5 is H or alkyl, aryl, or
alkaryl
containing from 1 to 10 carbon atoms, and L is any suitable leaving group. A
leaving group is any group that is displaced from the bleach activator as a
1o consequence of the nucleophilic attack on the bleach activator by the
perhydrolysis anion. A preferred leaving group is phenyl sulfonate.
Preferred examples of bleach activators of the above formulae include (6-
octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzene
sulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as
described in U.S. Patent 4,634,551, incorporated herein by reference.
Another class of bleach activators comprises the benzoxazin-type activators
disclosed by Hodge et al in U.S. Patent 4,966,723. A highly preferred
activator of
2o the benzoxazin-type is:
O
II
CEO
~C
'N
Still another class of preferred bleach activators includes the acyl lactam
activators, especially acyl caprolactams and acyl valerolactams of the
formulae:
O O
O C-C H2-C H2 O C-C H2-C H2
II I
R6-C-N~ ~CH2 R6-C-N~CH - H
C H2-C H2 2 z
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
17
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing
from 1 to
12 carbon atoms. Highly preferred lactam activators include benzoyl
caprolactam,
octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl
caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl
valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl
valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and
mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October
8, 1985, incorporated herein by reference, which discloses acyl caprolactams,
including benzoyl caprolactam, adsorbed into sodium perborate.
ii)-a preformed organic peroxyacid,
Another category of bleaching agent that can be used without restriction
encompasses preformed organic peroxyacid (hereafter referred to as peracid),
like percarboxylic acid bleaching agents and salts thereof. The term organic
peracid bleach, as used herein, includes the organic peroxyacids and their
salts,
which are well described in the literature as having the ability of effective
bleaching at lower wash temperatures of about 200-6000 C. Typical levels of
incorporation are of from 0.1 % to 30%, more preferably from 0.5% to 18% and
most preferably 1 % to 12% by weight of the composition.
Any suitable peracid known in the art may be used herein. Preferably the
peracid is in solid form.
In a preferred embodiment of the present invention the peracid has the general
formula
X-R-C(O)OOH
wherein R is a linear or branched alkyl chain having at least 1 carbon atoms
and
so X is hydrogen or a substituent group selected from the group consisting of
alkyl,
especially alkyl chains of from 1 to 24 carbon atoms, aryl, halogen, ester,
ether,
amine, amide, substituted phthalic amino, imide, hydroxide, sulphide,
sulphate,
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
18
sulphonate, carboxylic, heterocyclic, nitrate, aldehyde, phosphonate,
phosphonic
or mixtures thereof. Preferred examples of such peracid are selected from
diperoxydodecanoic acid, monononylamide of monoperoxysuccinic acid, and
mixtures thereof.
More particularly the R group preferably comprises up to 24 carbon atoms.
Alternatively, the R group may be a branched alkyl chain comprising one or
more
side chains which comprise substituent groups selected from the group
consisting of aryl, halogen, ester, ether, amine, amide, substituted phthalic
1o amino, imide, hydroxide, sulphide, sulphate, sulphonate, carboxylic,
heterocyclic,
nitrate, aldehyde, ketone or mixtures thereof._
In a preferred peracid the X group, according to the above general formula, is
phthalimido group. Thus, particularly preferred peracids are those having
general formula:
D O
II
C O
C ~ ~ ~N-(R)-COOH
B ~ C
II
A O
2o where R is C1-20 and where A, B, C and D are independently either hydrogen
or
substituent groups individually selected from the group consisting of alkyl,
hydroxyl, vitro, halogen, amine, ammonium, cyanide, carboxylic, sulphate,
sulphonate, aldehydes or mixtures thereof.
2s In a preferred aspect of the present invention R is an alkyl group having
from 3 to
12 carbon atoms, more preferably from 5 to 9 carbon atoms. Preferred
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
19
substituent groups A, B, C and D are linear or branched alkyl groups having
from 1 to 5 carbon atoms, but more preferably hydrogen.
Preferred peracids are selected from the group consisting of phthalimido
peroxy
hexanoic acid, phthalimido peroxy heptanoic acid, phthalimido peroxy octanoic
acid, phthalimido peroxy nonanoic acid, phthalimido peroxy decanoic acid and
mixtures thereof.
In a particularly preferred aspect of the present invention the peracid has
the
1o formula such that R is CSH,° i.e. phthalimido peroxy hexanoic acid
or PAP. This
peracid is preferably used as a substantially water-insoluble solid or wetcake
and
is available from Ausimont under the trade name Euroco.
Still another other suitable bleaching system for use herein is the diacyl
peroxide.
15 Suitable diacyl peroxides for use herein are selected from the group
consisting of
aliphatic, aromatic and aliphatic-aromatic diacyl peroxides, and mixtures
thereof.
Suitable aliphatic diacyl peroxides for use herein are dilauroyl peroxide,
didecanoyl peroxide, dimyristoyl peroxide, or mixtures thereof. A suitable
2o aromatic diacyl peroxide for use herein is for example benzoyl peroxide. A
suitable aliphatic-aromatic diacyl peroxide for use herein is for example
lauroyl
benzoyl peroxide. Such diacyl peroxides have the advantage to be particularly
safe to fabrics and fabric dyes while delivering excellent bleaching
performance.
25 iii)-a hypohalite bleach component; and
In another preferred execution, the bleaching system may comprise as an
alternative or in addition to one or both of the category mentioned above,
bleaching agents of the hypohalite type that are oxidative bleaches and
subsequently lead to the formation of halide ion. Hypohalites bleaches are
so typically at a level of from 1 % to 15% by weight, more preferably from 1 %
to 10%
by weight of the composition.
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
Common among these types of bleaches are the alkaline metal and alkaline
earth metal hypochlorites, hypobromites and hypoiodites although other
bleaches that are organic based sources of halide, such as
chloroisocyanurates,
are also applicable. Preferred bleach has the formula M(OX)y where:
5 M is member selected from sodium, potassium, magnesium, calcium and
mixtures thereof;
O is an oxygen atom;
X is member selected from chlorine, bromine, iodine and mixtures thereof; and
y is 1 or 2 depending on the charge of M.
Preferred hypohalite bleaches for the purpose of the invention are sodium
hypochlorite, potassium hypochlorite, calcium hypochlorite, magnesium
hypochlorite, sodium hypobromite, potassium hypobromite, calcium hypobromite,
magnesium hypobromite, sodium hypoiodite and potassium hypoiodite , more
preferably sodium hypochlorite, potassium hypochlorite, calcium hypochlorite,
magnesium hypochlorite, most preferably sodium hypochlorite.
iv)-Persulfate salts
Persulfate salts can also be used herein for the present invention as
bleaching
system. Persulfate bleaches (e.g., OXONE, manufactured commercially by
2o DuPont) can also be used. Typical level of these salts are of from 0.1 % to
40%
by weight, more preferably from 1 % to 20% by weight and most preferably from
2% to 15% by weight of the compositions.
In addition to the above bleaching system, the composition may comprises
bleaching agents other than oxygen bleaching agents are also known in the art
and can be utilized herein. One type of non-oxygen bleaching agent of
particular
interest includes photoactivated bleaching agents such as the sulfonated zinc
and/or aluminum phthalocyanines. See U.S. 4,033,718. If used, detergent
3o compositions will typically contain from 0.025% to 1.25%, by weight, of
such
bleaches, especially sulfonate zinc phthalocyanine.
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
21
If desired, the bleaching compounds can be catalyzed by means of a manganese
compound. Such compounds are well-known in the art and include, for example,
the manganese-based catalysts disclosed in U.S. 5,246,621, U.S. 5,244,594;
U.S. 5,194,416; U.S. 5,114,606; and EP 549,271A1, 549,272A1, 544,440A2, and
544,490A1; Preferred examples of these catalysts include MnIV2(u-O)3(1,4,7-
trimethyl-1,4,7-triazacyclononane)2(PFg)2, Mnlll2 (u-O)1 (u-OAc)2(1,4,7-
trimethyl-1,4,7-triazacyclononane)2-(C104)2, MnIV4(u-O)6(1,4,7-
triazacyclononane)4(C104)4, MnIIIMnIV4(u-O)1(u-OAc)2_(1,4,7-trimethyl-1,4,7-
triazacyclononane)2(C104)3, MnIV(1,4,7-trimethyl-1,4,7-triazacyclononane)-
(OCH3)3(PFg), and mixtures thereof. Other metal-based bleach catalysts include
those disclosed in U.S. Pat. 4,430,243 and U.S. 5,114,611. The use of
manganese with various complex ligands to enhance bleaching is also reported
in the following US Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779;
5,280,117; 5,274,147; 5,153,161; and 5,227,084.
As a practical matter, and not by way of limitation, the compositions and
processes herein can be adjusted to provide on the order of at least one part
per
ten million of the active bleach catalyst species in the aqueous washing
liquor,
and will preferably provide from 0.1 ppm to 700 ppm, more preferably from 1
ppm
2o to 500 ppm, of the catalyst species in the laundry liquor.
Typically the laundry and cleaning composition comprises a detersive
ingredient.
Detersive ingredients
Non-limiting examples of surfactants useful herein typically at levels from 1
% to
55%, by weight, include the conventional C11-C1g alkyl benzene sulfonates
("LAS") and primary, branched-chain and random C10-C20 alkyl sulfates ("AS"),
the C10-C1g secondary (2,3) alkyl sulfates of the formula
CH3(CH2)x(CHOS03-M+) CH3 and CH3(CH2)y(CHOS03 M+) CH2CH3 where x
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
22
and (y + 1 ) are integers of at least 7, preferably at least 9, and M is a
water-
solubilizing cation, especially sodium, unsaturated sulfates such as oleyl
sulfate,
the C10-C1 g alkyl alkoxy sulfates ("AEXS"; especially x up to 7 EO ethoxy
sulfates), C1 p-C1 g alkyl alkoxy carboxylates (especially the EO 1-5
ethoxycarboxylates), the C10-18 glycerol ethers, the C10-C1g alkyl
polyglycosides and their corresponding sulfated polyglycosides, and C12-C18
alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and
amphoteric surfactants such as the C10-C1g alkyl ethoxylates ("AE") including
the so-called narrow peaked alkyl ethoxylates like the commercially available
Empicol ESC 3/PG 2 from Albright & Wilson and C6-C12 alkyl phenol alkoxylates
(especially ethoxylates and mixed ethoxy/propoxy), C12-C1 g betaines and
sulfobetaines ("sultaines"), C10-C1g amine oxides, cationic surfactants and
the
like, can also be included in the overall compositions. The C10-C1 g N-alkyl
polyhydroxy fatty acid amides can also be used. Typical examples include the
C12-C1g N-methylglucamides. See WO 9,206,154. Other sugar-derived
surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-
C18
N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C12-C18
glucamides can be used for low sudsing. C1p-C20 conventional soaps may also
be used. If high sudsing is desired, the branched-chain C10-C1g soaps may be
2o used. Mixtures of anionic and nonionic surfactants are especially useful.
Other
conventional useful surfactants are listed in standard texts.
Fully formulated laundry and cleaning compositions preferably contain, in
addition to the hereinbefore described components, one or more of the
following
ingredients.
Builders
Detergent builders can optionally be included in the compositions herein to
assist
in controlling mineral hardness. Inorganic as well as organic builders can be
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
23
used. Builders are typically used in fabric laundering compositions to assist
in the
removal of particulate soils.
The level of builder can vary widely depending upon the end use of the
composition and its desired physical form. When present, the compositions will
typically comprise at least 1 % builder, preferably from 1 % to 80%. Liquid
formulations typically comprise from 5% to 50%, more typically 5% to 30%, by
weight, of detergent builder. Granular formulations typically comprise from 1
% to
80%, more typically from 5% to 50% by weight, of the detergent builder. Lower
or higher levels of builder, however, are not meant to be excluded.
Inorganic or P-containing detergent builders include, but are not limited to,
the
alkali metal, ammonium and alkanolammonium salts of polyphosphates
(exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric
meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including
bicarbonates and sesquicarbonates), sulphates, and aluminosilicates. However,
non-phosphate builders are required in some locales. Importantly, the
compositions herein function surprisingly well even in the presence of the so-
called "weak" builders (as compared with phosphates) such as citrate, or in
the
2o so-called "underbuilt" situation that may occur with zeolite or layered
silicate
builders.
Examples of silicate builders are the alkali metal silicates, particularly
those
having a Si02:Na20 ratio in the range 1.0:1 to 3.2:1 and layered silicates,
such
2~ as the layered sodium silicates described in U.S. 4,664,839. NaSKS-6 is the
trademark for a crystalline layered silicate marketed by Hoechst (commonly
abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate
builder does not contain aluminum. NaSKS-6 has the delta-Na2Si05
morphology form of layered silicate. It can be prepared by methods such as
3o those described in DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly
preferred layered silicate for use herein, but other such layered silicates,
such as
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
24
those having the general formula NaMSix02x+1 ~yH20 wherein M is sodium or
hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0
to
20, preferably 0 can be used herein. Various other layered silicates from
Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and
gamma forms. As noted above, the delta-Na2Si05 (NaSKS-6 form) is most
preferred for use herein. Other silicates may also be useful such as for
example
magnesium silicate, which can serve as a crispening agent in granular
formulations, as a stabilizing agent for oxygen bleaches, and as a component
of
suds control systems.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates
as disclosed in DE 2,321,001.
Aluminosilicate builders are useful in the present invention. Aluminosilicate
builders are of great importance in most currently marketed heavy duty
granular
detergent compositions, and can also be a significant builder ingredient in
liquid
detergent formulations. Aluminosilicate builders include those having the
empirical formula:
Mz/n~(A102)z(Si02)y]~xH20
wherein z and y are integers usually of at least 6, the molar ratio of z to y
is in the
2o range from 1.0 to 0, and x is an integer from 0 to 264, and M is a Group IA
or IIA
element, e.g., Na, K, Mg, Ca with valence n.
Useful aluminosilicate ion exchange materials are commercially available.
These
aluminosilicates can be crystalline or amorphous in structure and can be
2s naturally-occurring aluminosilicates or synthetically derived. A method for
producing aluminosilicate ion exchange materials is disclosed in U.S.
3,985,669.
