Note: Descriptions are shown in the official language in which they were submitted.
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LAUNDRY AND CLEANING COMPOSITIONS
Field of the invention
The present invention relates to laundry and cleanings compositions comprising
a
product of reaction between an amino functional polymer comprising at least
one primary and/or secondary and/or secondary amine group, and a perfume
component, in particular aldehyde or ketone perfumes.
Backgiround of the invention
Laundry and cleaning products are well-known in the art. However, consumer
acceptance of laundry and cleaning products is determined not only by the
performance achieved with these products but also by the aesthetics associated
therewith. The perfume components are therefore .an important aspect of the
successful formulation of such commercial products.
It is also desired by consumers for laundered fabrics to maintain the pleasing
fragrance over time. Indeed, perfume additives make laundry compositions
more aesthetically pleasing to the consumer, and in some cases the perfume
imparts a pleasant fragrance to fabrics treated therewith. However, the amount
of perfume carried-over from an aqueous laundry bath onto fabrics is often
marginal and does not last long on the fabric. Furthermore, fragrance
materials
are often very costly and their inefficient use in Laundry and cleaning
compositions and ineffective delivery to fabrics results in a very high cost
to both
consumers and laundry and cleaning manufacturers. Industry, therefore,
continues to seek with urgency for more efficient and effective fragrance
delivery
in laundry and cleaning products, especially for improvement in the provision
of
long-lasting fragrance to the fabrics.
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One solution is to use carrier mechanisms for perfume delivery, such as by
encapsulation. This is taught in the prior art and described in U.S.
5,188,753.
Still another solution is to formulate compounds whiclh provide a delayed
release
of the perfume over a longer period of time than by the use of the perfume
itself.
Disclosure of such compounds may be found in WO 95/04809, WO 95!08976
and co-pending application EP 95303762.9.
However, notwithstanding the advances in the art, there is still a need for a
compound which provides a delayed release of the pertume component.
That need is even more acute for perfume ingredients which are characteristic
of
the fresh notes, namely the aldehydes and ketones perfume ingredients. Indeed,
whilst these provide a fresh fragrance, these perfumes are also very volatile
and
have a low substantivity on the surface to be treated like fabrics.
Accordingly, it is a further object of the invention to provide a laundry and
cleaning composition comprising a perfume component which provides a fresh
fragrance and is substantive to the treated surface.
The Applicant has now found that specific reaction products of an amino
functional polymer comprising at least one primary and/or secondary amine
group with an active aldehyde or ketone; such as imines compounds, also
provide a delayed release of the active such as a perlfume.
/mine compounds are known in the art under the name of Schiff bases which is
the condensation of an aldehyde perfume ingredient with an anthranilate. A
typical description can be found in US 4853369. By means of this compound,
the aldehyde perfume is made substantive to the fabrics. However, a problem
encountered with these schiff bases is that the me~thyianthranilate compound
also exhibits a strong scent, which as a result produces a mixture of
fragrances,
thereby reducing or even inhibiting the aldehyde and/or ketone fragrance
perception.
To achieve such perfume composition with comparable aldehyde or ketones
fresh notes whilst still having satisfactory fabric substantivity, perfumers
have
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formulated around the composition. For example, by having a carrier or
encapsulating material for such notes such as with cyclodextrin, zeolites or
starch.
Still another solution is the use of a glucosamine as described in JP
09040687.
However, this compound has been found to give a very low stability in the
wash/cileaning process. As a result, insufficient perfume residuality on the
treated fabric and/or hard surface has been found with these giucosamine
compounds.
A further solution is described in Chemical release control, Kamogawa et AL,
J.
Poly. Sci. Polym. Chem. Ed. Vol 20, 3121 (1982) which describe the use of
amino styrene compounds condensed with aidehydes perfumes, whereby the
release of the perfume is triggered by means of copolymerisation or
acidification
of the compound. Its use in laundry and cleaning product is however not
mentioned.
The Applicant has now found that a reaction product of an amino functional
polymer comprising at least one primary and/or secondary amine group, and a
perfume component also fulfill such a need.
Another advantage of the compounds of the invention is their ease of
manufacture rendering their use most desirable.
Summary of the invention
The present invention relates to a laundry and cleaniing composition
comprising
a detersive ingredient and a product of reaction between an amino functional
polymer comprising at least one primary and/or secondary amine group and a
perfume component selected from ketone, aldehyde, and mixtures thereof,
characterised in that said amino functional polymer has an Odour Intensity
Index
of less than that of a 1 % solution of methylanthranilate in dipropyiene
glycol, and
the product of reaction a ~ry Surface Odour Index of amore than 5.
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In a further aspect of the invention, there is provided a method of delivering
residual fragrance to a surface by means of the compound or composition of the
invention.
Detailed description of the invention
I-Product of reaction between an amino functional polymer and a perfume
component
An essential component of the invention is a product of reaction an amino
functional polymer comprising at least one primary andlor secondary amine
group and a perfume component, so called hereinafter "amine reaction product".
A- Amino functional polymer
The amino functional polymer is characterized by an Odour Intensity Index of
less than that of a 1 % solution of methylanthranilate in dipropylene glycol.
Odour Intensity Index method
By Odour intensity Index, it meant that the pure chemicals were diluted at 1 %
in
Dipropylene Glycol, odor-free solvent used in perfumery. This percentage is
more representative of usage levels. Smelling strips, or so called "blotters",
were
dipped and presented to the expert panellist for evaluation. 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 an amino functional polymer, the panellist was presented two
blotters: one reference (Me Anthranilate, unknown from the panellist) and the
sample. The panellist was asked to rank both smelling strips on the 0-5 odor
intensity scale, 0 being no odor detected, 5 being very strong odor present.
Results:
The following represents Odour Intensity Index of an amino functional poiymer
suitable for use in the present invention and according to the above
procedure.
In each case, numbers are arithmetic averages among 5 expert panellists and
the results are statistically significantly different at 95% confidence level:
Methylanthraniiate 1 % (reference) 3.4
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1,4-bis-(3-aminopropyl) piperazine (BNPP) 1% 1.0
A general structure for the amino functional polymer containing at least one
primary amine group of the present invention, is as follows:
(NH2)n - [B]
wherein n is an index of at least 1 and B is the ~>olymer backbone. B can
optionally comprise a branching group, C and hence the amino functional
polymer is of the following formula:
(NH2)n - [B] - (C]x wherein x >_:0.
Amino functional polymer containing a secondary amine group have a structure
similar to the above excepted that the polymer comprises one or more -NH-
groups instead of -NH2. Further, the polymer structure may also have one or
more of both -NH2 and -NH- groups.
The amino functional polymer of the present invention contains at least one
free,
unmodified primary andlor secondary amino group attached to the main chain
by hydrogen substitution, or by other suitable insertion or substitution by
groups
referred to as R*. Also suitable is the amino functional polymer comprising an
unmodified primary and/or secondary amino group present on side chain(s).
Preferably, the amino functional polymers of the presE:nt invention will
comprise
several amino groups, more preferably more than 10 amino groups. The amino
functional polymers of the present invention will preferably present a
molecular
weight (M1I1~ ranging from 150 to 2.10EG; more preferably from 400-50,000;
most preferably from 600 to 40,000.
The amino functional polymer can be a linear homo-, co-polymer and optionally
branched, grafted andlor cross-linked.
Suitable polymer backbone B for the purpose of the present invention have the
following polymer units
i
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(1 ) (2) F (3)
-(CH2-CH)x- -( C- H )x- -(CH _ CHZ-O )x -
F I
COOHCOOH
wherein x = 2-105 O
I
F=H, - NH2, - COOH, COOK*, -C - CH3, - O-C -CH3,- OH, - CN, - OR*,
O
R*
\/ , \/ OH ~~~ ° N-~"O ,
O \ / N
I
Suitable branching units C for the polymer backbone B are
2,3 or 2,4 or 3,4 substitution
_ _ i
N ~ C N\
0
The polymer backbone B can also comprise insertion groups I such as
i
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-O- ~ -O-O- . -O-, -O-~-O- . -RH- -(CH2~
x>_1
R* or H
-C- , -C-N- , -N- ~ 'C-N- . \C =C\
bH O R* or H R or H * ~ or H '
* R or H
R* or H -~-O- ~ O O
-N- ~ " ~ -O-S-O- , -S-Nt-1- ' -S
O O O O
O
\ / ~ O C \ j ,
O
The arrow indicates substitution in position 2.3 or 4
n
-O_C \-/ C~O- -C \ / C- , ~ a -
O O O O
The backbone (B) can also contain several insertion groups linked together:
e.g.
\ / \ / . -yCH,)~ C- . -(CH~)WN- \ /
O
wherein x>- 1.
The aminofunctional polymers of the present invention can further comprise
substituents R* in the main chain or in the side chain(s). Typically, R*
replaces
an hydrogen atom. This R* group can either be linked directly or via a linker
group L to the main or side chain. Suitable linker groups L are the above
mentioned insertion groups I.
R* groups are C1 to C22 alkyl, alkenyl, alkylbenzene chain andlor their
corresponding substituted derivatives. Such corresponding substituted
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derivatives include alicyclic, aromatic, heteroaromatic or heterocyciic
systems,
either inserted in the main chain or incorporated by a substitution of an H
atom
in the main chain; an insertion group E in the main chain, as defined herein
above and/or an end group E as defined below.
Further, the polymer backbone B and R* encompass end groups E. Typically
end groups E can be an H, NH2 groups, an aromatic, alicyclic, heteroaromatic
or
heterocyclic group including mono-, di-, oligo-, poly-sa~ccharides
R* ~ CH
-OH, -OR*.. -NH,. -~( , -C-N-R* or H ~ -N -~ O '
R* or H I
R* or H CH
-S03H, -OS03H, -COOH.-COOK*.
_ I
\ / ~ ~ O ' ~ ~ H
CH3 CH,-CH,-OH
CH3 O
~N=CH3 ' X_~yCH3 ~ X=~N-CH,-CH_.,-OH . -C-OCH,-CH,-N+(CH3)3
CH3 X CH,-CH.,-OH CH3 -
wherein Y-= is an anion like C1-,Br ,SO;~'''
En addition, the R* group can also be modified via substitution of one or more
H
atoms. Said substitution can either be an end group E: or an insertion group I
as
defined above, where the insertion group is terminated by a H, E or R* group .
Preferred examples of suitable amino-functional polymers for use in the
present
invention are selected from the polyvinylamines, derivatives thereof,
copolymer
thereof, aikylene polyamine, polyaminoacid and copolymer thereof, cross-linked
poiyaminoacids, amino substituted polyvinylalcohof, polyoxyethylene bis amine
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or bis. aminoalkyl, aminoalkyl piperazine and derivatives, N,N'-bis-(3-
aminopropyl)-1,3-propanediamine linear or branched (TPTA), and mixtures
thereof.
Polyamino acid is one suitable and preferred class of amino-functional
polymer.
Polyaminoacids are compounds which are made up of amino acids or
chemicaily modified amino acids. They can contain alanine, serine, aspartic
acid, arginine, valine, threonine, glutamic acid, leucine, cysteine,
histidine,
lysine, isoleucine, tyrosine, asparagine, methionine, proiine, tryptophan,
phenylalanine, glutamine, glycine or mixtures thereof. In chemically modified
amino acids, the amine or acidic function of the amino acid has reacted with a
chemical reagent. This is often done to protect these chemical amine and acid
functions of the amino acid in a subsequent reaction or to give special
properties
to the amino acids, like improved solubility. Examples of such chemical
modifications are benzyloxycarbonyl, aminobutyric acid, butyl ester,
pyroglutamic acid. More examples of common modifications of amino acids and
small amino acid fragments can be found in the Bachem, 1996, Peptides and
Biochemicals Catalog.
Preferred polyamino acids are polylysines, polyarginine, polygiutamine,
poiyasparagine, polyhistidine, polytryptophane ar mixtures thereof. Most
preferred are polylysines or poiyamino acids where more than 50% of the amino
acids are lysine, since the primary amine function in the side chain of the
lysine
is the most reactive amine of all amino acids.
The preferred polyamino acid has a molecular weight of 500 to 10.000.000,
more preferably between 5,000 and 750.000.
The polyamino acid can be cross linked. The cross linking can be obtained for
example by condensation of the amine group in the side chain of the amino acid
like lysine with the carboxyl function on the amino acid or with protein cross
linkers like PEG derivatives. The cross linked polyamino acids still need to
have
free primary andlor secondary amino groups left for reaction with the active
ingredient.
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The preferred cross linked poiyamino acid has a molecular weight of 20.000 to
10.000.000, more preferably between 200.000 and 2.000.000.
The polyamino acid or the amino acid can be co-polymerized with other
reagents like for instance with acids, amides, acyl chlorides. More
specifically
with aminocaproic acid, adipic acid, ethylhexanoic acid, caproiactam or
mixture
thereof. The molar ratio used in these copolymers ranges from 1:1 (reagent/
amino acid (lysine)) to 1:20, more preferably from 1:1 to 1:10.
The polyamino acid like pofylysine can be partially ethoxylated.
Examples and supply of polyaminoacids containing lysine, arginine, giutamime,
asparagine are given in the Bachem 1996, Peptides and Biochemicals catalog.
The polyaminoacid can be obtained before reaction with the active ingredient,
under a salt form. For example polylysine can be supplied as polylysine
hydrobromide. Polylysine hydrobromide is commercially available from Sigma,
Applichem, Bachem and Fluka.
Examples of suitable amino functional polymers containing at least one primary
andlor secondary amine group for the purpose of the present invention are
- Polyvinylamine with a MW of about 300-2.10Efi;
- Polyvinyiamine aikoxylated with a MW of about 600, 1200 or 3000 and an
ethoxylation degree of 0.5;
- Polyvinylamine vinyialcohol - molar ratio 2:1, pofyvinylaminevinyiformarnide
-
molar ratio 1:2 and polyvinylamine vinyiformamide-molar ratio 2:1;
- Triethylenetetramine, diethylenetriamine, tetraethylenepentamine;
- Bis-aminopropylpiperazine;
Polyamino acid (L-lysine l lauric acid in a molar ratio of 10/1 ), Poiyamino
acid
(L-lysine I aminocaproic acid l adipic acid in a molar ratio of 5/511 ), ),
Poiyamino
acid (L-lysine / aminocaproic acid /ethylhexanoic acid in a molar ratio of
5/3/1 )
Poiyamino acid (polylysine-cocaprolactam); Polylys~ine hydrobromide, cross-
linked polylysine,
- amino substituted polyvinylalcohol with a MW ranging from 400-300,000;
- polyoxyethylene bis [amine] available from e.g. Sigma;
- polyoxyethyiene bis [6-aminohexyl] available from e.g. Sigma;
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- N,N'-bis-(3-aminopropyi)-1,3-propanediamine linear or branched (TPTA); and
- 1,4-bis-(3-aminopropyl) piperazine {BNPP).
Preferred amino functional polymers containing at least one primary and/or
secondary amine group are
- polyvinylamines with a MW ranging from 600, 1200, 3K, 20K, 2bK or 50K;
- amino substituted polyvinylalcohol with a MW ranging from 400-300,000;
polyoxyethylene bis [amine] available from e.g. Sigma;
- polyoxyethylene bis [fi-aminohexyl] available from e..g. Sigma;
- N,N'-bis-(3-aminopropyl)-1,3-propanediamine linear or branched (TPTA);
- 1,4-bis-(3-aminopropyl) piperazine (BNPP);
- Polylysine hydrobromide;
cross-linked polylysine.
