Field of the invention
[0001] The present invention relates to laundry and cleaning compositions comprising a product
of reaction between an amino functional polymer comprising at least one primary amine
group, and a perfume component, in particular aldehyde or ketone perfumes.
Background of the invention
[0002] Laundry and cleaning products are well-known in the art. However, consumer acceptance
of laundry and cleaning products is determined not only by the performance achieved
with these products but also by the aesthetics associated therewith. The perfume components
are therefore an important aspect of the successful formulation of such commercial
products.
[0003] It is also desired by consumers for laundered fabrics to maintain the pleasing fragrance
over time. Indeed, perfume additives make laundry compositions more aesthetically
pleasing to the consumer, and in some cases the perfume imparts a pleasant fragrance
to fabrics treated therewith. However, the amount of perfume carried-over from an
aqueous laundry bath onto fabrics is often marginal and does not last long on the
fabric. Furthermore, fragrance materials are often very costly and their inefficient
use in laundry and cleaning compositions and ineffective delivery to fabrics results
in a very high cost to both consumers and laundry and cleaning manufacturers. Industry,
therefore, continues to seek with urgency for more efficient and effective fragrance
delivery in laundry and cleaning products, especially for improvement in the provision
of long-lasting fragrance to the fabrics.
[0004] One solution is to use carrier mechanisms for perfume delivery, such as by encapsulation.
This is taught in the prior art and described in U.S. 5,188,753.
[0005] Still another solution is to formulate compounds which provide a delayed release
of the perfume over a longer period of time than by the use of the perfume itself.
Disclosure of such compounds may be found in WO 95/04809, WO 95/08976 and co-pending
application EP 95303762.9.
[0006] However, notwithstanding the advances in the art, there is still a need for a compound
which provides a delayed release of the perfume component.
[0007] That need is even more acute for perfume ingredients which are characteristic of
the fresh notes, namely the aldehydes and ketones perfume ingredients. Indeed, whilst
these provide a fresh fragrance, these perfumes are also very volatile and have a
low substantivity on the surface to be treated like fabrics.
[0008] Accordingly, it is a further object of the invention to provide a laundry and cleaning
composition comprising a perfume component which provides a fresh fragrance and is
substantive to the treated surface.
[0009] The Applicant has now found that specific reaction products of an amino functional
polymer comprising at least one primary amine group with an active aldehyde or ketone,
such as imines compounds, also provide a delayed release of the active such as a perfume.
[0010] Imine compounds are known in the art under the name of Schiff bases which is the
condensation of an aldehyde perfume ingredient with an anthranilate. A typical description
can be found in US 4853369. By means of this compound, the aldehyde perfume is made
substantive to the fabrics. However, a problem encountered with these schiff bases
is that the methylanthranilate compound also exhibits a strong scent, which as a result
produces a mixture of fragrances, thereby reducing or even inhibiting the aldehyde
fragrance perception.
[0011] To achieve such perfume composition with comparable aldehyde or ketones fresh notes
whilst still having satisfactory fabric substantivity, perfumers have formulated around
the composition. For example, by having a carrier or encapsulating material for such
notes such as with cyclodextrin, zeolites or starch.
[0012] Still another solution is the use of a glucosamine as described in JP 09040687. However,
this compound has been found to give a very low stability in the wash/cleaning process.
As a result, insufficient perfume residuality on the treated fabric and/or hard surface
has been found with these glucosamine compounds.
[0013] A further solution is described in Chemical release control, Kamogawa et Al., J.
Poly. Sci. Polym. Chem. Ed. Vol 20, 3121 (1982) which describe the use of amino styrene
compounds condensed with aldehydes perfumes, whereby the release of the perfume is
triggered by means of copolymerisation or acidification of the compound. Its use in
laundry and cleaning product is however not mentioned.
[0014] The Applicant has now found that a reaction product of an amino functional polymer
comprising at least one primary amine group, and a perfume component also fulfill
such a need.
[0015] Another advantage of the compounds of the invention is their ease of manufacture
rendering their use most desirable.
Summary of the invention
[0016] The present invention relates to a laundry and cleaning composition comprising a
detersive ingredient and a product of reaction between an amino functional polymer
comprising at least one primary amine group and a perfume component selected from
ketone, aldehyde, and mixtures thereof, characterised in that said amino functional
polymer has an Odour Intensity Index of less than that of a 1% solution of methylanthranilate
in dipropylene glycol, and the product of reaction a Dry Surface Odour Index of more
than 5.
[0017] In a further aspect of the invention, there is provided a method of delivering residual
fragrance to a surface by means of the compound or composition of the invention.
Detailed description of the invention
I-Product of reaction between an amino functional polymer and a perfume component
[0018] An essential component of the invention is a product of reaction an amino functional
polymer comprising at least one primary amine group and a perfume component, so called
hereinafter "amine reaction product".
A- Amino functional polymer
[0019] The amino functional polymer is characterized by an Odour Intensity Index of less
than that of a 1 % solution of methylanthranilate in dipropylene glycol.
Odour Intensity Index method
[0020] 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 ongoing basis. For each an amino functional
polymer, the panellist was presented two blotters: one reference (Me Anthranilate,
unknown from the panellist) and the sample. The panellist was asked to rank both smelling
strips on the 0-5 odor intensity scale, 0 being no odor detected, 5 being very strong
odor present.
Results:
[0021] The following represents Odour Intensity Index of an amino functional polymer suitable
for use in the present invention and according to the above procedure.
[0022] 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 |
1,4-bis-(3-aminopropyl)piperazine (BNPP) 1% |
1.0 |
[0023] A general structure for the amino functional polymer containing at least one primary
amine group of the present invention, is as follows:

wherein n is an index of at least 1 and B is the polymer backbone. B can optionally
comprise a branching group, C and hence the amino functional polymer is of the following
formula:

[0024] The amino functional polymer of the present invention contains at least one free,
unmodified primary amino group attached to the main chain by hydrogen substitution,
or by other suitable insertion or substitution by groups referred to as R*. Also suitable
is the amino functional polymer comprising an unmodified primary amino group present
on side chain(s).
[0025] Preferably, the amino functional polymers of the present invention will comprise
several amino groups, more preferably more than 10 amino groups. The amino functional
polymers of the present invention will preferably present a molecular weight (MW)
ranging from 150 to 2.10E6; more preferably from 400-50,000; most preferably from
600 to 40,000.
[0026] The amino functional polymer can be a linear homo-, co-polymer and optionally branched,
grafted and/or cross-linked.
[0028] Suitable branching units C for the polymer backbone B are :

[0030] The arrow indicates substitution in position 2,3 or 4

[0031] The backbone (B) can also contain several insertion groups linked together: e.g.

wherein x≥ 1.
[0032] The aminofunctional polymers of the present invention can further comprise substituents
R* in the main chain or in the side chain(s). Typically, R* replaces an hydrogen atom.
This R* group can either be linked directly or via a linker group L to the main or
side chain. Suitable linker groups L are the above mentioned insertion groups I.
[0033] R* groups are C1 to C22 alkyl, alkenyl, alkylbenzene chain and/or their corresponding
substituted derivatives. Such corresponding substituted derivatives include alicyclic,
aromatic, heteroaromatic or heterocyclic systems, either inserted in the main chain
or incorporated by a substitution of an H atom in the main chain; an insertion group
I in the main chain, as defined herein above and/or an end group E as defined below.
[0034] Further, the polymer backbone B and R* encompass end groups E. Typically end groups
E can be an H, NH2 groups, an aromatic, alicyclic, heteroaromatic or heterocyclic
group including mono-, di-, oligo-, poly-saccharides :

-SO
3H, -OSO
3H, -COOH,-COOR*,

wherein x
-= is an anion like Cl
-,Br
-,SO
42-.
[0035] In addition, the R* group can also be modified via substitution of one or more H
atoms. Said substitution can either be an end group E or an insertion group I as defined
above, where the insertion group is terminated by a H, E or R* group .
[0036] Examples of suitable amino functional polymers containing at least one primary 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 5/3/1) Polyamino acid
(polylysine-cocaprolactam);
- 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).
[0037] Preferred amino functional polymers containing at least one primary amine group are
:
- polyvinylamines with a MW ranging from 600, 1200, 3K, 20K, 25K or 50K;
- 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)
- 1,4-bis-(3-aminopropyl) piperazine (BNPP).
[0038] Furthermore, such amino functional polymers comprising at least one primary amine
group and the amine reaction product provide fabric appearance benefits, in particular
color care and protection against fabric wear.
The appearance of fabrics, e.g., clothing, bedding, household fabrics like table linens
is one of the area of concern to consumers. Indeed, upon typical consumer's uses of
the fabrics such as wearing, washing, rinsing and/or tumble-drying of fabrics, a loss
in the fabric appearance; which can be at least partly due to loss of color fidelity
and color definition, is observed. Such a problem of color loss is even more acute
after multiwash cycles. It has been found that the compositions of the present invention
provide improved fabric appearance and protection against fabric wear and improved
color care to laundered fabrics, especially after multiwash cycles.
[0039] Therefore, the softening compositions of the present invention can provide simultaneously
fabric care and long lasting perfume benefits.
B-Perfume
[0040] Preferably, for the above mentioned compounds, by perfume ketone or aldehyde, it
is meant any chain containing at least 1 carbon atom, preferably at least 5 carbon
atoms.
[0041] A typical disclosure of suitable ketone and/or aldehydes, traditionally used in perfumery,
can be found in "perfume and Flavor Chemicals", Vol. I and II, S. Arctander, Allured
Publishing, 1994, ISBN 0-931710-35-5.
[0042] Perfume ketones components include components having odoriferous properties.
[0043] Preferably, for the above mentioned compounds, the perfume ketone is selected for
its odor character from buccoxime; iso jasmone; methyl beta naphthyl ketone; musk
indanone; 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)-lndanone,
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,
Undecalactone and Gamma undecalactone.
[0044] For the above mentioned compounds, the more preferred ketones are selected for its
odor character from Alpha Damascone, Delta Damascone, Iso Damascone, Carvone, Gamma-Methyl-lonone,
Iso-E-Super, 2,4,4,7-Tetramethyl-oct-6-en-3-one, Benzyl Acetone, Beta Damascone, Damascenone,
methyl dihydrojasmonate, methyl cedrylone, and mixtures thereof.
[0045] Perfume aldehyde components include components having odoriferous properties.
[0046] Preferably, for the above mentioned compounds, the perfume aldehyde is selected for
its odor character from adoxal; anisic aldehyde; cymal; ethyl vanillin; florhydral;
helional; heliotropin; hydroxycitronellal; koavone; lauric aldehyde; lyral; methyl
nonyl 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-dimethyl-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-(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-1H-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-1or 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, paratolylacetaldehyde;
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, hexanal, trans-2-hexenal, 1-p-menthene-q-carboxaldehyde
and mixtures thereof.
[0047] More preferred aldehydes are selected for its odor character from 1-decanal, benzaldehyde,
florhydral, 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde; cis/trans-3,7-dimethyl-2,6-octadien-1-al;
heliotropin; 2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde; 2,6-nonadienal; alpha-n-amyl
cinnamic aldehyde, alpha-n-hexyl cinnamic aldehyde, P.T. Bucinal, lyral, cymal, methyl
nonyl acetaldehyde, hexanal, trans-2-hexenal, and mixture thereof.
[0048] In the above list of perfume ingredients, some are commercial names conventionally
known to one skilled in the art, and also includes isomers. Such isomers are also
suitable for use in the present invention.
[0049] In another embodiment, especially suitable for the purpose of the present invention
are the perfume compounds, preferably the perfume ketones or aldehydes, characterized
by having a low Odor Detection Threshold. Such Odor Detection Threshold (ODT) should
be lower than 1ppm, preferably lower than 10ppb - measured at controlled Gas Chromatography
(GC) conditions such as described here below. This parameter refers to the value commonly
used in the perfumery arts and which is the lowest concentration at which significant
detection takes place that some odorous material is present. Please refer for example
in "Compilation of Odor and Taste 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: 17/1 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
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
[0050] 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 hydroxyphenyl-butanone, cymal, benzyl
acetone, ionone alpha, p.t.bucinal, damascenone, ionone beta and methyl-nonyl ketone:
Process
[0051] Preparation of the component is made as follows in the Synthesis Examples. In general,
the nitrogen analogs of ketones and aldehydes are called azomethines, Schiff bases
or the more preferred name imines. These imines can easily be prepared by condensation
of primary amines and carbonyl compounds by elimination of water.
[0052] A typical reaction profile is as follows:

α,β-Unsaturated ketones do not only condense with amines to form imines, but can
also undergo a competitive 1,4-addition to form β-aminoketones.

[0053] By means of this simple method, compound and composition containing said compounds
are made which achieve a delayed release of the active ingredient.
[0054] As can be observed, the perfume ingredient needs to be present in equimolar amount
to the amine function so as to enable the reaction to take place and provide the resulting
amine reaction product. Of course, higher amount are not excluded and even preferred
when the amine compound comprises more than one amine function.
Mechanism of release
[0055] By the present invention, a delayed release of a perfume ingredient, i.e. ketone
or aldehyde is obtained. Not to be bound by theory, the release is believed to occur
by the following mechanisms:
[0056] For imine compounds, the perfume components are released upon breaking down of the
imine bond, leading to the release of the perfume component and of the primary amine
compound. This can be achieved by either hydrolysis, photochemical cleavage, oxidative
cleavage, or enzymatic cleavage.
[0057] For β-aminoketone compounds, treatment with air moisture and/or water successfully
releases the perfume component and the primary amine compound. However, other means
of release are not excluded like hydrolysis, photochemical cleavage, oxidative cleavage,
or enzymatic cleavage.
[0058] Still other means of release for imine as well as β-aminoketone compounds can be
considered such as by the steaming step of ironing the treated fabric, tumble-drying,
and/or wearing.