Preferred synthetic crystalline aluminosilicate ion exchange materials useful
herein are available under the designations Zeolite A, Zeolite P (B), Zeolite
MAP
and Zeolite X. In an especially preferred embodiment, the crystalline
3o aluminosilicate ion exchange material has the formula:
Nal2~(A102)12(Si02)12]~xH20
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
wherein x is from 20 to 30, especially 27. This material is known as Zeolite
A.
Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the
aluminosilicate has a particle size of 0.1-10 microns in diameter.
5 Organic detergent builders suitable for the purposes of the present
invention
include, but are not restricted to, a wide variety of polycarboxylate
compounds.
As used herein, "polycarboxylate" refers to compounds having a plurality of
carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate
builder
can generally be added to the composition in acid form, but can also be added
in
the form of a neutralized salt. When utilized in salt form, alkali metals,
such as
sodium, potassium, and lithium, or alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of
useful
materials. One important category of polycarboxylate builders encompasses the
~5 ether polycarboxylates, including oxydisuccinate, as disclosed in Berg,
U.S.
3,128,287, U.S. 3,635,830. See also "TMS/TDS" builders of U.S. 4,663,071.
Suitable ether polycarboxylates also include cyclic compounds, particularly
alicyclic compounds, such as those described in U.S. 3,923,679; 3,835,163;
4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether hydroxypolycarboxylates,
copolymers of malefic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-
trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic
acid,
the various alkali metal, ammonium and substituted ammonium salts of
polyacetic
acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as
well as
polycarboxylates such as mellitic acid, pyromellitic, succinic acid,
oxydisuccinic
acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,
carboxymethyloxysuccinic
acid, and soluble salts thereof.
3o Citrate builders, e.g., citric acid and soluble salts thereof (particularly
sodium
salt), are polycarboxylate builders of particular importance for heavy duty
liquid
detergent formulations due to their availability from renewable resources and
their
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
26
biodegradability. Citrates can also be used in granular compositions,
especially
in combination with zeolite and/or layered silicate builders. Oxydisuccinates
are
also especially useful in such compositions and combinations.
Also suitable in the detergent compositions of the present invention are the
3,3-
dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S.
4,566,984. Useful succinic acid builders include the C5-C20 alkyl and alkenyl
succinic acids and salts thereof. A particularly preferred compound of this
type is
dodecenylsuccinic acid. Specific examples of succinate builders include:
laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate
(preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the
preferred builders of this group, and are described in EP 0,200,263.
Other suitable polycarboxylates are disclosed in U.S 4,144,226 and in U.S.
~5 3,308,067. See also U.S. 3,723,322.
Fatty acids, e.g., C12-C1g monocarboxylic acids such as oleic acid and/or its
salts, can also be incorporated into the compositions alone, or in combination
with the aforesaid builders, especially citrate and/or the succinate builders,
to
2o provide additional builder activity. Such use of fatty acids will generally
result in a
diminution of sudsing, which should be taken into account by the formulator.
In situations where phosphorus-based builders can be used, and especially in
the
formulation of bars used for hand-laundering operations, the various alkali
metal
25 phosphates such as the well-known sodium tripolyphosphates, sodium
pyrophosphate and sodium orthophosphate can be used. Phosphonate builders
such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates
(see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and
3,422,137) can also be used.
Polyamines
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
27
Polyamines are useful optional components for providing care, in particular
color
care to the treated surface like fabric. Accordingly, a preferred composition
of the
present invention comprises from 0.1 %, preferably from 5%, more preferably
from 10% to 80%, preferably to 50%, more preferably to 25% by weight, of a
polyamine having the formula:
R' B
[ ~RI)2N - R,W ~N- R Ix ~N R ] y N~R~)z
wherein R, R1 and B are suitably described in U.S. 5,565,145 Watson et al.,
issued October 15, 1996 incorporated herein by reference, and w, x, and y have
values which provide for a backbone prior to substitution of preferably at
least
about 1200 daltons, more preferably 1800 daltons.
R1 units are preferably alkyleneoxy units having the formula:
-(CH2CHR'O)m(CHZCHzO)~H
wherein R' is methyl or ethyl, m and n are preferably from about 0 to about
50,
2o provided the average value of alkoxylation provided by m + n is at least
about
0.5.
A further description of polyamine dispersants suitable for use in the present
invention is found in U.S. 4,891,160 Vander Meer, issued January 2, 1990; U.S.
4,597,898 Vander Meer, issued July 1, 1986; EP-0,111,965, Oh and Gosselink,
published June 27, 1984; EP-0,111,984, Gosselink, published June 27, 1984;
EP-0,112,592, Gosselink, published July 4, 1984; U.S. 4,548,744, Connor,
issued October 22, 1985; and U.S. 5,565,145 Watson et al., issued October 15,
1996; all of which are included herein by reference.
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
28
Preferred polyamines are selected from polyethylene imines with molecular
weight of 1200 or 1800 and with either 1 or 4 ethoxylation, as described in US
5,565,145.
s Brighteners
The compositions herein can also optionally contain from 0.005% to 5% by
weight of certain types of optical brighteners like hydrophilic brighteners
which
also provide a dye transfer inhibition action, and/or hydrophobic brighteners.
If
used, the compositions herein will preferably comprise from 0.001 % to 1 % by
weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are those
having the structural formula:
R~ R2
H H NO
N OOIj O C C O NOO N
H H NO
RZ S03M S~3M Ri
15 wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl;
R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino, chloro and amino; and M is a salt-forming cation such as sodium or
potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is
a
2o cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium
salt.
This particular brightener species is commercially marketed under the
tradename
Tinopal-UNPA-GX~ by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the
preferred hydrophilic optical brightener useful in the rinse added
compositions
25 herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
29
anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-
stilbenedisulfonic acid disodium salt. This particular brightener species is
commercially marketed under the tradename Tinopal 5BM-GX~ by Ciba-Geigy
Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a cation
such
as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-
yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener
species is commercially marketed under the tradename Tinopal AMS-GX~ by
Ciba Geigy Corporation.
Also useful herein are the hydrophobic brighteners, preferably hydrophobic
nonionic brighteners. These optical brighteners are substantially insoluble in
water. Wherein substantially insoluble means that less than 1 gram of the
brightener will dissolve in 1 liter of distilled water at pH 7. Nonionic
brighteners,
meaning those brighteners that do not have any permanently charged group or a
group selected from sulphonic, sulphate, carboxylic, phosphonate, phosphate
and quaternary ammonium.
Preferably, the optical brightener is a substantially insoluble compound
selected
2o from compounds comprising stilbene, pyrazoline, coumarin, carboxylic acids,
methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ring
heterocyclic, benzene or derivatives thereof and mixtures thereof. More
preferably the brightener comprises a benzoxozol, pyrazole, triazole,
triazine,
imidazole, furan group or mixtures thereof.
Examples of preferred commerically available hydrophobic optical brighteners
include those selected from the group consisting of Benzoxazole, 2,2'-(2,5-
thiophenediyl)bis- (7C1, 8C1, 9C1) sold under the tradename Tinopal SOP (from
Ciba-Geigy, C.I. Fluorescent Brightener 140 (9C1), 7-(dimethylamino)-4-methyl-
2H-1-benzopyran-2-one (9C1) sold under the tradename Tinopal SWN (from
Ciba-Geigy), Benzoxazole, 2,2'-(1,2-ethenediyl)bis[5-methyl- (9C1) sold under
the
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
tradename Tinopal K (from Ciba-Geigy), C.I. Fluorescent Brightener 352 (9C1)
1 H-Benzimidazole, 2,2'-(2,5-furandiyl)bis[1-methyl- (9C1) sold under the
tradename Uvitex AT (from Ciba-Geigy).
5 Soil Release Aqent
In the present invention, an optional soil release agent can be added. Typical
levels of incorporation in the composition are from 0% to 10%, preferably from
0.2% to 5%, of a soil release agent. Preferably, such a soil release agent is
a
polymer.
Soil Release agents are desirably used in fabric softening compositions of the
instant invention. Any polymeric soil release agent known to those skilled in
the
art can optionally be employed in the compositions of this invention.
Polymeric
soil release agents are characterized by having both hydrophilic segments, to
hydrophilize the surface of hydrophobic fibers, such as polyester and nylon,
and
hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered
thereto through completion of washing and rinsing cycles and, thus, serve as
an
anchor for the hydrophilic segments. This can enable stains occurring
subsequent to treatment with the soil release agent to be more easily cleaned
in
later washing procedures.
If utilized, soil release agents will generally comprise from about 0.01 % to
about
10.0%, by weight, of the detergent compositions herein, typically from about
0.1 % to about 5%, preferably from about 0.2% to about 3.0%.
The following, all included herein by reference, describe soil release
polymers
suitable for use in the present invention. U.S. 3,959,230 Hays, issued May 25,
1976; U.S. 3,893,929 Basadur, issued July 8, 1975; U.S. 4,000,093, Nicol, et
al.,
issued December 28, 1976; U.S. Patent 4,702,857 Gosselink, issued October
27, 1987; U.S. 4,968,451, Scheibel et al., issued November 6; U.S. 4,702,857,
Gosselink, issued October 27, 1987; U.S. 4,711,730, Gosselink et al., issued
December 8, 1987; U.S. 4,721,580, Gosselink, issued January 26, 1988; U.S.
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
31
4,877,896, Maldonado et al., issued October 31, 1989; U.S. 4,956,447,
Gosselink et al., issued September 11, 1990; U.S. 5,415,807 Gosselink et al.,
issued May 16, 1995; European Patent Application 0 219 048, published April
22, 1987 by Kud, et al..
Further suitable soil release agents are described in U.S. 4,201,824, Violland
et
al.; U.S. 4,240,918 Lagasse et al.; U.S. 4,525,524 Tung et al.; U.S.
4,579,681,
Ruppert et al.; U.S. 4,240,918; U.S. 4,787,989; U.S. 4,525,524; EP 279,134 A,
1988, to Rhone-Poulenc Chemie; EP 457,205 A to BASF (1991 ); and DE
2,335,044 to Unilever N. V., 1974 all incorporated herein by reference.
Commercially available soil release agents include the METOLOSE SM100,
METOLOSE SM200 manufactured by Shin-etsu Kagaku Kogyo K.K., SOKALAN
type of material, e.g., SOKALAN HP-22, available from BASF (Germany),
ZELCON 5126 (from Dupont) and MILEASE T (from ICI).
Scum Disaersant
In the present invention, the premix can be combined with an optional scum
dispersant, other than the soil release agent, and heated to a temperature at
or
2o above the melting points) of the components.
The preferred scum dispersants herein are formed by highly ethoxylating
hydrophobic materials. The hydrophobic material can be a fatty alcohol, fatty
acid, fatty amine, fatty acid amide, amine oxide, quaternary ammonium
compound, or the hydrophobic moieties used to form soil release polymers. The
preferred scum dispersants are highly ethoxylated, e.g., more than 17,
preferably
more than 25, more preferably more than 40, moles of ethylene oxide per
molecule on the average, with the polyethylene oxide portion being from 76% to
97%, preferably from 81 % to 94%, of the total molecular weight.
The level of scum dispersant is sufficient to keep the scum at an acceptable,
3o preferably unnoticeable to the consumer, level under the conditions of use,
but
not enough to adversely affect softening. For some purposes it is desirable
that
the scum is nonexistent. Depending on the amount of anionic or nonionic
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
32
detergent, etc., used in the wash cycle of a typical laundering process, the
efficiency of the rinsing steps prior to the introduction of the compositions
herein,
and the water hardness, the amount of anionic or nonionic detergent surfactant
and detergency builder (especially phosphates and zeolites) entrapped in the
fabric (laundry) will vary. Normally, the minimum amount of scum dispersant
should be used to avoid adversely affecting softening properties. Typically
scum
dispersion requires at least 2%, preferably at least 4% (at least 6% and
preferably at least 10% for maximum scum avoidance) based upon the level of
softener active. However, at levels of 10% (relative to the softener material)
or
more, one risks loss of softening efficacy of the product especially when the
fabrics contain high proportions of nonionic surfactant which has been
absorbed
during the washing operation.
Preferred scum dispersants are: Brij 700~; Varonic U-250~; Genapol T-500~,
Genapol T-800~; Plurafac A-79~; and Neodol 25-50~
Bactericides
Examples of bactericides used in the compositions of this invention include
glutaraldehyde, formaldehyde, 2-bromo-2-vitro-propane-1,3-diol sold by Inolex
Chemicals, located in Philadelphia, Pennsylvania, under the trade name
2o Bronopol~, and a mixture of 5-chloro-2-methyl-4-isothiazoline-3-one and 2-
methyl-4-isothiazoline-3-one sold by Rohm and Haas Company under the trade
name Kathon 1 to 1,000 ppm by weight of the agent.
Chelating Agents
The compositions and processes herein can optionally employ one or more
copper and/or nickel chelating agents ("chelators"). Such water-soluble
chelating
agents can be selected from the group consisting of amino carboxylates, amino
phosphonates, polyfunctionally-substituted aromatic chelating agents and
mixtures thereof, all as hereinafter defined. The whiteness and/or brightness
of
3o fabrics are substantially improved or restored by such chelating agents and
the
stability of the materials in the compositions are improved. Without intending
to
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
33
be bound by theory, it is believed that the benefit of these materials is due
in part
to their exceptional ability to remove iron and manganese ions from washing
solutions by formation of soluble chelates.
Amino carboxylates useful as optional chelating agents include
ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilo-
triacetates, ethylenediamine tetraproprionates, triethylenetetra-amine-
hexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali
metal, ammonium, and substituted ammonium salts therein and mixtures therein.
Amino phosphonates are also suitable for use as chelating agents in the
compositions of the invention when at lease low levels of total phosphorus are
permitted in detergent compositions, and include ethylenediaminetetrakis
(methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates
do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are also useful in the
compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to
Connor et al. Preferred compounds of this type in acid form are
2o dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
A preferred biodegradable chelator for use herein is ethylenediamine
disuccinate
("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233,
November 3, 1987, to Hartman and Perkins.
The compositions herein may also contain water-soluble methyl glycine diacetic
acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for
example, insoluble builders such as zeolites, layered silicates and the like.
