FIELD OF INVENTION
The present invention relates to laundry detergent formulation for machine or hand
wash comprising an antifoam powder involving delay antifoam composition, and in
particular, relates to the preparation of the said antifoam powder comprising
modified anti foam amino silicone/ organopolysiloxane fluid absorbed in carrier filler,
its preparation and use in laundry detergent formulation specially in fabric wash
adapted for excellent antifoaming effect in rinsing cycle while maintaining almost
similar foaming nature compare to 'detergent without antifoam' in washing cycles.
The present invention also relates to a process of synthesis of the said modified
amino silicone/ organopolysiloxane based delay antifoam compound/ agent present
in the said antifoam powder or antifoam fluid for use in detergent formulation.
Specifically, the present invention is thus directed to not only save huge amount of
waste water but also help to preserve massive amount precious clean water for
desirable use and application. Advantageously, therefore the present invention in
other words is in the line of green water balance targeted to reduce pollution and
save the world from future massive climatic disasters or ecological imbalances.
More specifically, the modified amino silicone or organopolysiloxane in powder form
or fluid form can be readily used for diverse applications such as in personnel care,
specially hair care, home care, textile care, and the like.
BACKGROUND ART
In hand washing process, water is taken in a bucket or in fabric's soaking container
or washing tub in washing machine. Thereafter, desired quantity of detergent is
added to generate lather by hand shaking or run for a while the washing tub in
machines. This is followed by immersion of the dirt fabrics for soaking for 10 to 30
min. After soaking period, the fabric is rubbed by hand to remove dirt or the washing
cycle is run for 10 to 20 min in case of machines wash.
For rinsing, the dirt water is drained out and removes excess dirt water by squeezing
the fabrics. Thus each such rinsing cycle consists of squeezing the fabrics and
washing the fabrics with fresh water. Such rinsing cycle is repeated for four to five

times for hand wash or in case of machine, four to five times rinse cycle is followed
to remove all foams before final spinning.
It is important due to the fact of traditional concept of no foam means in washing
cycle means not a good detergent. So, all detergent manufacturers have a common
requirement of foaming during washing and no foaming during rinsing that claims of
saving cost and water of such kind of detergent.
Attempts have been made in the past to resolve this problem by secondary method,
called single rinse concept where during rinsing cycle, use a defoamer containing
fabric conditioner where fabric conditioner conditioned the fabric at rinsing cycle and
in addition kills the all residual foam. This concept was not very much successful in
case of hand washing process, since use of fabric conditioner in this class is
considered to be a luxury and people of hand-washing segment uses hand washing
due to money constraint for fabric cleaning.
Considering the wastage of water and formulation cost for normal detergent used in
hand wash or machine wash, there has been a need for detergent formulations which
when used for washing fabrics most likely generates preferred amount of foaming
during washing cycle without affecting the cleaning nature of the detergent but also
have antifoaming activity in rinsing cycle so that one or two rinse is enough to clean
the fabric. It is however extremely difficult to provide for such characteristics in
detergent formulations which would favour both the washing and rinsing cycles and
make washing of clothes/fabrics more convenient and user friendly apart from taking
care of avoiding unnecessary wastage of valuable water and saving the environment
from unnecessarily wastage of water in hand wash and/or machine washing. It is
also important that such advancement directed to washing formulations adapted for
effective washing avoiding wastage of water is attended at cost-effective rates since
the market is very much price sensitive and the success of new detergent heavily
depend on cost as well.
US 4637890 disclosed a detergent composition that acts as defoamer in rinsing
cycles. Detergent composition revealed a composition for suds/foams controlling
prills comprising fatty acid soap, quaternary ammonium salt and silicone fluid for
suds suppresser. It is indicated in the patent that the prills dissolve in the relatively

high pH (from 9 to 10.5 pH) in washing cycles and prills are not active at high pH.
Prills become active to suppress suds at low pH with a concept of lower pH at rinsing
cycles where detergent contained less in rinsed water. However, the examples didn't
direct to any actual applications and additionally it was not clear whether the
detergent was effective in hand washing or machine-assisted hand washing. It is
understood from the diclosure that effectiveness of suppressing foam by silicone
defoamer was highly dependent on prills formation with the help of fatty acid soap
and quaternary ammonium compound. According to the disclosure a normal silicone
fluid (alkylated polysiloxane) used as defoamer where normal silicones defoaming
activity was controlled in washing cycle by way of insolubility of prills at alkaline pH.
US 4894117 disclosed a composition of agglomerated granules for the delay release
of antifoaming agent in laundry system. It particularly relates to a laundry detergent
composition comprising silicone antifoam adsorbed on a powdered water soluble
carrier selected from modified cellulose carriers which is subsequently agglomerated
into granular form by mixing in presence of a solvent for the carrier. This prior art
disclosed a series of granulated laundry additives wherein standard silicone antifoam
were encapsulated. These different granulated laundry additives have different
silicone antifoam release time depending on type of cellulosed used and size of the
granules. It is clearly apparent that such type encapsulated laundry additive is only
suitable for machine wash but totally not suited in case of hand washing or machine-
assisted hand washing since time of washing would vary from one user to another,
one region to another region and one country to another country. Thus while a
detergent composition having laundry additive granules with encapsulated silicone
antifoam may be acceptable to one user but not suited to the requirement of another
user due to different washing time where user can see no foam in washing cycles
due to longer washing time or more water used in rinsing cycle due to shorter
washing time since particular granules used in the detergent for washing would have
a fixed time for releasing encapsulated silicones. According to the disclosure
conventional silica filled polydimethyl siloxane used as defoamer to make
encapsulated defoamer granules.
EP 254 499 B1 disclosed a method for the preparation of a silicone defoamer
composition, said method comprising heating a mixture comprising
a blend of organopolysiloxanes (1) and (2)