Furthermore, such amino functional polymers comprising at least one primary
and/or secondary amine group and the amine reaction product provide fabric
appearance benefits, in particular color care and protection against fabric
wear.
Indeed, the appearance of fabrics, e.g., clothing, bedding, household fabrics
like
table linens is one of the area of concern to consumers. Indeed, upon typical
consumer's uses of the fabrics such as wearing, washing, rinsing andlor tumble-
drying of fabrics, a loss in the fabric appearance; which can be at least
partly
due to loss of color fidelity and color definition, is observed. Such a
problem of
color loss is even more acute after multiwash cycles. It has been found that
the
compositions of the present invention provide improved fabric appearance and
protection against fabric wear and improved color care to laundered fabrics,
especially after muitiwash cycles.
Therefore, the compositions of the present invention can provide
simultaneously
fabric care and long lasting perfume benefits.
B-Perfume
Preferably, for the above mentioned compounds, by perfume ketone or
aldehyde, it is meant any chain containing at least 1 carbon atom, preferably
at
least 5 carbon atoms.
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A typical disclosure of suitable ketone and/or aldehydes, traditionally used
in
perfumery, can be found in "perfume and Flavor Chemicals", Vol. I and II, S.
Arctander, Allured Publishing, 1994, ISBN 0-931710-35-5.
Perfume ketones components include components having odoriferous
properties.
Preferably, for the above mentioned compounds, the perfume ketone is selected
for its odor character from buccoxime; iso jasmone; methyl beta naphthyl
ketone; musk indanone; tonaiid/musk plus; Alpha-Damascone, Beta-
Damascone, Delta-Damascone, Iso-Damascone, Damascenone, Damarose,
Methyl-Dihydrojasmonate, Menthone, Carvone, Camphor, Fenchone, Alpha-
lonone, Beta-lonone, Gamma-Methyl so-callecl lonone, Fleuramone,
Dihydrojasrnone. Cis-Jasmone, lso-E-Super, Methyl- Cedrenyl-ketone or Methyl-
Cedrylone, Acetophenone, Methyl-AcetophE:none, Para-Methoxy-
Acetophenone, Methyl-Beta-Naphtyl-Ketone, Benzyl-Acetone, Benzophenone,
Para-Hydroxy-Phenyl-Butanone, Celery Ketone~ or Livescone, 6-
Isopropyidecahydro-2-naphtone, Dimethyl-Octenon~:, Freskomenthe, 4-(1-
Ethoxyvinyl)-3,3,5,5,-tetramethy(-Cyclohexanone, Methyl-Heptenone, 2-(2-(4-
Methyl-3-cyclohexen-1-yl)propyl)-cyclopentanone, 1-(p-Menthen-6(2}-yl)-1-
propanone, 4-(4-Hydroxy-3-methoxyphenyl)-2-butanone, 2-Acetyl-3,3-Dimethyl-
Norbornane, 6,7-Dihydro-1,1,2,3,3-Pentamethyl-4(5H)-Indanone, 4-C)amascol,
Dulcinyl or Cassione, Gelsone, Hexalon, lsocyciemone E, Methyl Cyclocitrone,
Methyl-Lavender-Ketone, Orivon, Para-tertiary-Butyl-Cyclohexanone, Verdone,
Delphone, Muscone, Neobutenone, Plicatone, Veloutone, 2,4,4,7-Tetramethyl-
oct-6-en-3-one, Tetrameran, Undecaiactone and Gamma undecalactone.
For the above mentioned compounds, the more preferred ketones are selected
for its odor character from Alpha Damascone, Delta Damascone, Iso
Damascone, Carvone, Gamma-Methyl-ionone, Iso-E-Super, 2,4,4,7-
Tetramethyl-oct-6-en-3-one, Benzyl Acetone, Beta Damascone, Damascenone,
methyl dihydrojasmonate, methyl cedrylone, and mixtures thereof.
Perfume aldehyde components include components having odoriferous
properties.
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Preferably, for the above mentioned compounds, the perfume aidehyde is
selected for its odor character from adoxal; anisic aidE:hyde; cymai; ethyl
vanillin;
florhydral; helionai: heliotropin; hydroxycitronellai; koavone; lauric
aldehyde;
lyral; methyl nonyl acetaldehyde; P. T, bucinal; phenyl acetaldehyde;
undecylenic aidehyde; vanillin; 2,6,10-trimethyl-9-undecenal, 3-dodecen-1-al,
alpha-n-amyl cinnamic aldehyde, 4-methoxybenzaidehyde, benzaldehyde, 3-(4-
tert butylphenyl)-propanal, 2-methyl-3-(para-methoxyphenyf propanal, 2-methyl-
4-(2,6,6-trimethyl-2(1)-cyciohexen-1-yl) butanal, 3-phenyl-2-propenal, cis-
/traps-
3,7-dimethyi-2,6-octadien-1-al, 3,7-dimethyi-6-octen-1-al, [(3,7-dimethyl-6-
octenyl)oxy] acetaldehyde, 4-isopropylbenzyaldehyde, 1,2,3,4,5,6,7,8-
octahydro-8,8-dimethyl-2-naphthaldehyde, 2,4-dimethyl-3-cyciohexen-1-
carboxaidehyde, 2-methyl-3-(isopropyiphenyl)propanai, 1-decanal; decyl
aldehyde, 2,6-dimethyi-5-heptenal, 4-(tricycto[5.2.1.0(2,6)]-decyiidene-8)-
butanal, octahydro-4,7-methano-1 H-indenecarboxaldehyde, 3-ethoxy-4-hydroxy
benzaldehyde, para-ethyl-alpha, alpha-dimethyi hydrocinnamaldehyde, alpha-
methyl-3,4-(methyienedioxy)-hydrocinnamaidehyde, 3,4-
methylenedioxybenzaldehyde, alpha-n-hexyl cinnamic aldehyde, m-cymene-7-
carboxaidehyde, alpha-methyl phenyl acetaldehyde, 7-hydroxy-3,7-dimethyl
octanai, Undecenal, 2,4,6-trimethyl-3-cyciohexene-'I-carboxaldehyde, 4-{3)(4-
methyl-3-pentenyl)-3-cyclohexen-carboxaidehyde, 1-dodecanal, 2,4-dimethyl
cyclohexene-3-carboxaldehyde, 4-(4-hydroxy-4-methyl pentyl)-3-cylohexene-1-
carboxaldehyde, 7-methoxy-3,7-dimethyloctan-1-al, 2-methyl undecanal, 2-
methyl decanal, 1-nonanal, 1-octanal, 2,6,10-trimethyl-5,9-undecadienal, 2-
methyl-3-(4-tertbutyl)propanal, dihydrocinnamic aldehyde, 1-methyl-4-(4-methyl-
3-pentenyl)-3-cyclohexene-1-carboxaldehyde, 5 or Ei methoxy0hexahydro-4,7-
methanoindan-1 or 2- carboxaldehyde, 3,7-dimethyloctan-1-al, 1-undecanal, 10-
undecen-1-al, 4-hydroxy-3-methoxy benzaldehyde, 1-methyl-3-{4-methylpentyl)-
3-cycihexenecarboxaldehyde, 7-hydroxy-3,7-dimethyl-octanal, traps-4-decenal,
2,6-nonadienal, para-tolylacetaldehyde; 4-methylphenylacetaldehyde, 2-methyl-
4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal; ortho-methoxycinnamic
aldehyde, 3,5,6-trimethyl-3-cyclohexene carboxaldehyde, 3,7-dimethyl-2-
methylene-6-octenal, phenoxyacetaldehyde, 5,9-dime~thyl-4,8-decadienal, peony
aldehyde (6,10-dimethyl-3-oxa-5,9-undecadien-1-al), hexahydro-4,7-
methanoindan-1-carboxaldehyde, 2-methyl octanal, alpha-methyl-4.-(1-methyl
ethyl) benzene acetaldehyde, 6,6-dimethyl-2-norpinene-2-propionaldehyde, para
methyl phenoxy acetaldehyde, 2-methyl-3-phenyl-2-propen-1-al, 3,5,5-trimethyl
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hexanal, Hexahydro-8,8-dimethyl-2-naphthaldehyde, 3-propyl-bicycio[2.2.1]-
hept-5-ene-2-carbaldehyde, 9-decenal, 3-nnethyl-5-phenyl-1-pentanal,
rnethylnonyl acetaldehyde, hexanal, traps-2-hexenal, 1-p-menthene-q-
carboxaldehyde and mixtures thereof.
More preferred aldehydes are selected for its odor character from 1-decanat,
benzaldehyde, florhydral, 2,4-dimethyl-3-cyclohexen-1-carbaxaldehyde;
cis/traps-3,7-dimethyl-2,6-octadien-1-al; heliotropin; 2,4,6-trimethyl-3-
cyclohexene-1-carboxaldehyde; 2,6-nonadienal; alpha-n-amyl cinnamic
aldehyde, alpha-n-hexyi cinnamic aldehyde, P.T. Bucinal, lyral, cymal, methyl
nonyl acetaldehyde, hexanal, traps-2-hexenal, and mixture thereof.
In the above list of perfume ingredients, sorne~ are commercial names
conventionally known to one skilled in the art, and also includes isomers.
Such
isomers are also suitable for use in the present invention.
In another embodiment, especially suitable for the purpose of the present
invention are the perfume compounds, preferably the perfume ketoses or
aldehydes, characterized by having a low Odor Detection Threshold. Such
Odor Detection Threshold (ODT) should be lower than 1 ppm, preferably lower
than 10ppb - measured at controlled Gas Chromatography {GC) conditions
such as described here below. This parameter refers to the value commonly
used in the perfumery arts and which is the lowest concentration at which
significant detection takes place that some odorous material is present.
Please
refer for example in "Compilation of Odor and Tasi:e Threshold Value Data
(ASTM DS 48 A)", edited by F. A. Fazzalari, International Business Machines,
Hopwell Junction, NY and in Catkin et al., Perfumery, Practice and Principles,
John Willey & Sons, Inc., page 243 et seq (1994). For the purpose of the
present invention, the Odor Detection Threshold is measured according to the
following method
The gas chromatograph is characterized to determine the exact volume of
material injected by the syringe, the precise spfit ratio, and the hydrocarbon
response using a hydrocarbon standard of known concentration and chain-
length distribution. The air flow rate is accurately measured and, assuming
the
duration of a human inhalation to last 0.02 minutes, the sampled volume is
calculated. Since the precise concentration at the detector at any paint in
time
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is known, the mass per volume inhaled is known and hence the concentration
of material. To determine the ODT of a perfume material, solutions are
delivered to the sniff port at the back-calculated concentration. A panelist
sniffs the GC effluent and identifies the retention time when odor is noticed.
The average over all panelists determines the threshold of noticeability. The
necessary amount of analyte is injected onto the column to achieve a certain
concentration, such as 10 ppb, at the detector. Typical gas chromatograph
parameters for determining odor detection thresholds are listed below.
GC: 5890 Series Il with FID detector
7673 Autosampler
Column: J&W Scientific DB-1
Length 30 meters ID 0.25 mm film thickness 1 micron
Method:
Split Injection: 17/1 split ratio
Autosampler: 1.13 microliters per injection
Column Flow: 1.10 mUminute
Air Flow: 345 mUminute
Inlet Temp. 245°C
Detector Temp. 285°C
Temperature Information
Initial Temperature: 50°C
Rate: 5C/minute
Final Temperature: 280°C
Final Time: 6 minutes
Leading assumptions: 0.02 minutes per sniff
GC air adds to sample dilution
Examples of such preferred perfume components are those selected from : 2-
methyl-2-(para-iso-propyiphenyl)-propionaldehyde, 1-(2,6,6-trimethyl-2-
cyclohexan-1-yl)-2-buten-1-one andlor para-methoxy-acetophenone. Even more
preferred are the following compounds having an ODT <_ l0ppb measured with
the method described above : undecylenic aldehydE~, undecalactone gamma,
heliotropin, dodecalactone gamma, p-anisic aldehyde, pats hydroxy-phenyl-
butanone, cymal, benzyl acetone, ionone alpha, p.t.bucinai, damascenone,
ionone beta and methyl-nonyl ketone.
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Typically the level of perfume is of from 10 to 90%, preferably from 30 to
85%,
more preferably from 45 to 80% by weight of the amine reaction product.
Preferred amine reaction products are those resulting from the reaction of
polyaminoacid like Polylysine, BNPP, or TPTA with one or more of the following
Alpha Damascone, Delta Damascone, Canrone, fiedione, Florhydral, Lilial,
Heliotropine, Gamma-Methyl-lonone and 2,~4-dimethyl-3-cyclohexen-1-
carboxaldehyde, and mixture thereof.
Most preferred amine reaction products are those from the reaction of BNPP or
TPTA with Alpha and Delta Damascone.
Process
Preparation of the component is made as follows in the Synthesis Examples. In
general, the nitrogen analogs of ketones and aldehyd~es are called
azornethines,
Schiff bases or the more preferred name imines. These imines can easily be
prepared by condensation of primary amines and carbonyl compounds by
elimination of water.
A typical reaction profile is as follows:
R,yR ' HEN.-R" ~- R--C-NH-R"
I
R'
R
v
/c=N-R" + HBO
R'
a,~i-Unsaturated ketones do not only condense with amines to form imines, but
can also undergo a competitive 1,4-addition to form ~3-;aminoketones.
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R"
O
R-CH=CH-IC-R' + H N-R" ---~ f H O
R-CH-CH-C-R'
By means of this simple method, compound and composition containing said
compounds are made which achieve a delayed release of the active ingredient.
As can be observed, the perfume ingredient preferably needs to be present in
equimolar amount to the amine function so as to enable the reaction to take
place and provide the resulting amine reaction product. Of course, higher
amount are not excluded and even preferred when the amine compound
comprises more than one amine function.
Mechanism of release
By the present invention, a delayed release of a perfume ingredient, i.e.
ketone
or aldehyde is obtained. Not to be bound by theory, the release is believed to
occur by the following mechanisms:
For imine compounds, the perfume components are released upon breaking
down of the imine bond, leading to the release of the perfume component and of
the primary amine compound. This can be achieved by either hydrolysis,
photochemical cleavage, oxidative cleavage, or enzymatic cleavage.
For ~-aminoketone compounds, treatment with air moisture andlor water
successfully releases the perfume component and the amine compound.
However, other means of release are not excluded like hydrolysis,
photochemical cleavage, oxidative cleavage, or enzymatic cleavage.
Still other means of release for imine as well as ~-aminoketone compounds can
be considered such as by the steaming step of ironing the treated fabric,
tumble-
drying, and/or wearing.
Laundry and cleaning compositions
The present invention include both laundry and cleaning compositions which are
typically used for Laundering fabrics and cleanings hard surfaces such as
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dishware, floors, bathrooms, toilet, kitchen and other surfaces in need of a
delayed release of perfume ketone andlor aldehyde. 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 result in contacting the
compound of the invention with fabric.