3o Preferred chelating agents include DETMP, DETPA, NTA, EDDS and mixtures
thereof.
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
34
If utilized, these chelating agents will generally comprise from about 0.1 %
to
about 15% by weight of the fabric care compositions herein. More preferably,
if
utilized, the chelating agents will comprise from about 0.1 % to about 3.0% by
weight of such compositions.
Cr)rstal growth inhibitor component CGI component)
The compositions of the present invention can further contain a crystal growth
inhibitor component, preferably an organodiphosphonic acid component,
incorporated preferably at a level of from 0.01 % to 5%, more preferably from
0.1 % to 2% by weight of the compositions.
By organo diphosphonic acid it is meant herein an organo diphosphonic acid
which does not contain nitrogen as part of its chemical structure. This
definition
therefore excludes the organo aminophosphonates, which however may be
~5 included in compositions of the invention as heavy metal ion sequestrant
components.
The organo diphosphonic acid is preferably a C1-C4 diphosphonic acid, more
preferably a C2 diphosphonic acid, such as ethylene diphosphonic acid, or most
2o preferably ethane 1-hydroxy-1,1-diphosphonic acid (HEDP) and may be present
in partially or fully ionized form, particularly as a salt or complex.
Still useful herein as crystal growth inhibitor are the organic monophosphonic
acids.
25 Organo monophosphonic acid or one of its salts or complexes is also
suitable for
use herein as a CGI.
By organo monophosphonic acid it is meant herein an organo monophosphonic
acid which does not contain nitrogen as part of its chemical structure. This
3o definition therefore excludes the organo aminophosphonates, which however
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
may be included in compositions of the invention as heavy metal ion
sequestrants.
The organo monophosphonic acid component may be present in its acid form or
5 in the form of one of its salts or complexes with a suitable counter cation.
Preferably any salts/complexes are water soluble, with the alkali metal and
alkaline earth metal salts/complexes being especially preferred.
A prefered organo monophosphonic acid is 2-phosphonobutane-1,2,4-
tricarboxylic acid commercially available from Bayer under the tradename of
Bayhibit.
Enzyme
The compositions and processes herein can optionally employ one or more
~5 enzymes such as lipases, proteases, cellulase, amylases and peroxidases. A
preferred enzyme for use herein is a cellulase enzyme. Indeed, this type of
enzyme will further provide a color care benefit to the treated fabric.
Cellulases
usable herein include both bacterial and fungal types, preferably having a pH
optimum between 5 and 9.5. U.S. 4,435,307 discloses suitable fungal cellulases
2o from Humicola insolens or Humicola strain DSM1800 or a cellulase 212-
producing fungus belonging to the genus Aeromonas, and cellulase extracted
from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander.
Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and
DE-OS-2.247.832. CAREZYME~ and CELLUZYME~ (Novo) are especially
25 useful. Other suitable cellulases are also disclosed in WO 91/17243 to
Novo,
WO 96/34092, WO 96/34945 and EP-A-0,739,982. In practical terms for current
commercial preparations, typical amounts are up to 5 mg by weight, more
typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent
composition. Stated otherwise, the compositions herein will typically comprise
3o from 0.001 % to 5%, preferably 0.01 %-1 % by weight of a commercial enzyme
preparation. In the particular cases where activity of the enzyme preparation
can
be defined otherwise such as with cellulases, corresponding activity units are
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
36
preferred (e.g. CEVU or cellulase Equivalent Viscosity Units). For instance,
the
compositions of the present invention can contain cellulase enzymes at a level
equivalent to an activity from 0.5 to 1000 CEVU/gram of composition. Cellulase
enzyme preparations used for the purpose of formulating the compositions of
this
invention typically have an activity comprised between 1,000 and 10,000
CEVU/gram in liquid form, around 1,000 CEVU/gram in solid form.
Clay
The compositions of the invention may preferably contain a clay, preferably
1 o present at a level of from 0.05% to 40%, more preferably from 0.5% to 30%,
most preferably from 2% to 20% by weight of the composition. For clarity, it
is
noted that the term clay mineral compound, as used herein, excludes sodium
aluminosilicate zeolite builder compounds, which however, may be included in
the compositions of the invention as optional components.
One preferred clay may be a bentonite clay. Highly preferred are smectite
clays,
as for example disclosed in the US Patents No.s 3,862,058 3,948,790, 3,954,632
and 4,062,647 and European Patents No.s EP-A-299,575 and EP-A-313,146 all
in the name of the Procter and Gamble Company.
The term smectite clays herein includes both the clays in which aluminium
oxide
is present in a silicate lattice and the clays in which magnesium oxide is
present
in a silicate lattice. Smectite clays tend to adopt an expandable three layer
structure.
Specific examples of suitable smectite clays include those selected from the
classes of the montmorillonites, hectorites, volchonskoites, nontronites,
saponites and sauconites, particularly those having an alkali or alkaline
earth
metal ion within the crystal lattice structure. Sodium or calcium
montmorillonite
3o are particularly preferred.
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
37
Suitable smectite clays, particularly montmorillonites, are sold by various
suppliers including English China Clays, Laviosa, Georgia Kaolin and Colin
Stewart Minerals.
Clays for use herein preferably have a particle dimension of from 10nm to
800nm
more preferably from 20nm to 500 mm, most preferably from 50nm to 200 mm.
Particles of the clay mineral compound may be included as components of
agglomerate particles containing other detergent compounds. Where present as
such components, the term "largest particle dimension" of the clay mineral
compound refers to the largest dimension of the clay mineral component as
such, and not to the agglomerated particle as a whole.
Substitution of small cations, such as protons, sodium ions, potassium ions,
magnesium ions and calcium ions, and of certain organic molecules including
those having positively charged functional groups can typically take place
within
the crystal lattice structure of the smectite clays. A clay may be chosen for
its
ability to preferentially absorb one cation type, such ability being assessed
by
measurements of relative ion exchange capacity. The smectite clays suitable
2o herein typically have a cation exchange capacity of at least 50 meq/100g.
U.S.
Patent No. 3,954,632 describes a method for measurement of cation exchange
capacity.
The crystal lattice structure of the clay mineral compounds may have, in a
25 preferred execution, a cationic fabric softening agent substituted therein.
Such
substituted clays have been termed 'hydrophobically activated' clays. The
cationic fabric softening agents are typically present at a weight ratio,
cationic
fabric softening agent to clay, of from 1:200 to 1:10, preferably from 1:100
to
1:20. Suitable cationic fabric softening agents include the water insoluble
tertiary
3o amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and
EP-
B-0 011 340.
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
38
A preferred commercially available "hydrophobically activated" clay is a
bentonite
clay containing approximately 40% by weight of a dimethyl ditallow quaternary
ammonium salt sold under the tradename Claytone EM by English China Clays
International.
In a highly preferred embodiment of the invention, the clay is present in an
intimate mixture or in a particle with a humectant and a hydrophobic compound,
preferably a wax or oil, such as paraffin oil. Preferred humectants are
organic
compounds, including propylene glycol, ethylene glycol, dimers or trimers of
1o glycol, most preferably glycerol. The particle is preferably an
agglomerate.
Alternatively, the particle may be such that the wax or oil and optionally the
humectant form an encapsulate on the clay or alternatively, the clay be a
encapsulate for the wax or oil and the humectant. It may be preferred that the
particle comprises an organic salt or silica or silicate.
However, in another embodiment of the invention, the clay is preferably mixed
with one or more surfactants and optionally builders and optionally water, in
which case the mixture is preferably subsequently dried. Preferably, such a
mixture is further processed in a spray-drying method to obtain a spray dried
2o particle comprising the clay.
It may be preferred that a flocculating agent is also comprised in the
particle or
granule comprising the clay.
Flocculating accent
The compositions of the invention may contain a clay flocculating agent,
preferably present at a level of from 0.005% to 10%, more preferably from
0.05%
to 5%, most preferably from 0.1 % to 2% by weight of the composition.
The clay flocculating agent functions such as to bring together the particles
of
clay compound in the wash solution and hence to aid their deposition onto the
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
39
surface of the fabrics in the wash. This functional requirement is hence
different
from that of clay dispersant compounds which are commonly added to laundry
detergent compositions to aid the removal of clay soils from fabrics and
enable
their dispersion within the wash solution.
Preferred as clay flocculating agents herein are organic polymeric materials
having an average weight of from 100,000 to 10,000,000, preferably from
150,000 to 5,000,000, more preferably from 200,000 to 2,000,000.
1o Suitable organic polymeric materials comprise homopolymers or copolymers
containing monomeric units selected from alkylene oxide, ' particularly
ethylene
oxide, acrylamide, acrylic acid, vinyl alcohol, vinyl pyrrolidone, and
ethylene
imine. Homopolymers of, on particular, ethylene oxide, but also acrylamide and
acrylic acid are preferred.
European Patents No.s EP-A-299,575 and EP-A-313,146 in the name of the
Procter and Gamble Company describe preferred organic polymeric clay
flocculating agents for use herein.
2o The weight ratio of clay to the flocculating polymer is preferably from
1000:1 to
1:1, more preferably from 500:1 to 1:1, most preferably from 300:1 to 1:1, or
even more preferably from 80:1 to 10:1, or in certain applications even from
60:1
to 20:1.
Inorganic clay flocculating agents are also suitable herein, typical examples
of
which include lime and alum.
The flocculating agent is preferably present in a detergent base granule such
as
a detergent agglomerate, extrudate or spray-dried particle, comprising
generally
one or more surfactants and builders.
Effervescent
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
Effervescent means may also be optionally used in the compositions of the
invention.
Effervescency as defined herein means the evolution of bubbles of gas from a
liquid, as the result of a chemical reaction between a soluble acid source and
an
alkali metal carbonate, to produce carbon dioxide gas,
i.e. CgH807 + 3NaHC03 -~ Na3CgH5O7 + 3C02 T + 3H20
Further examples of acid and carbonate sources and other effervescent systems
may be found in : (Pharmaceutical Dosage Forms : Tablets Volume 1 Page 287
to 291 ).
Carbonate salts
Suitable alkali and/ or earth alkali inorganic carbonate salts herein include
carbonate and hydrogen carbonate of potassium, lithium, sodium, and the like
amongst which sodium and potassium carbonate are preferred. Suitable
bicarbonates to be used herein include any alkali metal salt of bicarbonate
like
lithium, sodium, potassium and the like, amongst which sodium and potassium
bicarbonate are preferred. However, the choice of carbonate or bicarbonate or
2o mixtures thereof may be made depending on the pH desired in the aqueous
medium wherein the granules are dissolved. For example where a relative high
pH is desired in the aqueous medium (e.g., above pH 9.5) it may be preferred
to
use carbonate alone or to use a combination of carbonate and bicarbonate
wherein the level of carbonate is higher than the level of bicarbonate. The
25 inorganic alkali and/ or earth alkali carbonate salt of the compositions of
the
invention comprises preferably a potassium or more preferably a sodium salt of
carbonate and/ or bicarbonate. Preferably, the carbonate salt comprises sodium
carbonate, optionally also a sodium bicarbonate.
so The inorganic carbonate salts herein are preferably present at a level of
at least
20% by weight of the composition. Preferably they are present at a level of at
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
41
least 23% or even 25% or even 30% by weight, preferably up to about 60% by
weight or more preferably up to 55% or even 50% by weight.
They may be added completely or partially as separate powdered or granular
component, as co-granules with other detergent ingredients, for example other
salts or surfactants. In solid detergent compositions of the invention, they
may
also completely or partially be present in detergent granules such as
agglomerates or spray dried granules.
1o In one embodiment of the invention, an effervescence source is present,
preferably comprising an organic acid, such as carboxylic acids or aminoacids,
and a carbonate. Then it may be preferred that part or all of the carbonate
salt
herein is premixed with the organic acid, and thus present in an separate
granular component.
Preferred effervescent source are selected from compressed particles of citric
acid and carbonate optionally with a binder; and particle of carbonate,
bicarbonate and malic or malefic acid in weight ratios of 4:2:4. The dry add
form
of citric acid and carbonate are preferably used.
The carbonate may have any particle size. In one embodiment, in particular
when the carbonate salt is present in a granule and not as separately added
compound, the carbonate salt has preferably a volume median particle size from
5 to 375 microns, whereby preferably at least 60%, preferably at least 70% or
even at least 80% or even at least 90% by volume, has a particle size of from
1
to 425 microns. More preferably, the carbon dioxide source has a volume median
particle size of 10 to 250, whereby preferably at least 60 %, or even at least
70%
or even at least 80% or even at least 90% by volume, has a particle size of
from
1 to 375 microns; or even preferably a volume median particle size from 10 to
200 microns, whereby preferably at least 60 %, preferably at least 70% or even
at least 80% or even at least 90% by volume, has a particle size of from 1 to
250
microns.
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
42
In particular when the carbonate salt is added as separate component, so to
say
'dry-added' or admixed to the other detergent ingredients, the carbonate may
have any particle size, including the above specified particle sizes, but
preferably
at least an volume average particle size of 200 microns or even 250 microns or
even 300 microns.
It may be preferred that the carbon dioxide source of the required particle
size is
obtained by grinding a larger particle size material, optionally followed by
selecting the material with the required particle size by any suitable method.
Whilst percarbonate salts may be present in the compositions of the invention
as
a bleaching agent, they are not included in the carbonate salts as defined
herein
15 Other preferred optional ingredients include enzyme stabilisers, polymeric
soil
release agents, materials effective for inhibiting the transfer of dyes from
one
fabric to another during the cleaning process (i.e., dye transfer inhibiting
agents),
suds suppressors, optical brighteners or other brightening or whitening
agents,
anti-static agents, carriers, hydrotropes, processing aids, dyes or pigments,
20 radical scavengers, antioxidants, stabilisers, pH control agents, solvents,
suds
controlling agents, suds booster, colouring agent, solvents for liquid
formulations
and solid fillers for bar compositions.
Form of the composition
2s The composition of the invention may take a variety of physical form
including
liquid, liquid suspension form, gel, foam in either aqueous or non-aqueous
form,
granular and tablet forms.
Liquid detergent compositions can contain water and other solvents as
carriers.