Laundry and cleaning compositions
[0059] The present invention include both laundry and cleaning compositions which are typically
used for laundering fabrics and cleaning hard surfaces such as dishware, floors, bathrooms,
toilet, kitchen and other surfaces in need of a delayed release of perfume ketone
and/or aldehyde. Accordingly, by laundry and cleaning compositions, these are to be
understood to include not only detergent compositions which provide fabric cleaning
benefits, but also compositions such as hard surface cleaning which provide hard surface
cleaning benefit.
[0060] Preferred are those laundry compositions which result in contacting the compound
of the invention with fabric.
[0061] Preferably, the amine reaction product(s) which is incorporated into such laundry
and cleaning compositions provides a dry surface Odour Index of more than 5 preferably
at least 10.
[0062] By Dry Surface Odour Index, it is meant that the amine reaction product(s) provides
a Delta of more than 5, wherein Delta is the difference between the Odour Index of
the dry surface treated with amine reaction product(s) and the Odour Index of the
dry surface treated with only the perfume raw material.
Measurement method of Dry Surface Odour Index:
[0063] For the above Dry Surface Odour Index, the amine reaction product suitable for use
in the present invention needs to fulfill at least one of the following two tests.
Preferred amine reaction product suitable for use in the present invention fulfill
both test.
1)-For fabric surface
Product preparation:
[0064] The amine reaction product is added to the unperfumed product base. Levels of amine
reaction product are selected so as to obtain an odour grade on the dry fabric of
at least 20. After careful mixing, by shaking the container in case of a liquid, with
a spatula in case of a powder, the product is allowed to sit for 24 hrs.
Washing process:
[0065] The resulting product is added into the washing machine in the dosage and in the
dispenser appropriate for its category. The quantity corresponds to recommended dosages
made for the corresponding market products: typically between 70 and 150 g for a detergent
powder or liquid via current dosing device like granulette, or ariellette. The load
is composed of four bath towels (170g) using a Miele W830 washing machine at 40°C
short cycle, water input :15°Hardness at a temperature of 10-18°C, and full spin of
1200rpm.
[0066] The same process is applied for the corresponding free perfume ingredient in consideration
and is used as the reference. Dosages, fabric loads and washing cycles for the reference
and the sample are identical.
Drying Process:
[0067] Within two hours after the end of the washing cycle, spinned but still wet fabrics
are assessed for their odors using the scale mentioned below. Afterwards, half of
the fabric pieces are hung on a line for 24 hr drying, away from any possible contaminations.
Unless specified, this drying takes place indoor. Ambient conditions are at temperature
between 18-25C and air moisture between 50-80%. The other half is placed in a tumble
drier and undergoes a full "very dry" cycle, i.e. in a Miele, Novotronic T430 set
on program white-extra dry (full cycle). Tumble dry fabrics are also assessed on the
next day. Fabrics are then stored in opened aluminum bags in an odor free room, and
assessed again after 7 days.
Odor Evaluations:
[0068] Odor is assessed by expert panellist smelling the fabrics. A 0-100 scale is used
for all fabric odor gradings. The grading scale is as follows :
100 = extremely strong perfume odor
75 = very strong perfume odor
50 = strong odor
40 = moderate perfume odor
30 = slight perfume odor
20 = weak perfume odor
10 = very weak perfume odor
0 = no odor
[0069] A difference of more than 5 grades after one day and/or 7 days between the amine
reaction product and the perfume raw material is statistically significant. A difference
of 10 grades or more after one day and/or 7 days represents a step-change. In other
words, when a difference of grade of more than 5, preferably at least 10 is observed
between the amine reaction product and the perfume raw material, after either 1 day
or 7 days or both 1 day and 7 days, it can be concluded that the amine reaction product
is suitable for use in the present invention, provided that the amine compound fulfill
the Odour Intensity Index.
2)-For hard surface:
Product preparation:
[0070] The perfume raw material or blend thereof is added and carefully mixed at 0.255%
in the unperfumed Hard Surface Cleaner base. After mixing and standing for 24 hrs,
the homogeneity of the product is checked. In case of phase separation due to poor
solubility of the perfume ingredient(s) an appropriate amount of Sodium p. Cymene
Sulfonate or another solubilising agent is added till a homogeneous solution is obtained.
Cleaning process:
[0071] Five grams of this solution are evenly applied on the upper side of a ceramic tile
(875 square cm, e.g. from Vileroy-Boch). After 1 minute the tile is rinsed with 1
liter of tap water. The tile is then placed in a vertical position for 3 minutes to
allow the rinse water to drip off.
[0072] Finally, the tile is placed in a clean and aerated perspex box (38 x 40 x 32 cm)
with a removable cover that has a sliding-lid (10 x 10 cm) to allow expert evaluators
to smell the interior phase of the box.
The odor in the box is evaluated just after placing the tile in it (fresh reading)
and after 1, 2 and 6 hours.
Odor Evaluation:
[0073] The grading scale is as follows :
50 = very strong odor
40 = strong odor
30 = moderate odor
20 = slight odor
10 = weak odor
0 = no odor
[0074] Every test includes a blanc (unperfumed Hard Surface Cleaner) and in the case of
testing perfume precursor, so-called amine reaction product the corresponding free
perfume ingredient is also included so that the effect of the carrier is adequately
measured.
[0075] Again as for the Dry surface Odour Index method for fabrics, a difference of more
than 5 grades after 1 day and/or 7 days between the amine reaction product and the
perfume raw material is statistically significant. A difference of 10 grades or more
after 1 day and/or 7 days represents a step-change. In other words, when a difference
of grade of more than 5, preferably at least 10 is observed between the amine reaction
product and the perfume raw material, after either 1 day or 7 day or both 1 day and
7 days, it can be concluded that the amine reaction product is suitable for use in
the present, provided that the amine compound fulfill the Odour Intensity Index.
[0076] The amine reaction product as defined herein before is typically comprised from 0.0001%
to 10%, preferably from 0.001% to 5%, and more preferably from 0.01% to 2%, by weight
of the composition. Mixtures of the compounds may also be used herein.
[0077] Incorporation of the amine reaction product in the laundry and cleaning compositions
can conveniently be carried out, if necessary, by conventional incorporation means,
such as by spray-on, encapsulation like starch encapsulation, e.g. as described in
GB1464616, dry addition, or by encapsulation in cyclodextrin. Preferably, the amine
reaction product is preformed before incorporation into the laundry and cleaning compositions.
In other words, the perfume component and the amino functional polymer of the present
invention are first reacted together to obtain the resulting amine reaction product
as defined in the present invention and only once formed incorporated into the laundry
and cleaning compositions. By being preformed before the incorporation in fully formulated
composition, a better control of the compound being made is obtained. Hence, the interaction
with perfume composition which may be present in fully formulated composition is avoided
as well as side reaction that could occur. Further, by such means of incorporation,
efficient control of the yield and purity of the compound is obtained.
[0078] Most preferably, when the laundry and cleaning composition comprises a perfume, the
amine reaction product is incorporated in the composition separately from the perfume.
By this means, the amine reaction product and its subsequent perfume release is more
controlled.
[0079] Typically the laundry and cleaning composition comprises a detersive ingredient and
further optional ingredients as described hereinafter as optional ingredients.
Detersive ingredients
[0080] Non-limiting examples of surfactants useful herein typically at levels from 1 % to
55%, by weight, include the conventional C
11-C
18 alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C
10-C
20 alkyl sulfates ("AS"), the C
10-C
18 secondary (2,3) alkyl sulfates of the formula CH
3(CH
2)
x(CHOSO
3-M
+) CH
3 and CH
3(CH
2)
y(CHOSO
3-M
+) CH
2CH
3 where x and (y + 1) are integers of at least 7, preferably at least 9, and M is a
water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate,
the C
10-C
18 alkyl alkoxy sulfates ("AE
xS"; especially x up to 7 EO ethoxy sulfates), C
10-C
18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C
10-18 glycerol ethers, the C
10-C
18 alkyl polyglycosides and their corresponding sulfated polyglycosides, and C
12-C
18 alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric
surfactants such as the C
12-C
18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates
and C
6-C
12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C
12-C
18 betaines and sulfobetaines ("sultaines"), C
10-C
18 amine oxides, cationic surfactants and the like, can also be included in the overall
compositions. The C
10-C
18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include
the C
12-C
18 N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the
N-alkoxy polyhydroxy fatty acid amides, such as C
10-C
18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C
12-C
18 glucamides can be used for low sudsing. C
10-C
20 conventional soaps may also be used. If high sudsing is desired, the branched-chain
C
10-C
16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful.
Other conventional useful surfactants are listed in standard texts.
[0081] Fully formulated laundry and cleaning compositions preferably contain, in addition
to the hereinbefore described components, one or more of the following ingredients.
Builders
[0082] 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.
[0083] The level of builder can vary widely depending upon the end use of the composition
and its desired physical form. When present, the compositions will typically comprise
at least 1% builder, preferably from 1% to 80%. Liquid formulations typically comprise
from 5% to 50%, more typically 5% to 30%, by weight, of detergent builder. Granular
formulations typically comprise from 1 % to 80%, more typically from 5% to 50% by
weight, of the detergent builder. Lower or higher levels of builder, however, are
not meant to be excluded.
[0084] Inorganic or P-containing detergent builders include, but are not limited to, the
alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by
the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates,
phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates),
sulphates, and aluminosilicates. However, non-phosphate builders are required in some
locales. Importantly, the compositions herein function surprisingly well even in the
presence of the so-called "weak" builders (as compared with phosphates) such as citrate,
or in the so-called "underbuilt" situation that may occur with zeolite or layered
silicate builders.
[0085] Examples of silicate builders are the alkali metal silicates, particularly those
having a SiO
2:Na
2O ratio in the range 1.0:1 to 3.2:1 and layered silicates, such as the layered sodium
silicates described in U.S. 4,664,839. NaSKS-6 is the trademark for a crystalline
layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike
zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6
has the delta-Na
2SiO
5 morphology form of layered silicate. It can be prepared by methods such as those
described in DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred layered
silicate for use herein, but other such layered silicates, such as those having the
general formula NaMSi
xO
2x+1·yH
2O 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-Na
2SiO
5 (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful
such as for example magnesium silicate, which can serve as a crispening agent in granular
formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds
control systems.
Examples of carbonate builders are the alkaline earth and alkali metal carbonates
as disclosed in DE 2,321,001.
[0086] Aluminosilicate builders are useful in the present invention. Aluminosilicate builders
are of great importance in most currently marketed heavy duty granular detergent compositions,
and can also be a significant builder ingredient in liquid detergent formulations.
Aluminosilicate builders include those having the empirical formula:
M
z/n[(AlO
2)
z(SiO
2)
y]·xH
2O
wherein z and y are integers usually of at least 6, the molar ratio of z to y is in
the range from 1.0 to 0, and x is an integer from 0 to 264, and M is a Group IA or
IIA element, e.g., Na, K, Mg, Ca with valence n.
[0087] 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. 3,985,669. Preferred synthetic crystalline aluminosilicate ion
exchange materials useful herein are available under the designations Zeolite A, Zeolite
P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline
aluminosilicate ion exchange material has the formula:
Na
12[(AlO
2)
12(SiO
2)
12]·xH
2O
wherein x is from 20 to 30, especially 27. This material is known as Zeolite A. Dehydrated
zeolites (x = 0 - 10) may also be used herein. Preferably, the aluminosilicate has
a particle size of 0.1-10 microns in diameter.
[0088] 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.
[0089] Included among the polycarboxylate builders are a variety of categories of useful
materials. One important category of polycarboxylate builders encompasses the ether
polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. 3,128,287,
U.S. 3,635,830. See also "TMS/TDS" builders of U.S. 4,663,071. Suitable ether polycarboxylates
also include cyclic compounds, particularly alicyclic compounds, such as those described
in U.S. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
[0090] Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers
of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2,
4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal,
ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine
tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic
acid, pyromellitic, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic
acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
[0091] Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium
salt), are polycarboxylate builders of particular importance for heavy duty liquid
detergent formulations due to their availability from renewable resources and their
biodegradability. Citrates can also be used in granular compositions, especially in
combination with zeolite and/or layered silicate builders. Oxydisuccinates are also
especially useful in such compositions and combinations.
[0092] Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates
and the related compounds disclosed in U.S. 4,566,984. Useful succinic acid builders
include the C
5-C
20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound
of this type is dodecenylsuccinic acid. Specific examples of succinate builders include:
laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred),
2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders
of this group, and are described in EP 0,200,263.
[0093] Other suitable polycarboxylates are disclosed in U.S 4,144,226 and in U.S. 3,308,067.
See also U.S. 3,723,322.
[0094] Fatty acids, e.g., C
12-C
18 monocarboxylic acids such as oleic acid and/or its salts, can also be incorporated
into the compositions alone, or in combination with the aforesaid builders, especially
citrate and/or the succinate builders, to 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.
[0095] In situations where phosphorus-based builders can be used, and especially in the
formulation of bars used for hand-laundering operations, the various alkali metal
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.
Bleaching Compounds - Bleaching Agents and Bleach Activators
[0096] The detergent compositions herein may optionally contain bleaching agents or bleaching
compositions containing a bleaching agent and one or more bleach activators. When
present, bleaching agents will typically be at levels of from 1% to 30%, more typically
from 5% to 20%, of the detergent composition, especially for fabric laundering. If
present, the amount of bleach activators will typically be from 0.1% to 60%, more
typically from 0.5% to 40% of the bleaching composition comprising the bleaching agent-plus-bleach
activator.
[0097] The bleaching agents used herein can be any of the bleaching agents useful for detergent
compositions in textile cleaning or other cleaning purposes that are now known or
become known. These include oxygen bleaches as well as other bleaching agents like
hypochlorite bleaching agents. Perborate bleaches, e.g., sodium perborate (e.g., mono-
or tetra-hydrate) can be used herein. When hypochlorite is used, a highly preferred
hypochlorite bleaching component is an alkali metal hypochlorite. Although alkali
metal hypochlorites are preferred, other hypochlorite compounds may also be used herein
and can be selected from calcium and magnesium hypochlorite. A preferred alkali metal
hypochlorite for use herein is sodium hypochlorite.