Preferably, the amine reaction products) which is incorporated into such
laundry
and cleaning compositions provides a dry surface Odour Index of more than 5
preferably at least '! 0.
By Dry Surface Odour Index, it is meant that the amine reaction products)
provides a Delta of more than 5, wherein Delta is the difference between the
Odour Index of the dry surface treated with amine reaction products) and the
Odour Index of the dry surface treated with only the perfume raw material.
Measurement method of Dry Surface Odour Index:
For the above Dry Surface Odour Index, the amine reaction product suitable for
use in the present invention needs to fulfill at least one of the following
two tests.
Preferred amine reaction product suitable for use in the present invention
fulfill
both test.
1)-For fabric surface
Product preparation:
The amine reaction product is added to the unperfumed product base.
The unperfumed product base, wherein the abreviations are as defined herein
after for the examples, is as follows:
Composition . % by weight
~.AS 1 s
NaSKS-6
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PB1 8
TAED 2.4
Carbonate 1
Sodium Carbonate 1
HEDP 0.4
SRP1 0.2
Photobleach 0.013
Citric acid 1.0
Protease 0.3
Lipase 0.1
Cellulase 0.1
Amylase 0.3
Zeolilte 3.0
TFAA 3.0
QAS1 2.5
Silicone antifoam 1.0
Misclminors to balance
to 100%
Levels of amine reaction product are selected so as to obtain an odour grade
on
the dry fabric of at least 20. After careful mixing, by shaking the container
in
case of a liquid, with a spatula in case of a powder, tlhe product is allowed
to sit
for 24 hrs.
Washing process:
The resulting product is added into the washing machine in the dosage and in
the dispenser appropriate for its category. The quantity corresponds to
recommended dosages made for the corresponding market products: typically
between 70 and 150 g for a detergent powder or liquid via current dosing
device
like granulette, or ariellette. The load is composed of four bath towels
(170g)
using a Mieie W830 washing machine at 40°C short cycle, water input
:15°Hardness at a temperature of 10-18°C, and full spin of
1200rpm.
The same process is applied for the corresponding free perfume ingredient in
consideration and is used as the reference. Dosages, fabric toads and washing
cycles for the reference and the sample are identical.
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Drying Process:
Within two hours after the end of the washing cycle, the spinned but still wet
fabrics are assessed for their odors using the scale mentioned below.
Afterwards, half of the fabric pieces are hung on a line for 24 hr drying,
away
from any possible contaminations. Unless specified, this drying takes place
indoor. Ambient conditions are at temperature between 18-25C and air moisture
between 50-80%. The other half is placed in a tumble drier and undergoes a
full
"very dry" cycle, i.e. in a Miele, Novotronic T430 set on program white-extra
dry
(full cycle). Tumble dry fabrics are also assessed on the next day. Fabrics
are
then stored in opened aluminum bags in an odor free room, and assessed again
after 7 days.
Odor Evaluations:
Odor is assessed by expert panellist smelling the fabrics. A 0-100 scale is
used
for all fabric odor gradings. The grading scale is as follows
100 = extremely strong perfume odor
7a = very strong perfume odor
50 = strong odor
40 = moderate perfume odor
= slight perfume odor
20 = weak perfume odor
10 = very weak perfume odor
0 = no odor
A difference of more than 5 grades after one day and/or 7 days between the
amine reaction product and the perfume raw material is statistically
significant. A
difference of 10 grades or more after one day and/or 7 days represents a step-
change. In other words, when a difference of grade of more than 5, preferably
at
least 10 is observed between the amine reaction product and the perfume raw
material, after either 1 day or 7 days or both 1 day and 7 days, it can be
concluded that the amine reaction product is suitable for use in the present
invention, provided that the amine compound fulfill the Odour Intensity Index.
2)-For hard surface:
Product preparation:
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The perfume raw material or blend thereof is added and carefully mixed at
0.255% in the unperfumed Hard Surface Cleaner base.
The unperfumed product base, wherein the abreviations ace as defined herein
after for the examples, is as follows:
Composition for hard surface test % by weight
C12-14 EO 21 2
C12-14 EO 5 2,~
C9-11 EO 5 2.5
~S 0.8
Na2C03 0,2
Citric acid p.g
Caustic acid 0.5
Fatty acid 0,5
SCS 1.5
Water &Misc/Minors to balance to
100%
After mixing and standing for 24 hrs, the homogeneity of the product is
checked.
In case of phase separation due to poor solubility of the perfume ingredients)
an appropriate amount of Sodium p. Cymene Sulfonate or another solubilising
agent is added till a homogeneous solution is obtained.
Cleaning process:
Five grams of this solution are evenly applied on the upper side of a ceramic
tile
(875 square cm, e.g. from Vileroy-Boch). After 1 minute the tile is rinsed
with 1
liter of tap water. The tile is then placed in a vertical position for 3
minutes to
allow the rinse water to drip off.
Finally, the tile is placed in a clean and aerated perspex box {38 x 40 x 32
cm)
with a removable cover that has a sliding-lid (10 x 10 cm) to allow expert
evaluators to smell the interior phase of the box.
The odor in the box is evaluated just after placing the tile in it (fresh
reading) and
after 1, 2 and 6 hours.
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Odor Evaluation:
The grading scale is as follows
50 = very strong odor
40 = strong odor
30 = moderate odor
20 = slight odor
= weak odor
0 = no odor
Every test includes a blanc (unperfumed Hard Surface Cleaner) and in the case
of testing perfume precursor, so-called amine. reaction product the
corresponding free perfume ingredient is also included so that the effect of
the
carrier is adequately measured.
Again as for the Dry surface Odour Index method for fabrics, a difference of
more than 5 grades after 1 day andlor 7 days between , the amine reaction
product and the perfume raw material is statistically significant. A
difference of
10 grades or more after 1 day andlor 7 days represents a step-change. In other
words, when a difference of grade of more than 5, preferably at least 10 is
observed between the amine reaction product and t:he perfume raw material,
after either 1 day or 7 day or both 1 day and 7 days, it can be concluded that
the
amine reaction product is suitable for use in the present, provided that the
amine
compound fulfill the Odour Intensity Index.
The amine reaction product as defined herein before is typically comprised
from
0.0001 % to 10%, preferably from 0.001% to 5%, and more preferably from
0.01 % to 2%, by weight of the composition. Mixture, of the compounds may
also be used herein.
Incorporation of the amine reaction product in the laundry and cleaning
compositions can conveniently be carried out, if necessary, by conventional
incorporation means, such as by spray-on, encapsulation like starch
encapsulation, e.g. as described in GB1464616, dry addition, or by
encapsulation in cyclodextrin. Preferably, the amine reaction product is
preformed before incorporation into the laundry and cleaning compositions. In
other words, the perfume component and the amino functional polymer of the
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present invention are first reacted together to obtain tlhe resulting amine
reaction
product as defined in the present invention and only once formed incorporated
into the laundry and cleaning compositions. By be;ing preformed before the
incorporation in fully formulated composition, a better control of the
compound
being made is obtained. Hence, the interaction with perfume composition which
may be present in fully formulated composition is avoided as well as side
reaction that could occur. Further, by such means of incorporation, efficient
control of the yield and purity of the compound is obtained.
Most preferably, when the laundry and cleaning composition comprises a
perfume, the amine reaction product is incorporated in the composition
separately from the perfume. By this means, the amine reaction product and its
subsequent perfume release is more controlled.
Typically the laundry and cleaning composition comprises a detersive
ingredient
and further optional ingredients as described hereinafter as optional
ingredients.
Detersive ingredients
Non-limiting examples of surfactants useful herein typically at levels from 1
% to
55%, by weight, include the conventional C11-C1EI alkyl benzene sulfonates
("LAS"} and primary, branched-chain and random C10-C20 alkyl sulfates ("AS"),
the C10-C1g secondary (2,3) alkyl suff,ates of the formula
CH3(CH2)x(CHOS03-M+) CH3 and CH3(CH2)y(CHOS03-M+) CH2CH3 where
x and (y + 1 ) are integers..of at least 7, preferably ai: least 9, and M is a
water-
solubilizing cation, especially sodium, unsaturated sulfates such as oley!
sulfate,
the C10-C1g alkyl alkoxy sulfates ("AEXS"; especially x up to 7 EO ethoxy
sulfates), C10-C1g alkyl alkoxy carboxyiates (especially the EO 1-5
ethoxycarboxylates), the C10-18 glycerol ethers, the C10-C1 g alkyl
poiyglycosides and their corresponding sulfated polyglycosides, and C12-C18
alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and
amphoteric surfactants such as the C12-C1g alkyl e~thoxylates ("AE") including
the so-called narrow peaked alkyl ethoxylates and Cg-C12 alkyl phenol
alkoxylates {especially ethoxylates and mixed ethoxylpropoxy), C12-C18
betaines and sulfobetaines ("sultaines"), C10-C~;g amine oxides, cationic
surfactants and the like, can also be included in the overall compositions.
The
C10-C1g N-alkyl polyhydroxy fatty acid amides can also be used. Typical
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examples include the C12-C1g N-methyiglucamides. See WO 9,206,154. Other
sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides,
such as C1p-C1g N-(3-methoxypropyl) glucamide. The N-propyl through N-
hexyl C12-C1g glucamides can be used for low sudsing. C10-C20 conventional
soaps may also be used. if high sudsing is desired, the branched-chain C10-
C1g soaps may be used. Mixtures of anionic and nonionic surfactants are
especially useful. Other conventional useful surfaci:ants 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
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%, mare 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 aikanolammonium 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
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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
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 method such as
those described in DE-A-3,417,649 and DE-A-3,74:?,043. SKS-6 is a highly
preferred layered silicate for use herein, but other such layered silicates,
such as
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-Na2SiO~i (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 alkaiine~ earth and alkali metal
carbonates as disclosed in DE 2,321,001.
Aluminosilicate builders are useful in the present invention. Aluminosiiicate
builders are of great importance in most currently marketed heavy duty
granutar
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)yj~xH20
wherein z and y are integers usually of at least 6, the molar ratio of z to y
is in
the range from 1.O 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 aiuminosilicates can be crystalline or amorphous in structure and can be
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naturally-occurring aluminosilicates or synthetically derived. A method for
producing aluminosilicate ion exchange materials is ciisciosed 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 Zeoiite X. In an especially preferred embodiment, the crystalline
aluminosilicate ion exchange material has the formula:
Na l 2~(A102)12(Si02) 121~xH20
wherein x is from 20 to 30, especially 27. This matssrial 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.
Organic detergent builders suitable for the purposes of the present invention
include, but are not restricted to; a wide variety of poiycarboxylate
compounds.
As used herein, "polycarboxylate" refers to compounds having a plurality of
carboxylate groups, preferably at least 3 carboxylatE~s. Polycarbaxylate
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 alkanoiammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of
useful
materials. One important category of polycarboxylate builders encompasses the
ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S.
3,128,287, U.S. 3,635,830. See also "TMSITDS" builders of U.S. 4,663,071.
Suitable ether polycarboxylates also include cyclic compounds, particularly
aiicyclic 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 hydroxypoiycarboxylates,
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 anti
nitrilotriacetic acid,
as well as polycarboxylates such as mellitic acid, pyromeliitic, succinic
acid,
oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,
carboxymethyloxysuccinic acid, and soluble salts thereof.
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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 biodegradability. Citrates can also be used in granular compositions,
especially in combination with zeolite andlor layered silicate builders.
Oxydisuccinates are also especially useful in such compositions and
combinations.
Also suitable in the detergent compositions of the preaent 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 E=P 0,200,263.
Other suitable polycarboxylates are disclosed in U.S 4,144,226 and in U.S.
3,308,067. See also U.S. 3,723,322.
Fatty acids, e.g., C12-C1g monocarboxyfic 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 andlor the succinate builders,
to
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 1be used, and especially in
the formulation of bars used for hand-laundering operations, the various
alkali
metal phosphates such as the well-known sodium tripoiyphosphates, 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.
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Bleaching ComAOUnds - Bleaching Aqents and Bleach Activators
The detergent compositions herein may optionally contain bleaching agents or
bleaching compositions containing .a bleaching agent and one or more bleach
activators. When present, bleaching agents will typically be at levels of from
1
to 30%, more typically from 5% to 20%, of the detergent composition,
especially
for fabric laundering. If present, the amount of bleach activators will
typically be
from 0.1 % to 60%, more typically from 0.5% to 40% of the bleaching
composition
comprising the bleaching agent-plus-bleach activator,
The bleaching agents used herein can be any. of the bleaching agents useful
for
detergent compositions in textile cleaning or other cleaning purposes that are
now known or become known. These include oxygen bleaches as well as other
bleaching agents like hypochiorite bleaching agents. Perborate bleaches, e.g.,
sodium perborate (e.g., mono- or tetra-hydrate) can be used herein. When
hypochiorite is used, a highly preferred hypochlorite bleaching component is
an
alkali metal hypochlorite. Although alkali metal hypochlorites are preferred,
other
hypochiorite compounds may also be used herein and can be selected from
calcium and magnesium hypochlorite. A preferred alkali metal hypochlorite for
use herein is sodium hypochlorite.
Another category of bleaching agent that can be used without restriction
encompasses percarboxylic acid bleaching agents <~nd salts thereof. Suitable
examples of this class of agents include magnesium monoperoxyphthalate
hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-
4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents
are disclosed in U.S 4,483,781, U.S 740,446, EP 0,133,354, and U.S 4,412,934.
Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic
acid as described in U.S 4,634,551.
Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching
compounds include sodium carbonate peroxyhydrate and equivalent
"percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea
peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE,
manufactured commercially by DuPont) can also be used.
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A preferred percarbonate bleach comprises dry particles having an average
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
FMC, Sofvay and Tokai Denka.
Mixtures of bleaching agents can also be used.
Peroxygen bleaching agents, the perborates, the percarbonates, etc., are
preferably 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. 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) and tetraacetyl ethylene diamine (TAED) 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:
R1N(R5)C(O)R2C(O)L or R1C(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
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)oxybenzenesuifonate, (6-nonanamidacaproyl)oxybenzene
sulfonate, (6-decanamido-caproyl)oxybenzenesuifonaite, 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 the benzoxazin-type is:
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O
II
CEO
~~C o.J
N
Still another class of preferred bleach activators includes the acyl lactam
activators, especially acyl caprolactams and acyl valerolactams of the
formulae:
0 0
s~0 C-CH2-CH2\ 6-O C-CHz-CH2
R C-N~CH2-CH2~CH2 R C-NCH - ~ H
2
wherein R6 is H or an alkyl, aryl, aikoxyaryl, or alkaryl group containing
from 1 to
12 carbon atoms. Highly preferred lactam activators include benzoyl
caprolactam, octanoyl caprolactam, 3,5,5-trimet:hylhexanoyl caprolactam,
nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl
valerolactam, octanoyl valerolactam, decanoyl valerolac~am, undecenoyi
valerolactam, nonanoyi valeroiactam, 3,5,5-trimethylhexanoyi valerolactam and
mixtures thereof. See also U.S. Patent 4,545,784, is:>ued to Sanderson,
October
8, 1985; incorporated herein by reference, which discloses acyl caprolactams,
including benzoyl caprolactam, adsorbed into sodium perborate.