3o Low molecular weight primary or secondary alcohols exemplified by methanol,
ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are
preferred for solubilizing surfactant, but polyols such as those containing
from 2
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
43
to 6 carbon atoms and from 2 to 6 hydroxy groups (e.g., 1,3-propanediol,
ethylene glycol, glycerine, and 1,2-propanediol) can also be used. The
compositions may contain from 5% to 90%, typically 10% to 50% of such
carriers.
Granular detergents can be prepared, for example, by spray-drying (final
product
density 520 g/1) or agglomerating (final product density above 600 g/1) the
Base
Granule. The remaining dry ingredients can then be admixed in granular or
powder form with the Base Granule, for example in a rotary mixing drum, and
the
liquid ingredients (e.g., nonionic surfactant and perfume) can be sprayed on.
The detergent compositions herein will preferably be formulated such that,
during
use in aqueous cleaning operations, the wash water will have a pH of between
6.5 and 11, preferably between 7.0 and 10Ø Laundry products are typically at
pH 7.5-9Ø Techniques for controlling pH at recommended usage levels include
the use of buffers, alkalis, acids, etc., and are well-known to those skilled
in the
art.
Packaging form of the liquid compositions:
Depending on the end-use envisioned, the compositions herein can be packaged
2o in a variety of containers including conventional bottles, bottles equipped
with roll-
on, sponge, brusher, sprayers, or aerosol dispensers.
In one embodiment of the present invention the composition is packaged in a
two
compartment container, wherein the bleaching composition as described herein
is
packaged in one compartment and a second composition is packaged in the
second compartment. In a particularly preferred aspect, the second composition
is a conventional heavy duty liquid detergent composition, preferably
comprising
ingredients, particularly bleach-sensitive ingredients such as surfactants,
and
enzymes.
Spray Dispenser
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
44
The present invention also relates to such compositions incorporated into a
spray
dispenser to create an article of manufacture that can facilitate treatment or
pre-
treatment of fabric articles and/or surfaces with the invention compositions.
The
spray dispenser comprises manually activated and non-manual powered
(operated) spray means and a container containing the treating composition.
Typical disclosure of such spray dispenser can be found in WO 96/04940 page
19 line 21 to page 22 line 27. The articles of manufacture preferably are in
association with instructions for use to ensure that the consumer applies
sufficient ingredient of the composition to provide the desired benefit.
Processes of treating surfaces
In the present invention, the surface to be cleaned is treated with a
composition,
preferably in liquid form, of the present invention.
By "surfaces", it is meant herein any inanimate surface. These inanimate
surfaces include, but are not limited to, hard-surfaces typically found in
houses
like kitchens, bathrooms, or in car interiors, e.g., tiles, walls, floors,
chrome, glass,
smooth vinyl, any plastic, plastified wood, table top, sinks, cooker tops,
dishes,
sanitary fittings such as sinks, showers, shower curtains, wash basins, WCs
and
2o the like, as well as fabrics including clothes, curtains, drapes, bed
linens, bath
linens, table cloths, sleeping bags, tents, upholstered furniture and the
like, and
carpets. Inanimate surfaces also include household appliances including, but
not
limited to, refrigerators, freezers, washing machines, automatic dryers,
ovens,
microwave ovens, dishwashers and so on.
By "treating a surface", it is meant herein bleaching said surfaces as the
compositions of the present invention comprise a bleaching system, preferably
based on a peracid compound or a mixture thereof and optionally cleaning as
said compositions may comprise a surfactant or any other conventional cleaning
so agents.
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
Thus, the present invention also encompasses a process of treating, especially
bleaching a fabric, of the inanimate surface. In such a process a composition
according to the present invention is contacted with the fabrics to be
treated.
5 This can be done either in a so-called "pretreatment mode", where a liquid
bleaching composition, as defined herein, is applied neat onto said fabrics
before
the fabrics are rinsed, or washed then rinsed, or in a "soaking mode" where a
liquid bleaching composition, as defined herein, is first diluted in an
aqueous bath
and the fabrics are immersed and soaked in the bath, before they are rinsed,
or
1o in a "through the wash mode", where a liquid bleaching composition, as
defined
herein, is added on top of a wash liquor formed by dissolution or dispersion
of a
typical laundry detergent. It is also essential in both cases, that the
fabrics be
rinsed after they have been contacted with said composition, before said
composition has completely dried off.
The compositions according to the present invention may be used in neat or
diluted form. However the compositions herein are typically used in diluted
form
in a laundry operation. By "in diluted form", it is meant herein that the
compositions for the bleaching of fabrics according to the present invention
may
2o be diluted by the user, preferably with water. Such dilution may occur for
instance in hand laundry applications as well as by other means such as in a
washing machine. Said compositions can be diluted up to 500 times, preferably
from 5 to 200 times and more preferably from 10 to 80 times.
More specifically, the process of bleaching fabrics according to the present
invention comprises the steps of first contacting said fabrics with a
bleaching
composition according to the present invention, in its diluted form, then
allowing
said fabrics to remain in contact with said composition, for a period of time
sufficient to bleach said fabrics, typically 1 to 60 minutes, preferably 5 to
30
3o minutes, then rinsing said fabrics with water. If said fabrics are to be
washed, i.e.,
with a conventional detergent composition preferably comprising at least one
surface active agent, said washing may be conducted together with the
bleaching
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
46
of said fabrics by contacting said fabrics at the same time with a bleaching
composition according to the present invention and said detergent composition,
or said washing may be conducted before or after said fabrics have been
bleached. Accordingly, said process according to the present invention allows
bleaching of fabrics and optionally washing of fabrics with a detergent
composition preferably comprising at least one surface active agent before the
step of contacting said fabrics with said bleaching composition and/or in the
step
where said fabrics are contacted with said bleaching composition and/or after
the
step where said fabrics are contacted with said bleaching composition and
before
the rinsing step and/or after the rinsing step.
In another embodiment of the present invention the process of bleaching
fabrics
comprises the step of contacting fabrics with a liquid bleaching composition
according to the present invention, in its neat form and allowing said fabrics
to
remain in contact with sa+d bleaching composition for a period of time
sufficient to
bleach said fabrics, typically 5 seconds to 30 minutes, preferably 1 minute to
10
minutes and then rinsing said fabrics with water. If said fabrics are to be
washed,
i.e., with a conventional composition comprising at least one surface active
agent,
said washing may be conducted before or after that said fabrics have been
2o bleached. Advantageously, the present invention provides liquid bleaching
compositions that may be applied neat onto a fabric to bleach, despite a
standing
prejudice against using bleach-containing compositions neat on fabrics since
the
present compositions are safe to colors and fabrics perse.
2s Alternatively instead of following the neat bleaching method as described
herein
above (pretreater application) by a rinsing step with water and/or a
conventional
washing step with a liquid or powder conventional detergent, the bleaching pre
treatment operation may also be followed by the diluted bleaching process as
described herein before either in bucket (hand operation) or in a washing
30 machine.
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
47
It is preferred to perform the bleaching processes herein after said fabrics
have
been washed with a conventional laundry detergent composition. Indeed, it has
been observed that bleaching said fabrics with the compositions according to
the
present invention (typically diluted bleaching methods) after to washing them
with
a detergent composition provides superior whiteness and stain removal with
less
energy and detergent than if said fabrics are bleached first then washed.
In another embodiment the present invention also encompasses a process of
treating a hard-surface, as the inanimate surface. In such a process a
composition, as defined herein, is contacted with the hard-surfaces to be
treated.
Thus, the present invention also encompasses a process of treating a hard-
surface with a composition, as defined herein, wherein said process comprises
the step of applying said composition to said hard-surface, preferably only
soiled
portions thereof, and optionally rinsing said hard-surface.
In the process of treating hard-surfaces according to the present invention
the
composition, as defined herein, may be applied to the surface to be treated in
its
neat form or in its diluted form typically up to 200 times their weight of
water,
preferably into 80 to 2 times their weight of water, and more preferably 60 to
2
times.
When used as hard surfaces bleaching/disinfecting compositions the
compositions of the present invention are easy to rinse and provide good shine
characteristics on the treated surfaces.
By "hard-surfaces", it is understood any hard-surfaces as mentioned herein
before as well as dishes.
so Perfume formulation examples
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
48
The following are perfume formulations examples according to the present
invention which are incorporated in the following laundry and cleaning
compositions:
Perfume A
AMYL SALICYLATE 10.00
BENZYL SAL1CYLATE 30.00
HEXYL SALICYLATE 35.00
CITRONELLOL* 15.00 15.00
FLORALOL* 7.00 7.00
HABANOLIDE 100%* 2.00 2.00
PRENYL ACETATE* 1.00 1.00
Total > 100.00 25.00
Perfume A contains 25% by weight of unsaturated perfume ingredient having a
bleach stability index (BSI) of at least 80%, an odour character of value A or
B
and an odour intensity of at least 6.
Perfume B
AMYL SALICYLATE 5.00
ANISIC ALDEHYDE 3.00
BENZYL SALICYLATE 7.00
CITRONELLOL* 12.00 12.00
DIPHENYL OXIDE 1.00
FLOROPAL 5.00
FRUTINAT* 2.50 2.50
ISO E SUPER* 9.00 9.00
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
49
ISOANANAT 660567* 1.50 1.50
KOAVONE* 8.00 8.00
LI NALOOL* 10.00 10.00
METHYL DIHYDRO JASMONATE 9.00
PHENYL ETHYL ALCOHOL 15.00
ROSE NITRILE* 1.00 1.00
TERPINEOL* 10.00 10.00
UNDECYLENIC ALDEHYDE* 1.00 1.00
Total > 100.00 55.00
Perfume B contains 55% by weight of unsaturated perfume ingredient having a
bleach stability index (BSI) of at least 80%, an odour character of value A or
B
and an odour intensity of at least 6.
Perfume C
BEAUVERTATE* 2.00 2.00
CIS 3 HEXENYL ACETATE* 1.00 1.00
CITRONELLAL* 2.00 2.00
CITRONELLOL* 15.00 15.00
COUMARIN* 4.00 4.00
FRUTINAT* 5.00 5.00.
HABANOLIDE 100%* 5.00 5.00
ISO E SUPER* 8.00 8.00
METHYL DIHYDRO JASMONATE 15.00
PHENYL ETHYL ALCOHOL 20.00
PHENYL HEXANOL 10.00
ROSALVA* 1.00 1.00
SANJINOL* 1.00 1.00
TERPINEOL* 8.00 8.00
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
UNDECAVERTOL* 3.00 3.00
Total > 100.001 55.00
Perfume C contains 55% by weight of unsaturated perfume ingredient having a
bleach stability index (BSI) of at least 80%, an odour character of value A or
B
and an odour intensity of at least 6.
5
Perfume D
BEAUVERTATE* 1.00 1.00
BORONAL .EXP* 0.50 0.50
BUTYL CINNAMIC ALDEHYDE 3.00
CITRONELLOL* 20.00 20.00
DIHYDRO ISO JASMONATE 1.00
FLORALOL* 20.00 20.00
GERANIOL 5.00
HABANOLIDE 100%* 8.00 8.00
LACTOSCATONE 0.20
LAURIC ALDEHYDE 0.30
LINALOOL* 15.00 15.00
LYRAL 5.00
P. T. BUCINAL 5.00
PRENYL ACETATE 5.00
SANDALORE* 1.00 1.00
TERPINEOL* 10.00 10.00
Total > 100.00 75.50
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
51
Perfume D contains 75.5% by weight of unsaturated perfume ingredient having a
bleach stability index (BSI) of at least 80%, an odour character of value A or
B
and an odour intensity of at least 6.
Perfume E
ANISIC ALDEHYDE 0.50
BEAUVERTATE* 0.20 0.20'
BORONAL .EXP* 0.50 0.50
CITRONELLOL* 3.00 3.00
COUMARIN* 1.30 1.30
FLOR ACETATE* 3.00 3.00
FLORALOL* 12.00 12.00
FRUTENE* 6.00 6.00
HABANOLIDE 100%* 12.00 12.00
HEXYL CINNAMIC ALDEHYDE 12.00
HEXYL CROTONATE* 5.00 5.00
ISO E SUPER* 10.00 10.00
KOAVONE* 13.00 13.00
LINALOOL* 2.50 2.50
NEOBUTENONE 10%* 0.20 0.02
PARA HYDROXY PHENYL BUTANONE 0.20
SANDALORE* 0.60 0.60
TERPINEOL* 10.00 10.00
VERDOX 1.00
VERTOFIX COEUR* 7.00 7.00
Total > 100.00 86.12
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
52
Perfume E contains 86.12% by weight of unsaturated perfume ingredient having
a bleach stability index (BSI) of at least 80%, an odour character of value A
or B
and an odour intensity of at least 6.
Perfume F
ALPHA DAMASCONE* 0.20 0.20
CITRONELLOL* 15.00 15.00
COUMARIN* 3.00 3.00
DIHYDRO MYRCENOL* 5.00 5.00
ETHYL SAFRANATE* 2.00 2.00
FLOR ACETATE* 4.00 4.00
FLORALOL* 10.00 10.00
FRUTENE* 3.00 3.00
FRUTINAT* 3.00 3.00
GIVESCONE* 1.00 1.00
GYRANE* 1.00 1.00
HABANOLIDE 100%* 5.00 5.00
HEXYL CROTONATE* 5.00 5.00
ISO E SUPER* 5.00 5.00
KOAVONE* 12.00 12.00
LINALOOL* 5.00 5.00
MYRCENYL ACETATE CRUDE* 3.00 3.00
PRENYL ACETATE* 1.00 1.00
ROSE NITRILE* 0.50 0.50
TERPINEOL* 9.00 9.00
UNDECYLENIC ALDEHYDE* 1.30 1.30
VERTOFIX COEUR* 6.00 6.00
Total > 100.00 100.00
CA 02379200 2002-O1-16
WO 01/05919 53 PCT/US00/19369
Perfume F contains 100% by weight of unsaturated perfume ingredient having a
bleach stability index (BSI) of at least 80%, an odour character of value A or
B
and an odour intensity of at least 6.
Abbreviations used in the following laundr~and cleaning composition Examples
In the laundry and cleaning composition examples of the invention, the enzymes
levels are expressed by pure enzyme by weight of the total composition and
unless otherwise specified, the detergent ingredients are expressed by weight
of
the total compositions, and incorporation of the perfume composition in the
fully
formulated composition is carried out by spray-on unless otherwise mentioned.