[0098] Another category of bleaching agent that can be used without restriction encompasses
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 4,483,781, U.S 740,446, EP 0,133,354,
and U.S 4,412,934. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic
acid as described in U.S 4,634,551.
[0099] Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds
include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium
pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach
(e.g., OXONE, manufactured commercially by DuPont) can also be used.
[0100] A preferred percarbonate bleach comprises dry particles having an average particle
size in the range from 500 micrometers to 1,000 micrometers, not more than 10% by
weight of said particles being smaller than 200 micrometers and not more than 10%
by weight of said particles being larger than 1,250 micrometers. Optionally, the percarbonate
can be coated with silicate, borate or water-soluble surfactants. Percarbonate is
available from various commercial sources such as FMC, Solvay and Tokai Denka.
[0101] Mixtures of bleaching agents can also be used.
[0102] Peroxygen bleaching agents, the perborates, the percarbonates, etc., are preferably
combined with bleach activators, which lead to the
in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid
corresponding to the bleach activator. Various non-limiting examples of activators
are disclosed in U.S 4,915,854, and U.S 4,412,934. The nonanoyloxybenzene sulfonate
(NOBS), 3,5,5-tri-methyl hexanoyl oxybenzene sulfonate (ISONOBS) and tetraacetyl ethylene
diamine (TAED) activators are typical, and mixtures thereof can also be used. See
also U.S. 4,634,551 for other typical bleaches and activators useful herein.
Highly preferred amido-derived bleach activators are those of the formulae:
R
1N(R
5)C(O)R
2C(O)L or R
1C(O)N(R
5)R
2C(O)L
wherein R
1 is an alkyl group containing from 6 to 12 carbon atoms, R
2 is an alkylene containing from 1 to 6 carbon atoms, R
5 is H or alkyl, aryl, or alkaryl containing from 1 to 10 carbon atoms, and L is any
suitable leaving group. A leaving group is any group that is displaced from the bleach
activator as a consequence of the nucleophilic attack on the bleach activator by the
perhydrolysis anion. A preferred leaving group is phenyl sulfonate.
[0103] Preferred examples of bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate,
(6-nonanamidocaproyl)oxybenzene sulfonate, (6-decanamido-caproyl)oxybenzenesulfonate,
and mixtures thereof as described in U.S. Patent 4,634,551, incorporated herein by
reference.
[0104] Another class of bleach activators comprises the benzoxazin-type activators disclosed
by Hodge et al in U.S. Patent 4,966,723. A highly preferred activator of the benzoxazin-type
is:

[0105] Still another class of preferred bleach activators includes the acyl lactam activators,
especially acyl caprolactams and acyl valerolactams of the formulae:

wherein R
6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to 12 carbon
atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam,
3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl
caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl
valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures
thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated
herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam,
adsorbed into sodium perborate.
[0106] Bleaching agents other than oxygen bleaching agents are also known in the art and
can be utilized herein. One type of non-oxygen bleaching agent of particular interest
includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum
phthalocyanines. See U.S. 4,033,718. If used, detergent compositions will typically
contain from 0.025% to 1.25%, by weight, of such bleaches, especially sulfonate zinc
phthalocyanine.
[0107] If desired, the bleaching compounds can be catalyzed by means of a manganese compound.
Such compounds are well-known in the art and include, for example, the manganese-based
catalysts disclosed in U.S. 5,246,621, U.S. 5,244,594; U.S. 5,194,416; U.S. 5,114,606;
and EP 549,271A1, 549,272A1, 544,440A2, and 544,490A1; Preferred examples of these
catalysts include Mn
IV2(u-O)
3(1,4,7-trimethyl-1,4,7-triazacyclononane)
2(PF
6)
2, Mn
III2 (u-O)
1(u-OAc)
2(1,4,7-trimethyl-1,4,7-triazacyclononane)
2-(ClO
4)
2, Mn
IV4(u-O)
6(1,4,7-triazacyclononane)
4(ClO
4)
4, Mn
IIIMn
IV4(u-O)
1(u-OAc)
2-(1,4,7-trimethyl-1,4,7-triazacyclononane)
2(ClO
4)
3, Mn
IV(1,4,7-trimethyl-1,4,7-triazacyclononane)- (OCH
3)
3(PF
6), and mixtures thereof. Other metal-based bleach catalysts include those disclosed
in U.S. Pat. 4,430,243 and U.S. 5,114,611. The use of manganese with various complex
ligands to enhance bleaching is also reported in the following US Patents: 4,728,455;
5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.
[0108] As a practical matter, and not by way of limitation, the compositions and processes
herein can be adjusted to provide on the order of at least one part per ten million
of the active bleach catalyst species in the aqueous washing liquor, and will preferably
provide from 0.1 ppm to 700 ppm, more preferably from 1 ppm to 500 ppm, of the catalyst
species in the laundry liquor.
Brighteners
[0109] The compositions herein can also optionally contain from 0.005% to 5% by weight of
certain types of hydrophilic optical brighteners which also provide a dye transfer
inhibition action. If used, the compositions herein will preferably comprise from
0.001% to 1 % by weight of such optical brighteners. The hydrophilic optical brighteners
useful in the present invention are those having the structural formula:

wherein R
1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R
2 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, R
1 is anilino, R
2 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 rinse added compositions
herein.
When in the above formula, R
1 is anilino, R
2 is N-2-hydroxyethyl-N-2-methylamino 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'-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, R
1 is anilino, R
2 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.
Soil Release Agent
[0110] In the present invention, an optional soil release agent can be added. Typical levels
of incorporation in the composition are from 0% to 10%, preferably from 0.2% to 5%,
of a soil release agent. Preferably, such a soil release agent is a polymer.
[0111] Soil Release agents are desirably used in fabric softening compositions of the instant
invention. Any polymeric soil release agent known to those skilled in the art can
optionally be employed in the compositions of this invention. Polymeric soil release
agents are characterized by having both hydrophilic segments, to hydrophilize the
surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments,
to deposit upon hydrophobic fibers and remain adhered thereto through completion of
washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments.
This can enable stains occurring subsequent to treatment with the soil release agent
to be more easily cleaned in later washing procedures.
[0112] 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%.
[0113] The following, all included herein by reference, describe soil release polymers suitable
for use in the present invention. U.S. 3,959,230 Hays, issued May 25, 1976; U.S. 3,893,929
Basadur, issued July 8, 1975; U.S. 4,000,093, Nicol,
et al., issued December 28, 1976; U.S. Patent 4,702,857 Gosselink, issued October 27, 1987;
U.S. 4,968,451, Scheibel
et al., issued November 6; U.S. 4,702,857, Gosselink, issued October 27, 1987; U.S. 4,711,730,
Gosselink
et al., issued December 8, 1987; U.S. 4,721,580, Gosselink, issued January 26, 1988; U.S.
4,877,896, Maldonado
et al., issued October 31, 1989; U.S. 4,956,447, Gosselink
et al., issued September 11, 1990; U.S. 5,415,807 Gosselink
et al., issued May 16, 1995; European Patent Application 0 219 048, published April 22, 1987
by Kud,
et al..
[0114] Further suitable soil release agents are described in U.S. 4,201,824, Violland
et al.; U.S. 4,240,918 Lagasse
et al.; U.S. 4,525,524 Tung
et al.; U.S. 4,579,681, Ruppert
et al.; U.S. 4,240,918; U.S. 4,787,989; U.S. 4,525,524; EP 279,134 A, 1988, to Rhone-Poulenc
Chemie; EP 457,205 A to BASF (1991); and DE 2,335,044 to Unilever N. V., 1974 all
incorporated herein by reference.
[0115] Commercially available soil release agents include the METOLOSE SM100, METOLOSE SM200
manufactured by Shin-etsu Kagaku Kogyo K.K., SOKALAN type of material, e.g., SOKALAN
HP-22, available from BASF (Germany), ZELCON 5126 (from Dupont) and MILEASE T (from
ICI).
Scum Dispersant
[0116] In the present invention, the premix can be combined with an optional scum dispersant,
other than the soil release agent, and heated to a temperature at or above the melting
point(s) of the components.
The preferred scum dispersants herein are formed by highly ethoxylating hydrophobic
materials. The hydrophobic material can be a fatty alcohol, fatty acid, fatty amine,
fatty acid amide, amine oxide, quaternary ammonium compound, or the hydrophobic moieties
used to form soil release polymers. The preferred scum dispersants are highly ethoxylated,
e.g., more than 17, preferably more than 25, more preferably more than 40, moles of
ethylene oxide per molecule on the average, with the polyethylene oxide portion being
from 76% to 97%, preferably from 81% to 94%, of the total molecular weight. The level
of scum dispersant is sufficient to keep the scum at an acceptable, preferably unnoticeable
to the consumer, level under the conditions of use, but not enough to adversely affect
softening. For some purposes it is desirable that the scum is nonexistent. Depending
on the amount of anionic or nonionic detergent, etc., used in the wash cycle of a
typical laundering process, the efficiency of the rinsing steps prior to the introduction
of the compositions herein, and the water hardness, the amount of anionic or nonionic
detergent surfactant and detergency builder (especially phosphates and zeolites) entrapped
in the fabric (laundry) will vary. Normally, the minimum amount of scum dispersant
should be used to avoid adversely affecting softening properties. Typically scum dispersion
requires at least 2%, preferably at least 4% (at least 6% and preferably at least
10% for maximum scum avoidance) based upon the level of softener active. However,
at levels of 10% (relative to the softener material) or more, one risks loss of softening
efficacy of the product especially when the fabrics contain high proportions of nonionic
surfactant which has been absorbed during the washing operation.
Preferred scum dispersants are: Brij 700®; Varonic U-250®; Genapol T-500®, Genapol
T-800®; Plurafac A-79®; and Neodol 25-50®.
Bactericides
[0117] Examples of bactericides used in the compositions of this invention include glutaraldehyde,
formaldehyde, 2-bromo-2-nitro-propane-1,3-diol sold by Inolex Chemicals, located in
Philadelphia, Pennsylvania, under the trade name Bronopol®, and a mixture of 5-chloro-2-methyl-4-isothiazoline-3-one
and 2-methyl-4-isothiazoline-3-one sold by Rohm and Haas Company under the trade name
Kathon 1 to 1,000 ppm by weight of the agent.
Perfume
[0118] The present invention can contain any detergent compatible perfume. Suitable perfumes
are disclosed in U.S. Pat. 5,500,138, said patent being incorporated herein by reference.
As used herein, perfume includes fragrant substance or mixture of substances including
natural (i.e., obtained by extraction of flowers, herbs, leaves, roots, barks, wood,
blossoms or plants), artificial (i.e., a mixture of different nature oils or oil constituents)
and synthetic (i.e., synthetically produced) odoriferous substances. Such materials
are often accompanied 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.
Examples of perfume ingredients useful in the perfumes of the present invention compositions
include, but are not limited to, hexyl cinnamic aldehyde; amyl cinnamic aldehyde;
amyl salicylate; hexyl salicylate; terpineol; 3,7-dimethyl-cis-2,6-octadien-1-ol;
2,6-dimethyl-2-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-octen-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; methyl-2-(2-pentyl-3-oxo-cyclopentyl)
acetate; beta-naphthol methylether; methyl-beta-naphthylketone; coumarin; decylaldehyde;
benzaldehyde; 4-tert-butylcyclohexyl acetate; alpha,alpha-dimethylphenethyl acetate;
methylphenylcarbinyl acetate; Schiff's base of 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde
and methyl anthranilate; cyclic ethyleneglycol diester of tridecandioic acid; 3,7-dimethyl-2,6-octadiene-1-nitrile;
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-ol; caryophyllene alcohol;
cedryl acetate; para-tert-butylcyclohexyl acetate; patchouli; olibanum resinoid; labdanum;
vetivert; copaiba balsam; fir balsam; and condensation products of: hydroxycitronellal
and methyl anthranilate; hydroxycitronellal and indol; phenyl acetaldehyde and indol;
4-(4-hydroxy-4-methyl pentyl)-3-cyclohexene-1-carboxaldehyde and methyl anthranilate.
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;
geranonitrile; citronellonitrile; cedryl acetal; 3-isocamphylcyclohexanol; cedryl
methylether; isolongifolanone; aubepine nitrile; 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.
The perfumes useful in the present invention compositions are substantially free of
halogenated materials and nitromusks.
Suitable solvents, diluents or carriers for perfumes ingredients mentioned above are
for examples, ethanol, isopropanol, diethylene glycol, monoethyl ether, dipropylene
glycol, diethyl phthalate, triethyl citrate, etc. The amount of such solvents, diluents
or carriers incorporated in the perfumes is preferably kept to the minimum needed
to provide a homogeneous perfume solution. Perfume can be present at a level of from
0% to 10%, preferably from 0.1% to 5%, and more preferably from 0.2% to 3%, by weight
of the finished composition. Fabric softener compositions of the present invention
provide improved fabric perfume deposition.
Chelating Agents
[0119] The compositions and processes herein can optionally employ one or more copper and/or
nickel chelating agents ("chelators"). Such water-soluble chelating agents can be
selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted
aromatic chelating agents and mixtures thereof, all as hereinafter defined. The whiteness
and/or brightness of fabrics are substantially improved or restored by such chelating
agents and the stability of the materials in the compositions are improved. Without
intending to be bound by theory, it is believed that the benefit of these materials
is due in part to their exceptional ability to remove iron and manganese ions from
washing solutions by formation of soluble chelates.
[0120] Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates,
N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates,
triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines,
alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
[0121] Amino phosphonates are also suitable for use as chelating agents in the compositions
of the invention when at lease low levels of total phosphorus are permitted in detergent
compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST.
Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more
than about 6 carbon atoms.
[0122] 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.
[0123] A preferred biodegradable chelator for use herein is ethylenediamine disuccinate
("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November
3, 1987, to Hartman and Perkins.