(3) silanes or their partial hydrolysis condensates or siloxane resins,
(4) finely divided filler, preferably silica,
(5) reaction catalyst, preferably KOH,
(6) compounds like alkylene glycols, polyhydric alcohols, carboxylic acids and their
esters, nonionic surfactants, polyoxyethylene anionic surfactants, polyether-modified
silicones, nonionic fluorinated surfactants and OH-containing polymeric compounds
like hydroxyethylcellulose.
A silicone defoamer composition is obtained by reacting a blend of trimethylsilyl-
terminated polydimethylsiloxane and silanol-terminated polydimethylsiloxane with
polyoxyethylene-polyoxypropylene copolymers and with silica.
The defoaming activity of the composition is disclosed but neither the use in a
detergent composition is described nor can it be used as a delay defoamer by
permitting foaming during the washing stage but inhibiting foaming during rinsing
operations.
It is thus apparently clear from the above state of the art that all prior arts depend
on encapsulation of silicone or silicone defoamer where both the type of chemicals
have strong antifoaming action. The activity of delay antifoam or suppression of suds
in rinsing cycles is dependent on many other parameters as discussed above.
Therefore, application of such type of available antifoams is only possible in
systematic washing system like machine wash but impossible to work in hand
washing or machine-assisted hand washing because of wide variation of washing
habit from one user to another user. On the other hand, a product that have delayed
antifoam action or suppresion of suds in the rinsing cycle of hand washing or
machine-assisted hand washing, obviously performs better in all automated machine
wash.
OBJECTS OF THE INVENTION
It is thus the basic object of the invention to develop a powder antifoam composition
comprising modified anti foam amino silicone/ organopolysiloxane fluid together with
carrier filler that would easily mix with hand wash detergent or machine wash
detergent having no negative effect on detergent effect and preferred foaming
nature of the detergent during washing cycle while providing for excellent
antifoaming activity in the rinsing cycle.

Another object of the present invention is directed to provide for a laundry detergent
formulation comprising of the said powder antifoam composition which will save huge
amount of fresh water and reduce the wastage of valuable water required in hand
wash detergent or machine detergent applications for cloth/fabric washing.
Another object of the present invention is directed to a selective provision of a
powder antifoam composition comprising modified amino silicone/
organopolysiloxane fluid together with carrier filler which would favour obtaining the
desired detergent composition with minimum dosage of powder antifoam
incorporation in the detergent formulation directed to effective washing and avoiding
wastage of water during the rinsing stage.
Another object of the present invention is directed to synthesize modified amino
silicone/ organopolysiloxane based delay antifoam formulations in simple way to
optimize the cost of the organopolysiloxane compound that would have minimum
impact in the formulation cost of final detergent.
Yet another object of the present invention is directed to a detergent composition
with excellent anti-foaming effect during rinsing while generate preferred foaming in
washing cycle.
Still another object of the present invention is directed to a modified amino silicone /
organopolysiloxane in fluid form or in powder form for use in diverse applications
such as in personnel care, specially hair care, home care, textile care, and the like.
Yet another object of the present invention is directed to a detergent formulation
comprising a low effective amount of the said powder antifoam composition adapted
for making the said detergent formulation cost effective.