The abbreviated component identifications therein have the following meanings:
LAS : Sodium linear C11-13 alkyl benzene sulphonate.
TAS : Sodium tallow alkyl sulphate.
CxyAS : Sodium C1x - C1y alkyl sulfate.
CxySAS : Sodium C1x - C1y secondary (2,3) alkyl sulfate.
CxyEz : C1x - C1y predominantly linear primary alcohol condensed
with an average of z moles of ethylene oxide.
CxyEzS : C1x - C1y sodium alkyl sulfate condensed with an average
of z moles of ethylene oxide.
CxEOy : Cy alcohol with an average of ethoxylation of y.
Nonionic : Mixed ethoxylated/propoxylated fatty alcohol e.g. Plurafac
LF404 being an alcohol with an average degree of
ethoxylation of 3.8 and an average degree of propoxylation
of 4.5.
QAS : R2.N+(CH3)2(C2H40H) with R2 = C12-C14
QAS 1 : R2.N+(CH3)2(C2H40H) with R2 = Cg-C11
SADS : Sodium C14-22 alkyl disulphate of fromula 2-(R).C4H7-1,4-
(S04-)2 where R=C10-18
MBAS : C12-18 mid branched alkyl sulphate surfactant with an
CA 02379200 2002-O1-16
WO 01/05919 54 PCT/US00/19369
average branching of 1.5 methyl or ethyl branching groups
MES : x-Sulpho methylester of C18 fatty acid
APA : Cg_1 p amido propyl dimethyl amine.
Soap : Sodium linear alkyl carboxylate derived from a 80/20
mixture of tallow and coconut fatty acids.
STS : Sodium toluene sulphonate.
TFAA : C16-C1 g alkyl N-methyl glucamide.
TPKFA : C12-C14 topped whole cut fatty acids.
DEQA : Di-(tallow-oxy-ethyl) dimethyl ammonium chloride.
DEQA (2) : Di-(soft-tallowyloxyethyl) hydroxyethyl methyl ammonium
methylsulfate.
SDASA : 1:2 ratio of stearyldimethyl amineariple-pressed stearic
acid.
DTMAMS : Ditallow dimethyl ammonium methylsulfate.
Silicate : Amorphous Sodium Silicate (Si02:Na20 ratio = 1.6-3.2:1 ).
Metasilicate : Sodium metasilicate (Si02:Na20 ratio = 1.0).
Zeolite A : Hydrated Sodium Aluminosilicate of formula
Nal2(A102Si02)12- 27H20 having a primary particle
size
in the range from 0.1 to 10 micrometers (Weight
expressed
on an anhydrous basis).
SKS-6 : Crystalline layered silicate of formula -Na2Si205.
Citrate : Tri-sodium citrate dihydrate.
Citric : Anhydrous citric acid.
Carbonate : Anhydrous sodium carbonate.
Bicarbonate : Sodium hydrogen carbonate.
Sulphate : Anhydrous sodium sulphate.
Mg Sulphate : Anhydrous magnesium sulfate.
STPP : Sodium tripolyphosphate.
TSPP : Tetrasodium pyrophosphate.
MA/AA : Random copolymer of 4:1 acrylate/maleate, average
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
molecular weight about 70,000-80,000.
MA/AA 1 : Random copolymer of 6:4 acrylate/maleate,
average
molecular weight about 10,000.
AA : Sodium polyacrylate polymer of average molecular
weight
4,500.
Polycarboxylate: Copolymer comprising mixture of carboxylated
monomers
such as acrylate, maleate and methyacrylate
with a MW
ranging between 2,000-80,000 such as Sokolan
commercially available from BASF, being a copolymer
of
acrylic acid, MW4,500.
PB1 : Anhydrous sodium perborate monohydrate.
PB4 : Sodium perborate tetrahydrate of nominal formula
NaB03.4H20.
Percarbonate : Anhydrous sodium percarbonate of nominal formula
Na2C03.3H202 .
NaDCC : Sodium dichloroisocyanurate.
TAED : Tetraacetyl ethylene diamine.
NOBS : Nonanoyloxybenzene sulfonate in the form of
the sodium
salt.
NACA-OBS : (6-nonamidocaproyl) oxybenzene sulfonate.
LOBS : Dodecanoyloxybenzene sulfonate in the form
of the Na
salt.
DOBA : Dodecanoylbenzoic acid
DTPA : Diethylene triamine pentaacetic acid.
HEDP : 1,1-hydroxyethane diphosphonic acid.
DETPMP : Diethyltriamine penta (methylene) phosphonate,
marketed
by Monsanto under the Trade name bequest 2060.
EDDS : Ethylenediamine-N,N'-disuccinic acid, (S,S)
isomer in the
form of its sodium salt
MnTACN : Manganese 1,4,7-trimethyl-1,4,7-triazacyclononane.
Photoactivated: Sulfonated zinc or alumino phtalocyanine encapsulated
in
CA 02379200 2002-O1-16
WO 01/05919 56 PCT/US00/19369
Bleach dextrin soluble polymer.
PAAC : Pentaamine acetate cobalt(///) salt.
Paraffin : Paraffin oil sold under the tradename Winog
70 by
Wintershall.
NaBz : Sodium benzoate.
Protease : Proteolytic enzyme sold under the tradename
Savinase,
Alcalase by Novo Nordisk A/S, the "protease D"
variant with
the substitution set N76D/S103A/V1041 and the
protease
described in PCT application Nos. PCT/US98/22588,
PCT/US98/22482 and PCT/US98/22486 with the amino
acid substitution set
101 G/103A/1041/159D/232V/236HI245R/248D/252K.
Amylase : Amylolytic enzyme sold under the tradename
Termamyl
and Duramyl~ available from Novo Nordisk A/S
and those
variants having improved thermal stability with
amino acid
deletions R181* + G182* or T183* + G184* as described
in
W095/35382.
Lipase : Lipolytic enzyme sold under the tradename Lipolase,
Lipolase Ultra by Novo Nordisk A/S and Lipomax
by Gist-
Brocades.
Cellulase : Cellulytic enzyme sold under the tradename
Carezyme,
Celluzyme and/or Endolase by Novo Nordisk A/S.
CMC : Sodium carboxymethyl cellulose.
PVP : Polyvinyl polymer, with an average molecular
weight of
60,000.
PVNO : Polyvinylpyridine-N-Oxide, with an average
molecular
weight of 50,000.
PVPVI : Copolymer of vinylimidazole and vinylpyrrolidone,
with an
average molecular weight of 20,000.
Brightener : Disodium 4,4'-bis(2-sulphostyryl)biphenyl.
1
Brightener : Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl)
2
CA 02379200 2002-O1-16
WO 01/05919 5~ PCT/US00/19369
stilbene-2:2'-disulfonate.
Brightener : Disodium 4,4'bis (4,6-dianilino-1,3,5-triazin-2-yl)amino
3
stilbene-2-2'-disulfonate.
Silicone : Polydimethylsiloxane foam controller with siloxane-
antifoam oxyalkylene copolymer as dispersing agent with
a ratio of
said foam controller to said dispersing agent
of 10:1 to
100:1.
Suds : 12% Silicone/silica, 18% stearyl alcoho1,70%
starch in
Suppressor granular form.
Thickener : High molecular weight crosslinked polyacrylates
such as
Carbopol offered by B.F. Goodrich Chemical Company
and
Polygel.
SRP 1 : Anionically end capped poly esters.
SRP 2 : Soil Release Polymer selected from 1 ) Non-cotton
soil
release polymer according to U.S. Patent 5,415,807,
Gosselink, Pan, Kellett and Hall, issued May 16,
1995 or
and/or from 2) Non-cotton soil release polymer
according to
US application no.60/051517.
QEA : bis((C2H50)(C2H40)n)(CH3) -N+-C6H12-N+-(CH3)
bis((C2H50)-(C2H40))n, wherein n = from 20 to
30.
PEI : Polyethyleneimine with an average molecular
weight of
between 600-1800 and an average ethoxylation degree
of
7-20 ethyleneoxy residues per nitrogen.
SCS : Sodium cumene sulphonate.
HMWPEO : High molecular weight polyethylene oxide.
PEG X : Polyethylene glycol, of a molecular weight of
X
PEO : Polyethylene oxide, with an average molecular
weight of
5,000.
TEPAE : Tetreaethylenepentaamine ethoxylate.
BTA : Benzotriazole.
pH : Measured as a 1 % solution in distilled water
at 20C.
CA 02379200 2002-O1-16
WO 01/05919 58 PCT/US00/19369
Example 1
The following granular laundry detergent compositions were
prepared according to the present invention
I II III IV V
Sprav-dried Granules
LAS 10.0 10.0 15.0 5.0 5.0
TAS - 1.0 - - -
M BAS - - - 5.0 5.0
C45AS - - 1.0 - 2.0
C45AE3S _ _ - 1.0 -
QAS - - 1.0 1.0 -
DTPA, HEDP and/or 0.3 0.3 0.5 0.3 -
EDDS
Mg Sulfate 0.5 0.5 0.1 -
Citrate - - - 3.0 5.0
Carbonate 10.0 7.0 15.0 - -
Sulphate 5.0 5.0 - - 5.0
Silicate - - - - 2.0
Zeolite A 16.0 18.0 20.0 20.0 -
SKS-6 - - - 3.0 5.0
MA/AA or AA 1.0 2.0 11.0 - -
PEG 4000 - 2.0 - 1.0 -
QEA 1.0 - - - 1.0
Brightener 1 or 2 0.05 0.05 0.05 - 0.05
or 3
Silicone oil 0.01 0.01 0.01 - -
Aqglomerate
Carbonate - - - - 4.0
SKS-6 6.0 - - - 6.0
LAS 4.0 5.0 - - 5.0
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
59
Dr~add particulate
components
Malefic acid / carbonate8.0 10.0 10.0 4.0 -
/
bicarbonate (40:20:40)
QEA - - - 0.2 0.5
NACA-OBS 3.0 - - 4.5 -
NOBS 1.0 3.0 3.0 - -
TAED 2.5 - - 1.5 2.5
MBAS - - - 8.0 -
LAS (flake) 10.0 10.0 - - -
Spra r~-on
Brightener 1 or 2 0.2 0.2 0.3 0.1 0.2
or 3
Perfume A 1.0 0.5 1.1 0.8 0.3
~r~add
Citrate - - 20.0 4.0 -
Percarbonate 15.0 3.0 6.0 10.0 -
Perborate - - - - 6.0
Photoactivated bleach0.02 0.02 0.02 0.1 0.05
Enzymes (cellulase, 0.04 0.01 0.02 0.02 0.05
amylase, protease
and/or lipase)
Carbonate 0.0 10.0 - - -
Perfume - 0.5 0.5 - 0.3
A(encapsulated )
Suds suppressor 1.0 0.6 0.3 - 0.10
Soap 0.5 0.2 0.3 3.0 0.5
Citric - - - 6.0 6.0
SKS-6 - - - 4.0 -
Fillers up to 100%
Example 2
CA 02379200 2002-O1-16
WO 01/05919 6~ PCT/US00/19369
The following granular laundry detergent compositions were
prepared according to the present invention
I II 111 IV
Blown powder
MES 2.0 0.5 1.0 -
SADS - - - 2.0
LAS 6.0 5.0 11.0 6.0
TAS 2.0 - - 2.0
Zeolite A 24.0 - - 20.0
STPP - 27.0 24.0 -
Sulfate 4.0 6.0 13.0 -
MA/AA 1.0 4.0 6.0 2.0
Silicate 1.0 7.0 3.0 3.0
CMC 1.0 1.0 0.5 0.6
Brightener 1 0.2 0.2 0.2 0.2
Silicone antifoam 1.0 1.0 1.0 0.3
DTPMP 0.4 0.4 0.2 0.4
Spray on
Brightener 1 or 0.02 - - 0.02
2 or 3
C45E7 - - - 5.0
C45E2 2.5 2.5 2.0 -
C45E3 2.6 2.5 2.0
Perfume B 0.5 0.3 0.5 0.2
Silicone antifoam 0.3 0.3 0.3 -
Dry additives
QEA - - - 1.0
EDDS 0.3 - - -
Sulfate 2.0 3.0 5.0 10.0
Carbonate 6.0 13.0 15.0 14.0
Citric 2.5 - - 2.0
QAS 0.5 - - 0.5
CA 02379200 2002-O1-16
WO 01/05919 6~ PCT/US00/19369
SKS-6 10.0 - - -
Percarbonate 4.0 3.0 - 1.9
PB4 - - -
NOBS 0.5 - - 0.3
TAED 0.75 4.5 - 0.5
Clay - - 10.0 -
Protease 0.03 0.03 0.03 0.03
Lipase 0.008 0.008 0.008 0.004
Amylase 0.003 - 0.003 0.006
Brightener 1 0.05 - - 0.05
Misc/mi
nor and
speckle
s
Example 3
The following granular laundry detergent compositions were
prepared according to the invention
I II III IV V VI
Blown powder
LAS 23.0 8.0 7.0 9.0 7.0 7.0
QAS - - - - 1.0 -
C45AS 6.0 6.0 5.0 8.0 - -
C45AE 11 - 1.0 1.0 1.0 - -
S
MES 2.0 - - - 2.0 4.0
Zeolite 10.0 18.0 14.0 12.0 10.0 10.0
A
MA/AA - 0.5 - _ _ 2.0
MA/AA 1 7.0 - - - - -
AA - 3.0 3.0 2.0 3.0 3.0
Sulfate 5.0 6.3 11.1 11.0 11.0 18.1
CA 02379200 2002-O1-16
WO 01/05919 g2 PCT/US00/19369
Silicate 10.0 1.0 1.0 1.0 1.0 1.0