[0124] The compositions herein may also contain water-soluble methyl glycine diacetic acid
(MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble
builders such as zeolites, layered silicates and the like.
[0125] Preferred chelating agents include DETMP, DETPA, NTA, EDDS and mixtures thereof.
[0126] If utilized, these chelating agents will generally comprise from about 0.1% to about
15% by weight of the fabric care compositions herein. More preferably, if utilized,
the chelating agents will comprise from about 0.1% to about 3.0% by weight of such
compositions.
Crystal growth inhibitor component
[0127] The compositions of the present invention can further contain a crystal growth inhibitor
component, preferably an organodiphosphonic acid component, incorporated preferably
at a level of from 0.01% to 5%, more preferably from 0.1% to 2% by weight of the compositions.
[0128] By organo diphosphonic acid it is meant herein an organo diphosphonic acid which
does not contain nitrogen as part of its chemical structure. This definition therefore
excludes the organo aminophosphonates, which however may be included in compositions
of the invention as heavy metal ion sequestrant components.
[0129] The organo diphosphonic acid is preferably a C
1-C
4 diphosphonic acid, more preferably a C
2 diphosphonic acid, such as ethylene diphosphonic acid, or most preferably ethane
1-hydroxy-1,1-diphosphonic acid (HEDP) and may be present in partially or fully ionized
form, particularly as a salt or complex.
[0130] Still useful herein as crystal growth inhibitor are the organic monophosphonic acid
Organo monophosphonic acid or one of its salts or complexes is also suitable for use
herein as a CGI.
[0131] By organo monophosphonic acid it is meant herein an organo monophosphonic acid which
does not contain nitrogen as part of its chemical structure. This definition therefore
excludes the organo aminophosphonates, which however may be included in compositions
of the invention as heavy metal ion sequestrants.
[0132] The organo monophosphonic acid component may be present in its acid form or in the
form of one of its salts or complexes with a suitable counter cation. Preferably any
salts/complexes are water soluble, with the alkali metal and alkaline earth metal
salts/complexes being especially preferred.
[0133] A preferred organo monophosphonic acid is 2-phosphonobutane-1,2,4-tricarboxylic acid
commercially available from Bayer under the tradename of Bayhibit.
Enzyme
[0134] The compositions and processes herein can optionally employ one or more enzymes such
as lipases, proteases, cellulase, amylases and peroxidases. A preferred enzyme for
use herein is a cellulase enzyme. Indeed, this type of enzyme will further provide
a color care benefit to the treated fabric. Cellulases usable herein include both
bacterial and fungal types, preferably having a pH optimum between 5 and 9.5. U.S.
4,435,307 discloses suitable fungal cellulases from
Humicola insolens or
Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus
Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk,
Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
CAREZYME® and CELLUZYME® (Novo) are especially useful. Other suitable cellulases are
also disclosed in WO 91/17243 to Novo, WO 96/34092, WO 96/34945 and EP-A-0,739,982.
In practical terms for current commercial preparations, typical amounts are up to
5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent
composition. Stated otherwise, the compositions herein will typically comprise from
0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation. In
the particular cases where activity of the enzyme preparation can be defined otherwise
such as with cellulases, corresponding activity units are preferred (e.g. CEVU or
cellulase Equivalent Viscosity Units). For instance, the compositions of the present
invention can contain cellulase enzymes at a level equivalent to an activity from
0.5 to 1000 CEVU/gram of composition. Cellulase enzyme preparations used for the purpose
of formulating the compositions of this invention typically have an activity comprised
between 1,000 and 10,000 CEVU/gram in liquid form, around 1,000 CEVU/gram in solid
form.
[0135] Other preferred optional ingredients include enzyme stabilisers, polymeric soil release
agents, materials effective for inhibiting the transfer of dyes from one fabric to
another during the cleaning process (i.e., dye transfer inhibiting agents), polymeric
dispersing agents, suds suppressors, optical brighteners or other brightening or whitening
agents, chelating agents, fabric softening clay, anti-static agents, other active
ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for
liquid formulations and solid fillers for bar compositions.
[0136] Liquid detergent compositions can contain water and other solvents as carriers. Low
molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol,
and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant,
but polyols such as those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy
groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol) can
also be used. The compositions may contain from 5% to 90%, typically 10% to 50% of
such carriers.
[0137] Granular detergents can be prepared, for example, by spray-drying (final product
density 520 g/l) or agglomerating (final product density above 600 g/l) the Base Granule.
The remaining dry ingredients can then be admixed in granular or powder form with
the Base Granule, for example in a rotary mixing drum, and the liquid ingredients
(e.g., nonionic surfactant and perfume) can be sprayed on.
[0138] The detergent compositions herein will preferably be formulated such that, during
use in aqueous cleaning operations, the wash water will have a pH of between 6.5 and
11, preferably between 7.5 and 10.5. Laundry products are typically at pH 9-11. Techniques
for controlling pH at recommended usage levels include the use of buffers, alkalis,
acids, etc., and are well-known to those skilled in the art.
Method of use
[0139] Also provided herein is a method for providing a delayed release of an active ketone
or aldehyde which comprises the step of contacting the surface to be treated with
a a compound or composition of the invention, and thereafter contacting the treated
surface with a material, preferably an aqueous medium like moisture or any other means
susceptible of releasing the perfume from the amine reaction product.
[0140] 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 ketone
and/or aldehyde such as that with litter like animal litter. Preferably, the surface
is selected from a fabric, a tile, a ceramic; more preferably is a fabric.
[0141] By "delayed release" is meant release of the active component (e.g perfume) over
a longer period of time than by the use of the active (e.g., perfume) itself.
Abbreviations used in the following laundry and cleaning composition Examples
[0142] In the laundry and cleaning compositions, the abbreviated component identifications
have the following meanings:
[0143] In the detergent compositions, the abbreviated component identifications have the
following meanings:
LAS |
Sodium linear C11-13 alkyl benzene sulfonate |
TAS |
Sodium tallow alkyl sulfate |
CxyAS |
Sodium C1x-C1y alkyl sulfate |
C46SAS |
Sodium C14-C16 secondary (2,3) alkyl sulfate |
CxyEzS |
Sodium C1x-C1y alkyl sulfate condensed with z moles of ethylene oxide |
CxyEz |
C1x-C1y predominantly linear primary alcohol condensed with an average of z moles of ethylene
oxide |
QAS |
R2.N+(CH3)2(C2H4OH) with R2 = C12 - C14 |
QAS 1 |
R2.N+(CH3)2(C2H4OH) with R2 = C8 - C11 |
APA |
C8 - C10 amido propyl dimethyl amine |
Soap |
Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut
fatty acids |
STS |
Sodium toluene sulphonate |
CFAA |
C12-C14 (coco) alkyl N-methyl glucamide |
TFAA |
C16-C18 alkyl N-methyl glucamide |
TPKFA |
C12-C14 topped whole cut fatty acids |
STPP |
Anhydrous sodium tripolyphosphate |
TSPP |
Tetrasodium pyrophosphate |
Zeolite A |
Hydrated sodium aluminosilicate of formula Na12(A1O2SiO2)12.27H2O having a primary particle size in the range from 0.1 to 10 micrometers (weight expressed
on an anhydrous basis) |
NaSKS-6 |
Crystalline layered silicate of formula δ-Na2Si2O5 |
Citric acid |
Anhydrous citric acid |
Borate |
Sodium borate |
Carbonate |
Anydrous sodium carbonate with a particle size between 200µm and 900µm |
Bicarbonate |
Anhydrous sodium bicarbonate with a particle size distribution between 400µm and 1200µm |
Silicate |
Amorphous sodium silicate (SiO2:Na2O = 2.0:1) |
Sulfate |
Anhydrous sodium sulfate |
Mg sulfate |
Anhydrous magnesium sulfate |
Citrate |
Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between
425µm and 850µm |
MA/AA |
Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 70,000 |
MA/AA(1) |
Copolymer of 4:6 maleic/acrylic acid, average molecular weight about 10,000 |
AA |
Sodium polyacrylate polymer of average molecular weight 4,500 |
CMC |
Sodium carboxymethyl cellulose |
Cellulose ether |
Methyl cellulose ether with a degree of polymerization of 650 available from Shin
Etsu Chemicals |
Protease |
Proteolytic enzyme, having 3.3% by weight of active enzyme, sold by NOVO Industries
A/S under the tradename Savinase |
Protease I |
Proteolytic enzyme, having 4% by weight of active enzyme, as described in WO 95/10591,
sold by Genencor Int. Inc. |
Alcalase |
Proteolytic enzyme, having 5.3% by weight of active enzyme, sold by NOVO Industries
A/S |
Cellulase |
Cellulytic enzyme, having 0.23% by weight of active enzyme, sold by NOVO Industries
A/S under the tradename Carezyme |
Amylase |
Amylolytic enzyme, having 1.6% by weight of active enzyme, sold by NOVO Industries
A/S under the tradename Termamyl 120T |
Lipase |
Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries
A/S under the tradename Lipolase |
Lipase (1) |
Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries
A/S under the tradename Lipolase Ultra |
Endolase |
Endoglucanase enzyme, having 1.5% by weight of active enzyme, sold by NOVO Industries
A/S |
PB4 |
Sodium perborate tetrahydrate of nominal formula NaBO2.3H2O.H2O2 |
PB1 |
Anhydrous sodium perborate bleach of nominal formula NaBO2.H2O2 |
Percarbonate |
Sodium percarbonate of nominal formula 2Na2CO3.3H2O2 |
NOBS |
Nonanoyloxybenzene sulfonate in the form of the sodium salt |
NAC-OBS |
(6-nonamidocaproyl) oxybenzene sulfonate |
TAED |
Tetraacetylethylenediamine |
DTPA |
Diethylene triamine pentaacetic acid |
DTPMP |
Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the
Tradename Dequest 2060 |
EDDS |
Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer in the form of its sodium salt. |
Photoactivated bleach (1) |
Sulfonated zinc phthlocyanine encapsulated in dextrin soluble polymer |
Photoactivated bleach (2) |
Sulfonated alumino phthlocyanine encapsulated in dextrin soluble polymer |
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 |
PEGx |
Polyethylene glycol, with a molecular weight of x (typically 4,000) |
PEO |
Polyethylene oxide, with an average molecular weight of 50,000 |
TEPAE |
Tetraethylenepentaamine ethoxylate |
PVI |
Polyvinyl imidosole, with an average molecular weight of 20,000 |
PVP |
Polyvinylpyrolidone polymer, with an average molecular weight of 60,000 |
PVNO |
Polyvinylpyridine N-oxide polymer, with an average molecular weight of 50,000 |
PVPVI |
Copolymer of polyvinylpyrolidone and vinylimidazole, with an average molecular weight
of 20,000 |
QEA |
bis((C2H5O)(C2H4O)n)(CH3) -N+-C6H12-N+-(CH3) bis((C2H5O)-(C2H4O))n, wherein n = from 20 to 30 |
SRP 1 |
Anionically end capped poly esters |
SRP 2 |
Diethoxylated poly (1, 2 propylene terephtalate) short block polymer |
PEI |
Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation
degree of 7 ethyleneoxy residues per nitrogen |
Silicone antifoam |
Polydimethylsiloxane foam controller with siloxaneoxyalkylene copolymer as dispersing
agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1 |
Opacifier |
Water based monostyrene latex mixture, sold by BASF Aktiengesellschaft under the tradename
Lytron 621 |
Wax |
Paraffin wax |
PA30 |
Polyacrylic acid of average molecular weight of between about 4,500 - 8,000. |
480N |
Random copolymer of 7:3 acrylate/methacrylate, average molecular weight about 3,500. |
Polygel/carbopol |
High molecular weight crosslinked polyacrylates. |
Metasilicate |
Sodium metasilicate (SiO2:Na2O ratio = 1.0). |
Nonionic |
C13-C15 mixed ethoxylated/propoxylated fatty alcohol with an average degree of ethoxylation
of 3.8 and an average degree of propoxylation of 4.5. |
Neodol 45-13 |
C14-C15 linear primary alcohol ethoxylate, sold by Shell Chemical CO. |
MnTACN |
Manganese 1 ,4,7-trimethyl-1 ,4,7-triazacyclononane. |
PAAC |
Pentaamine acetate cobalt(lll) salt. |
Paraffin |
Paraffin oil sold under the tradename Winog 70 by Wintershall. |
NaBz |
Sodium benzoate. |
BzP |
Benzoyl Peroxide. |
SCS |
Sodium cumene sulphonate. |
BTA |
Benzotriazole. |
pH |
Measured as a 1% solution in distilled water at 20°C. |
ARP1 |
Amine reaction product of 1,4-bis-(3-aminopropyl)-piperazine with α-Damascone as made
from Synthesis example I |
ARP2 |
Amine reaction product of N,N'bis(aminopropyl)1,3-propanediamine with δ-Damascone
as made from Synthesis example II |
ARP3 |
Amine reaction product of polyvinylamine MW1200 with α-Damascone as made from Synthesis
example III |
[0144] The following are synthesis examples of compounds as defined in the present invention:
I-Synthesis of 1,4-bis-(3-aminopropyl)-piperazine with α-Damascone
[0145] In order to substitute both primary amine groups with a perfume, 2eq of perfume were
used for 1eq of amino functional polymer. To an ice cooled stirred solution of 1mmol
of α-Damascone in 6 mL EtOH and molecular sieves (4A, 20 g), 0.5eq of 1,4-bis-(3-aminopropyl)-piperazine
was added via an addition funnel. The reaction mixture was stirred under nitrogen
atmosphere and protected from light. After the disappearance of the absorption peak
from the NMR spectrum of the free perfume raw material (from 3 to 16 hours), the mixture
was filtrated and the solvent was removed by vacuum distillation. The yield of β-aminoketone
formation is about 90%.
[0146] Similar results were obtained where the α-Damascone was replaced by Tripal, vertocitral,
bourgeonal, or citronellal. In these instances, Schiff-bases are formed.
