Note: Descriptions are shown in the official language in which they were submitted.
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PRO-PERFUME COMPOSITION
Technical field of the invention
The present invention relates to a pro-perfume composition, in particular for
use
in liquid detergent composition for imparting sustained release of the benefit
agent on the treated surfaces like fabrics, in particular dry fabrics.
Background of the invention
Perfumed products are well-known in the art. However, consumer acceptance of
such perfumed products like 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 treated surfaces like fabrics to maintain
the
pleasing fragrance over time. Indeed, perfume additives make such compositions
more aesthetically pleasing to the consumer, and in some cases the perfume
imparts a pleasant fragrance to surfaces, like fabrics, treated therewith.
However, the amount of perfume carried-over from an aqueous laundry or
cleaning bath onto fabrics is often marginal and does not last long on the
surface.
Furthermore, fragrance materials are often very costly and their inefficient
use in
laundry and cleaning compositions and ineffective delivery to surfaces like
fabrics
results in a very high cost to both consumers and laundry and cleaning
manufacturers. Industry, therefore, continues to seek with urgency for more
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efficient and effective fragrance delivery in laundry and cleaning products,
especially for improvement in the provision of long-lasting fragrance to the
surfaces like fabrics.
Recently, a new class of materials, namely the amine reaction product of a
compound containing a primary amine functional group and an active ketone or
aldehyde containing component, have found increasing use in the domestic
treatment of fabrics in order to provide long lasting perfume release on the
laundered fabric. Disclosure of such compounds can be found in recently filed
applications EP 98870227.0, EP 98870226.2, EP 99870026.4, and
EP 99870025.6, all incorporated herein by reference.
However, notwithstanding the advances in the art, there is still a need for
improving the incorporation of pro-perfumes into detergent compositions, in
particular liquid detergent compositions like heavy duty liquids, especially
from a
stability aspect.
Accordingly, it is an object of the present invention to provide a pro-perfume
composition that is effectively suspended, especially for further
incorporation into
liquid detergent compositions.
!t has now been found that the use of a suspension material like silicone
which is
in close physical proximity with the pro-perfume composition fulfills such a
need.
Summary of the invention
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The present invention is a pro-perfume composition comprising an amino-
functional polymer and a benefit agent, characterised in that the pro-perfume
composition and the suspending material are in close physical proximity.
For the purpose of the present invention, the term "close physical proximity"
means one of the following:
i)-a droplet in which said pro-perfume and said suspending material are in
intimate admixture;
ii)-a droplet in which the pro-perfume is coated with one or more layers
wherein
at least one layer contains the suspending material.
It has to be understood by "close physical proximity" that the pro-perfume and
the
suspending material are not two separate discrete particles in the detergent
composition.
Detailed description of the invention
An essential feature of the invention is a pro-perfume.
Pro perfume
Pro-perfume compounds for use in the present invention typically comprises an
amino-functional component and a benefit agent.
A-Amino-functional component
Examples of amino-functional component are those which have chemically
reacted with a benefit agent, so-called "amines which form amine reaction
products", i.e. a product of reaction between a compound containing a primary
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amine functional group and/or secondary amine functional group and an active
ketone or aldehyde containing component. Preferred compounds for use herein
are polymers which have been previously reacted with an aldehyde and/or ketone
perfume ingredient, thereby imparting a more effective scent to the fabrics.
A typical disclosure of amine reaction product suitable for use herein can be
found in recently filed applications EP 98870227.0, EP 98870226.2, EP
99870026.4, and EP 99870025.6, all incorporated herein by reference.
A-Primary amine and/or secondary amine
By "primary and/or secondary amine", it is mearit a component which carries at
least one primary and/or secondary amine and/or amide function.
Of course, one amine compound may carry both primary and secondary amine
compound, thereby enabling the reaction with several aldehydes and/or ketones.
Preferably, the primary amine and/or secondary amine compound is also
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 amine compound, 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.
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Results:
The following represents Odour Intensity Index of an amine compound 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:
Methylanthranilate 1 % (reference) 3.4
Ethyl-4-aminobenzoate (EAB) 1 % 0.9
1,4-bis-(3-aminopropyl)-piperazine (BNPP) 1% 1.0
A general structure for the primary amine compound of the invention is as
follows:
B-(NH2)n;
wherein B is a carrier material, and n is an index of value of at least 1.
Compounds containing a secondary amine group have a structure similar to the
above excepted that the compound comprises one or more -NH- groups instead
of -NH2. Further, the compound structure may also have one or more of both -
NH2 and -NH- groups.
Preferred B carriers are inorganic or organic carriers.
By "inorganic carrier", it is meant carrier which are non-or substantially non
carbon based backbones.
Preferred primary and/or secondary amines, among the inorganic carriers, are
those selected from mono or polymers or organic-organosilicon copolymers of
amino derivatised organo silane, siloxane, silazane, alumane, aluminum
siloxane,
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or aluminum silicate compounds. Typical examples of such carriers are:
organosiloxanes with at least one primary amine moiety like the
diaminoalkylsiloxane [H2NCH2(CH3) 2Si]O, or the organoaminosilane (C6H5)
3SiNH2 described in: Chemistry and Technology of Silicone, W. Noll, Academic
Press Inc. 1998, London, pp 209, 106).
Preferred primary and/or secondary amines, among the organic carriers, are
those selected from aminoaryl derivatives, polyamines, amino acids and
derivatives thereof, substituted amines and amides, glucamines, dendrimers,
polyvinylamines and derivatives thereof, andlor copolymer thereof, alkylene
polyamine, polyaminoacid and copolymer thereof, cross-linked polyaminoacids,
amino substituted polyvinylalcohol, polyoxyethylene bis amine or bis
aminoalkyl,
aminoalkyl piperazine and derivatives thereof, bis (amino alkyl) alkyl diamine
linear or branched, and mixtures thereof.
Preferred aminoaryl derivatives are the amino-benzene derivatives including
the
alkyl esters of 4-amino benzoate compounds, and more preferably selected from
ethyl-4-amino benzoate, phenylethyl-4-aminobenzoate, phenyl-4-aminobenzoate,
4-amino-N'-(3-aminopropyl)-benzamide, and mixtures thereof.
Polyamines suitable for use in the present invention are polyethyleneimines
polymers, poly[oxy(methyl-1,2-ethanediyl)], a-(2-aminomethylethyl)-c~-(2-
aminomethyl-ethoxy)- (= C.A.S No. 9046-10-0); poly[oxy(methyl-1,2-
ethanediyl)],
a-hydro-)-c~-(2-aminomethylethoxy)-, ether with 2-ethyl-2-(hydroxymethyl)-1,3-
propanediol (= C.A.S. No. 39423-51-3); commercially available under the
tradename Jeffamines T-403, D-230, D-400, D-2000; 2,2',2"-
triaminotriethylamine; 2,2'-diamino-diethylamine; 3,3'-diamino-dipropylamine,
1,3
bis aminoethyl-cyclohexane commercially available from Mitsubishi and the C12
Sternamines commercially available from Clariant like the C12
Sternamin(propylenamine)~ with n=3/4, and mixtures thereof. Preferred '
polyamines are polyethyleneimines commercially available under the tradename
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Lupasol like Lupasol FG (MW 800), G20wfv (MW 1300), PR8515 (MW 2000), WF
(MW 25000), FC (MW 800), G20 (MW 1300), G35 (MW 1200), 6100 (MW 2000),
HF (MW 25000), P (MW 750000), PS (MW 750000), SK (MW 2000000), SNA
(MW 1000000), most preferably Lupasol HF or WF (MW 25000), P (MW 750000),
PS (MW 750000), SK (MW 2000000), SNA (MW 1000000).
Preferred amino acids for use herein are selected from tyrosine, tryptophane,
lysine, glutamic acid, glutamine, aspartic acid, arginine, asparagine,
phenylalanine, proline, glycine, serine, histidine, threonine, methionine, and
mixture thereof, most preferably selected from tyrosine, tryptophane, and
mixture
thereof. Preferred amino acid derivatives are selected from tyrosine ethylate,
glycine methylate, tryptophane ethylate, and mixture thereof.
Preferred substituted amines and amides for use herein are selected from
nipecotamide, N-coco-1,3-propenediamine; N-oleyl-1,3-propenediamine; N-
(tallow alkyl)-1,3-propenediamine; 1,4-diamino cyclohexane; 1,2-diamino-
cyclohexane; 1,12-diaminododecane, and mixtures thereof.
Other primary amine compounds suitable for use herein are the glucamines,
preferably selected from 2,3,4,5,6-pentamethoxy-glucamine; 6-acetylgiucamine,
glucamine, and mixture thereof.
Also preferred compounds are the polyethylenimine and/or polypropylenimine
dendrimers and the commercially available Starburst" polyamidoamines
(PAMAM) dendrimers, generation G0-G10 from Dendritech and the dendrimers
Astromols°, generation 1-5 from DSM being DiAminoButane PolyAmine
DAB
(PA)x dendrimers with x = 2"x4 and n being generally comprised between 0 and
4.
Polyamino acid is one suitable and preferred class of amino-functional
polymer.
Polyaminoacids are compounds which are made up of amino acids or chemically
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modified amino acids. They can contain alanine, serine, aspartic acid,
arginine,
valine, threonine, glutamic acid, leucine, cysteine, histidine, lysine,
isoleucine,
tyrosine, asparagine, methionine, proline, 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, polyglutamine,
polyasparagine, polyhistidine, polytryptophane or mixtures thereof. Most
preferred are polylysines or polyamino 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 2.000 and 25.000.
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 and/or secondary amino groups left for reactiowivith the active
ingredient.
The preferred cross linked polyamino acid has a molecular weight of 20.000 to
10.000.000, more preferably between 200.000 and 2.000.000.
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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, caprolactam 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 polylysine can also be partially ethoxylated.
Examples and supply of polyaminoacids containing lysine, arginine, glutamine,
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
and/or secondary amine group for the purpose of the present invention are
-.Polyvinylamine with a MW of about 300 2.10E6;
- Polyvinylamine alkoxylated with a MW of about 600, 1200 or 3000 and an
ethoxylation degree of 0.5;
- Polyvinylamine vinylalcohol - molar ratio 2:1, polyvinylaminevinylformamide -
molar ratio 1:2 and polyvinylamine vinylformamide-molar ratio 2:1;
- Triethylenetetramine, diethylenetriamine, tetraethylenepentamine;
- Bis-aminopropylpiperazine;
- Polyamino acid (L-lysine / lauric acid in a molar ratio of 10/1 ), Polyamino
acid
(L-lysine / aminocaproic acid / adipic acid in a molar ratio of 5/5/1 ), ),
Polyamino
acid (L-lysine / aminocaproic acid /ethylhexanoic acid in a molar ratio of
5/311 )
Polyamino acid (polylysine-cocaprolactam); Polylysine; Polylysine
hydrobromide;
cross-linked polylysine,
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- amino substituted polyvinylalcohol with a MW ranging from 400-300,000;
- polyoxyethylene bis [amine] available from e.g. Sigma;
- polyoxyethylene bis [6-aminohexyl] available from e.g. Sigma;
- N,N'-bis-(3-aminopropyl)-1,3-propanediamine linear or branched (TPTA); and
- 1,4-bis-(3-aminopropyl) piperazine (BNPP).
The more preferred compounds are selected from ethyl-4-amino benzoate,
polyethyleneimine polymers commercially available under the tradename Lupasol
like Lupasol HF, P, PS, SK, SNA; the diaminobutane dendrimers
Astramol°,
polylysine, cross-linked polylysine, N,N'-bis-(3-aminopropyl)-1,3-
propanediamine
linear or branched; 1,4-bis-(3-aminopropyl) piperazine, and mixtures thereof.
Even most preferred compounds are those selected from ethyl-4-amino
benzoate, polyethyleneimine polymers commercially available under the
tradename Lupasol like Lupasol HF, P, PS, SK, SNA; polylysine, cross-linked
polylysine, N,N'-bis-(3-aminopropyl)-1,3-propanediamine linear or branched,
1,4-
bis-(3-aminopropyl) piperazine, and mixtures thereof.
Advantageously, such most preferred primary and/or secondary amine
compounds also provide fabric appearance benefit, in particular colour
appearance benefit, thus providing a resulting amine reaction product with the
properties of fabric appearance benefit, deposition onto the surface to be
treated,
and delayed release of the active as well as release of the perfume
composition.
Further, when the primary and/or secondary amine compound has more than one
free primary and/or secondary amine group, several different active
ingredients
(aldehyde and/or ketone) can be linked to the amine compound.
Of course, the primary and/or secondary amine compound may also be used as
is, i.e. without having been reacted with the above benefit agent like
aldehyde
and/or ketone perfume ingredient, but with a benefit agent like a perfume
composition which is entrapped or embedded within the primary and/or
secondary amine compound. Moreover, the primary and/or secondary amine
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compound may also be reacted with compounds other than the benefit agent
mentioned above like acyl halides, like acetylchloride, palmytoyl chloride or
myristoyl chloride, acid anhydrides like acetic anhydride, alkylhalides or
arylhalides to do alkylation or arylation, aldehydes or ketones not used as
perfume ingredients like formaldehyde, glutaraldehyde, unsaturated ketones,
aldehydes or carboxylic acids like 2-decylpropenoic acid, propenal, propenone
to
form reaction products with the required viscosity.
B-Benefit agent
The benefit agent is a component that will react with the amino-functional
polymer and provide a beneficial effect on the treated surface like fabric
upon
contact with water or humidity. Hence, the benefit agent may be selected from
a
flavour ingredient, a pharmaceutical ingredient, a biocontrol ingredient, a
perfume
composition, a refreshing cooling ingredient and mixtures thereof.
Typically, the benefit agent comprises from 10 to 90%, preferably from 30 to
85%, more preferably from 45 to 80% by weight of the pro-perfume component.
Flavour ingredients include spices, flavor enhancers that contribute to the
overall
flavour perception.
Pharmaceutical ingredients include drugs.
Biocontrol ingredients include biocides, antimicrobials, bactericides,
fungicides,
algaecides, mildewcides, disinfectants, antiseptics, insecticides, vermicides,
plant
growth hormones.
Typical antimicrobials which can be carried by the carrier material include
amine
oxide surfactanfis, photo-activated bleaches, chlorhexidine diacetate,
glutaraldehyde, cinnamon oil and cinnamaldehyde, citric acid, decanoic acid,
lactic acid, malefic acid, nonanoic acid, polybiguanide, propylene glycol,
cumene
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sulfonate, eugenol, thymol, benzalkonium chloride, geraniol, and mixtures
thereof. Preferred are compounds which can react with the carrier material.
Preferably, the carrier material is a polymer, preferably a polymer which is
reacted with another benefit agent, such as for example perfumes described
herein, and this polymer or polymer reaction product functions as a carrier
for the
biocide. Preferred carried compositions for use in fabric care and cleaning
compositions have a viscosity of at least 500,000 or even at least
1,OOO,OOOcps,
as described hereinafter. Preferred polymers are also described in more detail
hereinafter.
Typical insect and/or moth repellants are perfume ingredients, such as
citronellal,
citral, N, N diethyl meta toluamide, Rotundial, 8-acetoxycarvotanacetone, and
mixtures thereof. Other examples of insect and/or moth repellant for use
herein
are disclosed in US 4,449,987, 4,693,890, 4,696,676, 4,933,371, 5,030,660,
5,196,200, and "Semio Activity of Flavor and Fragrance molecules on various
Insect Species", B.D. Mookherjee et al., published in Bioactive Volatile
Compounds from Plants, ASC Symposium Series 525, R. Tera,nishi, R.G.
Buttery, and H. Sugisawa, 1993, pp. 35-48.
One preferred benefit agent is a perfume ingredient. One typical perfume
ingredient is a aldehyde perfume ingredient. Preferably, the perfume aldehyde
is
selected from adoxal; anisic aldehyde; cymal; ethyl vanillin; florhydral;
helional;
heliotropin; hydroxycitronellal; koavone; lauric aldehyde; lyral; methyl nonyi
acetaldehyde; P. T. bucinal; phenyl acetaldehyde; undecylenic aldehyde;
vanillin;
2,6,10-trimethyl-9-undecenal, 3-dodecen-1-al, alpha-n-amyl cinnamic aldehyde,
4-methoxybenzaldehyde, benzaldehyde, 3-(4-tert butylphenyl)-propanal, 2-
methyl-3-(para-methoxyphenyl propanal, 2-methyl-4-(2,6,6-trimethyl-2(1 )-
cyclohexen-1-yl) butanal, 3-phenyl-2-propenal, cis-/trans-3,7-dimethyl-2,6-
octadien-1-al, 3,7-dimefihyl-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-cyclohexen-1-carboxaldehyde, 2-methyl-3-
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(isopropylphenyl)propanal, 1-decanal; decyl aldehyde, 2,6-dimethyl-5-heptenal,
4-(tricyclo[5.2.1.0(2,6)]-decylidene-8)-butanal, octahydro-4,7-methano-1 H-
indenecarboxaldehyde, 3-ethoxy-4-hydroxy benzaldehyde, para-ethyl-alpha,
alpha-dimethyl hydrocinnamaldehyde, alpha-methyl-3,4-(methylenedioxy)-
hydrocinnamaldehyde, 3,4-methylenedioxybenzaldehyde, alpha-n-hexyl cinnamic
aldehyde, m-cymene-7-carboxaldehyde, alpha-methyl phenyl acetaldehyde, 7-
hydroxy-3,7-dimethyl octanal, Undecenal, 2,4,6-trimethyl-3-cyclohexene-1-
carboxaldehyde, 4-(3)(4-methyl-3-pentenyl)-3-cyclohexen-carboxaldehyde, 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 6
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-cyclhexenecarboxaldehyde, 7-
hydroxy-3,7-dimethyl-octanal, trans-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-dimethyl-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 hexanal,
Hexahydro-8,8-dimethyl-2-naphthaldehyde, 3-propyl-bicyclo[2.2.1]-hept-5-ene-2-
carbaldehyde, 9-decenal, 3-methyl-5-phenyl-1-pentanal, methylnonyl
acetaldehyde, 1-p-menthene-q-carboxaldehyde, citral, lilial and mixtures
thereof.