Carbonate 15.0 20.0 10.0 20.7 8.0 6.0
PEG 4000 0.4 1.5 1.5 1.0 1.0 1.0
DTPA - 0.9 0.5 - - 0.5
Brightener 0.3 0.2 0.3 - 0.1 0.3
2
Spray on
C45E7 - 2.0 - - 2.0 2.0
C25E9 3.0 - - - - -
C23E9 - - 1.5 2.0 - 2.0
Perfume C 0.3 0.3 0.3 2.0 0.3 0.3
Agglomerates
C45AS - 5.0 5.0 2.0 - 5.0
LAS - 2.0 2.0 - - 2.0
Zeolite A - 7.5 7.5 8.0 - 7.5
Carbonate - 4.0 4.0 5.0 - 4.0
PEG 4000 - 0.5 0.5 - - 0.5
Misc (water - 2.0 2.0 2.0 - 2.0
etc)
Dry additives
QAS I - - - - 1.0 -
Citric - - - - 2.0 -
PB4 _ _ _ _ 5 _
PB1 - - 4 1.0 - -
Percarbonate 2.0 - - 1.0 - 2.0
Carbonate - 5.3 1.8 - 4.0 4.0
NOBS 0.5 - 0.4 0.3 - -
Clay - - - - - 10.0
TAED 0.6 0.4 0.6 0.3 0.9 -
Methyl 0.2 - - - - 0.5
cellulose
DTPA 0.7 0.5 1.0 0.5 0.5 1.2
CA 02379200 2002-O1-16
WO 01/05919 63 PCT/US00/19369
speckle - - - 0.2. 0.5 -
SKS-6 8.0 - - - - -
STS - - 2.0 - 1.0 -
Cumene - 1.0 - - - 2.0
sulfonic acid
Lipase 0.004 - 0.004 - 0.004 0.008
Cellulase 0.000 0.000 0.0005 0.0007 0.000 0.000
5 5 5 5
Amylase 0.003 - 0.001 - 0.003 -
Protease 0.01 0.015 0.015 0.009 0.01 0.01
PVPVI - - - - 0.5 0.1
PVP - - - - 0.5 -
PVNO - - 0.5 0.3 - -
QEA - - - - 1.0 -
SRP1 0.2 0.5 0.3 - 0.2 -
Silicone 0.2 0.4 0.2 0.4 0.1 -
antifoam
Mg sulfate - - 0.2 - 0.2 -
Misc/minors
up
to 100%
Example 4
The following granular laundry detergent compositions were
prepared according to the present invention:
I II III IV
Base granule
STPP - 22.0 - 15.0
Zeolite A 30.0 - 24.0 5.0
Sulfate 5.5 5.0 7.0 7.0
MA/AA 3.0 - - -
CA 02379200 2002-O1-16
WO 01/05919 64 PCT/US00/19369
,o,A - 1.6 2.0 -
MA/AA 1 - 12.0 - 6.0
LAS 14.0 10.0 9.0 20.0
C45AS 8.0 7.0 9.0 7.0
C45AE11 S - 1.0 - 1.0
MES 0.5 4.0 6.0
SADS 2.5 - - 1.0
Silicate - 1.0 0.5 10.0
Soap - 2.0 - -
Brightener 0.2 0.2 0.2 0.2
1
Carbonate 6.0 9.0 8.0 10.0
PEG 4000 - 1.0 1.5 -
DTPA - 0.4 - -
Spray on
C25E9 - - - 5.0
C45E7 1.0 1.0 - -
C23E9 - 1.0 2.5 -
Perfume D 0.2 0.3 0.3 0.3
Dry additives
Carbonate 5.0 10.0 13.0 8.0
PVPVI/PVNO 0.5 - 0.3 -
Protease 0.03 0.03 0.03 0.015
Lipase 0.008 - - 0.008
Amylase 0.002 - - 0.002
Cellulase 0.0002 0.0005 0.0005 0.0003
DTPA 0.5 0.3 0.5 1.0
LOBS - 0.8 - 0.3
PB1 5 3.0 10 4.0
DOBA 1.0 - 0.4 -
TAED 0.5 0.3 0.5 0.6
Sulfate 4.0 5.0 - 5.0
CA 02379200 2002-O1-16
WO 01/05919 65 PCT/US00/19369
SRP 1 - 0.4 - -
Suds supressor - 0.5 - -
speckle 09 - 2.7 1.2
Misc/minor to
100% -
Example 5
The following granular laundrydetergent ns wereprepared
compositio
according to the present
invention
I II III IV IV V VI
C 13 LAS 12.0 16.0 23.0 19.0 18.0 20.016.0
C45 AS 4.5 - - - 4.0
C45AE (3)S - - 2.0 - 1.0 1.0 1.0
C45 AE (3.0) 2.0 2.0 - 1.3 - - 0.6
C9-C14 alkyl dimethyl - - 1.0 0.5 2.0
hydroxy ethyl quaternary
ammonium salt
Tallow fatty acid - - - - - - 1.0
STPP 23.0 25.0 24.0 22,0 20.0 15.020.0
Carbonate 15.0 12.0 15.0 10.0 13.0 11.010.0
AA 0.5 0.5 0.5 0.5 - - -
Mp/qq - - 1.0 1.0 1.0 2.0 0.5
Silicate 3.0 6.0 9.0 8.0 9.0 6.0 8.0
Sulfate 25.0 18.0 20.0 18.0 20.0 22.013.0
Sodium perborate 5.0 5.0 10.0 8.0 3.0 1.0 2.0
PEG 4000 1.5 1.5 1.0 1.0 - - 0.5
CMC 1.0 1.0 1.0 - 0.5 0.5 0.5
Citric - - - - - - -
NOBS/ DOBS 0.5 1.0 0.5 0.5 1.0 0.7 0.3
TAED 1.5 1.0 2.5 3.0 0.3 0.2 0.5
CA 02379200 2002-O1-16
WO 01/05919 66 PCT/US00/19369
SRP 2 1.5 1.5 1.0 1.0 1.0 1.0 1.0
Moisture 7.5 7.5 6.0 7.0 5.0 3.0 5.0
Mg _ - - - 1.0 0.5 1.5
DTPA, HEDP and/or - - - - 0.8 0.6 1.0
EDDS
Enzymes (amylase, - - - - 0.05 0.04 0.05
cellulase and/or
protease)
Perfume E 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Minors, e.g. Brightener,Up
photo-bleach, specklesto
100
Example 6
The following granular laundry detergent ositionswere
comp
s prepared according to the present
invention:
I II III IV
C13 LAS 13.3 13.7 10.4 8.0
C45 AS 3.9 4.0 4.5 -
C45 AE (0.5)S 2.0 2.0 -
C45 AE (6.5) 0.5 0.5 0.5 5.0
C9-C14 alkyl dimethyl hydroxy ethyl 1.0 - - 0.5
quaternary ammonium salt
Tallow fatty acid 0.5 - - -
Tallow alcohol ethoxylate (50) - - 1.0 0.3
STPP - 41.0 - 20.0
Zeolite A 26.3 - 21.3 1.0
Carbonate 23.9 12.4 25.2 17.0
qq 3.4 0.0 2.7 -
M,c~p~,~ - - 1.0 1.5
CA 02379200 2002-O1-16
WO 01/05919 6~ PCT/US00/19369
Silicate 2.4 6.4 2.1 6.0
Sulfate 10.5 10.9 8.2 15.0
Sodium perborate 1.0 1.0 1.0 2.0
PEG 4000 1.7 0.4 1.0 -
CMC 1.0 - - 0.3
Citric - - 3.0 -
NOBS/ DOBS 0.2 0.5 0.5 0.1
TAED 0.6 0.5 0.4 0.3
SRP 2 1.5 1.5 1.0 1.0
Moisture 7.5 3.1 6.1 7.3
Mg sulphate - - - 1.0
DTPA, HEDP and/or EDDS - - - 0.5
Enzymes (amylase, cellulase, - 0.025 - 0.04
protease
and/or lipase)
Perfume F 0.2 0.2 0.2 0.2
Misc / Minors including brightener,Up to
photo-bleach 100%
Example 7
The following laundry detergent compositions in the form of a
tablet or granular formulation were prepared according to the
present invention
I II III IV V VI
C13 LAS 20.0 16.0 8.5 5 20.0 6.0
C45 AS - 4.0 - _ _
C45 AE(3)S 1.0 1.0 - - -
C45 AE - 5.0 5.5 4.0 -
C9-C14 alkyl dimethyl hydroxy 0.5 2.0 - - -
ethyl quaternary ammonium
salt
CA 02379200 2002-O1-16
WO 01/05919 68 PCT/US00/19369
Tallow fatty acid - 1.0 - - - -
STPP / Zeolite 10.0 20.0 30.0 20.0 25.0 25.0
Carbonate 41.0 30.0 30.0 25.0 45.0 24.0
_ _ _ _ _ _
MA/AA 2.0 0.5 0.5 1.0 -
Silicate 6.0 8.0 5.0 6.0 8.0 5.0
Sulfate 2.0 3.0 - - - 8.0
Sodium perborate/ 1.0 - 20.0 14.0 - -
percarbonate
PEG 4000 - 0.5 - - - 0.5
CMC 0.5 0.5 0.5 0.5 - 0.5
Citric - - - - - -
NOBS/ DOBS 0.7 - - - -
TAED / Preformed peracid0.7 - 4.5 5.0 - -
DTPA, HEDP and/or EDDS - - 0.5 0.5 -
SRP 1.0 - 1.0 1.0 - -
Clay 4.0 3.0 7.0 1 0.0 6.0 8.0
PEO 1.0 0.5 2.0 0.5 1.0 0.5
Humectant 0.5 - - 0.5 - -
wax 0.5 - - 0.5 - -
Cellulose 2.0 - - 1.5 - 1.0
Sodium acetate - - 1.0 0.5 4.0 1.0
Moisture 3.0 5.0 5.0 5.0 8.0 10.0
Mg sulphate 0.5 1.5 - - - -
Soap/ suds suppressor 0.6 1.0 1.0 0.8 0.5
Enzymes (amylase, cellulase,0.04 0.04 0.01 0.02 0.02 0.03
protease and/or lipase)
Perfume E 0.2 0.2 0.2 0.2 0.2 0.2
Minors, e.g. PVP, Up
to
PVPVI/PVNO, brightener, 100%
photo-bleach, speckles,...
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
69
Example 8
The following laundry detergent were prepared
compositions
according to the present invention
I II III IV V
C 13 LAS 12.0 16.0 23.0 19.0 18.0
C45 AS - 4.5 - - -
C45 AE(3)S - - 2.0 - 1.0
C45 AE 2.0 2.0 - 1.3 -
C9-C14 alkyl dimethyl hydroxy - - - - 1.0
ethyl
quaternary ammonium salt
STPP / Zeolite 23.0 25.0 14.0 22,0 20.0
Carbonate 25.0 22.0 35.0 20.0 28.0
0.5 0.5 0.5 0.5 -
M~~ _ - 1.0 1.0 1.0
Silicate 3.0 6.0 9.0 8.0 9.0
Sodium perborate/ percarbonate5.0 5.0 10.0 - 3.0
PEG 4000 1.5 1.5 1.0 1.0 -
CMC 1.0 1.0 1.0 - 0.5
NOBS/ DOBS - 1.0 - - 1.0
TAED / Preformed peracid 1.5 1.0 2.5 - 3.0
DTPA, HEDP and/or EDDS 0.5 0.5 0.5 - 1.0
SRP 1.5 1.5 1.0 1.0
Clay 5.0 6.0 12.0 7.0 10.0
Flocculating agent PEO 0.2 0.2 3.0 2.0 0.1
- - - 0.5
Humectant -
wax 0.5 - - - _
Cellulose 0.5 2.0 - - 3.0
Sodium acetate 2.0 1.0 3.0 - -
Moisture 7.5 7.5 6.0 7.0 5.0
Soap/ suds suppressor - - 0.5 0.5 0.8
Enzymes (amylase, cellulase, - - - - 0.045
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
protease and/or lipase)
Perfume D 0.2 0.2 0.2 0.2 0.2
Misc / Minors, e.g. PVP, Up to
PVPVI/PVNO, speckles, brightener, 100%
photo-bleach, . . .
Example 9
The following liquid were
laundry detergent prepared
compositions
5 according to the
present invention
I II III IV V VI
LAS - - - 1.0 2.0 -
C25AS 16.0 13.0 14.0 5.0 - 6.5
C25AE3S 5.0 1.0 - 10.0 19.0 3.0
C25E7 2.0 3.5 - 2.5 2.0 5.0
TFAA 5.0 4.5 4.5 6.5 4.0 -
APA 2.0 1.0 - 3.0 - 0.5
QAS - - 2.0 - 1.5 -
TPKFA 4.5 8.0 15.0 - 5.0 5.0
Citric 2.2 3.0 - 0.5 1.0 2.0
Rapeseed fatty acid 2.0 - - 3.0 6.0 1.5
Ethanol 3.2 2.0 2.5 2.2 - 0.5
1,2 Propandiol 5.7 8.5 6.5 7.0 7.0 5.5
Monoethanolamine 5.0 7.5 - 5.0 1.0 2.0
TEPAE - 1.2 - 0.5 0.5 -
PE12 - 1.5 - 1.0 0.8 -
DTPMP 1.3 0.5 0.8 0.5 - 0.2
HEDP - 0.5 0.2 1.0 - -
Protease 0.02 0.03 0.02 0.02 0.02 0.01
Lipase 0.002 0.001 0.001 - 0.001
Amylase .0008 .0006 .0006 0.002 0.001 0.001
CA 02379200 2002-O1-16
WO 01/05919 7~ PCT/US00/19369
Cellulase 0.002 0.002 - 0.002 0.001 -
SRP1 0.20 0.15 0.10 - 0.17 0.04
PVNO - - - 0.05 0.10 -
Brightener 3 0.20 0.15 0.10 0.05 - 0.05
Suds Suppressor 0.25 0.20 0.15 0.15 0.30 0.10
Calcium Chloride 0.02 0.02 - 0.01 0.01 -
Boric acid 2.5 2.0 1.5 2.2 1.5 1.2
Bentonite Clay - - 5.5 - - -
NaOH to pH 8.0 7.5 7.7 8.0 7.0 7.5
Water/minors to
100%
Example 10
The following non-aqueous liquid detergent compositions were
prepared in accordance with the present invention
I II III
LAS 16.0 16.0 16.0
C23 E05S 21.5 21.5 19.0
Butoxy Propoxy Propanol 18.5 - 16.0
Hexylene Glycol - 18.5 5.0
Sodium citrate dihydrate 6.8 6.8 3.8
[4-[N-nonanoyl-6-aminohexanoyloxy]6.0 6.0 6.0
benzene sulfonate] Na salt
Methyl sulfate salt of methyl quaternized1.3 1.3 1.3
polyethoxylated hexamethylene diamine
EDDS 1.2 1.2 1.2
MA/AA - - 3.0
Sodium Carbonate 10.0 10.0 10.0
Protease 0.05 0.02 0.02
Amylase 0.01 0.01 0.01
Cellulase 0.0001 0.0001 0.0001
CA 02379200 2002-O1-16
WO 01/05919 ~ 72 PCT/US00/19369
PB1 12.0 12.0 12.0
Silicone antifoam 0.75 0.75 1.1
Perfume C 1.7 1.7 1.7
Titanium Dioxide 0.5 0.5 0.5
Dichloro -5,12-Dimethyl-1,5,8,12- - 0.03 0.03
tetraazabicyclo [6.6.2] hexadecane
Manganese (II)
Brightener 2 0.2 0.2 0.2
Sodium hydrogenated C16-18 fatty 1 1 0.5
soap
Colored Speckles 0.4 0.4 0.4
Miscellaneous up to 100%
CA 02379200 2002-O1-16
WO 01/05919 73 PCT/US00/19369
Example 11
The following laundry detergent compositions in the form of a tablet were
prepared according to the present invention
i) a detergent base powder of composition I was prepared as follows: all the
particulate material of base composition I were mixed together in a mixing
drum
to form a homogenous particulate mixture. During this mixing, the spray-ons
were carried out.
ii) Tablets were then made the following way: 50g of the matrix was
introduced into a mould of circular shape with a diameter of 5.5 cm, and
~o compressed to give a tablet tensile strength (or diametrical fracture
stress) of
10kPa.
iii) The tablets were then dipped in a bath comprising 90 parts of sebacic
acid and 10 parts per weight of Nymcel-ZSB16T"~ by Metsa Serla at 140
°C.