II-Synthesis of N,N'-bis(3-aminopropyl)-1,3-propanediamine with δ-Damascone
[0147] To an ice cooled solution of 1 mmol of δ-Damascone in 30 mL EtOH and molecular sieves
(4Å, 5 g), 0.5eq of the N,N'-bis(3-aminopropyl)-1,3-propanediamine was added. The
reaction was stirred under nitrogen atmosphere and protected from light. After 1 day,
the molecular sieves and the solvent were removed by filtration and vacuum distillation
respectively. β-Aminoketone were obtained in a 85 to 90% yield.
[0148] Similar results were obtained where the δ-Damascone was replaced by Tripal, vertocitral,
bourgeonal, or citronellal. In these instances, Schiff-bases are formed.
III-Synthesis of Polyvinylamine of MW1200 with α-Damascone
[0149] The following ingredients were mixed together : 0.6g of Sodium sulfate with 0.3g
of polyvinylamine MW 1200 in a 10% aqueous solution and 0.3g α-Damascone. The reaction
was completed after 18 days at room temperature in the dark.
[0150] Similar results were obtained where the α-Damascone was replaced by Tripal, or citral.
In these instances, Schiff-bases are formed.
[0151] In the following formulation examples all levels are quoted as % by weight of the
composition unless otherwise stated, and incorporation of the amine reaction product
so called herein after "ARP" in the fully formulated composition is carried out by
dry addition (d), spray on (s), encapsulation in starch (es) as described in GB-1,464,616
or cyclodextrin (ec) or as is in the composition as defined herein before. The term
in bracket for the ARP in the formulation examples refers to the means of incorporation.
When none is provided, the incorporation is made as it is.
Example 1
[0152] The following high density granular laundry detergent compositions A to F were prepared
in accord with the invention:
|
A |
B |
C |
D |
E |
F |
LAS |
8.0 |
8.0 |
8.0 |
2.0 |
6.0 |
6.0 |
TAS |
- |
0.5 |
- |
0.5 |
1.0 |
0.1 |
C46(S)AS |
2.0 |
2.5 |
- |
- |
- |
- |
C25AS |
- |
- |
- |
7.0 |
4.5 |
5.5 |
C68AS |
2.0 |
5.0 |
7.0 |
- |
- |
- |
C25E5 |
- |
- |
3.4 |
10.0 |
4.6 |
4.6 |
C25E7 |
3.4 |
3.4 |
1.0 |
- |
- |
- |
C25E3S |
- |
- |
- |
2.0 |
5.0 |
4.5 |
QAS |
- |
0.8 |
- |
- |
- |
- |
QAS (I) |
- |
- |
- |
0.8 |
0.5 |
1.0 |
Zeolite A |
18.1 |
18.0 |
14.1 |
18.1 |
20.0 |
18.1 |
Citric acid |
- |
- |
- |
2.5 |
- |
2.5 |
Carbonate |
13.0 |
13.0 |
27.0 |
10.0 |
10.0 |
13.0 |
SKS-6 |
- |
- |
- |
10.0 |
- |
10.0 |
Silicate |
1.4 |
1.4 |
3.0 |
0.3 |
0.5 |
0.3 |
Citrate |
- |
1.0 |
- |
3.0 |
- |
- |
Sulfate |
26.1 |
26.1 |
26.1 |
6.0 |
- |
- |
Mg sulfate |
0.3 |
- |
- |
0.2 |
- |
0.2 |
MA/AA |
0.3 |
0.3 |
0.3 |
4.0 |
1.0 |
1.0 |
CMC |
0.2 |
0.2 |
0.2 |
0.2 |
0.4 |
0.4 |
PB4 |
9.0 |
9.0 |
5.0 |
- |
- |
- |
Percarbonate |
- |
- |
- |
- |
18.0 |
18.0 |
TAED |
1.5 |
0.4 |
1.5 |
- |
3.9 |
4.2 |
NAC-OBS |
- |
2.0 |
1.0 |
- |
- |
- |
DTPMP |
0.25 |
0.25 |
0.25 |
0.25 |
- |
- |
SRP 2 |
- |
- |
- |
0.2 |
- |
0.2 |
EDDS |
- |
0.25 |
0.4 |
- |
0.5 |
0.5 |
CFAA |
- |
1.0 |
- |
2.0 |
- |
- |
HEDP |
0.3 |
0.3 |
0.3 |
0.3 |
0.4 |
0.4 |
QEA |
- |
- |
- |
0.2 |
- |
0.5 |
Protease I |
- |
- |
0.26 |
1.0 |
- |
- |
Protease |
0.26 |
0.26 |
- |
- |
1.5 |
1.0 |
Cellulase |
0.3 |
- |
- |
0.3 |
0.3 |
0.3 |
Amylase |
0.1 |
0.1 |
0.1 |
0.4 |
0.5 |
0.5 |
Lipase (1) |
0.3 |
- |
- |
0.5 |
0.5 |
0.5 |
Photoactivated bleach (ppm) |
15 ppm |
15 ppm |
15ppm |
- |
20 ppm |
20 ppm |
PVNO/PVPVI |
- |
- |
- |
0.1 |
- |
- |
Brightener 1 |
0.09 |
0.09 |
0.09 |
- |
0.09 |
0.09 |
Perfume spray on |
0.3 |
0.3 |
0.3 |
0.4 |
0.4 |
0.4 |
ARP 1 |
0.03(d) |
0.1(es) |
- |
- |
0.1(d) |
0.05(ec) |
ARP 2 |
- |
- |
0.04(s) |
0.04(ec) |
0.02(s) |
- |
Silicone antifoam |
0.5 |
0.5 |
0.5 |
- |
0.3 |
0.3 |
Misc/minors to 100% |
|
|
|
|
|
|
Density in g/litre |
850 |
850 |
850 |
850 |
850 |
850 |
Example 2
[0153] The following granular laundry detergent compositions G to L of particular utility
under European machine wash conditions were prepared in accord with the invention:
|
G |
H |
I |
J |
K |
L |
LAS |
5.5 |
7.5 |
5.0 |
5.0 |
6.0 |
7.0 |
TAS |
1.25 |
1.86 |
- |
0.8 |
0.4 |
0.3 |
C24AS/C25AS |
- |
2.24 |
5.0 |
5.0 |
5.0 |
2.2 |
C25E3S |
- |
0.76 |
1.0 |
1.5 |
3.0 |
1.0 |
C45E7 |
3.25 |
- |
- |
- |
- |
3.0 |
TFAA |
- |
- |
2.0 |
- |
- |
- |
C25E5 |
- |
5.5 |
- |
- |
- |
- |
QAS |
0.8 |
- |
- |
- |
- |
- |
QAS II |
- |
0.7 |
1.0 |
0.5 |
1.0 |
0.7 |
STPP |
19.7 |
- |
- |
- |
- |
- |
Zeolite A |
- |
19.5 |
25.0 |
19.5 |
20.0 |
17.0 |
NaSKS-6/citric acid (79:21) |
- |
10.6 |
- |
10.6 |
- |
- |
NaSKS-6 |
- |
- |
9.0 |
- |
10.0 |
10.0 |
Carbonate |
6.1 |
21.4 |
9.0 |
10.0 |
10.0 |
18.0 |
Bicarbonate |
- |
2.0 |
7.0 |
5.0 |
- |
2.0 |
Silicate |
6.8 |
- |
- |
0.3 |
0.5 |
- |
Citrate |
- |
- |
4.0 |
4.0 |
- |
- |
Sulfate |
39.8 |
- |
- |
5.0 |
- |
12.0 |
Mg sulfate |
- |
- |
0.1 |
0.2 |
0.2 |
- |
MA/AA |
0.5 |
1.6 |
3.0 |
4.0 |
1.0 |
1.0 |
CMC |
0.2 |
0.4 |
1.0 |
1.0 |
0.4 |
0.4 |
PB4 |
5.0 |
12.7 |
- |
- |
- |
- |
Percarbonate |
- |
- |
- |
- |
18.0 |
15.0 |
TAED |
0.5 |
3.1 |
- |
- |
5.0 |
- |
NAC-OBS |
1.0 |
3.5 |
- |
- |
- |
2.5 |
DTPMP |
0.25 |
0.2 |
0.3 |
0.4 |
- |
0.2 |
HEDP |
- |
0.3 |
- |
0.3 |
0.3 |
0.3 |
QEA |
- |
- |
1.0 |
1.0 |
1.0 |
- |
Protease I |
- |
- |
- |
0.5 |
1.2 |
- |
Protease |
0.26 |
0.85 |
0.9 |
1.0 |
- |
0.7 |
Lipase (1) |
0.15 |
0.15 |
0.3 |
0.3 |
0.3 |
0.2 |
Cellulase |
0.28 |
0.28 |
0.2 |
0.2 |
0.3 |
0.3 |
Amylase |
0.1 |
0.1 |
0.4 |
0.4 |
0.6 |
0.2 |
PVNO/PVPVI |
- |
- |
0.2 |
0.2 |
- |
- |
PVP |
0.9 |
1.3 |
- |
- |
- |
0.9 |
SRP 1 |
- |
- |
0.2 |
0.2 |
0.2 |
- |
Photoactivated bleach (1) in ppm |
15 |
27 |
- |
- |
20 |
20 |
Photoactivated bleach (2) in ppm |
15 |
- |
- |
- |
- |
- |
Brightener 1 |
0.08 |
0.19 |
- |
- |
0.09 |
0.15 |
Brightener 2 |
- |
0.04 |
- |
- |
- |
- |
Perfume |
0.3 |
0.3 |
0.4 |
0.3 |
0.4 |
0.3 |
ARP1 |
0.1(d) 0.1(es) |
1.0(d) |
- |
- |
- |
0.1(es) |
ARP2 |
- |
- |
0.04(s) |
0.02(ec) |
0.04(d) |
0.02(es) |
Silicone antifoam |
0.5 |
2.4 |
0.3 |
0.5 |
0.3 |
2.0 |
Minors/misc to 100% |
|
|
|
|
|
|
Density in g/litre |
750 |
750 |
750 |
750 |
750 |
750 |
Example 3
[0154] The following detergent formulations of particular utility under European machine
wash conditions were prepared in accord with the invention.
|
M |
N |
O |
P |
Blown powder |
|
|
|
|
LAS |
6.0 |
5.0 |
11.0 |
6.0 |
TAS |
2.0 |
- |
- |
2.0 |
Zeolite A |
24.0 |
- |
- |
20.0 |
STPP |
- |
27.0 |
24.0 |
- |
Sulfate |
4.0 |
6.0 |
13.0 |
- |
MA/AA |
1.0 |
4.0 |
6.0 |
2.0 |
Silicate |
1.0 |
7.0 |
3.0 |
3.0 |
CMC |
1.0 |
1.0 |
0.5 |
0.6 |
Brightener 1 |
0.2 |
0.2 |
0.2 |
0.2 |
Silicone antifoam |
1.0 |
1.0 |
1.0 |
0.3 |
DTPMP |
0.4 |
0.4 |
0.2 |
0.4 |
Spray on |
|
|
|
|
Brightener |
0.02 |
- |
- |
0.02 |
C45E7 |
- |
- |
- |
5.0 |
C45E2 |
2.5 |
2.5 |
2.0 |
- |
C45E3 |
2.6 |
2.5 |
2.0 |
- |
Perfume |
0.5 |
0.3 |
0.5 |
0.2 |
Silicone antifoam |
0.3 |
0.3 |
0.3 |
- |
Dry additives |
|
|
|
|
QEA |
- |
- |
- |
1.0 |
EDDS |
0.3 |
- |
- |
- |
Sulfate |
2.0 |
3.0 |
5.0 |
10.0 |
Carbonate |
6.0 |
13.0 |
15.0 |
14.0 |
Citric acid |
2.5 |
- |
- |
2.0 |
QAS II |
0.5 |
- |
- |
0.5 |
SKS-6 |
10.0 |
- |
- |
- |
Percarbonate |
18.5 |
- |
- |
- |
PB4 |
- |
18.0 |
10.0 |
21.5 |
TAED |
2.0 |
2.0 |
- |
2.0 |
NAC-OBS |
3.0 |
2.0 |
4.0 |
- |
Protease |
1.0 |
1.0 |
1.0 |
1.0 |
Lipase |
- |
0.4 |
- |
0.2 |
Lipase (1) |
0.4 |
- |
0.4 |
- |
Amylase |
0.2 |
0.2 |
0.2 |
0.4 |
Brightener 1 |
0.05 |
- |
- |
0.05 |
ARP3 |
0.03 |
0.1(es) |
1.0 |
0.1
0.05(ec) |
Misc/minor to 100% |
|
|
|
|
Example 4
[0155] The following granular detergent formulations were prepared in accord with the invention.