More preferred aldehydes are selected from citral, 1-decanal, benzaldehyde,
florhydral, 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde; cis/trans-3,7-dimethyl-
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2,6-octadien-1-al; heliotropin; 2,4,6-trimethyl-3-cyclohexene-1-
carboxaldehyde;
2,6-nonadienal; alpha-n-amyl cinnamic aldehyde, alpha-n-hexyl cinnamic
aldehyde, P.T. Bucinal, lyral, cymal, methyl nonyl acetaldehyde, trans-2-
nonenal,
filial, trans-2-nonenal, and mixture thereof.
Another typical perfume ingredient is a ketone perfume ingredient. Preferably,
the
perfume ketone is selected from buccoxime; iso jasmone; methyl beta naphthyl
ketone; musk indanone; tonalid/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-called lonone, Fleuramone, Dihydrojasmone,
Cis-Jasmone, Iso-E-Super, Methyl- Cedrenyl-ketone or Methyl- Cedrylone,
Acetophenone, Methyl-Acetophenone, Para-Methoxy-Acetophenone, Methyl-
Beta-Naphtyl-Ketone, Benzyl-Acetone, Benzophenone, Para-Hydroxy-Phenyl-
Butanone, Celery Ketone or Livescone, 6-Isopropyldecahydro-2-naphtone,
Dimethyl-Octenone, Freskomenthe, 4-(1-Ethoxyvinyl)-3,3,5,5,-tetramethyl-
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-Damascol, Dulcinyl or Cassione,
Gelsone, Hexalon, Isocyclemone 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, hedione, and mixtures thereof.
More preferably, for the above mentioned compounds, the preferred ketones are
selected from Alpha Damascone, Delta Damascone, Iso Damascone, Carvone,
Gamma-Methyl-lonone, Iso-E-Super, 2,4,4,7-Tetramethyl-oct-6-en-3-one, Benzyl
Acetone, Beta Damascone, Damascenone, methyl dihydrojasmonate, methyl
cedrylone, hedione, and mixtures thereof.
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Still, the benefit agent may also comprise a perfume composition made of
mixture
of perfume ingredients including or not the above mentioned aldehyde or
ketone.
This composition is then entrapped within the pro-perfume component by mixing.
By such means, a more fully complete perfume formulation can then be
deposited onto the contacted surface.
Typical of these ingredients include fragrant substance or mixfiure 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 by auxiliary materials, such
as fixatives, 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.
Suitable perfumes are disclosed in U.S. Pat. 5,500,138, said patent being
incorporated herein by reference.
Examples of perfume ingredients useful in the perfume compositions include,
but
are not limited to, amyl salicylate; hexyl salicylate; terpineol; 3,7-dimethyl-
cis-2,6-
octadien-1-ol; 2,6-dimethyl-2-octanol; 2,6-dimethyl-7-octen-2-ol; 3,7-dimethyl-
3-
octanol; 3,7-dimethyl-trans-2,6-octadien-1-ol; 3,7-dimethyl-6-octeri-1-ol; 3,7-
dimethyl-1-octanol; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; 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-
hydroxyphenyl)-butan-2-one; 1-(2,6,6-trimethyl-2-cyclohexen-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;
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methyl-2-(2-pentyl-3-oxo-cyclopentyl) acetate; beta-naphthol methylether;
methyl-
beta-naphthylketone; coumarin; 4-tent-butylcyclohexyl acetate; alpha,alpha-
dimethylphenethyl acetate; methylphenylcarbinyl acetate; cyclic ethyleneglycol
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 ketone; 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-tetramethyl
indane; 1-dodecanal; 7-hydroxy-3,7-dimethyl octanal; 10-undecen-1-al; iso-
hexenyl cyclohexyl carboxaldehyde; formyl tricyclodecan; cyclopentadecanolide;
16-hydroxy-9-hexadecenoic acid lactone; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-
hexamethylcyclopenta-gamma-2-benzopyrane; ambroxane; dodecahydro-
3a,6,6,9a-tetramethylnaphtho-[2,1b]furan; cedrol; 5-(2,2,3-trimethylcyclopent-
3-
enyl)-3-methylpentan-2-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-
buten-
1-0l; caryophyllene alcohol; cedryl acetate; para-tent-butylcyclohexyl
acetate;
patchouli; olibanum resinoid; labdanum; vetivert; copaiba balsam; fir balsam;
hydroxycitronellal and indol; phenyl acetaldehyde and indol;
More examples of perfume components are geraniol; geranyl acetate; linalool;
linalyl acetate; tetrahydrolinalool; citronellol; citronellyl acetate;
dihydromyrcenol;
dihydromyrcenyl acetate; tetrahydromyrcenol; terpinyl acetate; nopol; nopyl
acetate; 2-phenylethanol; 2-phenylethyl acetate; benzyl alcohol; benzyl
acetate;
benzyl salicylate; benzyl benzoate; styrallyl acetate; dimethylbenzylcarbinol;
trichloromethylphenylcarbinyl methylphenylcarbinyl acetate; isononyl acetate;
vetiveryl acetate; vetiverol; 2-methyl-3-(p-tert-butylphenyl)-propanal; 2-
methyl-3-
(p-isopropylphenyl)-propanal; 3-(p-tert-butylphenyl)-propanal; 4-(4-methyl-3-'
pentenyl)-3-cyclohexenecarbaldehyde; 4-acetoxy-3-pentyltetrahydropyran;
methyl dihydrojasmonate; 2-n-heptylcyclopentanone; 3-methyl-2-pentyl-
cyclopentanone; n-decanal; n-dodecanal; 9-decenol-1; phenoxyethyl isobutyrate;
phenylacetaldehyde dimethylacetal; phenylacetaldehyde diethylacetal;
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geranonitrile; citronellonitrile; cedryl acetal; 3-isocamphylcyclohexanol;
cedryl
methylether; isolongifolanone; aubepine nitrite; aubepine; heliotropine;
eugenol;
vanillin; diphenyl oxide; hydroxycitronellal ionones; methyl ionones;
isomethyl
ionomes; irones; cis-3-hexenol and esters thereof; indane .musk fragrances;
tetralin musk fragrances; isochroman musk fragrances; macrocyclic ketones;
macrolactone musk fragrances; ethylene brassylate. Also suitable herein as
perfume ingredients of the perfume composition are the so-called Schiff base.
Schiff-Bases are the condensation of an aldehyde perfume ingredient with an
anthranilate. A typical description can be found in US 4853369. Typical of
Schiff
bases are selected from SchifFs base of 4-(4-hydroxy-4-methylpentyl)-3-
cyclohexene-1-carboxaldehyde and methyl anthranilate; condensation products
of: hydroxycitronellal and methyl anthranilate; 4-(4-hydroxy-4-methyl pentyl)-
3-
cyclohexene-1-carboxaldehyde and methyl anthranilate; Methyl Anthranilate and
HydroxyCitronellal commercially available under the tradename Aurantiol;
Methyl
Anthranilate and Methyl Nonyl Acetaldehyde commercially available under the
tradename Agrumea; Methyl Anthranilate and PT Bucinal commercially available
under the tradename Verdantiol; Methyl anthranilate and Lyral commercially
available under the tradename Lyrame; Methyl Anthranilate and Ligustral
commercially available under the tradename Ligantral; and mixtures thereof.
Preferably, the perfume ingredients and/or compositions useful in the present
invention compositions are substantially free of halogenated materials and
nitromusks.
More preferably, the perfume compounds are characterised by having a low Odor
Deflection Threshold. Such Odor Detection Threshold (ODT) should be lower than
1 ppm, preferably lower than 1 Oppb - 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
Taste
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Threshold Value Data (ASTM DS 48 A)", edited by F. A. Fazzalari, International
Business Machines, Hopwell Junction, NY and in Calkin 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 split 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 point in time 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 II 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: 1711 split ratio
Autosampler: 1.13 microliters per injection
Column Flow: 1.10 mL/minute
Air Flow: 345 mL/minute
Inlet Temp. 245°C
Detector Temp. 285°C
Temperature Information
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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-propylphenyl)-propionaldehyde, 1-(2,6,6-trimethyl-2-
cyclohexan-1-yl)-2-buten-1-one and/or para-methoxy-acetophenone. Even more
preferred are the following compounds having an ODT ~ 10ppb measured with
the method described above : undecylenic aldehyde, undecalactone gamma,
heliotropin, dodecalactone gamma, p-anisic aldehyde, para hydroxy-phenyl-
butanone, cymal, benzyl acetone, ionone alpha, p.t.bucinal, damascenone,
ionone beta, methyl-nonyl ketone, methyl heptine carbonate, linalool, indol,
cis-3-
hexenyl salicylate, vanillin, methyl isobutenyl tetrahydropyran,~
ethylvanillin,
coumarin, ethyl methyl phenyl giycidate, eugenol, methylanthranilate, iso
eugenol, beta naphtol methyl ester, herbavert, lyral, allyl amyl glycolate,
dihydro
iso jasmonate, ethyl-2-methylbutyrate, nerol, and phenylacetaldehyde. Most
preferably the perfume composition comprises at least 5%, more preferably at
least 10% of such components
Most preferably, the perfume ingredients are those as described in WO 96/12785
on page 12-14. Even most preferred are those perfume compositions comprising
at least 10%, preferably 25%, by weight of perfume ingredient with an CIogP of
at
least 2.0, preferably of at least 3.0 and boiling point of at least 250C.
Still another
preferred perfume composition is a composition comprising at least 20%,
preferably 35%, by weight of perfume ingredient with an CIogP at least 2.0,
more
preferably of at least 3.0 and boiling point of less than or equal to 250C.
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Clog P is a commonly known calculated measure as defined in the following
references "Calculating log P°~t from Structures"; Albert Leo
(Medicinal Chemistry
Project, Pomona College, Claremont, CA USA. Chemical Reviews, Vol. 93,
number 4, June 1993; as well as from Comprehensive Medicinal Chemistry,
Albert Leo, C. Hansch, Ed. Pergamon Press: Oxford, 1990, Vol. 4, p.315; and
Calculation Procedures for molecular lipophilicity: a comparative Study,
Quant.
Struct. Act. Realt. 15, 403-409 (1996), Raymund Mannhold and Karl Dross.
Typically, the level of pro-perfume component is of from 10 to 70% by weight,
preferably of from 40 to 60% by weight, most preferably of 50% by weight of
the
pro-perfume composition.
Suspending material
A suspending material is another essential element of the present invention.
Indeed, a suspending material will provide improved incorporation and
stability
within the detergent composition, especially liquid detergent compositions.
In addition, when incorporated into aqueous liquid detergent composition, the
suspending material will preferably protect the pro-perfume component from the
aqueous medium.
Typically, the level of suspending aid is of from 30 to 90% by weight,
preferably of
from 45 to 75% by weight, most preferably of from 50% to 70% by weight of the
pro-perfume composition.
Typical of such suspending materials includes liquid as well as solid
suspending
aid. The liquid suspending material is preferably in a hydrophobic form.
As used herein in relation to suspending materials, "hydrophobic" means
substantially water insoluble. In this regard, "substantially water insoluble"
shall
refer to a material that is not soluble in distilled (or equivalent) water, at
25°C, at a
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WO 01/51599 PCT/USO1/00822
concentration of 0.2% by weight, and preferably not soluble at 0.1 % by weight
(calculated on a water plus suspending aid weight basis). The terms "soluble",
"solubility" and the like, for purposes hereof, corresponds to the maximum
concentration of suspending material, as applicable, that can dissolve in
water or
other solvents to form a homogeneous solution, as is well understood to those
skilled in the art.
Typical of materials that are in hydrophobic form and are useful as suspending
materials include ingredients useful in perfumery. Typical of such ingredients
are
the perfume raw materials, solvents, and mixtures thereof. Typical hydrophobic
raw materials include the ketones or aldehydes like hexyl cinnamic aidehyde,
hydrocarbons like Limolene, d-Limonene, esters like Hercolyn D, benzyl
salicylate, hexyl salicylate, triethyl citrate, iso propyl myristate, or
mixtures
thereof. Typical hydrophobic solvents include diethyl phtalate, ethers like
butoxypropoxypropanol, dipropylene glycol, and mixtures thereof.
Still other suitable suspending materials are the silicone materials. The word
"silicone" as used herein includes emulsified andlor microemulsified
silicones,
including those that are commercially available and those that are emulsified
andlor microemulsified in the composition.
Some non-limiting examples of silicones which are useful in fihe present
invention
are: cyclic silicones; non-volatile silicone fluids such as polydimethyl
siloxane
gums and fluids; such as linear silicone polymer fluids having the formula
(CH3)3Si0[(CH3)2Si0]mSi(CH)3 where m is 0 or more and whereby m has an
average value such that the viscosity at 25°C of the silicone fluid is
preferably 5
centistokes or more, more preferably 500 centistokes or more, the silicone
fluid
preferably having a weight average molecular weight of 800 or more, preferably
25,000 or more; or such as volatile silicone fluid which can be a cyclic
silicone
fluid of the formula [(CH3)2Si0]n where n ranges between about 3 to about 7,
preferably about 5 or 6; or such as silicone surfactants, such as
polyglycolethers;
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WO 01/51599 PCT/USO1/00822
other suitable silicone surfactants are desribed in 'Silicone Surfactants', by
R.M.Hill, ISBN 0-8247-0010-4, 1999, Marcel Dekker Inc. New York, Basel.
These silicone surfactants can be ABA type copolymers, grafted copolymers or
ter- or tri-siloxane polymers. The silicone surfactants can be silicone
polyether
copolymers and can have ethylene oxide, propylene oxide or butylene oxide
based chains and/or mixtures thereof. More preferably the silicone surfactant
has
a weight average molecular wiegth of more than 1000, more preferably more
than 2500 or even more than 3500 or even 5000 or more. The silicone or
silicone surfactants can be a fluorosilicone as well, preferably a
fluorosilicone with
a viscosity of at least 1000 centistokes.
The silicones and fluorosilicones also preferably have a weight average
molecular weight of 1000 or more, preferaby 2500 or more or even 3500 or more,
or even 500 or more.
Preferred may also be that the silicone surfactant has a HLB (-EO) value 5 or
less, or even 3 or less, as can be determined by known methods.
Suitable examples of silicone for use herein include silicones commercially
available from Dow Corning Corporation like the DC 3225C; DC5225C and
DC246 for cyclic silicones; silicone glycols ethers like DC5200, DC1248,
DC190;
the DC 244 Fluids, DC 245 Fluids, DC 344 Fluids, or DC 345 Fluids, or ABIL K4,
ABIL B 8839 for the cyclomethicone, or the DC 200 fluids, ABIL K 520
(hexamethyl disiloxane), ABIL 10 to ABIL 100000 (dimethicone), ABIL AV 8853
(Phenyl dimethicone) for the linear silicones; Dow Corning's FS1265
fluorosilicone.
Highly preferred are DC 3225C, DC5225 and dimethylpolysiloxanes available
from Sigma and Dow Corning.
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Still another suitable method is to use a combination of various silicone
materials,
such as those described herein before. Preferably, one or more silicone
materials) is (are) emulsified or microemulsified in one or more other.
silicone
materails, forming thus the suspending material herein. The pro-perfume
component can then be suspended herein.
Preferably, at least 80% or even 90% of such a silicone mixture is formed by 2
silicone materials. Then, the weight ratio of a first silicone material to a
second
silicone material in such a mixture is preferably from 1:50 to 2:1, more
preferably
1:19 to 3:2, or even 1:9 to 1:1.
Furthermore, particles with a mean particle size up to 20 microns or even up
to
10 microns, preferably 1 to 10 microns, can be added to the silicone mixture,
like
silica, quarz, Ti02, for density adjustment of the suspensing material, or pro
perfume composition.
Preferably, for the purpose of the invention, the suspending material has a
viscosity between 250 and 250000 cps, more preferably between 700 and
70000cps. More preferably, the suspending material is selected from benzyl
salicylate, diethyl phatalate, dipropylene glycol, butoxypropoxypropanol,
silicones,
and mixtures thereof, most preferably is selected from silicones.
Method for making the~ro~erfume composition
Typically, the close physical proximity between the pro-perfume and the
suspending aid is obtained by mixing together the reacted amino-functional
component and the suspending aid, typically present in a 50:50 weight ratio,
under high shear mixing (i.e. 50.000 rpm) using an Ultra Turrax apparatus at a
temperature of 50-60°C for 5 minutes.
Particle size
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For ease of handling and incorporation, e.g. suspension into the detergent
compositions of the invention, it is preferred to provide droplets of
specified size.
Typically, this is obtained upon high shear mixing of the above mentioned
mixture. However, this can also be obtained by means of a twin screw extruder
which provide one convenient way for making the pro-perfume composition in
industrial quantities via a continous process like by means of a twin Screw
Extruder (TSE). Suitable TSE include the TX-57 MAG, TX-85 MAG, TX-110
MAG, TX-144 MAG, or TX-178 MAG twin screw extruder from Wenger. One
preferred for use herein is the TX-57 MAG. TSE suitable for use herein
comprise
at one of their extremities so called herein after "first part of the TSE" two
distinct
inlet: one for the active and the other for the amine, and at about the middle
of
the TSE, so called hereinafter "second part of the TSE" another inlet for the
suspending aid. Temperature controllers are also distributed along the TSE.