Bleaching agents other than oxygen bleaching agenta 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
andlor aluminum phthalocyanines. See U.S. 4,033,718. If used, detergent
compositions will typically contain from 0.025% to 1.25%, by weight, of such
bleaches, especially sulfonate zinc phthalocyanine.
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 E:P 549,271A1, 549,272A1,
544,440A2, and 544,490A1; Preferred examples of these catalysts include
MnlV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, Mnlll2 (u-O}1(u-
\:
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OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2_{C104)2, MnlV4(u-O)6(1,4,7-
triazacyclononane)4(CI04)4, MnIIIMniV4(u-O)1(u-C)Ac)2_(1,4,7-trimethyl-1,4,7-
triazacyclononane)2(C104)3, MnIV(1,4,7-trimethyl-1,4,7-triazacyclononane)-
{OCH3)3(PF6), and mixtures thereof. Other metal-based bleach catalysts
include those disclosed in U.S. Pat. 4,430,243 and ll.S. 5,114,611. The use of
manganese with various complex Iigands to enhances 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 thie aqueous washing
liquor,
and will preferably provide from 0.1 ppm to 700 ppm, more preferably from 1
ppm to 500 ppm, of the catalyst species in the laundr)r liquor.
Briqhteners
The compositions herein can also optionally contaiin from 0.005% to 5% by
weight of certain types of hydrophilic optical brighteners which also provide
a
dye transfer inhibition action. If used, the compasi!tions 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:
Rt R
--N H H rl
N ~~--N a C=C ~ N--~{~ N
j"-N H H rf --C
R~~ SO;M S03M R~
wherein R1 is selected from aniiino, N-2-bis-hydroxyethyi and NH-2-
hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyi-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 anifino, R2 is N-2-l:>is-hydroxyethyl and M
is a
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
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tradename Tinopal-UNPA-GX~ by Ciba-Geigy Corporation. Tinopa!-UNPA-GX
is the preferred hydrophilic optical brightener useful in the rinse added
compositions 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, they brightener is 4,4'-bis[(4-
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 SBM-GX~ by Ciba-Geigy
Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a canon
such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-
2-
yi)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener
species is commercially marketed under the tradename Tinopal AMS-GX~ by
Ciba Geigy Corporation.
Soil Release Agent
In the present invention, an optional soil release agent can be added. Typical
levels of incorporation in the composition are from 0°~o 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
hydrophiiize 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%.
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33
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 Juiy 8, 1975; U.S. 4,000,093, Nicol, et
al., issued December 28, 197fi; 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, Gosaelink, issued January 26,
1988; U.S. 4,877,896, Maidonado 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, ef al..
Further suitable soil release agents are described in I,~,S. 4,201,824,
Vioiland et
al.; U.S. 4,240,918 I_agasse 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 Uniiever 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 512fi (from Dupont} and MILEASE T (from iCl).
Scum Dispersant
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
above the melting points) of the components.
The preferred scum dispersants herein are formE:d 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 :SOiI release polymers. The
preferred scum dispersants are highly ethoxylate:d, e.g., more than 17,
preferably more than 25, more preferably more than 4~0, moles of ethylene
oxide
per molecule on the average, with the poiyethylene~ oxide portion being from
76% to 97%, preferably from 81 % to 94%, of the total molecular weight.
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34
The level of scum dispersant is sufficient to keep the scum at an acceptable,
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
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 surfactanf: 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 25-50U.
Bactericides
Examples of bactericides used in the composition~~ of this invention include
glutaraldehyde, formaldehyde, 2-bromo-2-nitro-propane-1,3-dioi sold by inolex
Chemicals, located in Philadelphia, Pennsylvania,. under the trade name
Bronopol~, and a mixture of 5-chloro-2-methyl-4-isothiazoline-3-one and 2-
methyl-4-isothiazoiine-3-one sold by Rohm and Haas Company under the trade
name Kathon 1 to 1,000 ppm by weight of the agent.
Perfume
The present invention can contain any detergent compatible perfume. Suitable
perfumes are disclosed in U.S. Pat. 5,500,138, said patent being incorporated
herein by reference.
As used herein, perfume includes fragrant substance: or mixture of substances
including natural (i.e., obtained by extraction of flowers, herbs, leaves,
roots,
barks, wood, blossoms or plants), artificial (i.e., a mixture of different
nature oils
or oil constituents) and synthetic (i.e., synthetically produced) odoriferous
substances. Such materials are often accompanied try auxiliary materials, such
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as fxatives, extenders, stabilizers and solvents. These auxiliaries are also
included within the meaning of "perfume", as used herein. Typically, perfumes
are complex mixtures of a plurality of organic compounds.
Examples of perfume ingredients useful in the perfumes of the present
invention
compositions include, but are not limited to, hexyl cinnamic aldehyde; amyl
cinnamic aldehyde; amyl salicylate; hexyl salicylate; terpineol; 3,7-dimethyl-
cis-
2,6-octadien-1-ol; 2,6-dimethyl-2-actanol; 2,6-dimethyl-7-octen-2-ol; 3,7-
dimethyl-3-octanol; 3,7-dimethyl-frans-2,6-octadien-1~-ol; 3,7-dimethyl-6-
octen-1-
ol; 3,7-dimethyl-1-octanol; 2-methyl-3-(para-tert-butylphenyl}-
propionaidehyde;
4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde; tricyclodecenyl
propionate; tricyclodecenyl acetate; anisaldehyde; 2-methyl-2-(para-iso-
propylphenyl)-propionaldehyde; ethyl-3-methyl-3-phenyl glycidate; 4-(para-
hydraxyphenyi}-butan-2-one; 1-(2,6,6-trimethyl-2-c;yclohexen-1-yl}-2-buten-1-
one; para-methoxyacetophenone; para-methoxy-alpha-phenylpropene; methyl-
2-n-hexyl-3-oxo-cyclopentane carboxylate; undecalactone gamma.
Additional examples of fragrance materials include, but are not limited to,
orange
oil; lemon oil; grapefruit oil; bergamot oil; clove oil; dodecalactone gamma;
methyl-2-(2-pentyl-3-oxo-cyclopentyi) acetate; beta-naphthol methylether;
methyl-beta-naphthylketone; coumarin; decyialdehyde; benzaldehyde; 4-tert-
butylcyclohexyi acetate; alpha,alpha-dimethylphenethyl acetate;
methylphenylcarbinyl acetate; Schiffs base of 4-(4-hydroxy-4-methylpentyl}-3-
cyclohexene-1-carboxaldehyde and methyl anthranulate; cyclic ethylenegiycol
diester of tridecandioic acid; 3,7-dimethyl-2,6-octadiene-1-nitrite; ionone
gamma
methyl; ionone alpha; ionone beta; petitgrain; methyl cedrylone; 7-acetyl-
1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene; ionone methyl;
methyl-1,6,10-trimethyl-2,5,9-cyclododecatrien-1-yl ke~tone; 7-acetyl-
1,1,3,4,4,6-
hexamethyl tetralin; 4-acetyl-6-tert-butyl-1,1-dimethyl indane; benzophenone;
6-
acetyl-1,1,2,3,3,5-hexamethyl indane; 5-acetyl-3-isopropyl-1,1,2,6-
tetrarnethyl
indane; 1-dodecanal; 7-hydroxy-3,7-dimethyl octanal; 10-undecen-1-al; iso-
hexenyl cyclohexyl carboxaldehyde; formyl tricyclodec;an;
cyclopentadecanolide;
16-hydroxy-9-hexadecenoic acid lactose; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-
hexamethyicyclopenta-gamma-2-benzopyrane; ambroxane; dodecahydro-
3a,6,6,9a-tetramethylnaphtho-[2,1 b]furan; cedrol; 5-(2;2,3-trimethylcyclopent-
3-
enyl)-3-methylpentan-2-ol; 2-ethyl-4-(2,2,3-trimethyl-3~-cyciopenten-1-yl)-2-
buten-
1-0l; caryophyllene alcohol; cedryl acetate: para-tert-butylcyclohexyl
acetate;
patchouli; olibanum resinoid; labdanum; vetivert; copaiba balsam; fir balsam;
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PCT/US99/15678
and condensation products of: hydroxycitronellal and methyl anthranilate;
hydroxycitronellai and indol; phenyl acetaldehyde and indol; 4-(4-hydroxy-4-
methy! pentyl)-3-cyclohexene-1-carboxaldehyde and methyl anthranilate.
More examples of perfume components are, geraniol; geranyl acetate; iinalool;
linalyl acetate; tetrahydrolinalool; citroneilol; citronellyl acetate;
dihydromyrcenol;
dihydromyrcenyl acetate; tetrahydromyrcenol; terpinyl acetate; nopol; nopyl
acetate; 2-phenylethanol; 2-phenylethyl acetate; bE~nzyl alcohol; benzyl
acetate;
benzyi salicylate; benzyl benzoate; styrallyl acetate; dimethyibenzylcarbinol;
trichloromethylphenylcarbinyl methylpfienylcarbinyl acetate; isononyl acetate;
vetiveryi acetate; vetiverol; 2-methyl-3-(p-tert-butyl>henyl)-propanal; 2-
methyl-3-
(p-isopropyiphenyl)-propanal; 3-(p-tert-butylphenyl)-propanal; 4-(4-methyl-3-
pentenyl)-3-cyciohexenecarbaldehyde; 4-acet:oxy-3-pentyltetrahydropyran;
methyl dihydrojasmonate; 2-n-heptylcyclopentanone; 3-methyl-2-pentyl-
cyciopentanone; n-decanal; n-dodecanal; 9-decenol-1; phenoxyethyl
isobutyrate; phenylacetaldehyde dimethylac~etal; phenyiacetaldehyde
diethylacetal; geranonitriie; citroneilonitrile; cedryl acetal; 3-
isocamphylcyclohexanol; cedryi methylether; isolongifolanone; aubepine
nitrite;
aubepine; heliotropine; eugenol; vanillin; Biphenyl oxide; hydroxycitronellal
ionones; methyl ionones; isomethyi ionomes; irone~s; cis-3-hexenol and esters
thereof; indane musk fragrances; tetralin musk fragrances; isochroman musk
fragrances; macrocyclic ketones; macroiactone musk fragrances; ethylene
brassylate.
The perfumes useful in the present invention compositions are substantially
free
of halogenated materials and nitromusks.
Suitable solvents, diiuents or carriers for perfumes ingredients mentioned
above
are for examples, ethanol, isopropanol, diethylen~e glycol. monoethyl ether,
dipropylene glycol, diethyl phthalate, triethyl citrate, etc. The amount of
such
solvents, diluents or carriers incorporated in the perfumes is preferably kept
to
the minimum needed to provide a homogeneous perfume solution.
Perfume can be present at a level of from 0% to 10%, preferably from 0.1 % to
5%, and more preferably from 0.2% to 3%, by weight of the finished
composition. Fabric softener compositions of the present invention provide
improved fabric perfume deposition.
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Chelatinc~Agents
The compositions and processes herein can optionally employ one or more
copper andlor 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
andlor brightness of fabrics are substantially improved or restored by such
chelating agents and the stability of the materials in the compositions are
improved. Without intending to 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 cheiating agents include
ethylenediaminetetracetates, N-hydroxyethyle~thylenediaminetriacetates,
nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetra-
aminehexacetates, diethyierietriaminepentaacetates., 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
to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
Polyfunctionaliy-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
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 Perkin;~.
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38
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 dike.
Preferred chelating agents include DETMP, DETPA, NTA, EDDS and mixtures
thereof.
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.
Crystal growth inhibitor 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
included in compositions of the invention as heavy metal ion sec#uestrant
components.
The organo diphosphonic acid is preferably a C1-C~ diphosphonic acid, more
preferably a C2 diphosphonic acid, such as ethylene diphosphonic acid, or most
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
acid
Organo monophosphonic acid or one of its salts or compfexes is also suitable
far
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
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definition therefore excludes the organo aminophosphonates, which however
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
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 preferred 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
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 disctoses suitable fungal
cellulases from Humicola insolens or Humicola strain DSM1800 or a cellulase
212-producing fungus belonging to the genus Aeromonas, and ceilulase
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~ aind CELLUZYMEC~ (Novo}
are especially useful. Other suitable cellulases are also disclosed in WO
91/17243 to Novo, WO 96/34092, WO 9fil34945 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 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 preferred (e.g. CEVU or cellulase Equivalent Viscosity
Units).
Far instance, the compositions of the present invention can contain cellulase
enzymes at a level equivalent to an activity from 0.5 to 1000 CEVUlgram of
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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 CEVUlgram in liquid form, around 1,000 CEVUlgram in solid
form.
Clay
The compositions of the invention may preferably contain a clay, preferably
present at a level of from 0.05% to 40%, more ~prefPrabiy 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
aiuminosilicate zeolite builder compounds, which hovuever, 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. Typical smectite clay compounds include the compounds
having the general formula AI2(Si205)2(OH)2.nH20 amd the compounds having
the general formula Mg3(Si205)2(OH)2.nH20. Smectite clays tend to adopt an
expandable three layer structure.
Specific examples of suitable smectite clays includes those selected from the
classes of the montmorillonites, hectorites, vol~chonskoites, nontronites,
saponites and sauconites, particularly those having an alkali or alkaline
earth
metal ion within the crystal lattice structure. Sodium or calcium
montmorillonite
are particularly preferred.
Suitable smectite clays, particularly montmoriilonitEa, are sold by various
suppliers including English China Clays, Laviosa, Georgia Kaolin and Colin
Stewart Minerals.
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Clays for use herein preferably have a particle diimension of from l0nm 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 rations, 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 ration type, such ability being assessed
by
measurements of relative ion exchange capacity. The smectite clays suitable
herein typically have a ration exchange capacity of at least 50 meq/100g. U.S.
Patent No. 3,954,fi32 describes a method for measurement of ration exchange
capacity.
The crystal lattice structure of the clay mineral compounds may have, in a
preferred execution, a cationic fabric softening agent substituted therein.
Such
substituted clays have been termed 'hydrophobic:ally 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 7:11); preferably from 1:100
to
1:20. Suitable cationic fabric softening agents incfude> the water insoluble
tertiary
amines or dilong chain amide materials as disclosed in GB-A-1 514 27fi and EP-
B-0 011 340.
A preferred commercially available "hydrophobicaily activated" clay is a
bentonite clay containing approximately 40% by weight of a dimethyi ditallow
quaternary ammonium salt sold under the tradenarr~e 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,
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preferably a wax or oil, such as paraffin oil. Preferred humectants are
organic
compounds, including propylene glycol, ethylene glycol; dimers or trimers of
glycol, most preferably glycerol. The particle is preferably an agglomerate.
Alternatively, the particle may be such that the wax or oil and optionally the
humeetant form an encapsulate on the clay or alternatively, the clay be a
encapsulate for the wax or oil and the humectant. li: 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
particle comprising the clay.
It may be preferred that the flocculating agent is also comprised in the
particle or
granule comprising the clay.
It may also be preferred that the intimate mixture comprises a cheiating
agent.
Flocculatingi agent
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
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.