SUMMARY OF THE INVENTION
Thus according to the basic aspect of the present invention there is provided a
laundry detergent composition for machine or hand washing comprising:
a modified amino silicone antifoam fluid of the Formula
XR2Si(OSiAR)n(OSiR2)mOSiR2X (I)
where
A is a radical of the formula
-R1-[NR2-R3-]XNR22
X is R or a polyoxyalkylen group G of the formula
-R4-(O-R5)y-O-R6
R is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms,
R1 is a divalent C1-C10-alkylen radical, preferably a radical of the formula -
CH2CH2CH2-,
R2 is a hydrogen atom or a C1-C4-alkyl radical, preferably a hydrogen atom,
R3 is a divalent C1-C10-alkylen radical, preferably a radical of the formula -
CH2CH2-,
R4 is a divalent C1-C10-alkylen, preferably a radical of the formula -CH2CH2CH2-,
R5 is a C1-C4-alkylen radical, preferably a radical of the formula -CH2CH2- or -
CH2CH2(CH3)- or mixtures of them,
R6 is a hydrogen atom or an C1-C4-alkyl radical, preferably a hydrogen atom or a
methyl radical, more preferably a hydrogen atom,
n is an integer from 1 to 6, preferably from 1 to 3,
m is an integer from 1 to 200, preferably from 1 to 80,
x is 0 or 1 and
y is an integer from 5 to 20, preferably from 5 to 12,
with the proviso that on average from 30 to 60 Mol%, preferably 50 Mol%, of
radicals X are polyoxyalkylen groups G; and
a usual laundry detergent formulation for machine or hand washing.

According to another aspect of the invention there is provided a laundry detergent
composition for machine or hand washing in powder form comprising:
(A) an antifoam powder in an amount of 0.3 to 2.5 % by weight relating to the
total amount of the laundry detergent composition comprising of i) 10 to 35 % by
weight of the modified amino silicone antifoam fluid of Formula (I) and ii) 65 to 90 %
by weight of a carrier filler selected from the group consisting of sodium carbonate,
sodium sulphate, aluminium silicate, potassium carbonate, potassium sulphate,
sodium bicarbonate, potassium bicarbonate and zeolite; and
(B) a usual laundry detergent formulation for machine or hand washing.
According to yet another aspect of the present invention there is provided an
antifoam powder comprising of
(1) 10 to 35 % by weight of a modified amino silicone antifoam fluid of the
formula
XR2Si(OSiAR)n(OSiR2)mOSiR2X (I)
where
A is a radical of the formula
-R1-[NR2-R3-]xNR22
X is R or a polyoxyalkylen group G of the formula
-R4-(O-R5)y-O-R6
R is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms,
R1 is a divalent C1-C10-alkylen radical, preferably a radical of the formula -
CH2CH2CH2-,
R2 is a hydrogen atom or a C1-C4-alkyl radical, preferably a hydrogen atom,
R3 is a divalent C1-C10-alkylen radical, preferably a radical of the formula -
CH2CH2-,
R4 is a divalent C1-C10-alkylen, preferably a radical of the formula -CH2CH2CH2-,
R5 is a C1-C4-alkylen radical, preferably a radical of the formula -CH2CH2- or -
CH2CH2(CH3)- or mixtures of them,

R6 is a hydrogen atom or an C1-C4-alkyl radical, preferably a hydrogen atom or a
methyl, more preferably a hydrogen atom,
n is an integer from 1 to 6, preferably from 1 to 3,
m is an integer from 1 to 200, preferably from 1 to 80,
x is 0 or 1 and
y is an integer from 5 to 20, preferably from 5 to 12,
with the provision that on average from 30 to 60 Mol%, preferably 50 Mol%, of
radicals X are polyoxyalkylen groups G; and
(2) 65 to 90 % by weight of a carrier filler selected from the group comprising of
sodium carbonate, sodium sulphate, aluminium silicate, potassium carbonate,
potassium sulphate, sodium bicarbonate, potassium bicarbonate and zeolite.
According to another aspect of the present invention there is provided a process for
preparing the antifoam powder comprising the steps of
(i) stirring and drying the carrier filler at a temperature from 100°C to 150 °C, (ii)
mixing the dried carrier filler with the antifoam silicone fluid of Formula (I) at a
temperature from 100°C to 150°C and (iii) cooling and obtaining therefrom the said
antifoam powder.
According to yet another aspect of the present invention there is provided an
antifoam silicone fluid adapted for use in fluid/ powder based detergent formulations
comprising of formula
XR2Si(OSiAR)n(OSiR2)mOSiR2X (I)
where
A is a radical of the formula
-R^NR^RMxNR^
X is R or a polyoxyalkylen group G of the formula
-R4-(O-R5)y-O-R6
R is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms,