Typically, the particle size of the droplet within the detergent composition
is of
from 1 microns to 50 microns, more preferably from 2 or evne from 5 micron to
30
microns, and most preferably up to 20 or even up to 15 microns.
Incorporation into detergent composition
The pro-perfume composition is then incorporated in a detergent composition.
Means of incorporation into the detergent composition are conventionally known
in the art, and is typically made depending on its end form by either spraying
when in sprayable liquid form, or dry-addition, or mixing when in liquid
viscous
form, e.g. having a viscosity between 100 and 1000 cps. The viscosity is
measured on a rheometer, TA Instrument CSL~~oo at a temperature of 20°C
with
a gap setting of 500 microns.
Preferably, the pro-perfume composition is incorporated by mixing.
Typical level of incorporation of the pro-perfume composition within the
detergent
composition are of from 0.01 to 10%, more preferably from 0.02 to 5%, and most
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WO 01/51599 PCT/USO1/00822
preferably from 0.03, or even 0.1 or even 0.2 to 1 % by weight of the
detergent
composition.
The detergent composition typically comprises one or more detergent
ingredient.
Preferably, the detergent composition is a liquid detergent composition,
including
aqueous as well as non-aqueous liquid detergent compositions.
The aqueous and non-aqueous liquid detergent compositions of this invention
typically comprises one or more detergent ingredient. Suitable detergent
ingredients comprise a surfactant system.
NON-AQUEOUS BASED HEAVY DUTY LIQUID DETERGENTS
SURFACTANT-CONTAINING LIQUID PHASE
The present invention liquid detergent composition comprises non-aqueous,
liquid, heavy-duty detergent compositions in the form of a stable suspension
of
solid, substantially insoluble particulate material dispersed throughout a
structured, surfactant-containing liquid phase. The detergent composition
comprises from about 49% to 99.95% by weight of the composition of a
structured, surfactant-containing liquid phase formed by combining:
i) from about 1 % to 80% by weight of said liquid phase of one or more
nonaqueous organic diluents; and
ii) from about 20% to 99% by weight of said liquid phase of a surfactant
system comprising surfactants selected from the group consisting of anionic,
nonionic, cationic surfactants and combinations thereof.
The surfactant-containing, non-aqueous liquid phase of the present
invention will generally comprise from about 52% to about 98.9% by weight of
the
detergent compositions herein. More preferably, this liquid phase is
surfactant-
structured and will comprise from about 55% to 98% by weight of the
compositions. Most preferably, this non-aqueous liquid phase will comprise
from
about 55% to 70% by weight of the compositions herein. Such a surfactant-
containing liquid phase will frequently have a density of from about 0.6 to
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WO 01/51599 PCT/USO1/00822
g/cc, more preferably from about 0.9 to 1.3 g/cc. The liquid phase of the
detergent compositions herein is preferably formed from one or more non-
aqueous organic diluents into which is mixed a surfactant structuring agent
which
is preferably a specific type of anionic surfactant-containing powder.
Non-aqueous Organic Diluents
The major component of the liquid phase of the detergent compositions
herein comprises one or more non-aqueous organic diluents. The non-aqueous
organic diluents used in this invention may be either surface active, i.e.,
surfactant, liquids or non-aqueous, non-surfactant liquids referred to herein
as
non-aqueous solvents. The term "solvent" is used herein to connote the non-
surfactant, non-aqueous liquid portion of the compositions herein. While some
of
the essential and/or optional components of the compositions herein may
actually
dissolve in the "solvent"-containing liquid phase, other components will be
present as particulate material dispersed within the "solvent"-containing
liquid
phase. Thus the term "solvent" is not meant to require that the solvent
material
be capable of actually dissolving all of the detergent composition components
added thereto.
The non-aqueous liquid diluent component will generally comprise from
about 50% to 100%, more preferably from about 50% to 80%, most preferably
from about 55% to 75%, of a structured, surfactant-containing liquid phase.
Preferably the liquid phase of the compositions herein, i.e., the non-aqueous
liquid diluent component, will comprise both non-aqueous liquid surfactants
and
non-surfactant non-aqueous solvents.
i) Non-aqueous Surfactant Liquids
Suitable types of non-aqueous surfactant liquids which can be used to
form the liquid phase of the compositions herein include the alkoxylated
alcohols,
ethylene oxide (EO)-propylene oxide (PO) block polymers, polyhydroxy fatty
acid
amides, alkylpolysaccharides, and the like. Such normally liquid surfactants
are
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WO 01/51599 PCT/USO1/00822
those having an HLB ranging from 10 to 16. Most preferred of the surfactant
liquids are the alcohol alkoxylate nonionic surfactants.
Alcohol alkoxylates are materials which correspond to the general formula:
R1 (CmH2m0)nOH
wherein R1 is a Cg - C1 g alkyl group, m is from 2 to 4, and n ranges from
about 2
to 12. Preferably R1 is an alkyl group, which may be primary or secondary,
that
contains from about 9 to 15 carbon atoms, more preferably from about 10 to 14
carbon atoms. Preferably also the alkoxylated fatty alcohols will be
ethoxylated
materials that contain from about 2 to 12 ethylene oxide moieties per
molecule,
more preferably from about 3 to 10 ethylene oxide moieties per molecule.
The alkoxylated fatty alcohol materials useful in the liquid phase will
frequently have a hydrophilic-lipophilic balance (HLB) which ranges from about
3
to 17. More preferably, the HLB of this material will range from about 6 to
15,
most preferably from about 3 to 15.
Examples of fatty alcohol alkoxylates useful in or as the non-aqueous
liquid phase of the compositions herein will include those which are made from
alcohols of 12 to 15 carbon atoms and which contain about 7 moles of ethylene
oxide. Such materials have been commercially marketed under the trade names
Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company. Other useful
Neodols include Neodol 1-5, an ethoxylated fatty alcohol averaging 11 carbon
atoms in its alkyl chain with about 5 moles of ethylene oxide; Neodol 23-9, an
ethoxylated primary C12 - C13 alcohol having about 9 moles of ethylene oxide
and Neodol 91-10, an ethoxylated Cg-C11 primary alcohol having about 10 moles
of ethylene oxide. Alcohol ethoxylates of this type have also been marketed by
Shell Chemical Company under the Dobanol tradename. Dobanol 91-5 is an
ethoxylated Cg-C11 fatty alcohol with an average of 5 moles ethylene oxide and
Dobanol 25-7 is an ethoxylated C12-C15 fatty alcohol with an average of 7
moles
of ethylene oxide per mole of fatty alcohol.
Other examples of suitable ethoxylated alcohols include Tergitol 15-S-7
and Tergitol 15-S-9 both of which are linear secondary alcohol ethoxylates
that
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WO 01/51599 PCT/USO1/00822
have been commercially marketed by Union Carbide Corporation. The former is
a mixed ethoxylation product of C11 to C15 linear secondary alkanol with 7
moles
of ethylene oxide and the latter is a similar product but with 9 moles of
ethylene
oxide being reacted.
Other types of alcohol ethoxylates useful in the present compositions are
higher molecular weight nonionics, such as Neodol 45-11, which are similar
ethylene oxide condensation products of higher fatty alcohols, with the higher
fatty alcohol being of 14-15 carbon atoms and the number of ethylene oxide
groups per mole being about 11. Such products have also been commercially
marketed by Shell Chemical Company.
If alcohol alkoxylate nonionic surfactant is utilized as part of the non-
aqueous liquid phase in the detergent compositions herein, it will preferably
be
present to the extent of from about 1 % to 60% of the composition structured
liquid
phase. More preferably, the alcohol alkoxylate component will comprise about
5% to 40% of the structured liquid phase. Most preferably, an alcohol
alkoxylate
component will comprise from about 5% to 35% of the detergent composition
structured liquid phase. Utilization of alcohol alkoxylate in these
concentrations in
the liquid phase corresponds to an alcohol alkoxylate concentration in the
total
composition of from about 1 % to 60% by weight, more preferably from about 2%
to 40% by weight, and most preferably from about 5% to 25% by weight, of the
composition.
Another type of non-aqueous surfactant liquid which may be utilized in this
invention are the ethylene oxide (E0) - propylene oxide (PO) block polymers.
Materials of this type are well known nonionic surfactants which have been
marketed under the tradename Pluronic. These materials are formed by adding
blocks of ethylene oxide moieties to the ends of polypropylene glycol chains
to
adjust the surface active properties of the resulting block polymers. EO-PO
block
polymer nonionics of this type are described in greater detail in Davidsohn
and
Milwidsky; Synthetic Detergents, 7th Ed.; Longman Scientific and Technical
(1987) at pp. 34-36 and pp. 189-191 and in U.S. Patents 2,674,619 and
2,677,700. All of these publications are incorporated herein by reference.
These
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Pluronic type nonionic surfactants are also believed to function as effective
suspending agents for the particulate material which is dispersed in the
liquid
phase of the detergent compositions herein.
Another possible type of non-aqueous surfactant liquid useful in the
compositions herein comprises polyhydroxy fatty acid amide surfactants. If
present, the polyhydroxy fatty acid amide surfactants are preferably present
in a
concentration of from about 0.1 to about 8%. Materials of this type of
nonionic
surfactant are those which conform to the formula:
O i pH2p+1
R-C-N-Z
wherein R is a Cg_17 alkyl or alkenyl, p is from 1 to 6, and Z is glycityl
derived
from a reduced sugar or alkoxylated derivative thereof. Such materials include
the C12-C1 g N-methyl glucamides. Examples are N-methyl N-1-deoxyglucityl
cocoamide and N-methyl N-1-deoxyglucityl oleamide. Processes for making
polyhydroxy fatty acid, amides are know and can be found, for example, in
Wilson, U.S. Patent 2,965,576 and Schwartz, U.S. Patent 2,703,798, the
disclosures of which are incorporated herein by reference. The materials
themselves and their preparation are also described in greater detail in
Honsa,
U.S. Patent 5,174,937, Issued December 26, 1992, which patent is also
. incorporated herein by reference.
The amount of total liquid surfactant in the preferred surfactant-structured,
non-aqueous liquid phase herein will be determined by the type and amounts of
other composition components and by the desired composition properties.
Generally, the liquid surfactant can comprise from about 35% to 70% of the non-
aqueous liquid phase of the compositions herein. More preferably, the liquid
surfactant will comprise from about 50% to 65% of a non-aqueous structured
liquid phase. This corresponds to a non-aqueous liquid surfactant
concentration
in the total composition of from about 15% to 70% by weight, more preferably
from about 20% to 50% by weight, of the composition.
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ii) Non-surfactant Non-aaueous Organic Solvents
The liquid phase of the detergent compositions herein may also comprise
one or more non-surfactant, non-aqueous organic solvents. Such non-surfactant
non-aqueous liquids are preferably those of low polarity. For purposes of this
invention, "low-polarity" liquids are those which have little, if any,
tendency to
dissolve one of the preferred types of particulate material used in the
compositions herein, i.e., the peroxygen bleaching agents, sodium perborate or
sodium percarbonate. Thus relatively polar solvents such as ethanol are
preferably not utilized. Suitable types of low-polarity solvents useful in the
non-
aqueous liquid detergent compositions herein do include non-vicinal C4-Cg
alkylene glycols, alkylene glycol mono lower alkyl ethers, lower molecular
weight
polyethylene glycols, lower molecular weight methyl esters and amides, and the
like.
A preferred type of non-aqueous, low-polarity solvent for use in the
compositions herein comprises the non-vicinal C4-Cg branched or straight chain
alkylene glycols. Materials of this type include hexylene glycol (4-methyl-2,4-
pentanediol), 1,6-hexanediol, 1,3-butylene glycol and 1,4-butylene glycol.
Hexylene glycol is the most preferred.
Another preferred type of non-aqueous, low-polarity solvent for use herein
comprises the mono-, di-, tri-, or tetra- C2-C3 alkylene glycol mono C2-C6
alkyl
ethers. The specific examples of such . compounds include diethylene glycol
monobutyl ether, tetraethylene glycol monobutyl ether, dipropolyene glycol
monoethyl ether, and dipropylene glycol monobutyl ether. Diethylene glycol
monobutyl ether, dipropylene glycol monobutyl ether and butoxy-propoxy-
propanol (BPP) are especially preferred. Compounds of the type have been
commercially marketed under the firadenames Dowanol, Carbitol, and Cellosolve.
Another preferred type of non-aqueous, low-polarity organic solvent useful
herein comprises the lower molecular weight polyethylene glycols (PEGs). Such
materials are those having molecular weights of at least about 150. PEGs of
molecular weight ranging from about 200 to 600 are most preferred.
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Yet another preferred type of non-polar, non-aqueous solvent comprises
lower molecular weight methyl esters. Such materials are those of the general
formula: R1-C(O)-OCH3 wherein R1 ranges from 1 to about 18. Examples of
suitable lower molecular weight methyl esters include methyl acetate, methyl
propionate, methyl octanoate, and methyl dodecanoate.
The non-aqueous, generally low-polarity, non-surfactant organic solvents)
employed should, of course, be compatible and non-reactive with other
composition components, e.g., bleach and/or activators, used in the liquid
detergent compositions herein. Such a solvent component is preferably utilized
in
an amount of from about 1 % to 70% by weight of the liquid phase. More
preferably, a non-aqueous, low-polarity, non-surfactant solvent will comprise
from
about 10% to 60% by weight of a structured liquid phase, most preferably from
about 20% to 50% by weight, of a structured liquid phase of the composition.
Utilization of non-surfactant solvent in these concentrations in the liquid
phase
corresponds to a non-surfactant solvent concentration in the total composition
of
from about 1 % to 50% by weight, more preferably from about 5% to 40% by
weight, and most preferably from about 10% to 30% by weight, of the
composition.
iii) Blends of Surfactant and Non-surfactant Solvents
In systems which employ both non-aqueous surFactant liquids and non-
aqueous non-surfactant solvents, the ratio of surfactant to non-surfactant
liquids,
e.g., the ratio of alcohol alkoxylate to low polarity solvent, within a
structured,
surfactant-containing liquid phase can be used to vary. the rheological
properties
of the detergent compositions eventually formed. Generally, the weight ratio
of
surfactant liquid to non-surfactant organic solvent will range about 50:1 to
1:50.
More preferably, this ratio will range from about 3:1 to 1:3, most preferably
from
about 2:1 to 1:2.
Surfactant Structurant
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The non-aqueous liquid phase of the detergent compositions of this
invention is prepared by combining with the non-aqueous organic liquid
diluents
hereinbefore described a surfactant which is generally, but not necessarily,
selected to add structure to the non-aqueous liquid phase of the detergent
compositions herein. Structuring surfactants can be of the anionic, nonionic,
cationic, and/or amphoteric types.
Preferred structuring surfactants are the anionic surfactants such as the
alkyl sulfates, the alkyl polyalkxylate sulfates and the linear alkyl benzene
sulfonates. Another common type of anionic surfactant material which may be
optionally added to the detergent compositions herein as structurant comprises
carboxylate-type anionics. Carboxylate-type anionics include the C10-C1g alkyl
alkoxy carboxylates (especially the EO 1 to 5 ethoxycarboxylates) and the C10-
C1g sarcosinates, especially oleoyl sarcosinate. Yet another common type of
anionic surfactant material which may be employed as a structurant comprises
other sulfonated anionic surfactants such as the Cg-C1 g paraffin sulfonates
and
the Cg-C1 g olefin sulfonates. Structuring anionic surfactants will generally
comprise from about 1 % to 30% by weight of the compositions herein.
As indicated, one preferred type of structuring anionic surfactant comprises
primary or secondary alkyl sulfate anionic surfactants. Such surfactants are
those produced by the sulfation of higher Cg-C2p fatty alcohols.
Conventional primary alkyl sulfate surfactants have the general formula
ROS03-M+
wherein R is typically a linear Cg - C20 hydrocarbyl group, which may be
straight
chain or branched chain, and M is a water-solubilizing cation. Preferably R is
a
C10-14 alkyl, and M is alkali metal. Most preferably R is about C12 and M is
sodium.
Conventional secondary alkyl sulfates may also be utilized as a structuring
anionic surfactant for the liquid phase of the compositions herein.
Gonventional
secondary alkyl sulfate surfactants are those materials which have the sulfate
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moiety distributed randomly along the hydrocarbyl "backbone" of the molecule.
Such materials may be depicted by the structure:
CH3(CH2)n(CHOS03-M+) (CH2)mCH3
wherein m and n are integers of 2 or greater and the sum of m + n is typically
about 9 to 15, and M is a water-solubilizing cation.
If utilized, alkyl sulfates will generally comprise from about 1 % to 30% by
weight of the composition, more preferably from about 5% to 25% by weight of
the composition. Non-aqueous liquid detergent compositions containing alkyl
sulfates, peroxygen bleaching agents, and bleach activators are described in
greater detail in Kong-Chan et al.; WO 96/10073; Publiched April 4, 1996,
which
application is incorporated herein by reference.
Another preferred type of anionic surfactant material which may be
optionally added to the non-aqueous cleaning compositions herein as a
structurant comprises the alkyl polyalkoxylate sulfates. Alkyl polyalkoxylate
sulfates are also known as alkoxylated alkyl sulfates or alkyl ether sulfates.