The time the tablet was dipped in the heated bath was adjusted to allow
~5 application of 4g of the bath mixture. The tablet was then left to cool at
ambient
temperature of 25°C for 24 hours. The tensile strength of the coated
tablet was
increased to a tensile strength of 30 kPa.
I
Anionic agglomerates 1 (40% anionic, 27% zeolite and 33% 21.5
carbonate)
Anionic agglomerates 2 (40% anionic, 28% zeolite and 32% 13.0
carbonate)
Cationic agglomerates (20% cationic, 56% zeolite and 24% sulphate) 5.5
Layered silicate (95% SKS 6 and 5% silicate) 10.8
Sodium percarbonate 14.2
Bleach activator agglomerates (81 % TAED, 17% acrylic/maleic 5.5
copolymer (acid form) and 2% water)
Carbonate 10.98
EDDS/Suiphate particle (58% of EDDS, 23% of sulphate and 19% 0.5
water)
CA 02379200 2002-O1-16
WO 01/05919 74 PCT/US00/19369
HEDP 0.8
SRP 0.3
Fluorescer 0.2
Photoactivated bleach (Zinc phthalocyanine sulphonate 10% active) 0.02
Soap powder 1.4
Suds suppressor (11.5% silicone oil; 59% of zeolite and 29.5% of 1.9
water)
Citric 7.1
Protease 0.03
Lipase 0.006
Cellulase 0.0005
Amylase 0.02
Binder spray-on system (25% of Lutensit K-HD 96;75% by weight of 4.0
PEG)
Example 12
The following laundry bar detergent compositionsprepared
were
according to the present invention (Levels parts
are given in per
weight, enzyme are expressed in pure enzyme)
I II III IV V VI VII VIII
LAS - - 19.0 15.0 21.0 6.75 8.8 -
C28AS 30.0 13.5 - - - 15.75 11.2 22.5
Na Laurate 2.5 9.0 - - - - - -
Zeolite A 2.0 1.25 - - - 1.25 1.25 1.25
Carbonate 20.0 3.0 13.0 8.0 10.0 15.0 15.0 10.0
Ca 27.5 39.0 35.0 - - 40.0 - 40.0
Carbonate
Sulfate 5.0 5.0 3.0 5.0 3.0 - - 5.0
TSPP 5.0 - - - - 5.0 2.5 -
STPP 5.0 15.0 10.0 - - 7.0 8.0 10.0
CA 02379200 2002-O1-16
WO 01/05919 ~5 PCT/US00/19369
Bentonite - 10.0 - - 5.0 - - -
clay
DETPMP - 0.7 0.6 - 0.6 0.7 0.7 0.7
CMC - 1.0 1.0 1.0 1.0 - - 1.0
Talc - - 10.0 15.0 10.0 - - -
Silicate - - 4.0 5.0 3.0 - - -
PVNO 0.02 0.03 - 0.01 - 0.02 - -
MA/AA 0.4 1.0 - - 0.2 0.4 0.5 0.4
SRP 1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
Amylase - - 0.01 - - - 0.002 -
Protease - 0.004 - 0.003 0.003 - - 0.003
Lipase - 0.002 - 0.002 - - - -
Cellulase - .0003 - - .0003 .0002 - -
PEO - 0.2 - 0.2 0.3 - - 0.3
Perfume 1.0 0.5 0.3 0.2 0.4 0.4 0.4 0.4
E
Mg sulfate - - 3.0 3.0 3.0 - - -
Brightener 0.15 0.1 0.15 - - - - 0.1
Photoactivat- 15.0 15.0 15.0 15.0 - - 15.0
ed bleach
~Ppm)
Example 13
The following granular fabric detergent compositions which provide "softening
through the wash" capability were prepared according to the present invention
I II
C45AS - 10.0
LAS 7.6 -
C68AS 1.3 -
C45E7 4.0 -
C25E3 - 5.0
CA 02379200 2002-O1-16
WO 01/05919 76 PCT/US00/19369
Coco-alkyl-dimethyl hydroxy- 1.4 1.0
ethyl ammonium chloride
Citrate 5.0 3.0
Na-SKS-6 - 11.0
Zeolite A 15.0 15.0
M,n,~,4p, 4.0 4.0
DETPMP 0.4 0.4
PB 1 15.0 -
Percarbonate - 15.0
TAED 5.0 5.0
Smectite clay 10.0 10.0
HMWPEO - 0.1
Protease 0.02 0.01
Lipase 0.02 0.01
Amylase 0.03 0.005
Cellulase 0.001 -
Silicate 3.0 5.0
Carbonate 10.0 10.0
Suds suppressor 1.0 4.0
CMC 0.2 0.1
Miscellaneous.and
minors
Up to 100%
CA 02379200 2002-O1-16
WO 01/05919 7~ PCT/US00/19369
Example 14
The following rinse added
fabric softener composition
was prepared according
to the present invention
DEQA (2) 20.0
Cellulase 0.001
HCL 0.03
Antifoam agent 0.01
Blue dye 25ppm
CaCl2 0.20
Perfume E 0.90
Miscellaneous and water Up to 100%
Example 15
The following fabric softener and dryer added fabric conditioner
compositions were prepared according to the present invention
I II III IV V
DEQA 2.6 19.0 - - -
DEQA(2) - - - - 52.0
DTMAMS - - - 26.0 -
S DASA - - 70.0 42.0 40.2
Stearic acid of 0.3 - - - -
IV=0
C45E01-3 - - 13.0 - -
HCL 0.02 0.02 - - -
Ethanol - - 1.0 -
Perfume F 0.3 1.0 0.75 1.0 1.5
Glycoperse S-20 - - - - 15.4
Glycerol - - - 26.0 -
monostearate
Digeranyl Succinate- - 0.38 - -
Silicone antifoam0.01 0.01 - - -
CA 02379200 2002-O1-16
WO 01/05919 7$ PCT/US00/19369
Electrolyte - 0.1 - - -
Clay - - - 3.0 -
Dye 10ppm 25ppm 0.01 - -
Water and minors 100% 100% - - -
Example 16
s The followingcompact high den sity Kg/I) detergent
(0.96 dishwashing
compositions on
were prepared
according to
the present
inventi
I II III IV V VI
STPP - 51.0 51.0 - - 44.3
Citrate 17.0 - - 50.0 40.2 -
Carbonate 17.5 14.0 20.0 - 8.0 33.6
Bicarbonate - - - 26.0 - -
Silicate 15.0 15.0 8.0 - 25.0 3.6
Metasilicate 2.5 4.5 4.5 - - -
PB1 10.0 8.0 8.0 - - -
PB4 - - - 10.0 -
Percarbonat - - - - 11.8 4.8
a
Nonionic 2.0 1.5 1.5 3.0 1.9 5.9
TAED 2.0 - - 4.0 - 1.4
HEDP 1.0 - - - - -
DETPMP 0.6 - - - - -
MnTACN - - - - 0.01 -
PAAC - 0.01 0.01 - - -
Paraffin 0.5 0.4 0.4 0.6 - -
Protease 0.07 0.05 0.05 0.03 0.06 0.01
Lipase - 0.001 - 0.005 - -
BTA 0.3 0.2 0.2 0.3 0.3 0.3
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
79
Polycarboxyl 6.0 - - - 4.0 0.9
ate
Perfume B 0.2 0.1 0.1 0.2 0.2 0.2
pH 11.0 11.0 11.3 9.6 10.8 10.9
Miscellaneous, sulfate and water Up to 100%
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
Example 17
The following granular dishwashing detergent compositions of bulk
density 1.02Kg/L were prepared according to the present invention
I II III IV V VI
STPP 30.0 33.5 27.9 29.6 33.8 22.0
Carbonate 30.5 30.5 30.5 23.0 34.5 45.0
Silicate 7.0 7.5 12.6 13.3 3.2 6.2
Metasilicate- 4.5 - - - -
Percarbonate- - - - 4.0 -
PB1 4.4 4.5 4.3 - - -
NADCC - - - 2~0 -
Nonionic 1.0 0.7 1.0 1.9 0.7 0.5
TAED 1.0 - - - 0~9 -
PAAC - 0.004 - - - -
Paraffin 0.25 0.25 - - - -
Protease 0.036 0.021 0.03 - 0.006 -
Amylase 0.03 0.005 0.004 - 0.005 -
Lipase 0.005 - 0.001 - - -
BTA 0.15 0.15 - - 0.2 -
Perfume A 0.2 0.2 0.05 0.1 0.2 0.2
pH 10.8 11.3 11.0 10.7 11.5 10.9
Miscellaneous, sulfate and water Up to 100%
5
Example 18
The following tablet detergent compositions were prepared according to the
present invention by compression of a granular dishwashing detergent
composition at a pressure of 13KN/cm2 using a standard 12 head rotary press:
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
81
I II III IV V VI VII VIII
STPP - 48.8 54.7 38.2 - 52.4 56.1 36.0
Citrate 20.0 - - - 35.9 - - -
Carbonate 20.0 5.0 14.0 15.4 8.0 23.0 20.0 28.0
Silicate 15.0 14.8 15.0 12.6 23.4 2.9 4.3 4.2
Protease 0.042 0.072 0.042 0.031 0.052 0.023 0.023 0.029
Amylase 0.012 0.012 0.012 0.007 0.015 0.003 0.017 0.002
Lipase 0.005 - - - - - - -
PB1 14.3 7.8 11.7 12.2 - - 6.7 8.5
PB4 _ _ _ - 22.8 - 3.4 -
Percarbonate- - - - - 10.4 -
Nonionic 1.5 2.0 2.0 2.2 1.0 4.2 4.0 6.5
PAAC - - 0.02 0.009 - - _ _
MnTACN - - - - 0.007 - - -
TAED 2.7 2.4 - - - 2.1 0.7 1.6
HEDP 1.0 - - 0.9 - 0.4 0.2 -
DETPMP 0.7 - - - - - - -
Paraffin 0.4 0.5 0.5 0.5 - - 0.5 -
BTA 0.2 0.3 0.3 0.3 0.3 0.3 0.3 -
Polycarboxyla4.0 - - - 4.9 0.6 0.8 -
te
PEG 4,000- - - - - - 2.0 - . 2.0
30,000
Glycerol - - - - - 0.4 - 0.5
Perfume C 0.2 0.2 0.2 0.05 0.2 0.2 0.2 0.2
Weight of 20g 25g 20g 30g 18g 20g 25g 24g
tablet
pH 10.7 10.6 10.7 10.7 10.9 11.2 11.0 10.8
Miscellaneous, sulfate and water Up to 100%
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
82
Example 19
The following liquid dishwashing detergent compositions of density 1.40Kg/L
were prepared according to the present invention
I II III IV
STPP 17.5 17.2 23.2 23.1
Carbonate - 2.4 - -
Silicate 6.1 24.9 30.7 22.4
NaOCI 1.1 1.1 1.1 1.2
Thickener 1.0 1.1 1.1 1.0
Nonionic - 0.1 0.06 0.1
NaBz 0.7 - - -
NaOH 1.9 - -
KOH 3.6 3.0 -
Perfume D 0.05 0.1 0.05 0.05
pH 11.7 10.9 10.8 11.0
Water up to 100%
Example 20
The following dishwashing compositions in the tablet form were prepared
according to the present invention (Levels are indicated in g):
I II III IV V VI
Phase 1
STPP 9.6 9.6 10.4 9.6 9.6 11.5
Silicate 0.5 0.7 1.6 1.0 1.0 2.4
SKS-6 1.5 1.50 2.30 2.25
Carbonate 2.3 2.7 3.5 3.6 4.1 5.2
HEDP 0.2 0.2 0.2 0.3 0.3 0.3
PB1 2.4 2.4 2.4 3.7 3.7 3.7
PAAC 0.002 0.002 0.002 0.003 0.004 0.004
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
83
Amylase 0.002 0.001 0.001 0.004 0.003 0.003
Protease 0.002 0.002 0.002 0.003 0.003 0.003
Nonionic 0.4 0.8 0.8 1.2 1.2 1.2
PEG 6000 0.4 0.3 0.3 0.4 0.4 0.4
BTA 0.04 0.04 0.04 - 0.06 0.06
Paraffin 0.1 0.1 0.1 0.15 0.15 0.15
Perfume 0.02 0.02 0.02 0.01 0.01 0.01
F
Sulphate - - - 0.5 0.05 2.3
Phase 2
Amylase 0.0005 0.0005 0.0004 0.0005 0.006 0.0004
Protease 0.009 0.008 0.01 0.009 0.008 0.01
Citric 0.3 0.3 0.3 0.30
Sulphamic - 0.3 - - 0.3 -
acid
Bicarbonate1.1 0.4 0.4 1.1 0.4 0.4
Carbonate - 0.5 - - 0.5 -
Silicate - - 0.6 - - 0.6
CaCl2 - 0.07 - - 0.07
PEG 3000 0.06 0.06 0.06 0.06 0.06 0.06
The multi-phase tablet compositions are prepared as follows. The detergent
active composition of phase 1 is prepared by admixing the granular and liquid
components and is then passed into the die of a conventional rotary press. The
press includes a punch suitably shaped for forming the mould. The cross-
section of the die is approximately 30x38 mm. The composition is then
subjected to to a compression force of 940 kg/cm2 and the punch is then
elevated exposing the first phase of the tablet containing the mould in its
upper
surface. The detergent active composition of phase 2 is prepared in similar
manner and is passed into the die. The particulate active composition is then
subjected to a compression force of 170 kg/cm2, the punch is elevated, and
the multi-phase tablet ejected from the tablet press. The resulting tablets
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
84
dissolve or disintegratea washing 12
in machine
as
described
above
within
minutes, phase 2 of blets ide
the tablets dissolving prov
within 5 minutes. The
ta
excellent dissolution cleaningcharacteristics good
and together with tablet
integrity and strength.