|
Q |
R |
S |
T |
U |
V |
Blown powder |
|
|
|
|
|
|
LAS |
23.0 |
8.0 |
7.0 |
9.0 |
7.0 |
7.0 |
TAS |
- |
- |
- |
- |
1.0 |
- |
C45AS |
6.0 |
6.0 |
5.0 |
8.0 |
- |
- |
C45AES |
- |
1.0 |
1.0 |
1.0 |
- |
- |
C45E35 |
- |
- |
- |
- |
2.0 |
4.0 |
Zeolite A |
10.0 |
18.0 |
14.0 |
12.0 |
10.0 |
10.0 |
MA/AA |
- |
0.5 |
- |
- |
- |
2.0 |
MA/AA(1) |
7.0 |
- |
- |
- |
- |
- |
AA |
- |
3.0 |
3.0 |
2.0 |
3.0 |
3.0 |
Sulfate |
5.0 |
6.3 |
14.3 |
11.0 |
15.0 |
19.3 |
Silicate |
10.0 |
1.0 |
1.0 |
1.0 |
1.0 |
1.0 |
Carbonate |
15.0 |
20.0 |
10.0 |
20.7 |
8.0 |
6.0 |
PEG 4000 |
0.4 |
1.5 |
1.5 |
1.0 |
1.0 |
1.0 |
DTPA |
- |
0.9 |
0.5 |
- |
- |
0.5 |
Brightener 2 |
0.3 |
0.2 |
0.3 |
- |
0.1 |
0.3 |
Spray on |
|
|
|
|
|
|
C45E7 |
- |
2.0 |
- |
- |
2.0 |
2.0 |
C25E9 |
3.0 |
- |
- |
- |
- |
- |
C23E9 |
- |
- |
1.5 |
2.0 |
- |
2.0 |
Perfume |
0.3 |
0.3 |
0.3 |
2.0 |
0.3 |
0.3 |
ARP5 |
0.1(s) |
0.05(s) |
- |
- |
- |
- |
Agglomerates |
|
|
|
|
|
|
C45AS |
- |
5.0 |
5.0 |
2.0 |
- |
5.0 |
LAS |
- |
2.0 |
2.0 |
- |
- |
2.0 |
Zeolite A |
- |
7.5 |
7.5 |
8.0 |
- |
7.5 |
Carbonate |
- |
4.0 |
4.0 |
5.0 |
- |
4.0 |
PEG 4000 |
- |
0.5 |
0.5 |
- |
- |
0.5 |
Misc (water etc) |
- |
2.0 |
2.0 |
2.0 |
- |
2.0 |
Dry additives |
|
|
|
|
|
|
QAS (I) |
- |
- |
- |
- |
1.0 |
- |
Citric acid |
- |
- |
- |
- |
2.0 |
- |
PB4 |
- |
- |
- |
- |
12.0 |
1.0 |
PB1 |
4.0 |
1.0 |
3.0 |
2.0 |
- |
- |
Percarbonate |
- |
- |
- |
- |
2.0 |
10.0 |
Carbonate |
- |
5.3 |
1.8 |
- |
4.0 |
4.0 |
NOBS |
4.0 |
- |
6.0 |
- |
- |
0.6 |
Methyl cellulose |
0.2 |
- |
- |
- |
- |
- |
SKS-6 |
8.0 |
- |
- |
- |
- |
- |
STS |
- |
- |
2.0 |
- |
1.0 |
- |
Cumene sulfonic acid |
- |
1.0 |
- |
- |
- |
2.0 |
Lipase |
0.2 |
- |
0.2 |
- |
0.2 |
0.4 |
Cellulase |
0.2 |
0.2 |
0.2 |
0.3 |
0.2 |
0.2 |
Amylase |
0.2 |
- |
0.1 |
- |
0.2 |
- |
Protease |
0.5 |
0.5 |
0.5 |
0.3 |
0.5 |
0.5 |
PVPVI |
- |
- |
- |
- |
0.5 |
0.1 |
PVP |
- |
- |
- |
- |
0.5 |
- |
PVNO |
- |
- |
0.5 |
0.3 |
- |
- |
QEA |
- |
- |
- |
- |
1.0 |
- |
SRP1 |
0.2 |
0.5 |
0.3 |
- |
0.2 |
- |
ARP2 |
0.1 |
0.2 |
0.04(d) |
0.02 |
0.01(es) |
0.02(es) |
Silicone antifoam |
0.2 |
0.4 |
0.2 |
0.4 |
0.1 |
- |
Mg sulfate |
- |
- |
0.2 |
- |
0.2 |
- |
Misc/minors to 100% |
|
|
|
|
|
|
Example 5
[0156] The following nil bleach-containing detergent formulations of particular use in the
washing of coloured clothing, according to the present invention were prepared:
|
W |
X |
Y |
Blown Powder |
|
|
|
Zeolite A |
15.0 |
15.0 |
- |
Sulfate |
0.0 |
5.0 |
- |
LAS |
3.0 |
3.0 |
- |
DTPMP |
0.4 |
0.5 |
- |
CMC |
0.4 |
0.4 |
- |
MA/AA |
4.0 |
4.0 |
- |
Agglomerates |
|
|
|
C45AS |
- |
- |
11.0 |
LAS |
6.0 |
5.0 |
- |
TAS |
3.0 |
2.0 |
- |
Silicate |
4.0 |
4.0 |
- |
Zeolite A |
10.0 |
15.0 |
13.0 |
CMC |
- |
- |
0.5 |
MA/AA |
- |
- |
2.0 |
Carbonate |
9.0 |
7.0 |
7.0 |
Spray On |
|
|
|
Perfume |
0.3 |
0.3 |
0.5 |
C45E7 |
4.0 |
4.0 |
4.0 |
C25E3 |
2.0 |
2.0 |
2.0 |
ARP2 |
0.04(s) |
- |
- |
Dry additives |
|
|
|
MA/AA |
- |
- |
3.0 |
NaSKS-6 |
- |
- |
12.0 |
Citrate |
10.0 |
- |
8.0 |
Bicarbonate |
7.0 m |
3.0 |
5.0 |
Carbonate |
8.0 |
5.0 |
7.0 |
PVPVI/PVNO |
0.5 |
0.5 |
0.5 |
Alcalase |
0.5 |
0.3 |
0.9 |
Lipase |
0.4 |
0.4 |
0.4 |
Amylase |
0.6 |
0.6 |
0.6 |
Cellulase |
0.6 |
0.6 |
0.6 |
ARP1 |
0.05 |
0.08 |
0.1(es) |
Silicone antifoam |
5.0 |
5.0 |
5.0 |
Dry additives |
|
|
|
Sulfate |
0.0 |
9.0 |
0.0 |
Misc/minors to 100% |
100.0 |
100.0 |
100.0 |
Density (g/litre) |
700 |
700 |
700 |
Example 6
[0157] The following granular detergent formulations were prepared in accord with the invention.
|
Z |
AA |
BB |
CC |
Base granule |
|
|
|
|
Zeolite A |
30.0 |
22.0 |
24.0 |
10.0 |
Sulfate |
10.0 |
5.0 |
10.0 |
7.0 |
MA/AA |
3.0 |
- |
- |
- |
AA |
- |
1.6 |
2.0 |
- |
MA/AA(1) |
- |
12.0 |
- |
6.0 |
LAS |
14.0 |
10.0 |
9.0 |
20.0 |
C45AS |
8.0 |
7.0 |
9.0 |
7.0 |
C45AES |
- |
1.0 |
1.0 |
- |
Silicate |
- |
1.0 |
0.5 |
10.0 |
Soap |
- |
2.0 |
- |
- |
Brightener 1 |
0.2 |
0.2 |
0.2 |
0.2 |
Carbonate |
6.0 |
9.0 |
10.0 |
10.0 |
PEG 4000 |
- |
1.0 |
1.5 |
- |
DTPA |
- |
0.4 |
- |
- |
Spray on |
|
|
|
|
C25E9 |
- |
- |
- |
5.0 |
C45E7 |
1.0 |
1.0 |
- |
- |
C23E9 |
- |
1.0 |
2.5 |
- |
Perfume |
0.2 |
0.3 |
0.3 |
- |
ARP2 |
0.04(s) |
- |
- |
- |
Dry additives |
|
|
|
|
Carbonate |
5.0 |
10.0 |
18.0 |
8.0 |
PVPVI/PVNO |
0.5 |
- |
0.3 |
- |
Protease |
1.0 |
1.0 |
1.0 |
0.5 |
Lipase |
0.4 |
- |
- |
0.4 |
Amylase |
0.1 |
- |
- |
0.1 |
Cellulase |
0.1 |
0.2 |
0.2 |
0.1 |
NOBS |
- |
4.0 |
- |
4.5 |
PB1 |
1.0 |
5.0 |
1.5 |
6.0 |
Sulfate |
4.0 |
5.0 |
- |
5.0 |
SRPI |
- |
0.4 |
- |
- |
ARP1 |
0.05 |
0.08 |
0.1(es) |
- |
ARP2 |
0.05 |
- |
- |
0.02(es) |
Sud supressor |
- |
0.5 |
0.5 |
- |
Example 7
[0158] The following granular detergent compositions were prepared in accord with the invention.
|
DD |
EE |
FF |
Blown powder |
|
|
|
Zeolite A |
20.0 |
- |
15.0 |
STPP |
- |
20.0 |
- |
Sulphate |
- |
- |
5.0 |
Carbonate |
- |
- |
5.0 |
TAS |
- |
- |
1.0 |
LAS |
6.0 |
6.0 |
6.0 |
C68AS |
2.0 |
2.0 |
- |
Silicate |
3.0 |
8.0 |
- |
MA/AA |
4.0 |
2.0 |
2.0 |
CMC |
0.6 |
0.6 |
0.2 |
Brightener 1 |
0.2 |
0.2 |
0.1 |
DTPMP |
0.4 |
0.4 |
0.1 |
STS |
- |
- |
1.0 |
Spray on |
|
|
|
C45E7 |
5.0 |
5.0 |
4.0 |
Silicone antifoam |
0.3 |
0.3 |
0.1 |
Perfume |
0.2 |
0.2 |
0.3 |
ARP1 |
0.1(s) |
0.05(s) |
0.08(s) |
Dry additives |
|
|
|
QEA |
- |
- |
1.0 |
Carbonate |
14.0 |
9.0 |
10.0 |
PB1 |
1.5 |
2.0 |
- |
PB4 |
18.5 |
13.0 |
13.0 |
TAED |
2.0 |
2.0 |
2.0 |
QAS (I) |
- |
- |
1.0 |
Photoactivated bleach |
15 ppm |
15 ppm |
15ppm |
SKS-6 |
- |
- |
3.0 |
Protease |
1.0 |
1.0 |
0.2 |
Lipase |
0.2 |
0.2 |
0.2 |
Amylase |
0.4 |
0.4 |
0.2 |
Cellulase |
0.1 |
0.1 |
0.2 |
Sulfate |
10.0 |
20.0 |
5.0 |
Misc/minors to 100% |
|
|
|
Density (g/litre) |
700 |
700 |
700 |
Example 8
[0159] The following detergent compositions, according to the present invention were prepared:
|
GG |
HH |
II |
Blown Powder |
|
|
|
Zeolite A |
15.0 |
15.0 |
15.0 |
Sulfate |
0.0 |
5.0 |
0.0 |
LAS |
3.0 |
3.0 |
3.0 |
QAS |
- |
1.5 |
1.5 |
DTPMP |
0.4 |
0.2 |
0.4 |
EDDS |
- |
0.4 |
0.2 |
CMC |
0.4 |
0.4 |
0.4 |
MA/AA |
4.0 |
2.0 |
2.0 |
Agglomerates |
|
|
|
LAS |
5.0 |
5.0 |
5.0 |
TAS |
2.0 |
2.0 |
1.0 |
Silicate |
3.0 |
3.0 |
4.0 |
Zeolite A |
8.0 |
8.0 |
8.0 |
Carbonate |
8.0 |
8.0 |
4.0 |
Spray On |
|
|
|
Perfume |
0.3 |
0.3 |
0.3 |
C45E7 |
2.0 |
2.0 |
2.0 |
C25E3 |
2.0 |
- |
- |
ARP2 |
0.02(s) |
- |
- |
Dry additives |
|
|
|
Citrate |
5.0 |
- |
2.0 |
Bicarbonate |
- |
3.0 |
- |
Carbonate |
8.0 |
15.0 |
10.0 |
TAED |
6.0 |
2.0 |
5.0 |
PB1 |
14.0 |
7.0 |
10.0 |
PEO |
- |
- |
0.2 |
ARP1 |
0.1 |
0.2 |
0.08(ec) |
Bentonite clay |
- |
- |
10.0 |
Protease |
1.0 |
1.0 |
1.0 |
Lipase |
0.4 |
0.4 |
0.4 |
Amylase |
0.6 |
0.6 |
0.6 |
Cellulase |
0.6 |
0.6 |
0.6 |
Silicone antifoam |
5.0 |
5.0 |
5.0 |
Dry additives |
|
|
|
Sodium sulfate |
0.0 |
3.0 |
0.0 |
Misc/minors to 100% |
100.0 |
100.0 |
100.0 |
Density (g/litre) |
850 |
850 |
850 |
Example 9
[0160] The following detergent formulations, according to the present invention were prepared:
|
JJ |
KK |
LL |
MM |
LAS |
18.0 |
14.0 |
24.0 |
20.0 |
QAS |
0.7 |
1.0 |
- |
0.7 |
TFAA |
- |
1.0 |
- |
- |
C23E56.5 |
- |
- |
1.0 |
- |
C45E7 |
- |
1.0 |
- |
- |
C45E3S |
1.0 |
2.5 |
1.0 |
- |
STPP |
32.0 |
18.0 |
30.0 |
22.0 |
Silicate |
9.0 |
5.0 |
9.0 |
8.0 |
Carbonate |
11.0 |
7.5 |
10.0 |
5.0 |
Bicarbonate |
- |
7.5 |
- |
- |
PB1 |
3.0 |
1.0 |
- |
- |
PB4 |
- |
1.0 |
- |
- |
NOBS |
2.0 |
1.0 |
- |
- |
DTPMP |
- |
1.0 |
- |
- |
DTPA |
0.5 |
- |
0.2 |
0.3 |
SRP 1 |
0.3 |
0.2 |
- |
0.1 |
MA/AA |
1.0 |
1.5 |
2.0 |
0.5 |
CMC |
0.8 |
0.4 |
0.4 |
0.2 |
PEI |
- |
- |
0.4 |
- |
Sodium sulfate |
20.0 |
10.0 |
20.0 |
30.0 |
Mg sulfate |
0.2 |
- |
0.4 |
0.9 |
Protease |
0.8 |
1.0 |
0.5 |
0.5 |
Amylase |
0.5 |
0.4 |
- |
0.25 |
Lipase |
0.2 |
- |
0.1 |
- |
Cellulase |
0.15 |
- |
- |
0.05 |
Photoactivated bleach (ppm) |
30ppm |
20ppm |
- |
10ppm |
ARP3 |
0.04(s) |
0.02(ec) |
0.1(s) |
0.01(es) |
Perfume spray on |
0.3 |
0.3 |
0.1 |
0.2 |
Brightener 1/2 |
0.05 |
0.2 |
0.08 |
0.1 |
Misc/minors to 100% |
|
|
|
|
Example 10
[0161] The following liquid detergent formulations were prepared in accord with the invention
(levels are given as parts per weight).