Such
materials are those which correspond to the formula
R2-O-(CmH2m0)n-S03M
wherein R2 is a C10-C22 alkyl group, m is from 2 to 4, n is from about 1 to
15,
and M is a salt-forming cation. Preferably, R2 is a C12-C1g alkyl, m is 2, n
is
from about 1 to 10, and M is sodium, potassium, ammonium, alkylammonium or
alkanolammonium. Most preferably, R2 is a C12-C16, m is 2, n is from about 1
to
6, and M is sodium. Ammonium, alkylammonium and alkanolammonium
counterions are preferably avoided when used in the compositions herein
because of incompatibility with peroxygen bleaching agents.
if utilized, alkyl polyalkoxylate sulfates can also generally comprise from
about 1 % to 30% by weight of the composition, more preferably from about 5%
to
25% by weight of the composition. Non-aqueous liquid detergent compositions
containing alkyl polyalkoxylate sulfates, in combination with polyhydroxy
fatty acid
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amides, are described in greater detail in Boutique et al; PCT Application No.
PCT/US96/04223, which application is incorporated herein by reference.
The most preferred type of anionic surfactant for use as a structurant in the
compositions herein comprises the linear alkyl benzene sulfonate (LAS)
surfactants. In particular, such LAS surfactants can be formulated info a
specific
type of anionic surfactant-containing powder which is especially useful for
incorporation into the non-aqueous liquid detergent compositions of the
present
invention. Such a powder comprises two distinct phases. One of these.phases is
insoluble in the non-aqueous organic liquid diluents used in the compositions
herein; the other phase is soluble in the non-aqueous organic liquids. It is
the
insoluble phase of this preferred anionic surfactant-containing powder which
can
be dispersed in the non-aqueous liquid phase of the preferred compositions
herein and which forms a network of aggregated small particles that allows the
final product to stably suspend other solid particulate materials in the
composition.
Such a preferred anionic surfactant-containing powder is formed by co
drying an aqueous slurry which essentially contains a) one of more .alkali
metal
salts of C10-16 linear alkyl benzene sulfonic acids; and b) one or more non
surfactant diluent salts. Such a slurry is dried to a solid material,
generally in
powder form, which comprises both the soluble and insoluble phases.
The linear alkyl benzene sulfonate (LAS) materials used to form the
preferred anionic surfactant-containing powder are well known materials. Such
surfactants and their preparation are described for example in U.S. Patents
2,220,099 and 2,477,333, incorporated herein by reference. Especially
preferred
are the sodium and potassium linear straight chain alkylbenzene sulfonates in
which the average number of carbon atoms in the alkyl group is from about 11
to
74. Sodium C11-14~ e~g~~ C12~ LAS is especially preferred. The alkyl benzene
surfactant anionic surfactants are generally used in the powder-forming slurry
in
an amount from about 20 to 70% by weight of the slurry, more preferably from
about 20% to 60% by weight of the slurry.
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The powder-forming slurry also contains a non-surfactant, organic or
inorganic salt component that is co-dried with the LAS to form the two-phase
anionic surfactant-containing powder. Such salts can be any of the known
sodium, potassium or magnesium halides, sulfates, citrates, carbonates,
sulfates,
borates, succinates, sulfo-succinates and the like. Sodium sulfate, which is
generally a bi-product of LAS production, is the preferred non-surfactant
diluent
salt for use herein. Salts which function as hydrotropes such as sodium sulfo-
succinate may also usefully be included. The non-surfactant salts are
generally
used in the aqueous slurry, along with the LAS, in amounts ranging from about
1
to 50% by weight of the slurry, more preferably from about 5% to 40% by weight
of the slurry. Salts that act as hydrotropes can preferably comprise up to
about
3% by weight of the slurry.
The aqueous slurry containing the LAS and diluent salt components
hereinbefore described can be dried to form the anionic surfactant-containing
powder preferably added to the non-aqueous diluents in order to prepare a
structured liquid phase within the compositions herein. Any conventional
drying
technique, e.g., spray drying, drum drying, etc., or combination of drying
techniques, may be employed. Drying should take place until the residual water
content of the solid material which forms is within the range of from about
0.5% to
4% by weight, more preferably from about 1 % to 3% by weight.
The anionic surfactant-containing powder produced by fihe drying operation
constitutes two distinct phases, one of which is soluble in the inorganic
liquid
diluents used herein and one of which is insoluble in the diluents. The
insoluble
phase in the anionic surfactant-containing powder generally comprises from
about 10% to 45% by weight of the powder, more preferably from about 15% to
35% by weight of a powder.
The anionic surfactant-containing powder that results after drying can
comprise from about 45% to 94%, more preferably from about 60% to 94%, by
weight of the powder of alkyl benzene sulfonic acid salts. Such concentrations
are generally sufficient to provide from about 0.5% to 60%, more preferably
from
about 15% to 60%, by weight of the total detergent composition that is
eventually
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prepared, of the alkyl benzene sulfonic acid salts. The anionic surfactant-
containing powder itself can comprise from about 0.45% to 45% by weight of the
total composition that is eventually prepared. After drying, the anionic
surfactant-
containing powder will also generally contain from about 2% to 50%, more
preferably from about 2% to 25% by weight of the powder of the non-surfactant
salts.
After it is dried to the requisite extent, the combined LAS/salt material can
be
converted to flakes or powder form by any known suitable milling or
comminution
process. Generally at the time such material is combined with the non-aqueous
organic solvents to form the structured liquid phase of the compositions
herein,
the particle size of this powder will range from 0.1 to 2000 microns, more
preferably from about 0.1 to 1000 microns.
A structured, surfactant-containing liquid phase of the preferred detergent
compositions herein can be prepared by combining the non-aqueous organic
diluents hereinbefore described with the anionic surfactant-containing powder
as
hereinbefore described. Such combination results in the formation of a
structured
surfactant-containing liquid phase. Conditions for making this combination of
preferred structured liquid phase components are described more fully
hereinafter
in the "Composition Preparation and Use" section. As previously noted, the
formation of a structured, surfactant-containing liquid phase permits the
stable
suspension of colored speckles and additional functional particulate solid
materials within the preferred detergent compositions of this invention.
Additional suitable surfactants for use in the present invention included
nonionic surfactants, specifically, polyhydroxy fatty acid amides of the
formula:
R-C-N-Z
wherein R is a Cg_17 alkyl or alkenyl, R1 is a methyl group and Z is glycityl
derived from a reduced sugar or alkoxylated derivative thereof. Examples are N-
methyl N-1-deoxyglucityl cocoamide and N-methyl N-1-deoxyglucityl oleamide.
Processes for making polyhydroxy fatty acid amides are known and can be found
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in Wilson, U.S. Patent 2,965,576 and Schwartz, U.S. Patent 2,703,798, the
disclosures of which are incorporated herein by reference.
Preferred surfactants for use in the detergent compositions described
herein are amine based surfactants of the general formula:
R3
R1-X-(CH2)n-N
R4
wherein R1 is a Cg-C12 alkyl group; n is from about 2 to about 4, X is a
bridging
group which is selected from NH, CONH, COO, or O or X can be absent; and R3
and Rq, are individually selected from H, C1-Cq, alkyl, or (CH2-CH2-O(R5))
wherein R5 is H or methyl. Especially preferred amines based surfactants
include
the following:
R1-(CH2)2-NH2
R1-O-(CH2)3-NH2
R1-C(O)-NH-(CH2)3-N(CH3)2
CH2-CH(OH)-R5
R1-N
CH2-CH(OH)-R5
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wherein R1 is a C6-C12 alkyl group and R5 is H or CH3. Particularly preferred
amines for use in the surfactants defined above include those selected from
the
group consisting of octyl amine, hexyl amine, decyl amine, dodecyl amine, Cg
C12 bis(hydroxyethyl)amine, Cg-C12 bis(hydroxyisopropyl)amine, Cg-C12 amido
propyl dimethyl amine, or mixtures thereof.
In a highly preferred embodiment, the amine based surfactant is described
by the formula:
R1-C(O)-NH-(CH2)3-N(CH3)2
wherein R1 is Cg-C12 alkyl.
SOLID PARTICULATE MATERIALS
The non-aqueous detergent compositions herein preferably comprise from
about 0.01 % to 50% by weight, more preferably from about 0.2% to 30% by
weight, of solid phase particulate material which is dispersed and suspended
within the liquid phase. Generally such particulate material will range in
size from
about 0.1 to 1500 microns, more preferably from about 0.1 to 900 microns. Most
preferably, such material will range in size from about 5 to 200 microns.
The particulate material utilized herein can comprise one or more types of
detergent composition components which in particulate form are substantially ,
insoluble in the non-aqueous liquid phase of the composition. The types of
particulate materials which can be utilized are described in detail as
follows:
Peroxygen Bleaching Agent With Optional Bleach Activators
The most preferred type of particulate material useful in the detergent
compositions herein comprises particles of a peroxygen bleaching agent. Such
peroxygen bleaching agents may be organic or inorganic in nature. Inorganic
peroxygen bleaching agents are frequently utilized in combination with a
bleach
activator.
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Useful organic peroxygen bleaching agents include percarboxylic acid
bleaching agents and 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. Patent
4,483,781, Hartman,~ Issued November 20, 1984; European Patent Application
EP-A-133,354, Banks et al., Published February 20, 1985; and U.S. Patent
4,412,934, Chung et al., Issued November 1, 1983. Highly preferred bleaching
agents also include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as
described in U.S. Patent 4,634,551, Issued January 6, 1987 to Burns et al.
Inorganic peroxygen bleaching agents may also be used in particulate form
in the detergent compositions herein. Inorganic bleaching agents are in fact
preferred. Such inorganic peroxygen compounds include alkali metal perborate
and percarbonate materials, most preferably the percarbonates. For example,
sodium perborate (e.g. mono- or tetra-hydrate) can be used. Suitable inorganic
bleaching agents can also include sodium or potassium 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. Frequently inorganic
peroxygen bleaches will be coated with silicate, borate, sulfate or water-
soluble
surfactants. For example, coated percarbonate particles are available from
various commercial sources such as FMC, Solvay Interox, Tokai Denka and
Degussa.
Inorganic peroxygen bleaching agents, e.g., the perborates, the
percarbonates, etc., are preferably combined with bleach activators, which
lead to
the in situ production in aqueous solution (i.e., during use of the
compositions
herein for fabric launderingibleaching) of the peroxy acid corresponding to
the
bleach activator. Various non-limiting examples of activators are disclosed in
U.S. Patent 4,915,854, Issued April 10, 1990 to Mao et al.; and U.S. Patent
4,412,934 Issued November 1, 1983 to Chung et al. The nonanoyloxybenzene
sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are
typical.
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Mixtures thereof can also be used. See also the hereinbefore referenced U.S.
4,634,551 for other typical bleaches and activators useful herein.
Other useful amido-derived bleach activators are those of the formulae:
R1 N(R5)C(O)R2C(O)L or R1 C(O)N(R5)R2C(O)L
wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms,
R2 is an alkylene containing from 1 to about 6 carbon atoms, R5 is H or alkyl,
aryl, or alkaryl containing from aboufi 1 to about 10 carbon atoms, and L is
any
suitable leaving group, for example, oxybenzene sulfonate, -OOH, -OOM. 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 phenol sulfonate.
Preferred examples of bleach activators of the above formulae include (6-
octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)
oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate and mixtures
thereof as described in the hereinbefore referenced U.S. Patent 4,634,551.
Such
mixtures are characterized herein as (6-Cg-C10 alkamido-
caproyl)oxybenzenesulfonate.
Another class of useful bleach activators comprises the benzoxazin-type
activators disclosed by Hodge et al. in U.S. Patent 4,966, 723, Issued October
30, 1990, incorporated herein by reference. A highly preferred activator of
the
benzoxazin-type is:
O
~I.
C~O
,C
N
Still another class of useful bleach activators includes the acyl lactam
activators, especially acyl caprolactams and acyl valerolactams of the
formulae:
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O O
O C-CH2 CH2 O C-CH2 CH2
Rs C-N ~ H Rs-C-N
2
\CHz CH2~ \CH2 CH2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing
from 1 to
about 12 carbon atoms. Highly preferred lactam activators include benzoyl
caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam,
nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl
valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl
valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See
also U.S. Patent 4,545,784, Issued to Sanderson, October 8, 1985, incorporated
herein by reference, which discloses acyl caprolactams, including benzoyl
caprolactam, adsorbed into sodium perborate.
If peroxygen bleaching agents are used as all or part of the particulate
material, they will generally comprise from about 0.1 % to 30% by weight of
the
composition. More. preferably, peroxygen bleaching agent will comprise from
about 1 % to 20% by weight of the composition. Most preferably, peroxygen
bleaching agent will be present to the extent of from about 5% to 20% by
weight
of the composition. If utilized, bleach activators can comprise from about
0.5% to
20%, more preferably from about 3% to 10%, by weight of the composition.
Frequently, activators are employed such that the molar ratio of bleaching
agent
to activator ranges from about 1:1 to 10:1, more preferably from about 1.5:1
to
5:1.
In addition, if has been found that bleach activators, when agglomerated with
certain acids such as citric acid, are more chemically stable.
Organic Builder Material
Another possible type of particulate material which can be suspended in the
non-aqueous liquid detergent compositions herein comprises an organic
detergent builder material which serves to counteract the effects of calcium,
or
other ion, water hardness encountered during laundering/bleaching use of the
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compositions herein. Examples of such materials include the alkali metal,
citrates, succinates, malonates, fatty acids, carboxymethyl succinates,
carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples
include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic
acid,
benzene polycarboxylic acids and citric acid. Other examples of organic
phosphonate type sequestering agents such as those which have been sold by
Monsanto under the bequest tradename and alkanehydroxy phosphonates.
Citrate salts are highly preferred.
Other suitable organic builders include the higher molecular weight polymers
and copolymers known to have builder properties. For example, such materials
include appropriate polyacrylic acid, polymaleic acid, and
polyacrylic/polymaleic
acid copolymers and their salts, such as those sold by BASF under the Sokalan
trademark which have molecular weight ranging from about 5,000 to 100,000.
Another suitable type of organic builder comprises the water-soluble salts of
higher fatty acids, i.e., "soaps". These include alkali metal soaps such as
the
sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids
containing from about 8 to about 24 carbon atoms, and preferably from about 12
to about 18 carbon atoms. Soaps can be made by direct saponification of fats
and oils or by the neutralization of free fatty acids. Particularly useful are
the
sodium and potassium salts of the mixtures of fatty acids derived from coconut
oil
and tallow, i.e., sodium or potassium tallow and coconut soap.
If utilized as all or part of the particulate material, insoluble organic
detergent
builders can generally comprise from about 2% to 20% by weight of the
compositions herein. More preferably, such builder material can comprise from
about 4% to 10% by weight of the composition.
Inorganic Alkalinity Sources
Another possible type of particulate material which can be suspended in the
non-aqueous liquid detergent compositions herein can comprise a material which
serves to render aqueous washing solutions formed from such compositions
generally alkaline in nature. Such materials may or may not also act as
detergent
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builders, i.e., as materials which counteract the adverse effect of water
hardness
on detergency perfiormance.
Examples of suitable alkalinity sources include water-soluble alkali metal
carbonates, bicarbonates, borates, silicates and metasilicates. Although not
preferred for ecological reasons, water-soluble phosphate salts may also be
utilized as alkalinity sources. These include alkali metal pyrophosphates,
orthophosphates, polyphosphates and phosphonates. Of all of these alkalinity
sources, alkali metal carbonates such as sodium carbonate are the most
preferred.
The alkalinity source, if in the form of a hydratable salt, may also serve as
a
desiccant in the non-aqueous liquid detergent compositions herein. The
presence of an alkalinity source which is also a desiccant may provide
benefits in
terms of chemically stabilizing those composition components such as the
peroxygen bleaching agent which may be susceptible to deactivation by water.
If utilized as all or part of the particulate material component, the
alkalinity
source will generally comprise from about 1 % to 25% by weight of the
compositions herein. More preferably, the alkalinity source can comprise from
about 2% to 15% by weight of the composition. Such materials, while water-
soluble, will generally be insoluble in the non-aqueous detergent compositions
herein. Thus such materials will generally be dispersed in the non-aqueous
liquid
phase in the form of discrete particles.
(D) Colored Speckles
The non-aqueous liquid detergent compositions herein also essentially
contain from about 0.05% to 2%, more preferably 0.1 % to 1 %, of the
composition
of colored speckles. Such colored speckles themselves are combinations of a
conventional dye or pigment material with a certain kind of carrier material
that
imparts specific characteristics to the speckles. For purposes of this
invention,
"colored" speckles are those which have a color that is visibly distinct from
the
color of the liquid detergent composition in which they are dispersed.
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The colorant materials which can be used to form the colored speckles can
comprise any of the conventional dyes and pigments known and approved for
use in detergent products for use in the home. Such materials can include, for
example, Ultramarine Blue dye, Acid 80 Blue dye, Red HP Liquitint, Blue
Liquitint
and the like.
Dye or pigment material can be combined with a specific type of carrier
material to form the colored speckles for use in the detergent compositions
herein. The carrier material is selected to impart to the speckles certain
specific
density and solubility characteristics. Materials which have been found to be
suitable as carriers for the colored speckles include polyacrylates;
polysaccharides such as starches, celluloses, gums and derivatives thereof;
and
polyethylene glycols. Especially preferred carrier material comprises
polyethylene glycol having a molecular weight from about 4,000 to 20,000, more
preferably from about 4,000 to 10,000.
The colored speckles can be produced by dispersing the dye or pigment
material within the carrier material. This can be done, for example, by a)
melting
the carrier and dispersing the dye or pigment therein under mixing, b) mixing
the
dye/pigment powder and carrier powder together, or c) by dissolving the
dye/pigment and the carrier in aqueous solution. The colorant/carrier mixture
can
then be formed into particles by flaking, spray drying, grilling, extruding or
other
conventional techniques. Generally the colored speckles will contain from
about
0.1% to 5% by weight of the speckles of the colorant (dye or pigment)
material.