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Suitable organic polymeric materials comprise homopolymers or copolymers
containing monomeric units selected from aikylene oxide, particularly ethylene
oxide, acrylamide, acrylic acid, vinyl alcohol, vinyl pyrrolidone, and
ethylene
imine. Homopoiymers of, on particular, ethylene oxide, but also acrylamide and
acrylic acid are preferred.
European Patents No.s EP-A-299,575 and EP-A-3'13,146 in the name of the
Procter and Gamble Company describe preferred organic polymeric clay
flocculating agents for use herein.
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 therein, 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
general3y
one or more surfactants and builders.
Effervescent
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. C6H8O7 + 3NaHC03 ~ Na3CgH5O7 + 3C02 1' + 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 ).
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Carbonate salts
Suitable alkali andl or earth alkali inorganic carbonate salts herein include
carbonate and hydrogen carbonate of potassium, lithium, sodium, and the like
amongst which sodium and potassium ca:~bonate 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
mixtures thereof may be made depending on the pH desired in the aqueous
medium wherein the granules are dissolved. Far 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
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 andl or bicarbonate. Preferably, the carbonate salt comprises sodium
carbonate, optionally also a sodium bicarbonate.
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
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.
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,
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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
feast 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.
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 materiiai, 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
Other preferred optional ingredients include enzymes stabilisers, polymeric
soil
release agents, rnateriais effective for inhibiting the transfer of dyes from
one
fabric to another during the cleaning process (i.e., dye transfer inhibiting
agents),
polymeric dispersing agents, suds suppressers, optical brighteners or other
brightening or whitening agents, anti-static agents, other active ingredients,
carriers, hydrotropes: processing aids, dyes or pigments, solvents for liquid
formulations and solid fillers for bar compositions.
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Form of the composition
The composition of the invention may take a variety of physical form including
liquid, gel, foam in either aqueous or non-aqueous form, granular and tablet
forms.
Liquid detergent compositions can contain water and other solvents as
carriers.
Low molecular weight primary or secondary alcohols exemplified by methanol,
ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are
preferred for solubiiizing surfactant, but polyols such as those containing
from 2
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 gll) or agglomerating (anal product density above 600 g/l) 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 wilt 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 7.5 and 10.5. Laundry products are
typically at pH 9-11. 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.
When in a liquid form, the composition may also be dispensed by a dispensing
means such as a spray dispenser, or aerosol dispenser.
S~~ray Dispenser
The present invention also relates to such compositions incorporated into a
spray dispenser to create an article of manufacture that can facilitate
treatment
of fabric articles andlor surfaces with said compasiiuons containing the amine
reaction product and other ingredients (exannples are cyclodextrins,
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polysaccharides, polymers, surfactant, perfume, softener} at a level that is
effective, yet is not discernible when dried on the surfaces. 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. Typical compositions to be dispensed from a
sprayer contain a level of amine reaction product of 'from about 0.01 % to
about
5%, preferably from about 0.05% to about 2%, more preferably from about 0.1
to about 1 %, by weight of the usage composition.
Method of use
The composition of the invention are suitable for use in any step of the
domestic
treatment, that is a pre-treatment composition, as a wash additive, as a
composition suitable for use in the laundry and cleaning process. Obviously,
multiple application can be made such as treating the fabric with a pre-
treatment
composition of the invention and thereafter with the composition suitable for
use
in the laundry process.
Also provided herein is a method for providing a delayed release of an active
ketone or aldehyde which comprises the step of contacting the surface to be
treated with a compound or composition of the invention, and thereafter
contacting the treated surface with a material, preferably an aqueous medium
like moisture or any other means susceptible of releasing the perfume from the
amine reaction product.
By "surface", it is meant any surface onto which tree compound can deposit.
Typical examples of such material are fabrics, hard surfaces such as dishware,
floors, bathrooms, toilet, kitchen and other surfaces in need of a delayed
release
of a perfume ketone and/or aldehyde such as that with litter like animal
litter.
Preferably, the surface is selected from a fabric, a tile, a ceramic; more
preferably is a fabric.
By "delayed release" is meant release of the active component (e.g perfume)
over a longer period of time than by the use of the active (e.g., perFume)
itself.
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Abbreviations used in the followina laundr~r and cleanina composition Examples
In the laundry and cleaning compositions, the abbreviated component
identifications have the following meanings:
In the detergent compositions, the abbreviated component identifications have
the following meanings:
LAS : Sodium linear C11_13 alkyl benzene sulfonate
TAS : Sodium tallow alkyl sulfate
CxyAS : Sodium C1x - C1y alkyl sulfate
C46SAS : Sodium C14 - C16 secondary (2,3) alkyl sulfate
CxyEzS : Sodium C1x-C1y alkyl sulfate condensed with
z
moles of ethylene oxide
CxyEz : C1x-C1y predominantly linear primary alcohol
condensed with an average of z moles of ethylene
oxide
QAS : R2.N+{CH3)2(C2H40H) ~nrith R2 = C12 - C14
QAS 1 : R2.N+(CHg}2(C2H40H) with R2 = Cg - C11
APA : Cg - C10 amido propyl dimethyl amine
Soap : Sodium linear alkyl carboxylate derived from
an
80120 mixture of tallow and coconut tatty acids
STS : Sodium toluene sulphonate
CFAA : C12-C14 (coco} alkyl N-methyl glucamide
TFAA : C16-C1g alkyl N-methyl g~iucamide
TPKFA : C12-C14 toPPed whole cut fatty acids
STPP : Anhydrous sodium tripolyphosphate
TSPP : Tetrasodium pyrophosphate
Zeolite A : Hydrated sodium aluminosilicate of formula
Nal2(A102Si02)12.27Ha0 having a primary
particle size in the range from 0.1 to 10 micrometers
{weight expressed on an anhydrous basis)
NaSKS-6 : Crystalline layered silicatE: of formula 8-
Na2Si205
Citric acid : Anhydrous citric acid
Borate : Sodium borate
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Carbonate : Anydrous sodium carbonate with a particle
size
between 200pm and 9001am
Bicarbonate : Anhydrous sodium bicarbonate with a particle
size
distribution between 400ym and 1200Nm
Silicate : Amorphous sodium silical;e (Si02:Na20 = 2.0:1)
Sulfate : Anhydrous sodium sulfate:
Mg sulfate : Anhydrous magnesium sulfate
Citrate : Tri-sodium citrate dihydrate of activity
86.4% with a
particle size distribution between 425pm
and 850um
MA/AA : Copolymer of 1:4 malleiclacrylic acid, average
molecular weight about 70,000
MAIAA ~( 1 ) Copolymer of 4:6 malleic/acryiic acid, average
:
molecular weight about 11),000
AA : Sodium polyacrylate polymer of average molecular
weight 4,500
CMC : Sodium carboxymethyl cellulose
Cellulose ether Methyl cellulose ether with a degree of
:
polymerization of 650 available from Shin
Etsu
Chemicals
Protease : Proteolytic enzyme, having 3.3% by weight
of active
enzyme, sold by NOVO Industries AIS under
the
tradename Savinase
Protease I : Proteolytic enzyme, having 4% by weight of
active
enzyme, as described in WO 95/10591, sold
by
Genencor Int. Inc.
Alcalase : Proteolytic enzyme, having 5.3% by weight
of active
enzyme, sold by NOVO Industries A/S
Cellulase : Cellulytic enzyme, having 0.23% by weight
of active
enzyme, sold by NOVO Industries A/S under
the
tradename Carezyme
Amylase : Amylolytic enzyme, having 1.6% by weight
of active
enzyme, sold by NOVO Industries A/S under
the
tradename Termamyl 120~T
Lipase : Lipolytic enzyme, having 2.0% by weight of
active
enzyme, sold by NOVO Industries A/S under
the
tradename Lipolase
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Lipase {1) : Lipolytic enzyme, having 2.0% by weight of active
enzyme, sold by NOVO Industries A/S under the
tradename Lipotase Ultra
Endolase : Endogtucanase enzyme, having 1.5% by weight of
active enzyme, sold by NOVO Industries A!S
PB4 : Sodium perborate tetrahydrate of nominal formula
NaB02.3H20.H202
PB1 : Anhydrous sodium perborate bleach of nominal
fom~ula NaB02.H202
Percarbonate : Sodium percarbonate of nominal formula
2Na2C03.3H202
NOBS : Nonanoyioxybenzene suifonate in the form of the
sodium salt
NAC-OBS : {6-nonamidocaproyl) oxybenzene sulfonate
TAED : Tetraacetylethylenediamine
DTPA : Diethylene triamine pentaacetic acid
DTPMP : Diethylene triamine penta (methylene phosphonate),
marketed by Monsanto under the Tradename
bequest 2060
EDDS : Ethytenediamine-N,N'-disuccinic acid, (S,S)
isomer
in the form of its sodium salt.
Photoactivated Sulfonated zinc phthlocyanine encapsulated
: in
bleach (1) dextrin soluble polymer
Photoactivated Sulfonated alumino phthlocyanine encapsulated
: in
bleach (2) dextrin soluble polymer
Brightener 1 Disodiurn 4,4'-bis(2-suiphostyryl)biphenyl
:
Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-
:
triazin-2-yl)amino) stilbene:-2:2'-disuifonate
HEDP : 1,1-hydroxyethane diphos;phonic acid
PEGx : Polyethylene glycol, with a molecular weight
of x
(typically 4,000)
PEO : Polyethylene oxide, with an average molecular
weight of 50,000
TEPAE : Tetraethyienepentaamine ethoxyiate
PVI : Polyvinyl imidosole, witlh an average molecular
weight of 20,000
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PVP : Polyvinylpyrolidone polymer, with an average
molecular weight of 60,00()
PVNO . Polyvinylpyridine N-oxide polymer, with an
average
molecular weight of 50,00()
PVPVI : Copolymer of polyvinylpyroiidone and
vinylimidazole, with an average molecular weight
of
20,000
QEA : bis((C2H50)(C2H40)n)(CIH3) -N~-C6H12-N+-(CH3)
bis((C2H50)-(C2H40))n, wherein n = from 20
to 30
SRP 1 : Anionically end capped poly esters
SRP 2 : Diethoxylated poly (1, 2 propylene terephtaiate)
short block polymer
PEI : Polyethyleneimine with an average molecular
weight
of 1800 and an average ethoxylation degree
of 7
ethyleneoxy residues per nitrogen
Silicone antifoamPolydimethylsiloxane foann controller with
: siloxane-
oxyalkylene copolymer as dispersing agent with
a
ratio of said foam controller to said dispersing
agent
of 10:1 to 100:1
Opacifier : Water based monostyrene latex mixture, sold
by
BASF Aktiengeseilschaft under the tradename
Lytron 621
Wax : Paraffin wax
PA30 : Polyacryfic acid of average molecular weight
of between
about 4,500 - 8,000.
480N : Random copolymer of 7:3 acrylatelmethacrylate,
average molecular weight about 3,500.
Polygellcarbopol: Higfi molecular weight crosslinked polyacrylates.
Metasilicate ; Sodium metasilicate (Si02:Na20 ratio = 1.0).
Nonionic : C13-C15 mixed ethoxyiated~propoxylated fatty
alcohol
with an average degree of ethoxyiation of 3.8
and an
average degree of propoxylation of 4.5.
Neodol 45-13 : C14-C15 linear primary alcohol ethoxylate,
sold by Shell
Chemical CO.
MnTACN : Manganese 1,4,7-trimethyl-1.4,7-triazacyclononane.
PAAC : Pentaamine acetate cobait(III) salt.
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Paraffin : Paraffin oil sold under they tradename Winog 70 by
Wintershall.
NaBz : Sodium benzoate.
BzP : Benzoyl Peroxide.
SCS : Sodium cumene sulphonate.
BTA : Benzotriazole.
pH : Measured as a 1 % solution in distilled water at 20°C.
ARP1 : Amine reaction product of 1,4-bis-(3-aminopropyl)-
piperazine with a-Damascone as made from Synthesis
example I
ARP2 : Amine reaction product of N,N'bis(arninopropyl)1,3-
propanediamine with 8-Da~mascone as made from
Synthesis example II
ARP3 : Amine reaction product of polyvinylamine MW1200 with
a-Damascone as made from Synthesis example III
Clay I : Bentonite clay
Clay II : Smectite clay
Flocculating agent t : polyethylene oxide of average molecular weight of
between 200,000 and 400,000
Flocculating agent II: polyethylene oxide of average molecular weight of
between 400,000 and 1,000,000
Flocculating agent III: polymer of acrylamide ancll or acrylic acid of
average molecular weight of 200,000 and
400,000
DOBS: Decanoyi oxybenzene suliFonate in the fofm of the
sodium salt
SRP 3 : Polysaccharide soil release polymer
SRP 4 : Nonionicaily end capped poly esters
The following are synthesis examples of compounds as defined in the present
invention:
I-Synthesis of 1,4-bis-(3-aminopropyil~-piperazine mith a-Damascone
In order to substitute both primary amine groups with .a perfume, 2eq of
perfume
were used for 1eq of amino functional polymer. To an ice cooled stirred
solution
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53
of 1 mmol of a-Damascene in 6 mL EtOH and molecular sieves {4A, 20 g),
0.5eq of 1,4-bis-(3-aminoprapyi)-piperazine was added via an addition funnel.
The reaction mixture was stirred under nitrogen atmosphere and protected from
light. After the disappearance of the absorption peak from the NMR spectrum of
the free perfume raw material (from 3 to 16 hours), tlhe mixture was filtrated
and
the solvent was removed by vacuum distillation. The yield of (i-aminoketone
formation is about 90%.
Simiiar results were obtained where the a-Damasccme was replaced by Tripal,
vertocitral, bourgeonal, or. citronellal. In these instances, Schiff bases are
formed.
II-Synthesis of N.N'-bis(3-aminolnropyl -1,3-prouanediamine with _8-
Damascone
To an ice cooled solution of 1 mmol of 8-Damascene in 30 ml_ EtOH and
molecular sieves (4A, 5 g), 0.5eq of the N,N'-bis(3-aminopropyl)-1,3-
propanediamine was added. The reaction wa:; stirred under nitrogen
atmosphere and protected from light. After 1 day, the molecular sieves and the
solvent were removed by filtration and vacuum distillation respectively. ~i-
Aminoketone were obtained in a 85 to 90% yield.
Similar results were obtained where the 8-Damascene was replaced by Tripal,
vertocitral, bourgeonal, or citronellal. In these instances, Schiff bases are
formed.
III-Synthesis of Poiyvinyiamine of MW1 Z00 with a..Damascone
The following ingredients were mixed together : 0.6g of Sodium sulfate with
0.3g
of polyvinylamine MW 1200 in a 10% aqueous solution and 0.3g a-Damascene.
The reaction was completed after 18 days at room temperature in the dark.
Similar results were obtained where the a-Damascene was replaced by Tripal,
or citral: In these instances, Schiff-bases are formed.
In the following formulation examples all levels are quoted as % by weight of
the
composition unless otherwise stated, and incorporation of the amine reaction
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product so called herein after "ARP" in the fully formulated composition is
carried
out by dry addition (d), spray on (s), encapsulation in starch (es) as
described in
GB-1,464,616 or cyclodextrin (ec) or as is in the composition as defined
herein
before. The term in bracket for the ARP in the formulation examples refers to
the
means of incorporation. When none is provided, the incorporation is made as it
is. The levels given for the ARP, whether processed or not, refer to the level
of
ARP as is and not to the processed ARP.