|
NN |
OO |
PP |
QQ |
RR |
LAS |
11.5 |
8.8 |
- |
3.9 |
- |
C25E2.5S |
- |
3.0 |
18.0 |
- |
16.0 |
C45E2.25S |
11.5 |
3.0 |
- |
15.7 |
- |
C23E9 |
- |
2.7 |
1.8 |
2.0 |
1.0 |
C23E7 |
3.2 |
- |
- |
- |
- |
CFAA |
- |
- |
5.2 |
- |
3.1 |
TPKFA |
1.6 |
- |
2.0 |
0.5 |
2.0 |
Citric acid (50%) |
6.5 |
1.2 |
2.5 |
4.4 |
2.5 |
Calcium formate |
0.1 |
0.06 |
0.1 |
- |
- |
Sodium formate |
0.5 |
0.06 |
0.1 |
0.05 |
0.05 |
Sodium cumene sulfonate |
4.0 |
1.0 |
3.0 |
1.18 |
- |
Borate |
0.6 |
- |
3.0 |
2.0 |
2.9 |
Sodium hydroxide |
5.8 |
2.0 |
3.5 |
3.7 |
2.7 |
Ethanol |
1.75 |
1.0 |
3.6 |
4.2 |
2.9 |
1, 2 propanediol |
3.3 |
2.0 |
8.0 |
7.9 |
5.3 |
Monoethanolamine |
3.0 |
1.5 |
1.3 |
2.5 |
0.8 |
TEPAE |
1.6 |
- |
1.3 |
1.2 |
1.2 |
Protease |
1.0 |
0.3 |
1.0 |
0.5 |
0.7 |
Lipase |
- |
- |
0.1 |
- |
- |
Cellulase |
- |
- |
0.1 |
0.2 |
0.05 |
Amylase |
- |
- |
- |
0.1 |
- |
SRP1 |
0.2 |
- |
0.1 |
- |
- |
DTPA |
- |
- |
0.3 |
- |
- |
PVNO |
- |
- |
0.3 |
- |
0.2 |
ARP1 |
0.3 |
- |
- |
0.1 |
- |
ARP2 |
- |
0.04 |
- |
- |
0.1 |
ARP3 |
- |
- |
0.3 |
- |
- |
Brightener 1 |
0.2 |
0.07 |
0.1 |
- |
- |
Silicone antifoam |
0.04 |
0.02 |
0.1 |
0.1 |
0.1 |
Water/minors |
|
|
|
|
|
Example 11
[0162] The following liquid detergent formulations were prepared in accord with the invention
(levels are given in parts per weight):
|
SS |
TT |
UU |
VV |
WW |
XX |
YY |
ZZ |
LAS |
10.0 |
13.0 |
9.0 |
- |
25.0 |
- |
- |
- |
C25AS |
4.0 |
1.0 |
2.0 |
10.0 |
- |
13.0 |
18.0 |
15.0 |
C25E3S |
1.0 |
- |
- |
3.0 |
- |
2.0 |
2.0 |
4.0 |
C25E7 |
6.0 |
8.0 |
13.0 |
2.5 |
- |
- |
4.0 |
4.0 |
TFAA |
- |
- |
- |
4.5 |
- |
6.0 |
8.0 |
8.0 |
APA |
- |
1.4 |
- |
- |
3.0 |
1.0 |
2.0 |
- |
TPKFA |
2.0 |
- |
13.0 |
7.0 |
- |
15.0 |
11.0 |
11.0 |
Citric acid |
2.0 |
3.0 |
1.0 |
1.5 |
1.0 |
1.0 |
1.0 |
1.0 |
Dodecenyl/tetradecenyl succinic acid |
12.0 |
10.0 |
- |
- |
15.0 |
- |
- |
- |
Rape seed fatty acid |
4.0 |
2.0 |
1.0 |
- |
1.0 |
- |
3.5 |
- |
Ethanol |
4.0 |
4.0 |
7.0 |
2.0 |
7.0 |
2.0 |
3.0 |
2.0 |
1,2 Propanediol |
4.0 |
4.0 |
2.0 |
7.0 |
6.0 |
8.0 |
10.0 |
13.0 |
Monoethanolamine |
- |
- |
- |
5.0 |
- |
- |
9.0 |
9.0 |
Triethanolamine |
- |
- |
8.0 |
- |
- |
- |
- |
- |
TEPAE |
0.5 |
- |
0.5 |
0.2 |
- |
- |
0.4 |
0.3 |
DTPMP |
1.0 |
1.0 |
0.5 |
1.0 |
2.0 |
1.2 |
1.0 |
- |
Protease |
0.5 |
0.5 |
0.4 |
0.25 |
- |
0.5 |
0.3 |
0.6 |
Alcalase |
- |
- |
- |
- |
1.5 |
- |
- |
- |
Lipase |
- |
0.10 |
- |
0.01 |
- |
- |
0.15 |
0.15 |
Amylase |
0.25 |
0.25 |
0.6 |
0.5 |
0.25 |
0.9 |
0.6 |
0.6 |
Cellulase |
- |
- |
- |
0.05 |
- |
- |
0.15 |
0.15 |
Endolase |
- |
- |
- |
0.10 |
- |
- |
0.07 |
- |
SRP2 |
0.3 |
- |
0.3 |
0.1 |
- |
- |
0.2 |
0.1 |
Boric acid |
0.1 |
0.2 |
1.0 |
2.0 |
1.0 |
1.5 |
2.5 |
2.5 |
Calcium chloride |
- |
0.02 |
- |
0.01 |
- |
- |
- |
- |
Bentonite clay |
- |
- |
- |
- |
4.0 |
4.0 |
- |
- |
Brightener 1 |
- |
0.4 |
- |
- |
0.1 |
0.2 |
0.3 |
- |
Sud supressor |
0.1 |
0.3 |
- |
0.1 |
0.4 |
- |
- |
- |
Opacifier |
0.5 |
0.4 |
- |
0.3 |
0.8 |
0.7 |
- |
- |
ARP1 |
0.3 |
- |
0.1 |
- |
0.05 |
- |
0.1 |
0.08 |
ARP2 |
- |
0.04 |
- |
0.02 |
- |
0.1 |
0.02 |
0.1 |
Water/minors |
|
|
|
|
|
|
|
|
NaOH up to pH |
8.0 |
8.0 |
7.6 |
7.7 |
8.0 |
7.5 |
8.0 |
8.2 |
Example 12
[0163] The following liquid detergent compositions were prepared in accord with the invention
(levels are given in parts per weight).
|
AB |
AC |
LAS |
27.6 |
18.9 |
C45AS |
13.8 |
5.9 |
C13E8 |
3.0 |
3.1 |
Oleic acid |
3.4 |
2.5 |
Citric acid |
5.4 |
5.4 |
Sodium hydroxide |
0.4 |
3.6 |
Calcium formate |
0.2 |
0.1 |
Sodium formate |
- |
0.5 |
Ethanol |
7.0 |
- |
Monoethanolamine |
16.5 |
8.0 |
1,2 propanediol |
5.9 |
5.5 |
Xylene sulfonic acid |
- |
2.4 |
TEPAE |
1.5 |
0.8 |
Protease |
1.5 |
0.6 |
PEG |
- |
0.7 |
Brightener 2 |
0.4 |
0.1 |
Perfume spray on |
0.5 |
0.3 |
ARP1 |
0.3 |
- |
ARP3 |
- |
0.04 |
Water/minors |
|
|
Example 13
[0164] The following laundry bar detergent compositions were prepared in accord with the
invention (levels are given in parts per weight).
|
AD |
AE |
AF |
AG |
AH |
AI |
AJ |
AK |
LAS |
- |
- |
19.0 |
15.0 |
21.0 |
6.75 |
8.8 |
- |
C28AS |
30.0 |
13.5 |
- |
- |
- |
15.75 |
11.2 |
22.5 |
Sodium laurate |
2.5 |
9.0 |
- |
- |
- |
- |
- |
- |
Zeolite A |
2.0 |
1.25 |
- |
- |
- |
1.25 |
1.25 |
1.25 |
Carbonate |
20.0 |
3.0 |
13.0 |
8.0 |
10.0 |
15.0 |
15.0 |
10.0 |
Calcium carbonate |
27.5 |
39.0 |
35.0 |
- |
- |
40.0 |
- |
40.0 |
Sulfate |
5.0 |
5.0 |
3.0 |
5.0 |
3.0 |
- |
- |
5.0 |
TSPP |
5.0 |
- |
- |
- |
- |
5.0 |
2.5 |
- |
STPP |
5.0 |
15.0 |
10.0 |
- |
- |
7.0 |
8.0 |
10.0 |
Bentonite clay |
- |
10.0 |
- |
- |
5.0 |
- |
- |
- |
DTPMP |
- |
0.7 |
0.6 |
- |
0.6 |
0.7 |
0.7 |
0.7 |
CMC |
- |
1.0 |
1.0 |
1.0 |
1.0 |
- |
- |
1.0 |
Talc |
- |
- |
10.0 |
15.0 |
10.0 |
- |
- |
- |
Silicate |
- |
- |
4.0 |
5.0 |
3.0 |
- |
- |
- |
PVNO |
0.02 |
0.03 |
- |
0.01 |
- |
0.02 |
- |
- |
MA/AA |
0.4 |
1.0 |
- |
- |
0.2 |
0.4 |
0.5 |
0.4 |
SRP1 |
0.3 |
0.3 |
0.3 |
0.3 |
0.3 |
0.3 |
0.3 |
0.3 |
Protease |
- |
0.12 |
- |
0.08 |
0.08 |
- |
- |
0.1 |
Lipase |
- |
0.1 |
- |
0.1 |
- |
- |
- |
- |
Amylase |
- |
- |
0.8 |
- |
- |
- |
0.1 |
- |
Cellulase |
- |
0.15 |
- |
- |
0.15 |
0.1 |
- |
- |
PEO |
- |
0.2 |
- |
0.2 |
0.3 |
- |
- |
0.3 |
Perfume |
1.0 |
0.5 |
0.3 |
0.2 |
0.4 |
- |
- |
0.4 |
Mg sulfate |
- |
- |
3.0 |
3.0 |
3.0 |
- |
- |
- |
ARP1 |
0.3 |
- |
- |
0.04 |
- |
0.5 |
- |
- |
ARP2 |
- |
0.04 |
- |
- |
0.1 |
- |
0.08 |
- |
ARP3 |
- |
- |
0.3 |
- |
- |
- |
- |
0.3 |
Brightener |
0.15 |
0.10 |
0.15 |
- |
- |
- |
- |
0.1 |
Photoactivated bleach (ppm) |
- |
15.0 |
15.0 |
15.0 |
15.0 |
- |
- |
15.0 |
Example 14
[0165] The following detergent additive compositions were prepared according to the present
invention :
|
AL |
AM |
AN |
LAS |
- |
5.0 |
5.0 |
STPP |
30.0 |
- |
20.0 |
Zeolite A |
- |
35.0 |
20.0 |
PB1 |
20.0 |
15.0 |
- |
TAED |
10.0 |
8.0 |
- |
ARP1 |
0.3 |
- |
0.1 |
ARP2 |
- |
0.04 |
0.02 |
Protease |
- |
0.3 |
0.3 |
Amylase |
- |
0.06 |
0.06 |
Minors, water and miscellaneous |
|
Up to 100% |
|
Example 15
[0166] The following compact high density (0.96Kg/l) dishwashing detergent compositions
were prepared according to the present invention :
|
AO |
AP |
AQ |
AR |
AS |
AT |
AU |
AV |
STPP |
- |
- |
54.3 |
51.4 |
51.4 |
- |
- |
50.9 |
Citrate |
35.0 |
17.0 |
- |
- |
- |
46.1 |
40.2 |
- |
Carbonate |
- |
17.5 |
14.0 |
14.0 |
14.0 |
- |
8.0 |
32.1 |
Bicarbonate |
- |
- |
- |
- |
- |
25.4 |
- |
- |
Silicate |
32.0 |
14.8 |
14.8 |
10.0 |
10.0 |
1.0 |
25.0 |
3.1 |
Metasilicate |
- |
2.5 |
- |
9.0 |
9.0 |
- |
- |
- |
PB1 |
1.9 |
9.7 |
7.8 |
7.8 |
7.8 |
- |
- |
- |
PB4 |
8.6 |
- |
- |
- |
- |
- |
- |
- |
Percarbonate |
- |
- |
- |
- |
- |
6.7 |
11.8 |
4.8 |
Nonionic |
1.5 |
2.0 |
1.5 |
1.7 |
1.5 |
2.6 |
1.9 |
5.3 |
TAED |
5.2 |
2.4 |
- |
- |
- |
2.2 |
- |
1.4 |
HEDP |
- |
1.0 |
- |
- |
- |
- |
- |
- |
DTPMP |
- |
0.6 |
- |
- |
- |
- |
- |
- |
MnTACN |
- |
- |
- |
- |
- |
- |
0.008 |
- |
PAAC |
- |
- |
0.008 |
0.01 |
0.007 |
- |
- |
- |
BzP |
- |
- |
- |
- |
1.4 |
- |
- |
- |
Paraffin |
0.5 |
0.5 |
0.5 |
0.5 |
0.5 |
0.6 |
- |
- |
ARP3 |
0.1 |
0.3 |
0.2 |
0.05 |
- |
- |
- |
0.8 |
ARP1 |
- |
- |
- |
- |
0.3 |
0.03 |
0.5 |
- |
Protease |
0.072 |
0.072 |
0.029 |
0.053 |
0.046 |
0.026 |
0.059 |
0.06 |
Amylase |
0.012 |
0.012 |
0.006 |
0.012 |
0.013 |
0.009 |
0.017 |
0.03 |
Lipase |
- |
0.001 |
- |
0.005 |
- |
- |
- |
- |
BTA |
0.3 |
0.3 |
0.3 |
0.3 |
0.3 |
- |
0.3 |
0.3 |
MA/AA |
- |
- |
- |
- |
- |
- |
4.2 |
- |
480N |
3.3 |
6.0 |
- |
- |
- |
- |
- |
0.9 |
Perfume |
0.2 |
0.2 |
0.2 |
0.2 |
0.2 |
0.2 |
0.1 |
0.1 |
Sulphate |
7.0 |
20.0 |
5.0 |
2.2 |
0.8 |
12.0 |
4.6 |
- |
pH |
10.8 |
11.0 |
10.8 |
11.3 |
11.3 |
9.6 |
10.8 |
10.9 |
Miscellaneous and water |
Up to 100% |
Example 16
[0167] The following granular dishwashing detergent compositions of bulk density 1.02Kg/L