The colored speckles produced in this manner will generally range in size
from aboufi 400 to 1,500 microns, more preferably from about 400 to 1,200
microns. Speckles made from the carrier materials specified will have a
density
less than about 1.4 g/cc, preferably from aboufi 1.0 to 1.4 g/cc. Such
speckles will
also be substantially insoluble in the non-aqueous liquid phase of the liquid
detergent compositions herein. Thus, the colored speckles can be stably
suspended in the non-aqueous matrix of the liquid detergent compositions of
this
invention without dissolving therein. Such speckles, however, rapidly dissolve
in
the aqueous wash liquors prepared from the liquid detergent compositions
herein.
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AQUEOUS BASED HEAVY DUTY LIQUID DETERGENTS SURFACTANTS
The present invention also comprises aqueous based liquid detergent
compositions. The aqueous liquid detergent compositions preferably comprise
from about 10% to about 98%, preferably from about 30% to about 95%, by
weight of an aqueous liquid carrier which is preferably water. Additionally,
the
aqueous liquid detergent compositions of the present invention comprise a
surfactant system which preferably contains one or more detersive surfactants.
The surfactants can be selected from nonionic detersive surfactant, anionic
detersive surfactant, zwitterionic detersive surfactant, amine oxide detersive
surfactant, and mixtures thereof. The surfactant system typically comprises
from
about 5% to about 70%, preferably from about 15% to about 30%, by weight of
the detergent composition.
Anionic Surfactant
Anionic surfactants include C11-C1g alkyl benzene sulfonates (LAS) and
primary, branched-chain and random C10-C20 alkyl sulfates (AS), the C10-C18
secondary (2,3) alkyl sulfates 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
about 7, preferably at least about 9, and M is a water-solubilizing cation,
especially sodium, unsaturated sulfates such as oleyl sulfate, the C10-C18
alkyl
alkoxy sulfates ("AEXS"; especially EO 1-7 ethoxy sulfates), C1 p-C1 g alkyl
alkoxy
carboxylates (especially the EO 1-5 ethoxycarboxylates), the C10-18 glycerol
ethers, the C10-C1g alkyl polyglycosides and their corresponding sulfated
polyglycosides, and C12-C1g alpha-sulfonated fatty acid esters.
Generally speaking, anionic surfactants useful herein are disclosed in U.S.
Patent No. 4,285,841, Barrat et al, issued August 25, 1981, and in U.S. Patent
No. 3,919,678, Laughlin et al, issued December 30, 1975.
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Useful anionic surfactants include the water-soluble salts, particularly the
alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or
triethanolammonium) salts, of organic sulfuric reaction products having in
their
molecular structure an alkyl group containing from about 10 to about 20 carbon
atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term
"alkyl" is the alkyl portion of aryl groups.) Examples of this group of
synthetic
surfactants are the alkyl sulfates, especially those obtained by sulfating the
higher
alcohols (Cg-C1g carbon atoms) such as those produced by reducing the
glycerides of tallow or coconut oil.
Other anionic surfactants herein are the water-soluble salts of alkyl phenol
ethylene oxide ether sulfates containing from about 1 to about 4 units of
ethylene
oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl
group.
Other useful anionic surfactants herein include the water-soluble salts of
esters of a-sulfonated fatty acids containing from about 6 to 20 carbon atoms
in
the fatty acid group and from about 1 to 10 carbon atoms in the ester group;
water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about
2 to
9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in
the alkane moiety; water-soluble salts of olefin sulfonates containing from
about
72 to 24 carbon atoms; and b-alkyloxy alkane sulfonates containing from about
1
to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in
the
alkane moiety.
Particularly preferred anionic surfactants herein are the alkyl polyethoxylate
sulfates of the formula
RO(C2H40)xSOg M+
wherein R is an alkyl chain having from about 10 to about 22 carbon atoms,
saturated or unsaturated, M is a cation which makes the compound water-
soluble,
especially an alkali metal, ammonium or substituted ammonium cation, and x
averages from about 1 to about 15.
Preferred alkyl sulfate surfactants are the non-ethoxylated C12-15 primary
and secondary alkyl sulfates. Under cold water washing conditions, i.e., less
than
abut 65°F (18.3°C), it is preferred that there be a mixture of
such ethoxylated and
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non-ethoxylated alkyl sulfates. Examples of fatty acids include capric,
lauric,
myristic, palmitic, stearic, arachidic, and behenic acid. Other fatty acids
include
palmitoleic, oleic, linoleic, (inolenic, and ricinoleic acid.
Nonionic Surfactant
Conventional nonionic and amphoteric surfactants include C12-C1 g alkyl
ethoxylates (AE) including the so-called narrow peaked alkyl ethoxylates and
Cg-
C12 alkyl phenol alkoxylates (especially ethoxylates and mixed
ethoxy/propoxy).
The C1 p-C1 g N-alkyl polyhydroxy fatty acid amides can also be used. Typical
examples include the C12-C1g N-methylglucamides. See WO 9,206,154. Other
sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides,
such as C10-C1 g N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl
C12-C1 g glucamides can be used for low sudsing. C1 p-C20 conventional soaps
may also be used. If high sudsing is desired, the branched-chain C10-C1 g
soaps
may be used. Examples of nonionic surfactants are described in U.S. Patent No.
4,285,841, Barrat et al, issued August 25, 1981.
Preferred examples of these surfactants include ethoxylated alcohols and
ethoxylated alkyl phenols of the formula R(OC2H4)nOH, wherein R is selected
from the group consisting of aliphatic hydrocarbon radicals containing from
about
8 to about 15 carbon atoms and alkyl phenyl radicals in which the alkyl groups
contain from about 8 to about 12 carbon atoms, and the average value of n is
from about 5 to about 15. These surfactants are more fully described in U.S.
Patent No. 4,284,532, Leikhim et al, issued August 18, 1981. Particularly
preferred are ethoxylated alcohols having an average of from about 10 to abut
15
carbon atoms in the alcohol and an average degree of ethoxylation of from
about
6 to about 12 moles of ethylene oxide per mole of alcohol. Mixtures of anionic
and nonionic surfactants are especially useful.
Other conventional useful surfactants are listed in standard texts, including
C12-C1g betaines and sulfobetaines (sultaines).
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Amine Oxide Surfactants
The compositions herein also contain amine oxide surfactants of the formula:
R1 (EO)x(PO)y(BO)zN(O)(CH2R~)2~qH20 (I)
In general, it can be seen that the structure (I) provides one long-chain
moiety R1 (EO)x(PO)y(BO)z and two short chain moieties, CH2R'. R' is
preferably
selected from hydrogen, methyl and -CH20H. In general R1 is a primary or
branched hydrocarbyl moiety which can be saturated or unsaturated, preferably,
R1 is a primary alkyl moiety. When x+y+z = 0, R1 is a hydrocarbyl moiety
having
chainlength of from about 8 to about 18. When x+y+z is different from 0, R1
may
be somewhat longer, having a chainlength in the range C12-C24. The general
formula also encompasses amine oxides wherein x+y+z = 0, R1 = Cg-Clg, R' is
H and q is 0-2, preferably 2. These amine oxides are illustrated by C12-14
alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide
and their hydrates, especially the dihydrates as disclosed in U.S. Patents
5,075,501 and 5,071,594, incorporated herein by reference.
The invention also encompasses amine oxides wherein x+y+z is different
from zero, specifically x+y+z is from about 1 to about 10, R1 is a primary
alkyl
group containing 8 to about 24 carbons, preferably from about 12 to about 16
carbon atoms; in these embodiments y + z is preferably 0 and x is preferably
from
about 1 to about 6, more preferably from about 2 to about 4; EO represents
ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy. Such
amine oxides can be prepared by conventional synthetic methods, e.g., by the
reaction of alkylethoxysulfates with dimethylamine followed by oxidation of
the
ethoxylated amine with hydrogen peroxide.
Highly preferred amine oxides herein are solids at ambient temperature,
more preferably they have melting-points in the range 30°C to
90°C. Amine
oxides suitable for use herein are made commercially by a number of suppliers,
including Akzo Chemie, Ethyl Corp., and Procter & Gamble. See McCutcheon's
compilation and Kirk-Othmer review article for alternate amine oxide
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manufacturers. Preferred commercially available amine oxides are the solid,
dehydrate ADMOX 16 and ADMOX 18, ADMOX 12 and especially ADMOX 14
from Ethyl Corp.
Preferred embodiments include dodecyldimethylamine oxide dehydrate,
hexadecyldimethylamine oxide dehydrate, octadecyldimethylamine oxide
dehydrate, hexadecyltris(ethyleneoxy)dimethyl-amine oxide,
tetradecyldimethylamine oxide dehydrate, and mixtures thereof.
Whereas in certain of the preferred embodiments R' is H, there is some
latitude with respect to having R' slightly larger than H. Specifically, the
invention
further encompasses embodiments wherein R' is CH20H, such as
hexadecylbis(2- hydroxyethyl)amine oxide, taliowbis(2-hydroxyethyl)amine
oxide,
stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine
oxide.
Builders
The compositions herein also optionally, but preferably, contain up to about
50%, more preferably from about 1 % to about 40%, even more preferably from
about 5% to about 30%, by weight of a detergent builder material. Lower or
higher levels of builder, however, are not , meant to be excluded. 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. Detergent builders are described in U.S. Patent
No.
4,321,165, Smith et al, issued March 23, 1982. Preferred builders for use in
liquid
detergents herein are described in U.S. Patent No. 4,284,532, Leikhim et al,
issued August 18, 1981.
Examples of silicate builders are the alkali metal silicates, particularly
those
having a Si02:Na20 ratio in the range 1.6:1 to 3.2:1 and layered silicates,
such
as the layered sodium silicates described in U.S. Patent 4,664,839, issued May
12, 1987 to H. P. Rieck. 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.
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NaSKS-6 has the delta-Na2Si05 morphology form of layered silicate. It can be
prepared by methods such as those described in German DE-A-3,417,649 and
DE-A-3,742,043. SKS-6 is a highly preferred layered silicate for use herein,
but
other such layered silicates, such as those having the general formula
NaMSix02x+1 ~yH20 wherein M is sodium or hydrogen, x is a number from 1.9 to
4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used
herein.
Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and
NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-
Na2Si05 (NaSKS-6 form) is most preferred for use herein. Other silicates may
also be useful such as for example magnesium silicate, which can serve as a
stabilizing agent for oxygen bleaches and as a component of suds control
systems.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates as disclosed in German Patent Application No. 2,321,001 published
on November 15, 1973.
Aluminosilicate builders are useful in the present invention. Aluminosilicate
builders can be a significant builder ingredient in liquid detergent
formulations.
Aluminosilicate builders include those having the empirical formula:
Mz(zA102)y]~xH20
wherein z and y are integers of at least 6, the molar ratio of z to y is in
the range
from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
Useful aluminosilicate ion exchange materials are commercially available.
These aluminosilicates can be crystalline or amorphous in structure and can be
naturally-occurring aluminosilicates or synthetically derived. A method for
producing aluminosilicate ion exchange materials is disclosed in U.S. Patent
3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic
crystalline aluminosilicate ion exchange materials useful herein are available
under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In
an
especially preferred embodiment, the crystalline aluminosilicate ion exchange
material has the formula:
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Nal2~(A102)12(Si02)121~xH20
wherein x is from about 20 to about 30, especially about 27. This material is
known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein.
Preferably, the aluminosilicate has a particle size of about 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 polycarboxylate
compounds.
As used herein, "polycarboxylate" refers to compounds having a plurality of
carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate
builder
can generally be added to the composition in acid form, but can also be added
in
the form of a neutralized salt. When utilized in salt form, alkali metals,
such as
sodium, potassium, and lithium, or alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of
useful materials. One important category of polycarboxylate builders
encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed
in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S.
Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S.
Patent 4,663,071, issued to Bush et al, on May 5, 1987. Suitable ether
polycarboxylates also include cyclic compounds, particularly alicyclic
compounds,
such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635;
4,120,874 and 4,102,903.
Other useful detergency builders include the ether hydroxypolycarboxylates,
copolymers of malefic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-
trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic
acid,
the various alkali metal, ammonium and substituted ammonium salts of
polyacetic
acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as
well as
polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid,
polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic
acid,
and soluble salts thereof.
. 30 Citrate builders, e.g., citric acid and soluble salts thereof
(particularly sodium
salt), are polycarboxylate builders of particular importance for heavy duty
liquid
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detergent formulations due to their availability from renewable resources and
their
biodegradability. Oxydisuccinates are also especially useful in such
compositions
and combinations.
Also suitable in the detergent compositions of the present invention are the
3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in
U.S. Patent 4,566,984, Bush, issued January 28, 1986. 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 European Patent Application 86200690.5!0,200,263, published
November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226,
Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl,
issued March 7, 1967. See also Diehl U.S. Patent 3,723,322.
Fatty acids, e.g., C12-C1 g monocarboxylic acids, can also be incorporated
into the compositions alone, or in combination with the aforesaid builders,
especially citrate and/or 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 be used the various
alkali metal phosphates such as the well-known sodium tripolyphosphates,
sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate
builders such as ethane-1-hydroxy-1,1-diphosphonate and other known
phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021;
3,400,148 and 3,422,137) can also be used.
OTHER OPTIONAL COMPOSITION COMPONENTS
In addition to the liquid and solid phase components as hereinbefore
described, the aqueous and non-aqueous based detergent compositions can,
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and preferably will, contain various other optional components. Such optional
components may be in either liquid or solid form. The optional components may
either dissolve in the liquid phase or may be dispersed within the liquid
phase in
the form of fine particles or droplets. Some of the other materials which may
optionally be utilized in the compositions herein are described in greater
detail as
follows:
Olotional Inorganic Detergent Builders
The detergent compositions herein may also optionally contain one or more
types of inorganic detergent builders beyond those listed hereinbefore that
also
function as alkalinity sources. Such optional inorganic builders can include,
for
example, aluminosilicates such as zeolites. Aluminosilicate zeolites, and
their
use as detergent builders are more fully discussed in Corkill et al., U.S.
Patent
No. 4,605,509; Issued August 12, 1986, the disclosure of which is incorporated
herein by reference. Also crystalline layered silicates, such as those
discussed in
this '509 U.S. patent, are also suitable for use in the detergent compositions
herein. If utilized, optional inorganic detergent builders can comprise from
about
2% to 15% by weight of the compositions herein.
Optional Enzymes
The detergent compositions herein may also optionally contain one or more
types of detergent enzymes. Such enzymes can include proteases, amylases,
cellulases and lipases. Such materials are known in the art and are
commercially
available. They may be incorporated into the non-aqueous liquid detergent
compositions herein in the form of suspensions, "marumes" or "prills". Another
suitable type of enzyme comprises those in the form of slurries of enzymes in
nonionic surfactants, e.g., the enzymes marketed by Novo Nordisk under the
tradename "SL" or the microencapsulated enzymes marketed by Novo Nordisk
under the tradename "LDP."
Enzymes added to the compositions herein in the form of conventional
enzyme prills are especially preferred for use herein. Such grills will
generally
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range in size from about 100 to 1,000 microns, more preferably from about 200
to
800 microns and will be suspended throughout the non-aqueous liquid phase of
the composition. Prills in the compositions of the present invention have been
found, in comparison with other enzyme forms, to exhibit especially desirable
enzyme stability in terms of retention of enzymatic activity over time. Thus,
compositions which utilize enzyme prills need not contain conventional enzyme
stabilizing such as must frequently be used when enzymes are incorporated into
aqueous liquid detergents.
If employed, enzymes will normally be incorporated into the non-aqueous
liquid compositions herein at levels sufficient to provide up to about 10 mg
by
weight, more typically from about 0.01 mg to about 5 mg, of active enzyme per
gram of the composition. Stated otherwise, the non-aqueous liquid detergent
compositions herein will typically comprise from about 0.001 % to 5%,
preferably
from about 0.01 % to 1 % by weight, of a commercial enzyme preparation.
,15 Protease enzymes, for example, are usually present in such commercial
preparations at levels sufficient to provide from 0.005 to 0.1 Anson units
(AU) of
activity per gram of composition.
Optional Chelatina Agents
The detergent compositions herein may also optionally contain a chelating
agent which serves to chelate metal ions, e.g., iron and/or manganese, within
the
non-aqueous detergent compositions herein. Such chelating agents thus serve
to form complexes with metal impurities in the composition which would
otherwise
tend to deactivate composition components such as the peroxygen bleaching
agent. Useful chelating agents can include amino carboxylates, phosphonates,
amino phosphonates, polyfunctionally-substituted aromatic chelating agents and
mixtures thereof.
Amino carboxylates useful as optional chelating agents include
ethylenediaminetetraacetates, N-hydroxyethyl-ethylenediaminetriacetates,
nitrilotriacetates, ethylene-diamine tetrapropionates,
triethylenetetraaminehexacetates, diethylenetriaminepentaacetates,
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ethylenediaminedisuccinates and ethanol diglycines. The alkali metal salts of
these materials are preferred.
Amino phosphonates are also suitable for use as chelating agents in the
compositions of this invention when at least low levels of total phosphorus
are
permitted in detergent compositions, and include ethylenediaminetetrakis
(methylene-phosphonates) as DEQUEST. Preferably, these amino phosphonates
do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are also useful in the
compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to
Connor et al. Preferred compounds of this type in acid form are
dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
Preferred chelating agents include hydroxy-ethyldiphosphonic acid (HEDP),
diethylene triamine penta acetic acid (DTPA), ethylenediamine disuccinic acid
(EDDS) and dipicolinic acid (DPA) and salts thereof. The chelating agent may,
of
course, also act as a detergent builder during use of the compositions herein
for
fabric laundering/bleaching. The chelating agent, if employed, can comprise
from
about 0.1 % to 10% by weight of the compositions herein. More preferably, the
chelating agent will comprise from about 0.2% to 3% by weight of the detergent
compositions herein.