Example 1
The following high density granular laundry detergent compositions were
prepared in accord with the invention:
A B C D E F G
LAS 8.0 8.0 8.0 2.0 6.0 6.0 5.0
TAS 0.5 - 0.5 1.0 0.1 1.5
C46(S)AS 2.0 2.5 - - _ -
C25AS - 7.0 4.5 5.5 2.5
C68AS 2.0 5.0 7.0 - - _ 0.2
C25E5 - - 3.4 10.0 4.6 4.6 2.6
C25E7 3.4 3.4 1.0 - - - -
C25E3S - - 2.0 5.0 4.5 0.5
QAS - 0.8 - - - _ -
QAS (I) _ _ _ 0.8 0.5 1.0 1.5
Zeolite A 18.1 18.0 14.1 18.1 20:0 18.1 16.2
Citric acid - - 2.5 _ 2.5 1.5
Carbonate 13.0 13.0 27.0 10.0 10.0 13.0 20.6
SKS-6 - - - 10.0 _ 10.0 4.3
Silicate 1.4 1.4 3.0 0.3 0.5 0.3
Citrate - 1.0 - 3.0 - - 1.4
Sulfate 26.1 26.1 26.1 6.0 - - -
Mg sulfate 0.3 - - 0.2 I - 0.2 0.03
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A B C D E F G
MAIAA 0.3 0.3 0.3 4.0 1.0 1.0 0.6
CMC 0.2 0.2 0.2 0.2 0.4 0.4 0.3
PB4 9.0 9.0 5.0 - - -
Percarbonat- - - - 18.0 18.0
a
TAED 1.5 0.4 1.5 - 3.9 4.2 3.2
NAC-OBS - 2.0 1.0 - - -
DTPMP 0.25 0.25 0.25 0.25 - -
'
SRP 2 - - - 0.2 0.2 -
EDDS - 0.25 0.4 - 0.5 0.5 0.1
TFAA - - - _ _ - 1.1
C FAA - 1.0 - 2. 0 - -
HEDP 0.3 0.3 0.3 0.3 0.4 0.4 0.3
QEA - - 0.2 - 0.5
Protease - - 0.26 1.0 - 0.3
I
Protease 0.26 0.26 1.5 1.0
Cellulase 0.3 - - 0.3 0.3 0.3 0.3
Amylase 0:1 0.1 0.1 0.4 0.5 0.5 0.1
Lipase ( 0.3 - . 0.5 0.5 0.5 0.1
1 )
Photoactivat15 15 15 - 20 20 ppm 20
ed bleach ppm ppm ppm ppm ppm
(ppm)
PVNOIPVP - - - 0.1 _
V1
Brightener 0.09 0.09 0.09 - 0.09 0.09 0.01
1
Brightener - - - - _ _ 0:09
2
Perfume 0.3 0.3 0.3 0.4 0.4 0.4 0.4
spray on
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A B C D E F G
ARP 1 0.08(d}0.1 - - ..~~ 0.1 0.05(ec)-
(es) (d}
ARP 2 - 0.08{s)0.1 (ec} 0.1 -
(s}
ARP 3 (es) - - - _ _ 0.4
Silicone 0.5 0.5 0.5 '~ 0.3 0.3 0.3
antifoam
Clay II 0.5 0,5 0.5 - 0.3 0.3 12.0
Flocculating0.5 0.5 0.5 - 0.3 0.3 0.3
agent
Glycerol 0.5 0.5 0.5 - 0.3 0.3 0.6
Wax 0.5 0.5 0.5 0.3 0.3 0.4
Misc/minors
to 100%
Density 850 850 850 850 850 85p 850
in
g/litre
Example 2
The following granular laundry detergent compositions A to F of particular
utility
under European machine wash conditions were prepared in accord with the
invention:
A B C D E F
1~4S 5.5 7.5 5.0 5.0 6.0 7.0~
TAS 1.25 ~ 1.86 - 0.8 0.4 0.3
C24ASIC25AS - 2.24 5.0 5.0 5.0 2.2
C25E3S - 0.76 1.0 1.5 3.0 1.0
C45E7 3.25 - - - - 3.0
TFAA - - 2.0 - - _
C25E5 - 5.5 - - _ _
QAS 0.8
QAS ll - 0.7 1.0 0.5 1.0 0.7
STPP 19.7 - - - _ _
Zeolite A - 19.5 25.0 19.5 20.0 17.0
I ~
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A B C D E F
NaSKS-6lcitric - 10.6 - 10.6 - -
acid
(79:21 }
NaSKS-6 - - 9.0 - 10.0 10.0
Carbonate 6.1 21.4 9.0 10.0 10.0 18.0
Bicarbonate - 2.0 7.0 5.0 - 2.0
Silicate 6.8 - 0.3 0.5 -
Citrate - 4.0 4.0 - -
Sulfate 39.8 - 5.0 - 12.0
Mg sulfate - - 0.1 0.2 0.2
MAIAA 0.5 1.6 3.0 4.0 1.0 1.0
CMC 0.2 0.4 1.0 1.0 0.4 0.4
PB4 5.0 12.7 - _ _
Percarbonate - - - - 18.0 15.0
TAED 0.5 3.1 - - 5.0
NAC-OBS 1.0 3.5 - - - 2.5
DTPMP 0.25 0.2 0.3 0.4 - 0.2
HEDP 0.3 - 0.3 0.3 0.3
QEA - 1.0 1.0 1.0 -
Protease I - - - 0.5 1.2 -
Protease 0.2fi 0.85 0.9 1.0 - 0.7
Lipase { 1 ) 0.15 0.15 0.3 0.3 0.3 0.2
Cellulase 0.28 0.28 0.2 0.2 0.3 0.3
Amylase 0.1 0.1 0.4 0.4 0.6 0.2
PVNOIPVPVI - 0.2 0.2 - -
PVP 0.9 1.3 - - - 0.9
SRP 1 - - 0.2 0.2 0.2 -
Photoactivated 15 27 - - 20 20
bleach (1) in
ppm
Photoactivated 15 - - - _ _
bleach (2) in
apm
Brightener 1 0.08 0.19 - - 0.09 0.15
Brightener 2 - 0.04 - - _ -
_
Pertume 0.3 0.3 0.4 0.3 0.4 0.3
ARP1 0.1 1.0(ci)- - - 0.1 {es)
(d}
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A B C C) E P .,_
ARP2~ - 0.04(s) 0.08(ec)0.1 (d) 0.1 (es)
Silicone antifoam0.5 2.4 0.3 0.5 0.3 2.0
Minorslmisc to
100%
Density in g/litre750 750 750 T50 750 750
Example 3
The following detergent formulations of particular utility under European
machine
wash conditions were prepared in accord with the invention.
A __
Blown powder
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 -
MAIAA 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 0.02 - - 0.02
C45E7 - - - 5.0
C45E2 2.5 2.5 2.0 -
C45E3 2.6 2.5 2.0 -
Pertume 0.5 0.3 0.5 0.2
Silicone antifoam 0.3 0.3 0.3 -
Dry additives
QEA ( - - - 1.0
EDDS I 0.3 - _
Sulfate 2.0 3.0 5.0 10.0
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A B C D
Carbonate 6.0 13.0 15.0 14.0
Citric acid 2.5 - - 2.0
QAS f 1 0.5 - - 0. 5
SKS-6 10.0 - - -
Percarbonate 18.5 - - -
PB4 - 18.0 10.0 21.5
TAED 2.0 2.0 - 2.0
NAC-OBS 3.0 2.0 4.0 -
Protease 1.0 1.0 1.0 1.0
Lipase - 0.4 - 0.2
Lipase (1} 0.4 - 0.4
Amylase 0.2 0.2 0.2 0.4
Brightener 1 0.05 - - 0.05
ARP3 0.03 0.1 (es) 1.0 0.1
0.05(ec)
Misclminor to 100%
Example 4
The following granular detergent formulations were prepared in accord with the
invention.
A B _C D E F
Blown powder
LAS 23.0 8.0 7.0 9.0 7.0 7.0
TAS - - - - 1.0 -
C45AS 6.0 6.0 5.0 8.0 - -
C45AES - 1.0 1.0 1.0 - -
C45E35 - - - - 2.0 4.0
Zeolite A 10.0 18.0 14.0 12.0 10.0 10.0
MAIAA - 0.5 - - - 2.0
MAIAA ('! ) 7.0 - _ _ _ _
AA - 3.0 3.0 2.0 3.0 3.0
Sulfate 5.0 6.3 14.3 11.0 15.0 19.3
Silicate 10.0 1.0 1.0 1.0 1.0 1.0
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A B C D E F
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 2 0.3 0.2 0.3 - 0.1 0.3
Spray on
C45E7 - 2.0 - - 2.0 2.0
C25E9 3.0 - - - - -
C23E9 - - 1.5 2.0 - 2.0
Perfume 0.3 0.3 0.3 2.0 0.3 0.3
ARP2 0.1 0.05(s) - - -
{s)
Agglomerates
C45AS - 5.0 5.0 2.0 - 5.0
BAS - 2.0 2.0 - - 2.0
Zeolite A - 7.5 7.5 8.0 - ?.5
Carbonate - 4.0 4.0 5.0 - 4.0
PEG 4000 - 0.5 0.5 - - 0.5
Misc (water etc) - 2.0 2.0 2.0 - 2.0
Dry additives
QAS (I) - _ _ - 1.0 -
Citric acid - - - - 2.0 -
PB4 - - - - 12.0 1.0
PB1 4.0 1.0 3.0 2.0 - -
Percarbonate - - - - 2.0 10.0
Carbonate - 5.3 1.8 - 4.0 4.0
NOBS 4.0 - 6.0 - - 0.6
Methyl cellulose 0.2 - - - - -
SKS-6 8.0 - - - - -
STS - - 2.0 - 1.0 -
Cumene sulfonic acid- 1.0 - - - 2.0
Lipase 0.2 - 0.2 - 0.2 0.4
Cellulase 0.2 0.2 0.2 0.3 0.2 0.2
Amylase 0.2 - 0.1 - 0.2 -
Protease 0.5 0.5 0.5 0.3 0.5 0.5
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A B C D E F
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
ARP2 0.1 0.2 0.04(d) 0.02 0.01 0.02(es)
(es)
Silicone antifoam 0.2 0.4 0.2 0.4 0.1 -
Mg sulfate - - 0.2 - -
0.2
Misc/minors to 100%
G H I J
Blown powder
Clay I or ll 7.0 10.0 6.0 2.0
LAS 16.0 5.0 11.0 6.0
TAS - 5.0 ~- 2.0
Zeolite A - 20.0 ~- 10.0
STPP 24.0 - 14.0 -
Sulfate - 2.0 .- -
MA/AA - 2.0 1.0 1.0
Silicate 4.0 7.0 3.0 -
CMC 1.0 X0.5 0.6
Brightener 1 0.2 0.2 X0.2 0.2
Carbonate 10.0 10.0 20.0 -
DTPMP 0.4 0.4 iD.2
Spray on
Brightener 1 0.02 - ~- 0.02
C45E7 or E9 - - ;2.0 1.0
C45E3 or E4 - - 2.0 4.0
Perfume 0.5 - 0.5 0.2
Silicone antifoam 0.3 - .. _
Dry additives
Flocculating agent 0.3 1.0 1.0 0.5
I or il ~
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QEA - _ - 1.0
HEDP/ EDDS 0.3 -
Sulfate 2.0 - - -
Carbonate 20.0 13.0 15.0 24.0
Citric acid 2.5 - - 2:0
QAS - - Cl.S 0.5
NaSKS-6 3.5 - - 5.0
Percarbonate - - - 9.0
PB4 - - i.0
NOBS - - - 1.3
TAED - - c!.0 1.5
Protease 1.0 1.0 1.0 1.0
Lipase - 0.4 - 0.2
Amylase 0.2 0.2 C1.2 0.4
Brightener 2 0.05 - - 0.05
Perfume 1.0 0:2 C).5 0.3
Speckle 1.2 0.5 ~ 2.0 -
ARP1 0.08 1.5 (d) 0.2 0.05
ARP2 3.0(d) 0.6 C).2 0.1
Misc/minor to 100%
Exam,~~le 5
The following nii bleach-containing detergent formulations of particular use
in the
washing of coloured clothing, according to the present invention were
prepared:
A B C
Blown Powder
Zeolite A 15.0 15.0 -
Sulfate 0.0 5.0 -
LAS 3.0 3.0
DTPMP 0.4 0.5 -
CMC 0.4 0.4 -
MAlAA 4.0 4.0 -
Agglomerates
C45AS - - 11.0
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A B C
LAS 6.0 _ -
5.0
TAS 3.0 2.0 -
Silicate 4.0 4.0 -
Zeolite A 10.0 15.0 13.0
CMC - - 0,5
MAIAA - - 2.0
Carbonate 9.0 7.0 7.0
Spray On
Perfume 0.3 0.3 0.5
C45E7 4.0 4.0 4.0
C25E3 2.0 2.0 2,0
ARP2 0.08(s) - -
Dry additives
M~~ - - 3.0
NaSKS-6 - - 12.0
Citrate 10.0 - g,0
Bicarbonate 7.0 3.0 5.0
Carbonate 8.0 5.0 7.0
PVPVI/PVNO 0.5 0.5 0.5
Alcalase 0.5 0.3 0.9
Lipase 0.4 0.4 0.4
Amylase 0.6 0.6 0.6
Cellulase 0.6 0.6 0.6
ARP1 0.05 0.08 0.1 (es)
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sulfate 0.0 9.0 0.0
Misclminors to 100% 100.0 100.0 100.0
Density (g/litre) 700 700 700
Example 6
The following granular detergent formulations were prepared in accord with the
invention.
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A E3 C D
Base granule
Zeoiite A 30.0 22.0 24.0 10.0
Sulfate 10.0 5.,0 10.0 7.0
MA/AA 3.0 ~- - -
AA - 1..6 2.0 _
MAIAA ( 1 } - 12 .0 - 6.0
LAS 14.0 1CL0 9.0 20.0
C45AS 8.0 7..0 9.0 7.0
C45AES - 1..0 1.0 -
Silicate - 1..0 0.5 10.0
Soap - 2..0 -
Brightener 1 0.2 0..2 0.2 0.2
Carbonate 6.0 9..0 10.0 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 0.2 0.3 0.3 -
ARP2 0:04(s) -~ - -
Dry additives
Carbonate 5.0 10.0 18.0 8.0
PVPVI/PVNO 0.5 -~ 0.3 -
Protease 1.0 1.0 1.0 0.5
Lipase 0.4 -~ - 0.4
Amylase 0.1 -. - 0.1
Celiuiase 0.1 0.2 0.2 0.1
Noes - a.a - 4.5
PB1 1.0 5.0 1.5 6.0
Sulfate 4.0 5.0 - 5.0
SRPI - 0.4 - _
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___ A 8 C D
ARP1 0.05 O.CI8 0.1(es) -
~
ARP2 0.05 - - 0.02(es)
Sud supressor - 0..5 0.5 -
Misc/minor to 100%
Example 7
The following granular detergent compositions were prepared in accord with the
invention.