Example 21
The following manual compositions preparedaccordingto
dishwashing were
the present invention
I II III IV V VI VII VIII
C12-14E0-3S 26.0 34.2 25.0 26.0 37.0 26.0 22.0 32.0
C 11 LAS - - - - - - 13.0 -
C12-14 amine 2.0 4.9 2.1 6.5 5.5 6.5 1 -
oxide
C12-14 betaine 2.0 5.0 2.1 - - - - 4.0
C12-14 glucose 1.5 1.5 3.1 - - - - -
amide
C9-11 E8-9 4.5 1 4.1 3.0 1.0 3.0 - 1.0
Alkyl - - - - - - 12.0 3.0
Polyglucoside
C1-20 Mono - - - - - - 1.5 -
Ethanol Amine
DTPA - 0.1 0 0-500 0-500 0-500 0 0
ppm ppm ppm
Succinic acid - - - - - 0 - 4.5
Cumene - - 4.5 1 to 6 - 1 to - -
6
sulphonate
Ca ou Na - 5.0 - - 4.0 - 2.5 -
xylene
Sulphonate
Mg salts (in % 0.5 0.7 0.5 0.04 0.6 0.04 0.3 0
Mg)
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
1,3 bis - - - 0.5 - 0.5 - -
(methylamino)
cyclohexane
N.N- _ _ _ 0.2 - 0.2 - _
dimethylamino
ethyl
methacrylate
homopolymer
Citric - - - 0-3.5 0-3.5 - -
Ethanol 6-8 5-8 6-9 4-10 7.0 4-10 4.0 4.0
Protease - - - 0-0.08 - 0-0.08- -
Amylase - - - 0.002 - 0.005 0.04 0.05
Carbonate - - - - - 2.5 - -
Poly Propylene- - - 0 to - - - -
2
Glycol
(MW2000-4000)
pH 7-8 7- 7-8 8.5-11 7-8 8.5-117 7
8
Perfume E 0.1- 0.1- 0.1- 0.1-0.70.1- 0.1- 0.1- 0.1-
0.7 0.7 0.7 0.7 0.7 0.7 0.7
Balance (water Up to
and minors) 100%
Example 22
The following are hard surface compositions according to the present
invention:
5
I II III
Form of the composition Wipe Spray Liquid
H2O2 1.0 1.5 1.0
Na tetraborate 10.H20 - 1.0 -
C10 Amine Oxide - 0.9 0.9
C12-14 alkyl dimethyl amine oxide 0.4 - -
C7-10 Alkyl Sulphate - - 6.0
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
86
C9-11 E010 - 0.05 -
C8-18 Fatty acid - 0.1 0.2
Ethanol 9.0 1.0 2.5
Benzyl alcohol - 0.8
Propylene or diethylene glycol1.0 1.5 -
butyl ether
Poly(propylene glycol) monobutyl0.2 - -
ether
HEDP - 0.1 -
Butylated hydroxytoluene 0.01 0.06 0.03
Salicyclic acid 0.03 - 0.07
Perfume E 0.1 0.3 0.3
Citric 0.7 - 1.5
Dye - - 2.0
NaOH - 0.1 -
Miscellaneous and water ---------------------
up to 100%
-----------------
Examine 23
The following is a hard surface composition according to the present
invention:
I
H2O2 4.0
Tetra ethyl pentamine ethylene oxide 1.0
C8 Alkyl sulfate 3.0
Isopropyl alcohol 3.0
Propyl Gallate 0.03
Salicyclic acid 0.5
Dimethyl triamine penta (methylene phosphonic0.2
acid)
Perfume F 0.1
Miscellaneous and water -----
100%
-----
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
87
Example 24
The following are laundry detergent compositions according to the present
invention:
I II
C10 Alkyl sulfate - 1.6
C9 - C 11 E010 - 1.7
C12 - C13 E03 - 1.5
Sodium sulfate 18.47
Sodium bicarbonate 18.60 -
Polycarboxylate (EW base) 4.14 -
C18 Alpha Olefin 0.25 -
Enzyme blend 0.70 -
Brigthener 49 0.11 -
Quantum (zinc phthalocyanine sulfonate)0.04 -
Coated sodium percarbonate 45.0 -
TAED agglomerate (activator) 8.72 -
H2O2 - 6.8
n-propyl gallate (Nipanox) - 0.5
HEDP - 0.16
2-butyl octanol (Isofol 12) 0.5
Citric acid 2.5
Perfume D 0.11 0.16
Miscellaneous and water --------- -- 100%
-----------
Example 25
The following is a laundry detergent composition according to the present
invention:
I
Sodium hypochlorite (AvCl2) 3
Sodium hydroxyide 1.2
Sodium silicate (Si02) 0.5
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
88
Sodium metaborate 0.5 - 2
Sodium tripolyphosphate 0.065
m-methoxy benzoic acid 0 - 0.5
Sodium p-toluenesulfonate 0 - 5
Alkyl ether sulfate 3 - 6
Brightener 0.01 - 0.05
Pigment 0.009
Capped ethoxy-buthoxylated fatty0.3
alcohol
Coconut alkylcarboxylate (Fatty0.3
acid)
Perfume A 0.1
Miscellaneous and water ------ 100%
--
Example 26
The following are hard surface compositions according to the present
invention:
I II III IV V VI VII VIII IX
C9 - C 11 E05 - - - - - - 2.5 1.92 1.7
C12 - C14 E05 - - - - - - 2.5 2.88 1.7
C12-C14E021 - - - - - - 2.0 0.8 1.7
C12 - C14 alkyl- - 0.24 - 0.3 0.3 - - -
sulfate
Branched alkyl 3.5 3.5 - - - - - - -
sulfate
C12 - C14 amine0.7 0.7 - - - - - - -
oxide 0 0
C12-C14-C16 - - - 2.1 - - - -
amino oxide
NaLAS - - - - - - 0.8 - -
n-Butoxy-propanol2.0 5.8 2.0 - - - - - -
Amino-methyl- - - 0.025 - - - - - -
propanol
2-butyl-octanol- - - - - - 0.3 0.3 0.25
(Isofol 12)
Sodium paraffin- - - - - - - - 1.0
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
89
sulfonate
Sodium cumene - - - - - - 1.5 2.6 0.75
sulfate
Sodium C7 - - - - 0.9 3.0 3.0 - -
C9
sulfate
Sodium silicate- - - 0.4 0.04 0.04 - - -
0.5
MgS04 _ _ _ _ _ _ _ _
NaZC03 - - - - - - 0.2 0.13 0.3
NaOH - - - 1.0 0.87 0.87 - 0.33 -
PVP (mw _ _ _ _ _ _ _ _ 0.5
360,000)
PVP / AA (3:1 - - 0.040 - - - - - -
)
Dimethyl PEG - - - - - - - - 0.5
(mw 2000)
Hypochlorite - - - 1.4 1.4 2.1 - - -
H5106 (Periodic- - - 0.01 - - - -
acid)
Glutaraldehyde - - - - - - 0.03 0.03 0.02
5 5 5
Phenoxyethanol - - - - - - - 0.3 -
Coconut fatty - - - 0.9 - - - - -
acid
Fatty acid - - - - - - 0.4 0.3 0.25
Citric acid 3.5 5.5 - - - - 0.75 0.56 0.75
Ethanol - - 3.0 - - - -
pye _ _ _ 0.05 - _ _ _ _
8
Perfume F 0.4 0.3 0.09 0.2 0.35 0.35 0.5 0.4 0.5
- -
4 0.75 0.75
Miscellaneous _.._________________________________________________
and 100%
-_______________________________
water I
____________________
-
CA 02379200 2002-O1-16
WO 01/05919 PCT/US00/19369
Example
27
The following composition accordingto the
is a laundry present
detergent
invention:
Examples 2 3 4 5 6
1
(%) (%) (%) ( %) (%) (%)
First phase
Bleach Percarbonate 45.0 45.0 45.0 45.0 45.0
45.0 ~..
.................................._._._...__.___..TAED~.........._.............
.........................._....9.7'_..........
................9.7......_..._............_._9.7_._.._....._..._
9.7........__._._ 9.7
9.7~~
........._..............._......_..._...____._._.._.......___...._..._.__._._..
..._............._.....................__.
........................_.............._.......
Metal bleach-
catalyst
.Builders _._ 20.0~..._....__..._.15.0~..__._..
.~.. 15.0
~.~
Citric~acid~.~~~._......__..........1Ø0__.._._....._......15Ø._..._....
X5.0 ...
......_.___.__.
............___....._.__.._.__.._._..__.._._.._.______....._._..._...__._~__
6.0
....._...._.._..__._._....__w._....__.............____......_........_._.
- - - - -
STPP - _..
......_._._..._.....___.._...~...__._ACrylic-Maleic
....._.........S.p........____...___1.M0__..._._..._. .._ _ -
....._._............_....6Ø..._......
5.0_._...
copolymer
__ _____.__._._
... ._ ._._.._......_.___..______.____................__......._..._...._._.
..___.......__._._._____.__.___..__..._....__..._..-
____.._.....6.0 -
Silicates - - -
-
15.O~ ~_15:0...~-~.N~ ~15.0~~.~ 15.0 15.0
~ ~_10~0~ .
~ ~~~
Alkalinity.~~M~Bicarbonate
N.... .-..
~.N - __.
.~~
~Y~ .....
....
Carbonate
5.0
.....______...._...__._.______.._g..._....__.._.._._.__..._........._..........
........__............................._._............._.__._..__._...__.......
..._..__.._ ..__..._._.._._.....___.
0.11
Others Bri 0.11 0.11 ._..__
htener
0.11 0.11
0.11
.._.._.._....._....__...~..~....~.__.._._._._._....._..__..__.._..____.........
_.......w
............_..._._........._...._......_....__..._._...._.....__....._.__.....
....._..... __.._..~..._~__
Perfume 0.20 0.20 0.20 0.20
E 0.20 0.20
....._._.~.._.... ...._...~.__..._._...__.__ _._._. -
Fatty acid _._.__ ~......._._1.0 __._.
~~~.~~._.._.__.__.._.__._ _._
.
Enzymes 0.60~~M~ 0.94 0.60
Protease ~.
~~~~~~~~.~0.60~~~~~~~~.~~~~~W~~0.60~~~~~~~
~ ~ 0.60
~ ~
protease .__........_..... 0.34 - 0.34
- ._._.._.__._...._0.34'....... ~.34~_ ~.34~~T._~~
Savinase
_
... . . __..._..1.21~~y 1.21 1.21
. Amylase ~ 1.21
_~.~.._~..__.._._...__1.21_._____.._...__1..21....._
..
Termamyl
Second
phase
Protease 1.24 1.24 1.24 1.14 n .L4
~~.~~~.~.~
1.24
Amylase~~~ 1.34 ~~~ ~ 1.34 1.34 1.34
~~~~~~~~~.~...~~~~~..~.1~.34~~~.~~~~~~~ ~~~ 1.34
PEG ~~~ ~~_.._.....__Ø09~_Y~_..Ø09'~.._ ..x.09 0.09
~.09~.~....__.... ~4.~ 0.09w.~
PEG~4000~........._......._..................Ø33_.._....._._.
0.33._.__.._..._..Ø33_.._...._.__._.Ø33.._Ø33 ~ 0.33
CA 02379200 2002-O1-16
WO 01/05919 g~ PCT/US00/19369
Citric acid 1.06 1.06 1.06 1.06 1.06 1.06
...............................................................................
...............................................................................
...............................................................................
.........................................................
Bicarbonate 2.87 2.87 2.87 2.87 2.87 2.87
Example 28
The following are laundry detergent compositions according to the invention:
I II III IV V
PAP 3 - - 5 10
DPDA - 3 - - -
NAPAA _ _ 3 _ _
Carbopol ETD 2691 0.3 0.3 0.3 0.3 0.3
Xanthan gum 0.2 0.2 0.2 0.2 0.2
AE3S 2 2 2 4 4
HEDP 0.1 0.1 0.1 0.1 0.1
Tinopal SOP - - - 0.02 0.02
Norasol LMW 45N - - - 3 3
Colouring agent - - - 40 ppm 40 ppm
Perfume E 0.2 0.2 - - -
Perfume F - - 0.2 0.2 0.2
water to balance
to 100%
pH 3.8 3.8 3.8 3.8 3.8
PAP is pthaloylimido peroxy hexanoic acid
DPDA is diperoxydodecanoic acid
NAPAA is the monononylamide of monoperoxysuccinic acid
Carbopol ETD 2691 is a polyacrylate polymer available from BF Goodrich
1o Tinopal SOP is a brightener
Norasol LMW 45N is a polyacrylate polymer
Colouring agent is Cosmenyl Blue A2R