Optional Clay Soil Removal/Anti-redeposition Agents
The compositions of the present invention can also optionally contain water
soluble ethoxylated amines having clay soil removal and anti-redeposition
properties. If used, soil materials can contain from about 0.01 % to about 5%
by
weight of the compositions herein.
The most preferred soil release and anti-redeposition agent is ethoxylated
tetraethylenepentamine. Exemplary ethoxylated amines are further described in
U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of
preferred clay soil removal-anti-redeposition agents are the cationic
compounds
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disclosed in European Patent Application 111,965, Oh and Gosselink, published
June 27, 1984. Other clay soil removal/anti-redeposition agents which can be
used include the ethoxylated amine polymers disclosed in European Patent
Application 111,984, Gosselink, published June 27, 1984; the zwitterionic
polymers disclosed in European Patent Application 112,592, Gosselink,
published
July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor,
issued October 22, 1985. Other clay soil removal and/or anti-redeposition
agents
known in the art can also be utilized in the compositions herein. Another type
of
preferred anti-redeposition agent includes the carboxy methyl cellulose (CMC)
materials. These materials are well known in the art.
Optional Liauid Bleach Activators
The detergent compositions herein may also optionally contain bleach
activators which are liquid in form at room temperature and which can be added
as liquids to the non-aqueous liquid phase of the detergent compositions
herein.
One such liquid bleach activator is acetyl triethyl citrate (ATC). Other
examples
include glycerol triacetate and nonanoyl valerolactam. Liquid bleach
activators
20, can be dissolved in the non-aqueous liquid phase of the compositions
herein.
Optional Bleach Catalysts
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. Pat. 5,246,621,
U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European
Pat. App. Pub. Nos. 549,271 A1, 549,272A1, 544,440A2, and 544,490A1;
Preferred examples of these catalysts include MnIV2(u-O)3(1,4,7-trimethyl-
1,4,7-
triazacyclononane)2(PFg)2, Mnlll2(u-O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-
triazacyclononane)2(C104)2, MnIV4(u-O)g(1,4,7-triazacyclononane)4(CI04)4,
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Mnll IMnIV4(u-O)1 (u-OAc)2_(1,4,7-trimethyl-1,4,7-triazacyclononane)2(CI04)3,
MnIV(1,4,7-trimethyl-1,4,7-triazacyclononane)- (OCH3)3(PFg), and mixtures
thereof. Other metal-based bleach catalysts include those disclosed in U.S.
Pat.
4,430,243 and U.S. Pat. 5,114,611. The use of manganese with various complex
ligands to enhance bleaching is also reported in the following United States
Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147;
5,153,161; and 5,227,084.
As a practical matter, and not by way of limitation, the compositions and
processes herein can be adjusted to provide on the order of at least one part
per
ten million of the active bleach catalyst species in the aqueous washing
liquor,
and will preferably provide from about 0.1 ppm to about 700 ppm, more
preferably from about 1 ppm to about 500 ppm, of the catalyst species in the
laundry liquor.
Cobalt bleach catalysts useful herein are known, and are described, for
example, in M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv.
Inorg. Bioinorg. Mech., (1983), 2, pages 1-94. The most preferred cobalt
catalyst
useful herein are cobalt pentaamine acetate salts having the formula
[Co(NH3)50Ac] Ty, wherein "OAc" represents an acefiate moiety and "Ty' is an
anion, and especially cobalt pentaamine acetate chloride, [Co(NH3)50Ac]CI2; as
well as [Co(NH3)50Ac](OAc)2; [Co(NH3)50Ac](PFg)2; [Co(NH3)50Ac](S04);
[Co(NH3)50Ac](BF4)2; and [Co(NH3)50Ac](N03)2 (herein "PAC")
These cobalt catalysts are readily prepared by known procedures, such as
taught for example in the Tobe article and the references cited therein, in
U.S.
Patent 4,810,410, to Diakun et al, issued March 7,1989, J. Chem. Ed. (1989),
66
(12), 1043-45; The Synthesis and Characterization of Inorganic Compounds,
W.L. Jolly (Prentice-Hall; 1970), pp. 461-3; Inorg. Chem., 18, 1497-1502
(1979);
Inorg. Chem., 21, 2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979); Inorg.
Synthesis, 173-176 (1960); and Journal of Physical Chemistry, 56, 22-25
(1952).
As a practical matter, and not by way of limitation, the compositions and
cleaning processes herein can be adjusted to provide on the order of at least
one
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part per hundred million of the active bleach catalyst species in the aqueous
washing medium, and will preferably provide from about 0.01 ppm to about 25
ppm, more preferably from about 0.05 ppm to about 10 ppm, and most preferably
from about 0.1 ppm to about 5 ppm, of the bleach catalyst species in the wash
' liquor. In order to obtain such levels in the wash liquor of an automatic
washing
process, typical compositions herein will comprise from about 0.0005% to about
0.2%, more preferably from about 0.004% to about 0.08%, of bleach catalyst,
especially manganese or cobalt catalysts, by weight of the cleaning
compositions.
Optional Brighteners, Suds Suppressors, Dyes and/or Perfumes
The detergent compositions herein may also optionally contain
conventional brighteners, suds suppressors, dyes and/or perfume materials.
Such brighteners, suds suppressors, silicone oils, dyes and perfumes must, of
course, be compatible and non-reactive with the other composition components
in a non-aqueous environment. If present, brighteners suds suppressors, dyes
and/or perfumes will typically comprise from about 0.0001 % to 2% by weight of
the compositions herein.
Structure Elasticizing Agents
The non-aqueous liquid detergent compositions herein can also contain from
about 0.1 % to 5%, preferably from about 0.1 % to 2% by weight of a finely
divided,
solid particulate material which can include silica, e.g., fumed silica,
titanium
dioxide, insoluble carbonates, finely divided carbon or combinations of these
materials. Fine particulate material of this type functions as a structure
elasticizing agent in the products of this invenfiion. Such material has an
average
particle size ranging from about 7 to 40 nanometers, more preferably from
about
7 to 15 nanometers. Such material also has a specific surface area which
ranges
from about 40 to 400m2/g.
The finely divided elasticizing agent material can improve the shipping
stability of the non-aqueous liquid detergent products herein by increasing
the
elasticity of the surfactant-structured liquid phase without increasing
product
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viscosity. This permits such products to withstand high frequency vibration
which
may be encountered during shipping without undergoing undesirable structure
breakdown which could lead to sedimentation in the product.
In the case of titanium dioxide, the use of this material also imparts
whiteness to the suspension of particulate material within the detergent
compositions herein. This effect improves the overall appearance of the
product.
Polymeric Soil Release Agent
Any polymeric soil release agent known to those skilled in the art can
optionally be employed in the compositions and processes of this invention.
Polymeric soil release agents are characterized by having both hydrophilic
segments, to hydrophilize the surface of hydrophobic fibers, such as polyester
and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and
remain adhered thereto through completion of washing and rinsing cycles and,
thus, serve as an anchor for the hydrophilic segments. This can enable stains
occurring subsequent to treatment with the soil release agent to be more
easily
cleaned in later washing procedures.
Examples of polymeric soil release agents useful herein include U.S. Patent
4,721,580, issued January 26, 1988 to Gosselink; U.S. Patent 4,000,093, issued
December 28, 1976 to Nicol, et al.; European Patent Application 0 219 048,
published April 22, 1987 by Kud, et al.; U.S. Patent 4,702,857, issued October
27,
1987 to Gosselink; U.S. Patent 4,968,451, issued November 6, 1990 to J.J.
Scheibel. Commercially available soil release agents include the SOKALAN type
of material, e.g., SOKALAN HP-22, available from BASF (West Germany). Also
see U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent
3,893,929 to Basadur issued July 8, 1975. Examples of this polymer include the
commercially available material ZELCON 5126 (from Dupont) and MILEASE T
(from ICI). Other suitable polymeric soil release agents include the
terephthalate
polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et
al,
the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued
January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of
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U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink. Preferred
polymeric soil release agents also include the soil release agents of U.S.
Patent
4,877,896, issued October 31, 1989 to Maldonado et al.
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% by weight of
the detergent compositions.
Polymeric Dispersing Agents
Polymeric dispersing agents can advantageously be utilized at levels from
about 0.1 % to about 7%, by weight, in the compositions herein, especially in
the
presence of zeolite and/or layered silicate builders. Suitable polymeric
dispersing
agents include polymeric polycarboxylates and polyethylene glycols, although
others known in the art can also be used. It is believed, though it is not
intended
to be limited by theory, that polymeric dispersing agents enhance overall
detergent builder performance, when used in combination with other builders
(including lower molecular weight polycarboxylates) by crystal growth
inhibition,
particulate soil release peptization, and anti-redeposition.
Polymeric polycarboxylate materials can be prepared by polymerizing or
copolymerizing suitable unsaturated monomers, preferably in their acid form.
Unsaturated monomeric acids that can be polymerized to form suitable polymeric
polycarboxylates include acrylic acid, malefic acid (or malefic anhydride),
fumaric
acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and
methylenemalonic acid. The presence in the polymeric polycarboxylates herein
or monomeric segments, containing no carboxylate radicals such as vinylmethyl
ether, styrene, ethylene, etc. is suitable provided that such segments do not
constitute more than about 40% by weight.
Particularly suitable polymeric polycarboxylates can be derived from acrylic
acid. Such acrylic acid-based polymers which are useful herein are the water-
soluble salts of polymerized acrylic acid. The average molecular weight of
such
polymers in the acid form preferably ranges from about 2,000 to 10,000, more
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preferably from about 4,000 to 7,000 and most preferably from about 4,000 to
5,000. Water-soluble salts of such acrylic acid polymers can include, for
example, the alkali metal, ammonium and substituted ammonium salts. Soluble
polymers of this type are known materials. Use of polyacrylates of this type
in
detergent compositions has been disclosed, for example, in Diehl, U.S. Patent
3,308,067, issued march 7, 1967.
Acrylic/maleic-based copolymers may also be used as a preferred
component of the dispersing/anti-redeposition agent. Such materials include
the
water-soluble salts of copolymers of acrylic acid and malefic acid. The
average
molecular weight of such copolymers in the acid form preferably ranges from
about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most
preferably from about 7,000 to 65,000. The ratio of acrylate to maleate
segments
in such copolymers will generally range from about 30:1 to about 1:1, more
preferably from about 10:1 to 2:1. Water-soluble salts of such acrylic
acid/maleic
acid copolymers can include, for example, the alkali metal, ammonium and
substituted ammonium salts. Soluble acrylatelmaleate copolymers of this type
are known materials which are described in European Patent Application No.
66915, published December 15, 1982, as well as in EP 193,360, published
September 3, 1986, which also describes such polymers comprising
hydroxypropylacrylate. Still other useful dispersing agents include the
maleiclacrylic/vinyl alcohol terpolymers. Such materials are also disclosed in
EP
193,360, including, for example, the 45/45/10 terpolymer' of
acrylic/maleic/vinyl
alcohol.
Another polymeric material which can be included is polyethylene glycol
(PEG). PEG can exhibit dispersing agent performance as well as act as a clay
soil removal-antiredeposition agent. Typical molecular weight ranges for these
purposes range from about 500 to about 100,000, preferably from about 1,000 to
about 50,000, more preferably from about 1,500 to about 10,000.
Polyaspartate and polyglutamate dispersing agents may also be used,
especially in conjunction with zeolite builders. Dispersing agents such as
polyaspartate preferably have a molecular weight (avg.) of about 10,000.
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Dye Transfer Inhibiting Agents
The compositions of the present invention may also include one or more
materials effective for inhibiting the transfer of dyes from one fabric to
another
during the cleaning process. Generally, such dye transfer inhibiting agents
include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers
of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine,
peroxidases, and mixtures thereof. If used, these agents typically comprise
from
aboufi 0.01 % to about 10% by weight of the composition, preferably from about
0.01 % to about 5%, and more preferably from about 0.05% to about 2%.
More specifically, the polyamine N-oxide polymers preferred for use herein
contain units having the following structural formula: R-Ax-P; wherein P is a
polymerizable unit to which an N-O group can be attached or the N-O group can
form part of the polymerizable unit or the N-O group can be attached to both
units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=;
x is 0
or 1; and R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or
alicyclic
groups or any combination thereof to which the nitrogen of the N-O group can
be
attached or the N-O group is part of these groups. Preferred polyamine N-
oxides
are those wherein R is a heterocyclic group such as pyridine, pyrrole,
imidazole,
pyrrolidine, piperidine and derivatives thereof.
The N-O group can be represented by the following general structures:
O O
~Ri)X ~ -~R2)y~ =N-~R~)x
~R3)z
wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups
or
combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group
can
be attached or form part of any of the aforementioned groups. The amine oxide
unit of the polyamine N-oxides has a pKa <10, preferably pKa <7, more
preferred
pKa <6.
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Any polymer backbone can be used as long as the amine oxide polymer
formed is water-soluble and has dye transfer inhibiting properties. Examples
of
suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters,
polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These
polymers include random or block copolymers where one monomer type is an
amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide
polymers typically have a ratio of amine to the amine N-oxide of 10:1 to
1:1,000,000. However, the number of amine oxide groups present in the
polyamine oxide polymer can be varied by appropriate copolymerization or by an
appropriate degree of N-oxidation. The polyamine oxides can be obtained in
almost any degree of polymerization. Typically, the average molecular weight
is
within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most
preferred 5,000 to 100,000. This preferred class of materials can be referred
to
as "PVNO".
The most preferred polyamine N-oxide useful in the detergent compositions
herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight
of
about 50,000 and an amine to amine N-oxide ratio of about 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to
as a class as "PVPVI") are also preferred for use herein. Preferably the PVPVI
has an average molecular weight range from 5,000 to 1,000,000, more preferably
from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average
molecular weight range is determined by light scattering as described in
Barth, et
al., Chemical Analysis, Vol 113. "Modern Methods of Polymer Characterization",
the disclosures of which are incorporated herein by reference.) The PVPVI
copolymers typically have a molar ratio of N-vinylimidazole to N-
vinylpyrrolidone
from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from
0.6:1
to 0.4:1. These copolymers can be either linear or branched.
The present invention compositions also may employ a polyvinylpyrrolidone
("PVP") having an average molecular weight of from about 5,000 to about
400,000, preferably from about 5,000 to about 200,000, and more preferably
from
about 5,000 to about 50,000. PVP's are known to persons skilled in the
detergent
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field; see, for example, EP-A-262,897 and EP-A-256,696, incorporated herein by
reference. Compositions containing PVP can also contain polyethylene glycol
("PEG") having an average molecular weight from about 500 to about 100,000,
preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to
PVP
on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1,
and
more preferably from about 3:1 to about 10:1.
The detergent compositions herein may also optionally contain from about
0.005% to 5% by weight of certain types of hydrophilic optical brighteners
which
also provide a dye transfer inhibition action. If used, the compositions
herein will
preferably comprise from about 0.01 % to 1 % by weight of such optical
brighteners.
The hydrophilic optical brighteners useful in the present invention are those
having the strucfiural formula:
RI Ra
N H H N
N O>--N ~ C=C O N--~~ N
~N H H N
R2 S03M SC3~ Ri
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl;
R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino, chloro and amino; and M is a salt-forming cation such as sodium or
potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M
is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium
salt.
This particular brightener species is commercially marketed under the
tradename
Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred
hydrophilic optical brightener useful in the detergent compositions herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-
mefihylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-
anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-
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stilbenedisulfonic acid disodium salt. This particular brightener species is
commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy
Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a cation
such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-
2-
yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener
species is commercially marketed under the tradename Tinopal AMS-GX by Ciba
Geigy Corporation.
The specific optical brightener species selected for use in the present
invention provide especially effective dye transfer inhibition performance
benefits
when used in combination with the selected polymeric dye transfer inhibiting
agents hereinbefore described. The combination of such selected polymeric
materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners
(e.g.,
Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides
significantly better dye transfer inhibition in aqueous wash solutions than
does
either of these two detergent composition components when used alone. Without
being bound by theory, it is believed that such brighteners work this way
because
they have high affinity for fabrics in the wash solution and therefore deposit
relatively quick on these fabrics. The extent to which brighteners deposit on
fabrics in the wash solution can be defined by a parameter called the
"exhaustion
coefficient". The exhaustion coefficient is in general as the ratio of a) the
brightener material deposited on fabric to b) the initial brightener
concentration in
the wash liquor. Brighteners with relatively high exhaustion coefficients are
the
most suitable for inhibiting dye transfer in the context of the present
invention.
Of course, it will be appreciated that other, conventional optical brightener
types of compounds can optionally be used in the present compositions to
provide conventional fabric "brightness" benefits, rather than a true dye
transfer
inhibiting effect. Such usage is conventional and well-known to detergent
formulations.
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COMPOSITION FORM
As indicated, the non-aqueous liquid detergent compositions herein are in
the form of bleaching agent and/or other materials in particulate form as a
solid
phase suspended in and dispersed throughout a surfactant-containing,
preferably
structured non-aqueous liquid phase. Generally, the structured non-aqueous
liquid phase will comprise from about 45% to 95%, more preferably from about
50% to 90%, by weight of the composition with the dispersed additional solid
materials comprising from about 5% to 55%, more preferably from about 10% to
50%, by weight of the composition.