A B
T- C
Blown powder _
Zeolite A 20.0 - 15.0
STPP - 20.0 -
Sulphate - - 5.0
Carbonate - - 5.0
TAS - - 1.t)
LAS 6.0 6.0 6.0
C68AS 2.0 2.0 -
Siiicate 3.0 8.0 -
MA/AA 4.0 2.0 2.0
CMC O.fi 0.6 i 0.2
Brightener 1 0.2 0.2 0.'I
DTPMP 0.4 0.4 t 0.'I
STS - - 1.0
Spray on
C45 E7 5.0 5.0 ~ ~ 4.0
Silicone antifoam 0.3 0.3 I 0.'i
Perfume 0.2 0.2 0.3
ARP1 0.1 (s) 0.05(s) 0.08(s)
Dry additives
1. ()
Carbonate 14.0 9.0 ' 10.0
PB1 1.5 2.0 i -
PB4 '18.5 13.0 a 13.0
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A B C.
TAED 2.0 2.0 2.0
QAS (I) - - 1.0
Photoactivated bleach15 ppm 15 ppm l5ppm
SKS-6 - - 3.0
Protease 1.0 1.0 0.2
Lipase 0.2 0.2 0.2
Amylase 0.4 0.4 0.2
Cellulase 0.1 0.1 0.2
Sulfate 10.0 20.0 5.0
Misclminors to 100%
Density {g/litre) 700 700 7CE0
Example 8
The following detergent compositions, according to the present invention were
prepared:
A B C
Blown Powder _._
Zeolite A 15.0 15.0 15.0
Sulfate 0.0 5.0 0.0
LAS 3.0 3.0 3.0
QAS - 1.5 1.5
DTPMP 0.4 0.2 0.4
EDDS - 0.4 0.2
CMC 0.4 0.4 0.4
MA/AA 4.0 2.0 2.0
Agglomerates
LAS 5.0 5.0 5.0
TAS 2.0 2.0 1.0
Silicate 3.0 3.0 4.0
Zeolite A 8.0 8.0 8.0
Carbonate 8.0 8.0 4.0
Spray On
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A B C
Perfume 0.3 0.3 0.3
C45E7 2.0 2.0 2.0
C25E3 2.0 -
ARP2 0.02(s) - -
Dry additives
Citrate 5.0 - 2.0
Bicarbonate - 3.0 -
Carbonate 8.0 15.0 10.0
TAED 6.0 2.0 5.0
PB1 14.0 7.0 10.0
PEO - - 0.2
ARP1 0.1 0.2 0.08(ec)
Bentonite clay - - 10.0
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
Amylase 0.6 0.6 0.6
Cellulase 0.6 0.6 0.6
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 3.0 0.0
Misclminors to 100% 100.0 1100.0 100.0
Density (g/litre) 850 850 850
D E F G H
Blown Powder
STPPI Zeolite 9.0 15.0 15.0 9.0 9.0
A
Flocculating 0.5 0.2 0.9 1.5 -
agent II
or III
LAS 7.5 23.0 3.0 7.5 7.5
QAS 2.5 1.5 - - -
DTPMP 0.4 0.2 0.4 0.4 0.4
HEDP or EDDS - 0.4 0.2 - -
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CMC 0.7 0.4 0.4 0.1 0.1
Sodium carbonate _ 20.0 20.0 10.0
5.0
Brightener 0.05 - - 0.05 0.05
Clay I or II - 10.0 - - -
STS 0. 5 _ - 0.5 0.
5
MA/AA 1.5 2.0 2.0 1.5 1.5
Agglomerates
Suds suppresser 1.0 1.0 - Z.0 0.5
(silicon)
Agglomerate
Clay 9.0 - - 4Ø 10.0
Wax 0.5 - - 0.5 1.5
Glycerol 0.5 - - 0.5 0.5
Agglomerate
~S - 5.0 5.0 - _
TAS - 2.0 1.0 - -
Silicate 3.0 4.0 - -
Zeolite A - 8.0 8.0 -
Carbonate - g,0 4,0 _ -
Spray On
Perfume 0.3 - - 0.3 0.3
C45E7 or E9 2.0 - - 2.0 2.0
C25E3 or E4 2.0 - - 2.0 2.0
Dry additives
Citrate or citric2.5 - 2.0 2.5 2.5
acid
Clay I or II - 5.0 5.0 -
Flocculating agent - - - 0.2
l
or II
Bicarbonate - 3.0 - - -
Carbonate 15.0 - - 25.0 31.0
TAED 1.0 2.0 5.0 1.0 -
Sodium perborate 6.0 7.0 10.0 6.0
or percarbonate
SRP1,2,3or4 ~ 0.2 0.1 0.2 0.5 0.3
~ ~ ~
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CMC or nonionic 1.0 1.5 0.5 - -
ceflulose ether
Protease 0.3 1.0 1.0 0.3 0.3
Lipase - 0.4 0.4 -
Amylase 0.2 0.6 0.6 0.2 0.2
Cellulase 0.2 0.6 0.6 0.2 0.2
Silicone antifoam- 5.0 5.0 - -
Perfume (starch) 0.2 0.3 1.0 0.2 0.2
Speckle 0.5 0.5 0.1 _ 1.0
-
NaSKS-6 (silicate3.5 - -
3.5
2R)
Photobleach 0.1 - - 0, ~ 0,1
Soap 0.5 2.5 - 0.5 0.5
Sodium sulfate - 3.0 - -
ARP1 0.1 1.0(d)0.05 3.0(e:>)0.09
Misc/minors to 100.0 100.0 100.0 100.0 100.
100% 0
Density (g/litre)850 850 850 850 850
Example 9
The following detergent formulations, according to i;he present invention were
prepared:
A B C D
LAS 18.0 14.0 :?4.0 20.0
QAS 0.7 1.0 _ 0.7
TFAA - 1.0 - -
C23E56.5 - - 1.0 _
C45E7 - 1.0
C45E3S 1.0 2.5 1.0
STPP 32.0 18.0 30.0 22.0
Silicate 9.0 5.0 9.0 8.0
Carbonate 11.0 7.5 10.0 5.0
Bicarbonate - ! 7,5 1 _ _
~
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A B C D
PB1 3.0 1:0 - -
PB4 - 1.0 -
NOBS 2.0 1.0 - -
DTPMP - 1.p _
DTPA 0.5 - 0.2 0.3
SRP 1 0.3 0.2 - 0.1
MAIAA 1. 0 1: 5 2 . 0 - -0. 5
CMC 0.8 0.4 0.4 0.2
PEI - - 0.4 -
Sodium sulfate20.0 10.0 x'Ø0 30.0
Mg sulfate 0.2
0.4 0.9
Protease 0.8 1.0 0.5 0:5
Amylase 0.5 0:4 - 0.25
--
Lipase 0.2 - X0.1 _
Cellulase 0.15 - - 0.05
Photoactivated30ppm 20ppm - lOpp,r
bleach (ppm)
ARP3 0.04(s) 0.08(ec) 0..1 (s) 0.04(es)
Perfume spray 0.3 0:3 X0.1 0.2
on
Brightener 0.05 0.2 0.08 0.1
1l2
Misclminors
to
100%
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Example 10
The following liquid detergent formulations were prepared in accord with the
invention (levels are given as parts per weight}.
A B C D
~S 11.5 8.8 - 3.9 -
C25E2.5S - 3.0 18.0 - 16.0
C45E2.25S 11.5 3.0 - 15.7 -
C23E9 - 2.7 1.8 2.0 1.0
C23E7 3:2 - _
CFAA - - 5.2 - 3.1
TPKFA 1.6 - 2.0 0.5 2.0
Citric acid (50%} 6.5 1.2 2.5 4.4 2.5
Calcium formate 0.1 0.06 0.1 -
Sodium formate 0.5 0.06 0.1 0.05 0.05
Sodium cumene sulfonate4.0 1.0 3.0 1.18
Borate 0.6 - 3.0 2.0 2.9
Sodium hydroxide 5.8 2.0 3.5 3.7 2.7
Ethanol 1.75 1.0 3.6 4.2 2.9
1, 2 propanediol 3.3 2.0 8.0 7.9 5.3
Monoethanolamine 3.0 1.5 1.3 2.5 0.$
TEPAE 1.6 - 1.3 1.2 1.2
Protease 1.0 0.3 1.0 0.5 0.7
Lipase - - 0.1
Cellulase - - 0.1 0.2 0.05
Amylase _ _ _ 0.1
SRP1 0.2 - 0.1 -
DTPA - - 0.3 -
PVNO - - 0:3 - 0.2
ARP1 0.3 - - 0.1 _
ARP2 - 0.04 - -
0.1
ARP3 - - i0.3 -
Brightener 1 0.2 0.07 0.1 - _
Silicone antifoam 0.04 0.02 0.1 0.1 0.1
Water/minors
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Example 11
The following liquid detergent formulations were prepared in accord with the
invention (levels are given in parts per weight):
A B C 'D E F G H
LAS 10.0 '! 9.0 - 25.0 - - -
3.0
C25AS 4.0 1.0 2.0 10.0 - 13.0 18.0 15.0
C25E3S 1.0 - - 3.0 - 2.0 2.0 4.0
C25E7 6.0 8.0 13.0 2.5 - - 4.0 4.0
TFAA _ _ ~ 4.5 _ 6.0 8.0 8.0
APA - 1.4 - - 3.0 1.0 2.0 -
TPKFA 2.0 - 13.0 _ - 15.0 11.0 11.0
7.0
Citric acid 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0
Dodecenylltetradecenyl12.0 10.0 - - 15.0 - - -
succinic acid
Rape seed fatty acid4.0 2.0 1.0 - 1.0 - 3.5 -
Ethanol 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0
1,2 Propanediol 4.0 4.0 2.0 7.0 6.0 8.0 10.0 1
3.0
Monoethanolamine - - - 5.0 - - 9.0 _
9.0
Triethanolamine - - 8.0 _ - _ - -
TEPAE 0.5 - 0.5 0.2 - - 0.4 0.3
DTPM P 1.0 1. 0. 1. 2.0 1.2 1. -
0 5 0 0
Protease ~ 0.5 0.5 0.4 0.25 - 0.5 0.3 0.6
Alcalase - - - - 1.5 - - -
Lipase - 0.10 - 0.01 - - 0.15 0.15
Amylase 0.25 0:25 0.6 0.5 0.25 0.9 0.6 0.6
Cellulase - - - 0.05 - - 0.15 0.15
Endolase - - - 0.10 - - 0.07 -
SRP2 0.3 - 0.3 0.1 - - 0.2 0.1
Boric acid 0.1 0.2 1.0 2.0 1.0 1.5 2.5 2.5
Calcium chloride - 0.02 - 0.01 - - - -
Bentonite clay - - - - 4.0 4.0 - -
~
Brightener 1 - 0.4 - - 0.1 0.2 0.3 -
~
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A B C D E F G H
Sud supressor 0.1 0.3 - 0.1 0.4 - - -
Opacifier 0.5 0.4 - 0.3 0.8 0.7 - -
ARP1 0.3 - 0.1 - 0.05 - 0.1 0.08
ARP2 - 0.04 - 0.02 - 0.1 0.08 0.1
Water/minors
NaOH up to pH 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2
Example 12
The following liquid detergent compositions were prepared in accord with the
invention (levels are given in parts per weight).
A B
~S _ 18. g
.. 27.6
C45AS 13.8 5.9
C13E8 3.0 3.1
Oleic acid 3.4 2.5
Citric acid 5.4 5.4
Sodium hydroxide 0.4 3.6
Calcium formate 0,2 0.1
Sodium formate _ 0.5
Ethanol 7.0 _
Monoethanolamine 16.5 ~ 8.0
1,2 propanediol 5.9 5.5
Xylene sulfonic acid - 2.4
TEPAE 1.5 0.8
Protease 1.5 0.6
PEG - 0.7
Brightener 2 0.4 0.1
Perfume spray on 0.5 0.3
ARP1 0.3 -
ARP3 - 0.04
WateNminors
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Example 13
The following is a composition in the form of a tablet, bar, extrudate or
granule in
accord with the invention
A B C D E ~E ~r
,
Sodium C11-C13 12.0 16.0 23.0 191.0 18.0 20.0 16.0
alkylbenzenesulfonate
Sodium C14-C15 alcohol 4 -
5
. - - 4.0
sulfate
C,d-C..s alcohol ethoxyfate- - 2.0 - 1.0 1.0 1.0
(3) suifate
.-
Sodium C14-C15 alcohol2 2 - 1
0 0 '
3
. . . - - 5.0
,
ethoxylate
CQ C.r, alkyl dimethyl - - 1.0 0.5 2.0
hydroxy ethyl quaternary
ammonium salt
Tallow fatty acid _ - - - 1.0
Sodium tripolyphosphate23.0 25.0 14.0 22,0 20.0 10.0 20.0
I
Zeo I ite
Sodium carbonate 25.0 22.0 35.0 20.0 28.0 41.0 30.0
Sodium Polyacrylate 0.5 0.5 0.5 _ - - _
O.:i
(45%)
Sodium - - 1.0 1.CI 1.0 2.0 0.5
poiyacrylatelmaieate
polymer
Sodium silicate (1:6 3.0 6.0 9.0 8.0~ 9.0 6.0 8.0
ratio
NaOISi02)(46%)
Sodium sulfate - - - - - 2.0 3.0
Sodium perborate/ 5.0 5.0 10.0 - 3.0 1.0 -
percarbonate
Poly(ethyleneglycol), 1.5 1.5 1.0 1.0 - - 0.5
MW
w4000 (50%)
Sodium carboxy methyl 1.0 1.0 1.0 - 0.5 0.5 0.5
cellulose
NOBSI DOBS ~ - 1.0 ~ 1.0 0.7 -
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TAED 1.5 1.0 2.5 - 3.0 0.7 -
SRP 1 1.5 1.5 1.0 1.0 - 1.0 -
Clay I or I I 5.0 6.0 12.0 7, 0 10.04.0 3.0
Flocculating agent 0.2 0.2 3.0 2.0 0.1 1.0 0.5
I or fll
Humectant 0.5 1.0 0.5 1..0 0.5 0.5 -
Wax 0.5 0.5 1.0 - - 0.5 0.5
Moisture 7.5 7.5 6.0 7..0 5.0 3.0 5.0
Magnesium sulphate - - _ _ _ 0.5 1.5
Chefant - _ _ _ 0.8 0.6 1.0
Enzymes, including - - - - 2.0 1.5 2.0
amylase, cellulase.
protease and lipase
ARP2 0.3 3.0(dj- - - _ _
ARP1 0.08 0.1 3.0(d)1.5(es)0.051.0(d) 0.05
Speckle 2.5 4..1 4.2 4.4 5.6 5.0 5.2
minors, e.g. perfume, 2.0 1.0 1.0 1.0 2.5 1.5 1.0
PVP, PVPVI/PVNO,
brightener, photo-bleach.