were prepared according to the present invention :
|
AW |
AX |
AY |
AZ |
BA |
BC |
BD |
BE |
STPP |
30.0 |
30.0 |
33.0 |
34.2 |
29.6 |
31.1 |
26.6 |
17.6 |
Carbonate |
30.5 |
30.5 |
31.0 |
30.0 |
23.0 |
39.4 |
4.2 |
45.0 |
Silicate |
7.4 |
7.4 |
7.5 |
7.2 |
13.3 |
3.4 |
43.7 |
12.4 |
Metasilicate |
- |
- |
4.5 |
5.1 |
- |
- |
- |
- |
Percarbonate |
- |
- |
- |
- |
- |
4.0 |
- |
- |
PB1 |
4.4 |
4.2 |
4.5 |
4.5 |
- |
- |
- |
- |
NADCC |
- |
- |
- |
- |
2.0 |
- |
1.6 |
1.0 |
Nonionic |
1.2 |
1.0 |
0.7 |
0.8 |
1.9 |
0.7 |
0.6 |
0.3 |
TAED |
1.0 |
- |
- |
- |
- |
0.8 |
- |
- |
PAAC |
- |
0.004 |
0.004 |
0.004 |
- |
- |
- |
- |
BzP |
- |
- |
- |
1.4 |
- |
- |
- |
- |
Paraffin |
0.25 |
0.25 |
0.25 |
0.25 |
- |
- |
- |
- |
ARP3 |
0.3 |
0.1(ec) |
0.8 |
0.2(es) |
- |
- |
0.1(ec) |
0.2 |
ARP1 |
- |
- |
- |
- |
0.3 |
0.1(ec) |
0.1(ec) |
0.2 |
Protease |
0.036 |
0.015 |
0.03 |
0.028 |
- |
0.03 |
- |
- |
Amylase |
0.003 |
0.003 |
0.01 |
0.006 |
- |
0.01 |
- |
- |
Lipase |
0.005 |
- |
0.001 |
- |
- |
- |
- |
- |
BTA |
0.15 |
0.15 |
0.15 |
0.15 |
- |
- |
- |
- |
Perfume |
0.2 |
0.2 |
0.2 |
0.2 |
0.1 |
0.2 |
0.2 |
- |
Sulphate |
23.4 |
25.0 |
22.0 |
18.5 |
30.1 |
19.3 |
23.1 |
23.6 |
pH |
10.8 |
10.8 |
11.3 |
11.3 |
10.7 |
11.5 |
12.7 |
10.9 |
Miscellaneous and water |
Up to 100% |
Example 17
[0168] The following tablet detergent compositions were prepared according to the present
invention by compression of a granular dishwashing detergent composition at a pressure
of 13KN/cm
2 using a standard 12 head rotary press:
|
BF |
BJ |
BK |
BL |
BM |
BN |
STPP |
- |
48.8 |
49.2 |
38.0 |
- |
46.8 |
Citrate |
26.4 |
- |
- |
- |
31.1 |
- |
Carbonate |
- |
5.0 |
14.0 |
15.4 |
14.4 |
23.0 |
Silicate |
26.4 |
14.8 |
15.0 |
12.6 |
17.7 |
2.4 |
ARP1 |
0.3 |
- |
- |
- |
0.06 |
- |
ARP2 |
- |
0.04 |
- |
- |
- |
0.08 |
ARP3 |
- |
- |
0.3 |
0.1(ec) |
- |
- |
Protease |
0.058 |
0.072 |
0.041 |
0.033 |
0.052 |
0.013 |
Amylase |
0.01 |
0.03 |
0.012 |
0.007 |
0.016 |
0.002 |
Lipase |
0.005 |
- |
- |
- |
- |
- |
PB1 |
1.6 |
7.7 |
12.2 |
10.6 |
15.7 |
- |
PB4 |
6.9 |
- |
- |
- |
- |
14.4 |
Nonionic |
1.5 |
2.0 |
1.5 |
1.65 |
0.8 |
6.3 |
PAAC |
- |
- |
0.02 |
0.009 |
- |
- |
MnTACN |
- |
- |
- |
- |
0.007 |
- |
TAED |
4.3 |
2.5 |
- |
- |
1.3 |
1.8 |
HEDP |
0.7 |
- |
- |
0.7 |
- |
0.4 |
DTPMP |
0.65 |
- |
- |
- |
- |
- |
Paraffin |
0.4 |
0.5 |
0.5 |
0.55 |
- |
- |
BTA |
0.2 |
0.3 |
0.3 |
0.3 |
- |
- |
PA30 |
3.2 |
- |
- |
- |
- |
- |
MA/AA |
- |
- |
- |
- |
4.5 |
0.55 |
Perfume |
- |
- |
0.05 |
0.05 |
0.2 |
0.2 |
Sulphate |
24.0 |
13.0 |
2.3 |
- |
10.7 |
3.4 |
Weight of tablet |
25g |
25g |
20g |
30g |
18g |
20g |
pH |
10.6 |
10.6 |
10.7 |
10.7 |
10.9 |
11.2 |
Miscellaneous and water |
Up to 100% |
Example 18
[0169] The following liquid dishwashing detergent compositions of density 1.40Kg/L were
prepared according to the present invention :
|
BO |
BP |
BQ |
BR |
STPP |
17.5 |
17.5 |
17.2 |
16.0 |
Carbonate |
2.0 |
- |
2.4 |
- |
Silicate |
5.3 |
6.1 |
14.6 |
15.7 |
NaOCI |
1.15 |
1.15 |
1.15 |
1.25 |
Polygen/carbopol |
1.1 |
1.0 |
1.1 |
1.25 |
Nonionic |
- |
- |
0.1 |
- |
NaBz |
0.75 |
0.75 |
- |
- |
ARP3 |
0.3 |
0.5 |
0.05 |
0.1 |
NaOH |
- |
1.9 |
- |
3.5 |
KOH |
2.8 |
3.5 |
3.0 |
- |
pH |
11.0 |
11.7 |
10.9 |
11.0 |
Sulphate, miscellaneous and water |
up to 100% |
Example 19
[0170] The following liquid rinse aid compositions were prepared according to the present
invention :
|
BS |
BT |
BU |
Nonionic |
12.0 |
- |
14.5 |
Nonionic blend |
- |
64.0 |
- |
Citric |
3.2 |
- |
6.5 |
HEDP |
0.5 |
- |
- |
PEG |
- |
5.0 |
- |
SCS |
4.8 |
- |
7.0 |
Ethanol |
6.0 |
8.0 |
- |
ARP1 |
0.3 |
- |
0.1 |
ARP2 |
- |
0.04 |
0.01 |
pH of the liquid |
2.0 |
7.5 |
/ |
Miscellaneous and water |
Up to 100% |
Example 20
[0171] The following liquid dishwashing compositions were prepared according to the present
invention :
|
BV |
BW |
BX |
BY |
BZ |
C17ES |
28.5 |
27.4 |
19.2 |
34.1 |
34.1 |
Amine oxide |
2.6 |
5.0 |
2.0 |
3.0 |
3.0 |
C12 glucose amide |
- |
- |
6.0 |
- |
- |
Betaine |
0.9 |
- |
- |
2.0 |
2.0 |
Xylene sulfonate |
2.0 |
4.0 |
- |
2.0 |
- |
Neodol C11E9 |
- |
- |
5.0 |
- |
- |
Polyhydroxy fatty acid amide |
- |
- |
- |
6.5 |
6.5 |
Sodium diethylene penta acetate |
- |
- |
0.03 |
- |
- |
(40%) |
|
|
|
|
|
TAED |
- |
- |
- |
0.06 |
0.06 |
Sucrose |
- |
- |
- |
1.5 |
1.5 |
Ethanol |
4.0 |
5.5 |
5.5 |
9.1 |
9.1 |
Alkyl diphenyl oxide disulfonate |
- |
- |
- |
- |
2.3 |
Ca formate |
- |
- |
- |
0.5 |
1.1 |
Ammonium citrate |
0.06 |
0.1 |
- |
- |
- |
Na chloride |
- |
1.0 |
- |
- |
- |
Mg chloride |
3.3 |
- |
0.7 |
- |
- |
Ca chloride |
- |
- |
0.4 |
- |
- |
Na sulfate |
- |
- |
0.06 |
- |
- |
Mg sulfate |
0.08 |
- |
- |
- |
- |
Mg hydroxide |
- |
- |
- |
2.2 |
2.2 |
Na hydroxide |
- |
- |
- |
1.1 |
1.1 |
Hydrogen peroxide |
200ppm |
0.16 |
0.006 |
- |
- |
ARP3 |
0.3 |
- |
0.1 |
- |
0.1 |
ARP1 |
- |
0.3 |
- |
0.1 |
0.1 |
Protease |
0.017 |
0.005 |
.0035 |
0.003 |
0.002 |
Perfume |
0.18 |
0.09 |
0.09 |
0.2 |
0.2 |
Water and minors |
Up to 100% |
Example 21
[0172] The following liquid hard surface cleaning compositions were prepared according to
the present invention :
|
CA |
CB |
CD |
CE |
CF |
ARP2 |
0.04 |
- |
0.08 |
- |
0.01 |
ARP3 |
- |
0.3 |
- |
0.125 |
0.1 |
Amylase |
0.01 |
0.002 |
0.005 |
- |
- |
Protease |
0.05 |
0.01 |
0.02 |
- |
- |
Hydrogen peroxide |
- |
- |
- |
6.0 |
6.8 |
Acetyl triethyl citrate |
- |
- |
- |
2.5 |
- |
DTPA |
- |
- |
- |
0.2 |
- |
Butyl hydroxy toluene |
- |
- |
- |
0.05 |
- |
EDTA* |
0.05 |
0.05 |
0.05 |
- |
- |
Citric / Citrate |
2.9 |
2.9 |
2.9 |
1.0 |
- |
LAS |
0.5 |
0.5 |
0.5 |
- |
- |
C12 AS |
0.5 |
0.5 |
0.5 |
- |
- |
C10AS |
- |
- |
- |
- |
1.7 |
C12(E)S |
0.5 |
0.5 |
0.5 |
- |
- |
C12,13 E6.5 nonionic |
7.0 |
7.0 |
7.0 |
- |
- |
Neodol 23-6.5 |
- |
- |
- |
12.0 |
- |
Dobanol 23-3 |
- |
- |
- |
- |
1.5 |
Dobanol 91-10 |
- |
- |
- |
- |
1.6 |
C25AE1.8S |
- |
- |
- |
6.0 |
|
Na paraffin sulphonate |
- |
- |
- |
6.0 |
|
Perfume |
1.0 |
1.0 |
1.0 |
0.5 |
0.2 |
Propanediol |
- |
- |
- |
1.5 |
|
Ethoxylated tetraethylene |
- |
- |
- |
1.0 |
- |
pentaimine |
|
|
|
|
|
2, Butyl octanol |
- |
- |
- |
- |
0.5 |
Hexyl carbitol** |
1.0 |
1.0 |
1.0 |
- |
- |
SCS |
1.3 |
1.3 |
1.3 |
- |
- |
pH adjusted to |
7-12 |
7-12 |
7-12 |
4 |
- |
Miscellaneous and water |
Up to 100% |
*Na4 ethylenediamine diacetic acid |
**Diethylene glycol monohexyl ether |
Example 22
[0173] The following spray composition for cleaning of hard surfaces and removing household
mildew was prepared according to the present invention :
ARP2 |
0.04 |
Amylase |
0.01 |
Protease |
0.01 |
Na octyl 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 23
[0174] The following lavatory cleansing block compositions were prepared according to the
present invention.
|
CK |
CL |
CM |
C16-18 fatty alcohol/50EO |
80.0 |
- |
- |
LAS |
- |
- |
80.0 |
Nonionic |
- |
1.0 |
- |
Oleoamide surfactant |
- |
26.0 |
- |
Partially esterified copolymer of vinylmethyl |
5.0 |
- |
- |
ether and maleic anhydride, viscosity 0.1-0.5 |
|
|
|
Polyethylene glycol MW 8000 |
- |
39.0 |
- |
Water-soluble K-polyacrylate MW 4000-8000 |
- |
12.0 |
- |
Water-soluble Na-copolymer of acrylamide |
- |
19.0 |
- |
(70%) and acryclic acid (30%) low MW |
|
|
|
Na triphosphate |
10.0 |
- |
- |
Carbonate |
- |
- |
8.0 |
ARP2 |
0.04 |
- |
0.01 |
ARP3 |
- |
0.25 |
0.1 |
Dye |
2.5 |
1.0 |
1.0 |
Perfume |
3.0 |
- |
7.0 |
KOH / HCL solution |
|
pH 6-11 |
|
Example 24
[0175] The following toilet bowl cleaning composition was prepared according to the present
invention.
|
CN |
CO |
C14-15 linear alcohol 7EO |
2.0 |
10.0 |
Citric acid |
10.0 |
5.0 |
ARP2 |
0.04 |
- |
ARP3 |
- |
0.1 |
DTPMP |
- |
1.0 |
Dye |
2.0 |
1.0 |
Perfume |
3.0 |
3.0 |
NaOH |
pH 6-11 |
Water and minors |
Up to 100% |