The particulate-containing liquid detergent compositions of this invention are
substantially non-aqueous (or anhydrous) in character. While very small
amounts
of water may be incorporated into such compositions as an impurity in the
essential or optional components, the amount of water should in no event
exceed
about 5% by weight of the compositions herein. More preferably, water content
of the non-aqueous detergent compositions herein will comprise less than about
1 % by weight.
The particulate-containing non-aqueous liquid detergent compositions~herein
will be relatively viscous and phase stable under conditions of commercial
marketing and use of such compositions. Frequently the viscosity of the
compositions herein will range from about 300 to 5,000 cps, more preferably
from
about 500 to 3,000 cps. For purposes of this invention, viscosity is measured
with a Carrimed CSL2 Rheometer at a shear rate of 20 s-1.
The aqueous based heavy-duty liquid detergent compositions disclosed
herein 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 solubilizing
surfactant, but polyols such as those containing from 2 to about 6 carbon
atoms
and from 2 to about 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.
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The detergent compositions herein will preferably be formulated such that,
during use in aqueous cleaning operations, the wash water will have a pH of
between about 6.5 and about 11, preferably between about 7.5 and 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.
COMPOSITION PREPARATION AND USE
The aqueous based heavy-duty liquid detergent compositions of the present
invention can be made by mixing and blending the desired ingredients with the
desired sovent. The non-aqueous liquid detergent compositions herein can be
prepared by first forming the surfactant-containing, preferably structured non-
aqueous liquid phase and by thereafter adding to this structured phase the
particulate components in any convenient order and by mixing, e.g., agitating,
the
resulting component combination to form the phase stable compositions herein.
In a typical process for preparing such compositions, essential and certain
preferred optional components will be combined in a particular order and under
certain conditions.
In a first step of a preferred preparation process, the anionic surfactant
containing powder used to form the structured, surfactant-containing liquid
phase
is prepared. This pre-preparation step involves the formation of an aqueous
slurry containing from about 30% to 60% of one or more alkali metal salts of
linear C10-16 alkyl benzene sulfonic acid and from about 2% to 30% of one or
more diluent non-surfactant salts. In a subsequent step, this slurry is dried
to the
extent necessary to form a solid material containing less than about 4% by
weight
of residual water.
After preparation of this solid anionic surfactant-containing material, this
material can be combined with one or more of the non-aqueous organic diluents
to form a structured, surfactant-containing liquid phase of the detergent
compositions herein. This is done by reducing the anionic surfactant-
containing
material formed in the previously described pre-preparation step to powdered
form and by combining such powdered material with an agitated liquid medium
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comprising one or more of the non-aqueous organic diluents, either surfactant
or
non-surfactant or both, as hereinbefore described. This combination is carried
out under agitation conditions which are sufficient to form a thoroughly mixed
dispersion of particles of the insoluble fraction of the co-dried LAS/salt
material
throughout a non-aqueous organic liquid diluent.
In a subsequent processing step, the non-aqueous liquid dispersion so
prepared can then be subjected to milling or high shear agitation under
conditions
which are, sufficient to provide a structured, surfactant-containing liquid
phase of
the detergent compositions herein. Such milling or high shear agitation
conditions will generally include maintenance of a temperature between about
10°C and 90°C, preferably between about 20°C and
60°C; and a processing time
that is sufficient to form a network of aggregated small particles of the
insoluble
traction of the anionic surfactant-containing powdered material. Suitable
equipment for this purpose includes: stirred ball mills, co-ball mills
(Fryma),
colloid mills, high pressure homogenizers, high shear mixers, and the like.
The
colloid mill and high shear mixers are preferred for their high throughput and
low
capital and maintenance costs. The small particles produced in such equipment
will generally range in size from about 0.4 to 2 microns. Milling and high
shear
agitation of the liquid/solids combination will generally provide an increase
in the
yield value of the structured liquid phase to within the range of from about 1
Pa to
8 Pa, more preferably from about 1 Pa to 4 Pa.
After formation of the dispersion of LAS/salt co-dried material in the non-
aqueous liquid, either before or after such dispersion is milled or agitated
to
increase its yield value, the particulate material to be used in the detergent
compositions herein can be added. Such components which can be added under
high shear agitation include a silica or titanium dioxide elasticizing agent;
particles
of substantially all of an organic builder, e.g., citrate and/or fatty acid,
and/or an
alkalinity source, e.g., sodium carbonate, can be added while continuing to
maintain this admixture of composition components under shear agitation.
Agitation of the mixture is continued, and if necessary, can be increased at
this
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point to form a uniform dispersion of insoluble solid phase particulates
within the
liquid phase.
After some or all of the foregoing solid materials have been added to this
agitated mixture, the particles of the colored speckles and the highly
preferred
peroxygen bleaching agent can be added to the composition, again while the
mixture is maintained under shear agitation. By adding the peroxygen bleaching
agent material last, or after all or most of the other components, and
especially
after alkalinity source particles, have been added, desirable stability
benefits for
the peroxygen bleach can be realized. If enzyme prills are incorporated, they
are
preferably added to the non-aqueous liquid matrix last.
As a final process step, after addition of all of the particulate material,
agitation of the mixture is continued for a period of time sufficient to form
compositions having the requisite viscosity, yield value and phase stability
characteristics. Frequently this will involve agitation for a period of from
about 1
to 30 minutes.
In adding solid components to non-aqueous liquids in accordance with the
foregoing procedure, it is advantageous to maintain the free, unbound moisture
content of these solid materials below certain limits. Free moisture in such
solid
materials is frequently present at levels of 0.8% or greater. By reducing free
moisture content, e.g., by fluid bed drying, of solid particulate materials to
a free
moisture level of 0.5% or lower prior to their incorporation into the
detergent
composition matrix, significant stability advantages for the resulting
composition
can be realized.
The compositions of this invention, prepared as hereinbefore described, can
be used to form aqueous washing solutions for use in the laundering and
bleaching of fabrics. Generally, an effective amount of such compositions is
added to water, preferably in a conventional fabric laundering automatic
washing
machine, to form such aqueous laundering/bleaching solutions. The aqueous
washing/bleaching solution so formed is then contacted, preferably under
agitation, with the fabrics to be laundered and bleached therewith.
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An effective amount of the liquid detergent compositions herein added to
water to form aqueous launderinglbleaching solutions can comprise amounts
sufficient to form from about 500 to 7,000 ppm of composition in aqueous
solution. More preferably, from about 800 to 3,000 ppm of the detergent
compositions herein will be provided in aqueous washing/bleaching solution.
Method
The use of the suspending aid has been found beneficial in the chemical
stability
of the pro-perfume within the detergent matrix, whether it being aqueous or
non-
aqueous. Accordingly, there is provided a the use of the suspending aid for
stabilising the pro-perfume component within the detergent composition.
Also provided herein is a method for providing a delayed release of the
benefit
agent, preferably a perfume composition, which comprises the step of
contacting
the surface to be treated with a composition of the invention, and preferably
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 composition.
By "surface", it is meant any surface onto which the 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 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 benefit agent (e.g perfume) over
a
longer period of time than by the use of the benefit agent (e.g., perfume)
itself.
Where the carrier is a polymer or component which has been chemically reacted
with a benefit agent like perfume, the release of the benefit agent which is
entrapped or embedded within the reacted carrier, i.e. not chemically reacted,
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released from the carried benefit agent composition by hydrolysis of the
reacted
carrier. Indeed, the hydrolysis of the "protective shell" made by the reacted
carrier
into the respective aldehyde and/or ketone on the one hand and the polymer on
the other will gradually open the shell, thereby enabling release of the
entrapped
benefit agent.
Still in another aspect of the invention, there is provided the use of the
product of
the invention for the manufacture of a laundry and cleaning composition for
delivering residual fragrance onto the fabrics on which it is applied.
For the purposes of the present invention the term "contacting" is defined as
"intimate contact of a surface with an aqueous solution of the hereinabove
described composition." Contacting typically occurs by soaking, washing,
rinsing
the composition onto fabric, but can also include contact of a substrate inter
aiia a
material onto which the composition has been absorbed, with the fabric.
I-Synthesis of delta damascone with Lupasol WF
In a reaction vessel of 21, placed on a rotary evaporator, 1500g of 8-
Damascone
and 1800g of water-free Lupasol WF are mixed together for 4 hours at
42°C at a
stirring rate of 20 to100 rpm. The temperature of the reaction mixture, during
the
mixing, is controlled by means of a water bath and not allowed to go higher
than
42°C; the temperature inside the reaction container is of 40°C.
Subsequently, the
reaction mixture is kept during 16 hours at 42°C under vacuum to remove
most of
the water from the reaction vessel. 2741 g of product is obtained and only
traces
of unreacted b-Damascone remain. The viscosity of the obtained pro-perFume
component was of 10.000.OOOcps.
II- Synthesis of delta damascone with Luaasol HF and additional perFume
composition
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In a reaction vessel of 250m1, 20g of 8-Damascone and 16g of water-free
Lupasol
HF (water-free Lupasol HF is taken from the commercial Lupasol sample from
which the water has been removed by vaccum distillation) and 83g of a perfume
mixture are mixed together for 4 hours at 42°C. The temperature of the
reaction
mixture, during the mixing, is controlled via a thermostat and not allowed to
go
higher than 42°C. 118g of product is obtained and only traces of
unreacted 8-
Damascone remain. The viscosity of the synthesised pro-perfume component is
1600cps.
Any type of perfume mixture may be used. One preferred composition of the
perfume mixture is as follows:
Citronellol 7
Geraniol 7
Linalool 7
Para Tertiary Butyl Cyclohexyl 10
Acetate
Phenyl Ethyl Alcohol 19
Habanolide 4.5
Para Methoxy Acetophenone 1.5
Benzyl Acetate 4
Eugenol 2
Phenyl Ethyl Acetate 5 A
Verdyl Acetate 6
Verdyl Propionate 4
Hexyl Cinnamic Aldehyde 3
lonone Gamma Methyl 2
Methyl Cedrylone 10
P.T. Bucinal 7
Para Cresyl Methyl Ether 1
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Processing of the pro-perfume composition
The synthesised pro-perfume I or II above mentioned is then mixed with either
a
silicone glycol ether DC3225C from Dow Corning or an hexamethyl disiloxane
(linear silicone) DC 200 fluids with a viscosity of 100cps measured at
20°C from
Dow Corning or a dimethylpolysiloxoxane wifih a viscosity of 60.000 cps from
Sigma under high shear mixing (i.e. 50.000 rpm) using an Ultra Turrax
apparatus
at a temperature of 60°C for 5 minutes. The pro-perfume component and
the
suspending aid are present in weight ratios of 50:50. The obtained suspension
is
then added as such to the liquid detergent matrix under low shear mixing (i.e.
200
rpm).
The obtained suspension may be subject to creaming on the top, i.e. exhibiting
some physical separation. This can be overcome by the addition of Quartz
droplets or by adjusting the density as conventionally known by the skilled
person.
Abbreviations used in the following detergent composition Examples
In the detergent compositions, the abbreviated component identifications have
the following meanings:
LAS Sodium linear alkyl benzene sulfonate
MEA Monoethanolamine
PG Propanediol
BPP Butoxy - propoxy - propanol
EtOH Ethanol
NaOH Solution of sodium hydroxide
NaTS Sodium toluene sulfonate
Citric acid Anhydrous citric acid
CxyFA C1x-C1y fatty acid
TPKFA : C12-C14 topped whole cut fatty acids.
TFAA C16-18 alkyl N-methyl glucamide
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LMFAA C12-14 alkyl N-methyl glucamide
APA C8-C10 amido propyl dimethyl amine
CxyAS Sodium C1x-C1y alkyl sulfate (or other salt if specified)
CxyEzS Sodium C1x-C1y alkyl sulfate condensed
with z moles of ethylene oxide (or other salt if specified)
CxyEz A C1 x-1 y branched primary alcohol condensed with
an average of z moles of ethylene oxide
Nonionic : C13-C15 mixed ethoxylated/propoxylated fatty alcohol witr
average degree of ethoxylation of 3.8 and an average degre
propoxylation of 4.5.
SCS : Sodium cumene sulphonate.
QAS : R2.N+(CH3)2(C2Fi4OH) with R2 = C12'C14~
TEPAE : Tetreaethylenepentaamine ethoxylate.
PAEC methyl quaternized ethoxylated dihexylene triamine
MA/AA Copolymer of 1:4 maleic/acrylic acid, average
molecular weight about 70,000.
Protease Proteolytic enzyme of activity 4KNPU/g sold by
NOVO Industries A/S under the tradename Savinase
unless otherwise specified
Cellulase Cellulytic enzyme of activity 1000 CEVU/g sold by
NOVO industries A/S under the tradename Carezyme
Amylase Amylolytic enzyme of activity 60KNU/g sold by
NOVO Industries A/S under the tradename Termamyl
60T unless otherwise specified
Lipase Lipolytic enzyme of activity 100kLU/g sold by NOVO
Industries A/S under the tradename Lipolase unless
otherwise specified
Endolase Endoglunase enzyme of activity 3000 CEVU/g sold by
NOVO Industries A/S
PB1 Anhydrous sodium perborate bleach of nominal
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formula NaB02.H202
TAED Tetraacetylethylenediamine
DTPA : Diethylene triamine pentaacetic acid
DTPMP Diethylene triamine penta (methylene phosphonate),
marketed by Monsanto under Trade name bequest 2060
Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-
triazin-2-yl)amino) stilbene-2:2'-disulfonate.
HEDP 1,1-hydroxyethane diphosphonic acid
EDDS : Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer in the '
of its sodium salt
PVNO : Polyvinylpyridine-N-Oxide, with an average molecular wf
of 50,000.
SRP 1 Sulfobenzoyl end capped esters with oxyethylene oxy
and terephthaloyl backbone
Silicone antifoam Polydimethylsiloxane foam 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.
CaCl2 Calcium chloride
PPC1 Pro-perfume composition as given from Synthesis
Example I and mixed with a silicone glycol ether DC
3225C as above mentioned
PPC2 Pro-perfume composition as given from Synthesis
Example I and mixed with hexamethyl disiloxane DC 200
fluids or dimethylpolysiloxoxane with a viscosity of 60.000
cps as above mentioned
PPC3 Pro-perfume composition as given from Synthesis
Example II and mixed with a silicone glycol ether DC
3225C as above mentioned
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PPC4 Pro-perfume composition as given from Synthesis
Example II and mixed with hexamethyl disiloxane DC 200
fluids as above mentioned
Polymer : Polyvinylpyrrolidone K90 available from BASF
under the tradename Luviskol K90
Dye fixative : Dye fixative commercially available from
Clariant under
the tradename Cartafix CB
Polyamine : 1,4-Bis-(3-aminopropyl)piperazine
Bayhibit AM : 2-Phosphonobutane-1,2,4-tricarboxylic acid
commercially
available from Bayer
Fabric softener active:Di-(canoloyl-oxy-ethyl)hydroxyethyl methyl
ammonium
methylsulfate
Genamin C100 : Coco fatty amine ethoxylated with 10 moles
ethylene
oxide and commercially available from Clariant
Genapol V4463 : Coco alcohol ethoxylated with 10 moles ethylene
oxide and commercially available from Clariant
DEQA : Di-(tallowyl-oxy-ethyl) dimethyl ammonium
chloride
DTDMAC : Ditallow dimethylammonium chloride
Fatty acid : Stearic acid of lV=0
Electrolyte : Calcium chloride
PEG : Polyethylene Glycol 4000
Silicone antifoam: Polydimethylsiloxane foam 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.
EXAMPLE I
Preparation of LAS Powder for Use as a Structurant
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Sodium C12 linear alkyl benzene sulfonate (NaLAS) is processed into a powder
containing two phases. One of these phases is soluble in the non-aqueous
liquid
detergent compositions herein and the other phase is insoluble. It is the
insoluble
fraction which serves to add structure and particle suspending capability to
the
non-aqueous phase of the compositions herein.
NaLAS powder is produced by taking a slurry of NaLAS in water (approximately
40-50% active) combined with dissolved sodium sulfate (3-15%) and hydrotrope,
sodium sulfosuccinate (1-3%). The hydrotrope and sulfate are used to improve
the characteristics of the dry powder. A drum dryer is used to dry the slurry
into a
flake. When the NaLAS is dried with the sodium sulfate, two distinct phases
are
created within the flake. The insoluble phase creates a network structure of
aggregate small particles (0.4-2 um) which allows the finished non-aqueous
detergent product to stabiy suspend solids.
The NaLAS powder prepared according to this example has the following makeup
shown in Table III.
TABLE I
LAS Powder
Component Wt.
NaLAS 85%
Sulfate 11
Sulfosuccinate 2%
Water 2.5%
Unreacted, etc. balance to
100%
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insoluble LAS 17%
# of phase (via X-ray 2
diffraction)
EXAMPLE II
Non-aqueous based heavy duty liquid laundry detergent compositions (I to V)
according to the present invention are presented below.