H 1 _I a
Sodium C11-C13 23.0 13.0 20.0 18.0
alkylbenzenesuifonate
Sodium C14-C15 alcohol sulfate _ 4.0 - -
Clay I or I! 5.0 10.0 14.0 6.0
Flocculating agent I or il 0.2 0.3 0.1 0.9
Wax 0.5 0.5 1.0 -
Humectant (glyceroil silica) 0.5 2.0 1.5 -
C,~-C,~ alcohol ethoxylate sulfate- _ .0
2
Sodium C14-C15 alcohol ethoxylate2.5 3.5 -
(
C~-C,4 alkyl dimethyl hydroxy - - 0.5
ethyl
quaternary ammonium salt
Tallow fatty acid 0.5 - - _
Tallow alcohol ethoxylate (50) - - 1.3
Sodium tripolyphosphate - 4 - 20.0
1.0
Zeolite A, hydrate (0.1-10 micron26.3 _ 21.3 -
size) -
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Sodium carbonate 24.0 22.0 35.0 27.0
Sodium Polyacrylate (45%) 2.4 - 2.7 -
Sodium polyacrylate/maleate polymer- - 1.0 2.5
Sodium silicate (1.6 or 2 or 4.0 7.0 2.0 6.0
2.2 ratio
NaO/Si02)(46%)
Sodium sulfate - 6.0 2.0 -
Sodium perboratel percarbonate 8.0 4.0 - 12.0
Poly(ethyleneglycol), MW 4000 1.7 0.4 1.0 -
(50%)
Sodium carboxy methyl cellulose 1.0 - - 0.3
Citric acid _ _ 3.0 _
NOBSI DOBS 1.2 - - 1.0
TAED 0.6 1.5 - 3.0
Perfume 0.5 1.0 0.3 0.4
SRP 1 - 1.5 1.0 1.0
Moisture 7.5 3.1 6.1 7.3
Magnesium sulphate - _ _ 1.0
Chelant _ _ _ 0.5
speckle 1.0 0.5 0.2 2.7
Enzymes, including amylase. celiulase.- 1.0 - 1.5
protease and lipase
ARP1 0.1 3.0(CI)1.0(es)0.3
minors. e.g. brightener, photo-bleach1.0 1.0 1.0 1.0
Example 14
The following laundry bar detergent compositions weire prepared in accord with
the invention (levels are given in parts per weight).
A B C D . E F G H
~S - - 19.0 15.0 21.0 6.75 8.8
C28AS 30.0 13.5 - - - 15.75 11.2 22.5
Sodium laurate2.5 9.0 - - _ _ _ -
Zeoiite 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
Calcium 27.5 39.0 35.0 - - 40.0 - 40.0
carbonate
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A B C D E: F G H
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
Bentonite clay- 10.0 - - 5.0 _ _ _
DTPMP - 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 - - -
Siiicate - - 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
SRP1 0.3 0.3 0:3 0.3 0.3 0.3 0.3 0.3
Protease - 0.12 - 0.08 O.t)8 - - 0.1
Lipase - 0.1 - 0.1 - - - _
Amylase _ - 0.8 - - - 0.1 -
Celluiase - 0.15 - - 0.1i 0.1 - -
5
PEO - 0.2 - 0.2 0.3 _ - 0 3
Perfume 1.0 0.5 0.3 0.2 0.~4 - - 0.4
Mg sulfate - - 3.0 3.0 3.~0 - - -
ARP1 0.3 - - 0.04 - 0.5 - -
ARP2 - 0.04 - - 0.1 - 0.08 _
ARP3 - - 0.3 - - - - 0.3
Brightener 0.15 0.10 0.15 - - - - 0.1
Photoactivated- 15.0 15.0 15.0 15..0 - - 15.0
bleach (ppm)
Example 15
The following detergent additive compositions were prepared according to the
present invention
A B C
~S - 5.0 5.0
STPP 30.0 - 20.0
Zeolite A _ 35.0 20.0
PB1 ~ 20.0 15.0 -
ii;
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A B C
TAED 10.0 8.0 _
ARP 1 0.3 - 0.1
ARP2 - 0.04 0.02
Protease - 0.3 0.3
Amylase - 0.06 0.06
Minors, water and rnisceilaneous Up to 100%
Example 16
The following compact high density (0.96Kgll;l dishwashing detergent
compositions were prepared according to the present invention
A B C D E F G H
STPP - - 54.3 51.4 51.4 - - 50,g
Citrate 35.0 17.0 - - - 46.1 40.2
Carbonate - 17.5 14.0 14.0 14.0 - 8.0 32.1
Bicarbonate - - - - - 25.4 - _
Silicate 32.0 14.8 14.8 10.0 10.0 i .0 25.0 3.1
Metasilicate- 2.5 - 9.0 9.0 - - _
PB1 1.9 9.7 7.8 7.8 7.8 - -
PB4 8.6 - _ _ _ _ _ _
Percarbonate- - - - - 6.7 11.8 4.8
Nonionic 1.5 2.0 1.5 1.7 1.5 2:6 1.9 5.3
TAED 5.2 2:4 - - - 2.2 - 1.4
HEDP - 1.0 - _ _ _ _
DTPMP - 0,6 _ _ _ - _ -
MnTACN - _ _ _ _ _ 0.008 _
PAAC - - 0.008 0.01 0.00T _ _ _
BzP _ _ _ - 1.4 - _ _
Paraffin 0.5 0.5 0.5 0.5 0.5 0.6 - -
ARP3 0.1 0.3 0.2 0.05 - - - O.g
ARP1 - - - - 0.3 0.03 0.5 -
Protease 0.072 0.072 0.029 0.053 0.046 0.026 0.059 0.06
Amylase 0.012 0.012 0.006 0.012 0.013 0.009 0.017 0.03
Lipase - 0.001 - 0.005 - - - _
BTA 0.3 0.3 0.3 0.3 0.3 - 0.3 0.3
I ~;
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A B C D E F G H
~
- _ _ _ _ - 4.2 _
MAIAA
480N 3.3 - 6.0 _ _ _ _ _ 0.9
Perfume 0.2 0.2 0.2 0.2 0.2 0.2 0.1 0.1
Sulphate 7.0 20.0 5.0 2.2 0.8 12.0 4.6 -
pH 10.8 11.0 10.8 11.3 11.3 9.6 10.8 10.9
Miscellaneous and Up to '100%
water
Exama~le 77
The following granular dishwashing detergent compositions of bulk density
1.02Kg/L were prepared according to the present invention
A B C D E F G H
STPP 30.0 30.0 33.0 34.2 29.6 31.1 26.6 17.6
Carbonate 30.5 30.5 31.0 30.0 23.0 39.4 4.2 45.0
Silicate 7.4 7.4 7.5 7.2 13.3 3.4 43.7 12.4
Metasiiicate- - 4.5 5.1 - - - _
Percarbonate- - - - - 4.0 -
PB1 4.4 4.2 4.5 4.5 - - - -
NADCC - - - - 2.0 - 1.6 1.0
Nonionic 1.2 1.0 0.7 0.8 1.9 0.7 0.6 0.3
TAED 1.0 - - - _ O,g _ _
PAAC - 0.004 0.004 0.004 - - - -
BzP - _ - 1.4 - _ _
Paraffin 0.25 0.25 0.25 0.25 - - - -
ARP3 0.3 0.1 0.8 0.2(es} - - 0.1 (ec)0.2
(ec)
ARP 1 - - - - 0.3 0.1 0.1 (ec)0.2
{ec)
Protease 0.036 0.015 0.03 0.028 - 0.03 - -
Amyiase 0.003 0.003 0.01 0.006 - 0.01 - -
Lipase 0.005 - 0.001 - - - _ _
BTA 0.15 0.15 0.15 0.15 - - - _
Perfume 0.2 0.2 0.2 0.2 0.1 0.2 0.2 -
Sulphate 23.4 25.0 22.0 18.5 30.1 19.3 23.1 23.6
pH 10.8 10.8 11.3 11.3 10.7 11.5 12.7 10.9
Miscellaneous Up to 100%
and water
ii.
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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 13KNIcm2 using a standard 12 head rotary press:
A B C D E F
STPP - 48.8 49.2 38.0 - 46.8
Citrate 26.4 - - = 31.1 -
Carbonate - 5.0 14.0 '15.4 14.4 23.0
Silicate 26.4 14.8 15.0 '12.6 17.7 2.4
,
ARP1 0.3 - - - 0.06 -
ARP2 - 0.04 - - - 0.08
ARP3 - - 0.3 0.1 (ec)-
Protease 0.058 0.072 0.041 0.033 0.052 0.013
Amylase 0.01 0.03 0.012 0.007 0.016 0.002
Lipase 0.005 - - - - _
PB 1 1.6 7.7 12.2 110.6 15.7 -
PB4 6.9 - - - - 14.4
Nonionic 1.5 2.0 1.5 11.65 0.8 6.3
PAAC - - 0.02 0.009 -
MnTACN - - - - 0.007 -
TAE D 4.3 2.5 - - 1.3 1.8
HEDP 0.7 - - 0.7 - 0.4
DTPMP 0.65 - - - - _
Paraffin 0.4 0.5 0.5 0.55 - -
BTA 0.2 0.3 0.3 ~0.3 -
PA30 3.2 - _ _ _ _
MAIAA _ _ _ - 4.5 0.55
Perfume - - 0.05 Cl.05 0.2 0.2
Sulphate 24.0 13.0 2.3 - 10.7 3.4
Weight of tablet25g 25g 20g 30g 18g 20g
pH 10.6 10.6 10.7 10.7 10.9 11.2
Miscellaneous water Up to 1100%
and
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_ g1
Example 19
The following liquid dishwashing detergent compositions of density 1.40Kg/L
were prepared according to the present invention
A B C D
STPP 17.5 17.5 17.2 16.0
Carbonate 2.0 - 2.4 -
Sificate 5.3 6.1 14.6 15.7
NaOCI 1.15 1.15 1.15 1.25
Polygen/carbopol 1.1 1.0 1.1 1.25
Nonionic - - 0.1
NaBz 0.75 0.75 - -
ARP3 0.3 0.5 0.05 0.1
NaOH - 1.9 - 3.5
KON 2.8 3.5 3.0 -
pH 11.0 11.7 10.9 11.0
Sulphate, miscellaneousand water up to 00%
1
Example 20
The following liquid rinse aid compositions were prepared according to the
present invention
A B C
Nonionic 12.0 - 14.5
Nonipnic blend - 64.0
Citric 3.2 - fi.5
HEDP 0.5 - -
PEG - 5.0 _
SCS 4.8 - 7.0
Ethanol 6.0 8.0 -
ARP'f 0.3 - 0,1
ARP2 - 0.04 0.01
pH of the liquid 2.0 7.5 I
Miscellaneous and Up to 1100%
water
II
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Example 21
The following liquid dishwashing compositions were prepared according to the
present invention
A B C D E
C17ES 28.5 27.~G 19.2 34.1 34.1
Amine oxide 2.6 5.0 2.0 3.0 3.0
C12 glucose amide - - 6,p _
Betaine 0.9 - - 2.0 2.0
Xylene sulfonate 2.0 4.0 - 2.0 -
Neodol C11E9 - - 5.0 - -
Polyhydroxy fatty acid amide- - - 6.5 6.5
Sodium diethylene penta acetate- - 0.03 - -
(40%)
TAED - - - 0.06 0.06
Sucrose - - - 1.5 1.5
Ethanol 4.0 5.5 5.5 9.1 9.1
Alkyl diphenyl oxide disulfonate- - - - 2.3
Ca formate - - - 0.5 1.1
Ammonium citrate 0.06 0.1 - - -
Na chloride - 1.0 - - -
Mg chloride 3.3 - 0.7 - -
Ca chloride - - 0.4 - -
Na suffate - - 0.06 -
Mg sulfate O,Og _ _ _ _
Mg hydroxide - - - 2.2 2.2
Na hydroxide - - - 1.1 1.1
Hydrogen peroxide 200ppm 0.16 0.006 - -
ARP3 0.3 - 0.1 - 0.1
ARP'! - 0.3 - 0.1 0.1
Protease 0.017 0.005 .0035 0.003 0.002
Perfume 0.18 0.09 0.09 0.2 0.2
Water and minors
Up to
100%
i',
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83
Example 22
The following liquid hard surface cleaning compositions were prepared
according to the present invention
A B C. D E
ARP2 0.04 - 0.08 - 0.01
ARP3 - 0.3 - 0.125 0.1
Amylase 0.01 0.002 0.005 - -
Protease 0.05 0.01 0.02 - -
Hydrogen peroxide - - - 6.0 6.8
Acetyl triethyl citrate- - - 2.5 -
DTPA - - - 0.2 -
Butyl hydroxy toluene- - - 0.05 -
EDTA* 0.05 0.05 O.E)5 -
Citric l Citrate 2.9 2.9 2.9 1.0 -
LAS 0.5 0.5 0.5 - -
C 12 AS 0.5 0.5 0. 5 - -
C 1 OAS - - - - 1.7
C12(E)S 0.5 0.5 0.5 - -
C12,13 E6.5 nonionic 7.0 7.0 7.0 - -
Neodol23-6.5 - - - 12.0 -
Dobanol23-3 - - - - 1.5
Dobanol91-10 - - - - 1.6
C25AE1.8S - _ - 6.0
Na paraffin sulphonate- - - 6.0
Perfume 1.0 1.0 1.0 0.5 0.2
Propanediol - - - 1.5
Ethoxylated tetraethylene- - - 1.0 -
pentaimine
2, Butyl octanol - - - - 0.5
Hexyl carbitol** 1.0 1.0 1.0 - -
SCS 1.3 1.3 1.3 - -
pH adjusted to 7-12 7-12 7-12 4 -
Miscellaneous and Up to 100%
water
*Na4 ethylenediamine
diacetic acid
*Diethylene glycol
monohexyt ether
i i,
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Example 23
The following spray composition for cleaning of hard surfaces and removing
household mildew was prepared according to the present invention
ARP2 0.04
Amylase 0.01
Protease 0.01
Na octyl suifate 2.0
Na dodecyi sulfate 4.0
Na hydroxide 0.8
Silicate 0.04
Butyl carbitol* 4.0
Perfume 0.35
Waterlminors up to 100~0
*Diethylene glycol monobutyl
ether
Example 24
The following lavatory cleansing block compositions were prepared according to
the present invention.
A B C
C16-18 fatty alcoho1l50E0 80.0 - -
~S - - 80.0
Nonionic - 1.p
Oleoamide surfactant - 26:0 -
Partially esterified copolymer of vinylmethyl5.(1 - -
ether and malefic anhydride, viscosity 0.1-0.5
Polyethylene glycol MW 8000 - 39.0 -
Water-soluble K-polyacrylate MW 4000-8000 - 12.0 -
Water-soluble Na-copolymer of acryiamide - 19.0
(70%) and acryciic acid (30%) low MW
Na triphosphate 10.0 - -
Carbonate - _ g.0
ARP2 0Ø4 - 0.01
ARP3 - 0.25 0.1
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A B C
Dye 2.;i 1.0 1.0
Perfume 3.0 - 7.0
KOH J HCL solution pH 6-11
Example 25
The following toilet bowl cleaning composition was prepared according to the
present invention.
A B
C14-15 linear alcohol 7E0 2.0 10.0
Citric acid 10.0 5.0
ARP2 0.04 -
ARP3 - 0.1
DTPMP - 1.0
Dye 2.0 1.0
Perfume 3.0 3.0
NaOH
pH Ei-11
Water and minors Up to 100%