Non-Aaueous Liauid Deterctent Composition with Bleach
Component Wt % Wt % Wt % Wt % Wt
I II III IV V
LAS, From Example I 16 13 8 8 2
C24E5 22 25 28 30 34
BPP 19 19 19 19 19
Sodium citrate dihydrate3 3 3 3 3
TAED 5.9 5.9 5.9 5.9 5.9
Sodium carbonate 9 9 9 9 9
MA/AA 3 3 3 3 3
Colored speckles 0.4 0.4 0.4 0.4 0.4
EDDS 1 1 1 1 1
Cellulase Prills 0.1 0.1 0.1 0.1 0.1
Amylase Prills 0.4 0.4 0.4 0.4 0.4
PAEC 1.3 1.3 1.3 1.3 1.3
PB1 15 15 15 15 15
PPC1 0.4 - - - -
PPC2 - 0.4 - - -
PPC3 - - 0.4 - 0.2
PPC4 - - - 0.4 0.2
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Optionals including: balance balancebalance balance balance
brightener, colorant,
perfume, thickener,
suds
suppressor, colored
speckles etc. '
'
100% 100% 100% 100% 100%
The resulting Table II compositions are stable, anhydrous heavy-duty liquid
laundry detergents which provide excellent stain and soil removal performance
when used in normal fabric laundering operations whilst still providing good
stability of the pro-perfume withn the detergent matrix as well as delayed
release
of the perfume onto the contacted fabric.
EXAMPLE III
Liquid detergent compositions are made according to the following.
I n n1 Iv
C25 E3S 2 8 7 5
LAS 15 12 10 8
C12-C14 alkyldimethyl amine oxide - - - 2
C25 AS 6 4 6 8
C24 N-methyl glucamide 5 4 3 3
C24 AE5 6 1 1 1
C2g FA 11 4 4 3
Citric acid 1 3 3 2
DTPMP 1 1 1 0.5
MEA 8 5 5 2
NaOH 1 2.5 1 1.5
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PG 14.5 13.1 10.0 8
EtOH 1.8 4.7 5.4 1
Amylase (300KNU/g) 0.1 0.1 0.1 0.1
Lipase D96/L (100KNU/g) 0.15 0.15 0.15 0.15
Protease (35g/1) 0.5 0.5 0.5 0.5)
Endolase 0.05 0.05 0.05 0.05
Cellulase 0.09 0.09 0.09 0.09
SRP1 0.5 - 0.3 0.3
Boric acid 2.4 2.8 2.8 2.4
Sodium xylene sulfonate - 3 - -
2-butyl-octanol 1 1 1 1
silicone antifoam 0.3 0.3 0.3 0.3
PPC1 0.4 - 0.3 0.5
PPC3 - 0.4 - -
Water & minors Up
to
100%
The above liquid detergent compositions (A-D) are found to be very
efficient in the removal of a wide range of stains and soils from fabrics
under
various usage conditions whilst still providing good stability of the pro-
perfume
withn the detergent matrix as well as delayed release of the perfume onto the
contacted fabric.
EXAMPLE IV
The following compositions (I to VI) are heavy duty liquid laundry detergent
compositions according to the present invention.
Example #: I II III IV V VI
LAS 17 15 7.0 7.0 12 12
C35E3S1C25E3S 2.0 9.0 - - 7.0 7.0
C25E2.5S - - 12.0 12.0 - -
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LMFAA 6.0 5.0 4.5 3.7 4.0 4.0
C35 E7 6.0 1.0 - - - -
C23 E9 - - 2.0 1.0 5.0 5.0
APA - 1.5 - 2.0 - 2.5
C24 FA 7.5 1.1 2.0 4.0 5.0 5.0
C48 FA 3.0 3.5 - - - -
Citric Acid 1.0 3.5 3.0 3.0 3.0 3.0
Protease (34 g/#) 0.6 0.6 0.9 0.9 1.2 1.2
Lipase 0.1 0.1 0.1 0.1 0.2 0.2
Amylase (300KMU/g) 0.1 0.1 0.1 0.1 - 0.1
Cellulase 0.03 0.03 0.05 0.05 0.2 0.2
Endolase 0.1 0.1 - - - -
Brightener 2 0.1 0.1 - ~ - - -
Boric Acid 3.0 3.0 3.5 3.5 4.0 4.0
MEA 8.0 4.0 1.0 1.5 7.0 7.0
NaOH 1.0 4.0 3.0 2.5 1.0 1.0
PG 12.0 12.0 7.5 7.5 7.0 7.0
EtOH 1.0 1.0 3.5 3.5 6.0 6.0
NaTS - - 2.5 2.5 -
PPC2 0.4 - 0.1 - 0.3 -
PPC4 - 0.5 0.3 0.4 - 0.2
Minors Balan BalancBalanc Balanc Balan Balance
ce a a a ce
Example V
The following non-aqueous liquid detergent compositions were prepared in
accordance with the present invention
LAS 16.0 16.0 16.0
C23 E5S 21.5 21.5 19.0
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I II III
Butoxy Propoxy Propanol 18.5 - 16.0
Hexylene Glycol - 18.5 5.0
Sodium citrate dihydrate 6.8 6.8 3.8
[4-[N-nonanoyl-6-aminohexanoyloxy]6.0 6.0 6.0
benzene sulfonate] Na salt
Methyl sulfate salt of methyl 1.3 1.3 1.3
quaternized
polyethoxylated hexamethylene
diamine
EDDS 1.2 1.2 1.2
MA/AA - - 3.0
Sodium Carbonate 10.0 10.0 10.0
Protease 0.05 0.02 0.02
Amylase 0.01 0.01 0.01
Cellulase 0.0001 0.0001 0.0001
PB1 12.0 12.0 12.0
Silicone antifoam 0.75 0.75 1,1
Perfume 1.7 1.7 1.7
Titanium Dioxide 0.5 0.5 0.5
Dichloro -5,12-Dimethyl-1,5,8,12-- 0.03 0.03
tetraazabicyclo [6.6.2] hexadecane
Manganese (II)
Brightener 2 0.2 0.2 0.2
Sodium hydrogenated C16-18 fatty 1 1 0.5
soap
Colored Speckles 0.4 0.4 0.4
PPC1 0.4 0.4 0.4
Miscellaneous up to 100%
Example VI
The following aqueous liquid laundry detergent compositions were prepared
according to the present invention
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I II III IV V VI
LAS - - - 1.0 2.0 -
C25AS 16.0 13.0 14.0 5.0 - 6.5
C25E3S 5.0 1.0 - 10.0 19.0 3.0
C25E7 2.0 3.5 - 2.5 2.0 5.0
TFAA 5.0 4.5 4.5 6.5 4.0 -
APA 2.0 1.0 - 3.0 - 0.5
QAS - - 2.0 - 1.5 -
TPKFA 4.5 8.0 15.0 - 5.0 5.0
Citric acid 2.2 3.0 - 0.5 1.0 2.0
Rapeseed fatty acid 2.0 - - 3.0 6.0 1.5
Ethanol 3.2 2.0 2.5 2.2 - 0.5
1,2 Propanediol 5.7 8.5 6.5 7.0 7.0 5.5
Monoethanolamine 5.0 7.5 - 5.0 1.0 2.0
TEPAE - 1.2 - 0.5 0.5 -
DTPMP - 0.5 - 0.5 - 0.2
HEDP - 0.5 - 1.0 -
Protease 0.02 0.03 0.02 0.02 0.02 0.01
Lipase 0.002 0.0010.001 - 0.001 -
Amylase - .0006- - 0.001 -
Cellulase 0.002 0.002- 0.0020.001 -
SRP1 0.20 0.15 0.10 - 0.17 0.04
PVNO - - - 0.05 0.10 -
Brightener 1 0.20 0.15 0.10 0.05 - 0.05
Suds Suppressor 0.25 0.20 0.15 0.15 0.30 0.10
CaCl2 0.02 0.02 - 0.01 0.01 -
Boric acid 2.5 2.0 1.5 2.2 1.5 1.2
Bentonite Clay - - 5.5 - - -
PPC1 0.4 - 0.2 0.4 0.3 -
PPC3 - 0.4 0.1 - 0.1 0.2
NaOH to pH 8.0 7.5 7.7 8.0 7.0 7.5
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Water/minors to 100%
Example VII
The following describe high density liquid detergent compositions according to
the present invention:
weight
Ingredient I II III IV
Polyhydroxy Coco-Fatty Acid 2.50 2.50 -- --
Amide
C23 AEg -- -- 3.65 0.80
C25 AS -- -- 6.03 2.50
C25 El.g S 20.15 20.15 -- --
~
C45 E2.25S -- -- 18.00 18.00
Alkyl N-Methyl Glucose Amide -- -- 4.50 4.50
C10 Amidopropyl Amine 0.50 0.50 1.30 --
Citric Acid 2.44 3.00 3.00 3.00
C24FA -- -- 2.00 2.00
NEODOL 23-9 ~ 0.63 0.63 -- --
Ethanol 3.00 2.81 3.40 3.40
Monoethanoiamine 1.50 0.75 1.00 1.00
Propanediol 8.00 7.50 7.50 7.00
Boric Acid 3.50 3.50 3.50 3.50
~
Ethoxylated tetraethylenepentamine'0.50 -- -- --
Tetraethylenepentamine -- 1.18 -- --
Sodium Toluene Sulfonate 2.50 2.25 2.50 2.50
NaOH 2.08 2.43 2.62 2.62
Protease enzyme) 0.78 0.70 -- --
Protease enzyme4 -- -- 0.88 --
ALCALASE~ -- -- -- 1.00
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HEDP ' 0.5 0.7 2.5 0.5
Polyamine 0.50 0.50 -- --
PPC1 0.5 0.4 0.3 0.2
Water' balancebalance balancebalance
1. Eg Ethoxylated Alcohols as sold by the Shell Oil Co.
2. Ethoxylated tetraethylenepentarnine (PEI 189 E15-E1 g) according to U.S.
4,597,898 Vander Meer issued July 1, 1986.
3. Bleach stable variant of BPN' (Protease A-BSV) as disclosed in EP 130,756 A
January 9, 1985.
4. Subtilisin 309 Loop Region 6 variant.
5. Proteolytic enzyme as sold by Novo.
6. Polyamine PEI 600 E20
7. Balance to 100% can, for example, include minors like optical brightener,
perfume, suds suppresser, soil dispersant, chelating agents, dye transfer
inhibiting agents, additional water, and fillers, including CaC03, talc,
silicates,
etc.
Example VIII
The following liquid hard surface cleaning compositions were prepared
according
to the present invention
A B C D E
PPC1 0.5 - 0.2 - 0.1
PPC2 - 0.4 - 0.5 0.3
Amylase 0.01 0.002 0.005 - -
Protease 0.05 0.01 0.02 - '
-
Hydrogen peroxide - - - 6.0 6.8
Acetyl triethyl - - - 2.5 -
citrate
DTPA - - - 0.2 -
Butyl hydroxy toluene~ - - - 0.05 -
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EDTA* 0.05 0.05 0.05 - -
Citric / Citrate 2.9 2.9 2.9 1.0 -
LAS 0.5 0.5 0.5 - -
C 12 AS 0. 5 0 . 0. 5 - -
5
C10AS - - - - 1.7
C12(E)S 0.5 0.5 0.5 - -
a
C12,13 E6.5 nonionic 7.0 7.0 7.0 - -
Neodol23-6.5 - - - 12.0
Dobanol23-3 - - - - 1.5
Dobanol 91-10 - - - - 1,6
C25E1.8S - - - 6.0
Na paraffiin 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
monohexyl ether
Example IX
The following spray composition for cleaning of hard surfaces and removing
household mildew was prepared according to the present invention
PPC2 0.8
Amylase 0.01
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Protease 0.01
Na octyl sulfate 2.0
Na dodecyl sulfate 4.0
Na hydroxide 0.8
Silicate 0.04
Butyl carbitol* 4.0
Perfume 0.35
Water/minors up to 100%
*Diethylene glycol monobutyl
ether
Example X
The following lavatory cleansing block compositions were prepared according to
the present invention.
A B C
C16-18 fatty alcohol/50E0 70.0 - -
LAS - - 80.0
Nonionic - 1.0 -
Oleoamide surfactant . - 25.0 -
Partially esterified copolymer of 5.0 - -
vinylmethyl
ether and malefic anhydride, viscosity
0.1-0.5
Polyethylene glycol MW 8000 - 38.0 -
Water-soluble K-polyacrylate MW - 12.0 -
4000-8000
Water-soluble Na-copolymer of acrylamide- 19.0 -
(70%) and acryclic acid (30%) low
MW
Na triphosphate 10.0 - -
Carbonate - - -
PPC1 0.5 - 0.2
PPC2 - 0.5 0.2
Dye 2.5 1.0 1.0
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Perfume 3.0 - 7.0
KOH / HCL solution pH 6-11
Example XI
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
PPC1 0.5
PPC2 - 0.5
DTPMP - 1.0
Dye 2.0 . 1.0
Perfume 3.0 3.0
NaOH pH 6-11
Water and minors Up to 100%
Example XII
The following fabric softening compositions are in accordance with the present
invention
Component A B C D E F
DTDMAC - - - - 4.5 15.0
DEQA 2.6 2.9 18.0 19,0 - -
Fatty acid 0.3 - 1.0 - - -
HCI 0.02 0.02 0.02 0.02 0.02 0.02
PEG - - 0.6 0.6 - 0.6
Perfume 1.0 1.0 1.0 1.0 1.0 1.0
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Silicone antifoam0.01 0.01 0.01 0.01 0.01 0.01
PPC2 0.4 0.1 0.8 0.2 1.0 0.6
Electrolyte (ppm)- - 600 1200 - 1200
Dye (ppm) 10 10 50 50 10 50
Water and minors
to balance to
100%
Example XIII
The following are non-limiting examples of pre-soak fabric conditioning and/or
fabric enhancement compositions according to the present invention which can
be suitably used in the laundry rinse cycle
Ingredients A B C D E F
Polymer 3.5 3.5 3.5 3.5 3.5 3.5
Dye fixative 2.3 2.3 2.4 2.4 2.5 2.5
Polyamine 15.0 15.0 17.5 17.5 20.0 20.0
Bayhibit AM 1.0 1.0 1.0 1.0 1.0 1.0
C~2-Ci4 dimethyl- 5.0 5.0 - - -
hydroxyethyl
quaternary
ammonium
chloride
Fabric softener- - 2.5 2.5 - -
active
Genamin C100 0.33 - . 0.33 0.33 0.33 -
Genapol V4463 0.2 - 0.2 0.2 0.2 -
PPC2 0.5 1.0 0.2 0.8 0.1 0.4
Water & minorsbalance balancebalance balance balance balance
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Example XIV
Liquid compositions A to H comprise from 30wt% to 40wt% water
Ingredient A 8 C D E F G H
APA 1.5 1 2 1.5 1 1.3 1.2
CFAA 5 4 3 4 4
C28AS 15 12 17
C24E7 5 2 3 5 4.5 2.5
C25E1.25S 20 10 20 15
C25E3S 5 15 4
HLAS 5 4 5
QAS(1 ) 1.5
Boric acid(1 1
)
Boric acid(2) 0.2 0.15 0.15 0.2 2 2
Ethanol 1.5 3.5 3 1 1 2 1 3
Hydroxide 6.5 1.5 1.5 2
MEA 10 7 8 7 9 9 5
Propanediol 9 7 7 8 8 9 8 9
Citric Acid 1 1.5 2 0.5 2.5 1 1 2.5
RFA 3 5 1 3 3 2.5 4.5
TPKFA 7.5 17 3 8 5 4 7.5 3
DTPMP 1 1.5 1 0.3 0.5 0:6 1
HEDP 0.3 0.3 0.5 0.35
Brightener(2)0.1 0.15 0.2 0.1 0.15 0.2
PVNO 0.05 0.1
Clay 4
SRP(2) 0.1 0.15 0.1 0.15
Amylase 0.1 0.0 0.1 0.7 0.3 0.15 0.2
Cellulase 0.01 0.1 0.3 0.01 0.2
Lipase 0.05 0.06
CA 02392976 2002-05-28
WO 01/51599 PCT/USO1/00822
Mannanase 0.3 0.05 0.06
Protease 0.5 0.7 0.6 0.5 0.4 0.7 0.6
Perfume 0.5 1.0 0.3
Silicone 0.2 0.2 0.2 0.1 0.1 0.2 0.2 0.2
antifoam
PPC1, PPC2, 0.5 0.4 2.1 0.6 0.5 0.6 0.6 3.5
PPC3 and/or
PPC4
Miscellaneousto to to to to to to to
100% 100% 100% 100% 100% 100% 100% 100%
91
CA 02392976 2002-05-28
WO 01/51599 PCT/USO1/00822
Example XV
Liquid compositions A to H comprise from 30%wt to 40wt% water:
Ingredient A 8 C D E F G H
APA 1 1.5 1 1 2 1.5
C23E9 2.5 2 3 1 3.5 2.5
C25E1.1S 15 20 18 17 25 20 17 19
H LAS 2.5 2 3 1.5 2 2
Boric acid(2)2.5 2 2.5 1.5 2 1.5 2 2
Ethanol 1.5 2.5 2 2 3 4 3 1
Hydroxide 2 3 3 2 3 2 3 3
MEA 3 3 2 2 2.5 3 2 3
Propanediol 5 6 6 5 5 6 15 10
Citric Acid 3 2.5 2 3 3 2.5 3.5 3
TPKFA 4 4 3 5 2 3 4 3
Brightener(2)0.2 0.1 0.15 0.15 0.2 0.2 0.1 0.1
Amylase 0.1 0.05 0.2 0.1 0.15 0.05
Cellulase 0.05 0.1 0.06 0.01 0.05 0.15 0.07
Mannanase 0.1 0.05 0.15 0.1 0.1
Protease 0.6 0.9 0.1 1.2 0.8 0.5 1
PerFume 0.5 0.2 0.05
Silicone 0.01 0.02 0.01 0.02
antifoam
PPC, PPC2, 0.4 2.5 0.6 0.2 0.1 3.3 0.5 0.8
PPC3 and/
or
PPC4
Miscellaneousto to to to to to to to
100% 100% 100% 100% 100% 100% 100% 100%
92