R1 is a divalent C1-C10-alkylen radical, preferably a radical of the formula -
CH2CH2CH2-,
R2 is a hydrogen atom or a C1-C4-alkyl radical, preferably a hydrogen atom,
R3 is a divalent C1-C10-alkylen radical, preferably a radical of the formula -
CH2CH2-,
R4 is a divalent C1-C10-alkylen, preferably a radical of the formula -CH2CH2CH2-,
R5 is a C1-C4-alkylen radical, preferably a radical of the formula -CH2CH2- or -
CH2CH2(CH3)- or mixtures of them,
R6 is a hydrogen atom or an C1-C4-alkyl radical, preferably a hydrogen atom or a
methyl radical, more preferably a hydrogen atom,
n is an integer from 1 to 6, preferably from 1 to 3,
m is an integer from 1 to 200, preferably from 1 to 80,
x is 0 or 1 and
y is an integer from 5 to 20, preferably from 5 to 12,
with the provision that on average from 30 to 60 Mol%, preferably 50 Mol%, of
radicals X are polyoxyalkylen groups G
According to a preferred aspect of the present invention there is provided a process
preparing the antifoam silicone fluid comprising
(I) reacting in a first step
(a) an α, ω-dihydrogen-diorganopolysiloxane of the formula
HR2SiO-(R2SiO)p-SiR2H
with
(b) a polyoxyalkylen compound of the formula
R4'-(0-R5)γ-O-R6
in the presence of
(c) a hydrosilylation catalyst, preferably a platinum catalyst,
(II) reacting in a second step
(d) the resulting hydrosilylation product obtained from step (I) of the formula
XR2SiO-(R2SiO)p-SiR2X
and

(e) a diorganopolysiloxane of the formula
HOR2SiO-(R2SiO)s-SiR2OH
with
(f) an aminoalkyl silane of the formula
ASiR(OR7)3
in the presence of
(g) a basic catalyst, preferably potassium methoxide and potassium ethoxide,
and in the presence of
(h) a chain-terminating organopolysiloxane of the formula
R3SiO-(R2SiO)z-SiR3
at a temperature of from 80°C to 150°C,
and then, after the reaction (II)
(III) neutralizing the basic catalyst (g),
by addition of a neutralizing agent (k), preferably a triorganosilyl phosphate, more
preferably a trimethylsilyl phosphate,
where
A is a radical of the formula
-R1-[NR2-R3-]xNR2;.
X is R or a polyoxyalkylen group G of the formula
-R4-(O-R5)γ-O-R6
R is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms,
R1 is a divalent C1-C10-alkylen radical, preferably a radical of the formula -
CH2CH2CH2-,
R2 is a hydrogen atom or a C1-C4-alkyl radical, preferably a hydrogen atom,
R3 is a divalent C1-C10-alkylen radical, preferably a radical of the formula -
CH2Cn2_,

R4 is a divalent C1-C10-alkylen, preferably a radical of the formula -CH2CH2CH2-,
R4' is a monovalent C1-C10-alkenyl radical having a terminal carbon-carbon
double bond,
R5 is a C1-C4-alkylen radical, preferably a radical of the formula -CH2CH2- or -
CH2CH2(CH3)- and mixtures of them,
R6 is a hydrogen atom or an C1-C4-alkyl radical, preferably a hydrogen atom or a
methyl, more preferably a hydrogen atom,
R7 is a monovalent C1-C4-alkyl radical,
p is an integer from 10 to 25,
s is an integer from 20 to 60,
x is 0 or 1,
y is an integer from 5 to 20 and
z is an integer from 0 to 10.
DETAILED DESCRIPTION OF THE INVENTION
As discussed hereinbefore the present invention relates to laundry detergent
formulation for machine or hand wash comprising an antifoam powder involving
delay antifoam composition, and in particular, relates to the preparation of the said
antifoam powder comprising modified anti foam amino silicone/ organopolysiloxane
fluid absorbed in carrier filler, its preparation and use in laundry detergent
formulation specially in fabric wash adapted for excellent antifoaming effect in rinsing
cycle while maintaining almost similar foaming nature compare to 'detergent without
antifoam' in washing cycles.
Advantageously, the said detergent composition involving the delay antifoam
composition is found to have excellent antifoaming effect in rinsing cycle while
preferred foaming effect in washing cycle.
The present invention also relates to a process of synthesis of the said modified
amino silicone / organopolysiloxane based delay antifoam compound present in the
said antifoam powder for use in detergent formulation wherein the said silicone
compound generates preferred in-situ foaming properties of the said detergent
formulation in washing cycle but acts as antifoam in rinsing cycle.

According to the present invention, performance of powder silicone antifoam
comprising modified silicone fluid/ organopolysiloxane is confirmed by a unique
mechanism that governs its role as an antifoam agent in rinsing cycles while
maintaining preferred amount of foam in washing cycles.
Effective detergent compositions comprise anionic surfactants, particularly alkyl
benzene sulfonate and alkyl sulfate surfactants. It has also been found beneficial for
the appearance and cleaning of fabrics for laundry detergents to contain an amount
of a cellulose enzyme sufficient to improve the appearance and cleaning of such
fabrics, particularly after multiple cleaning cycles. But this anionic surfactant is
important for cleaning and cheap source of generating substantial foam in the
washing even at small amount. To improve upon the detergent effect of the laundry
detergent formulation, different other chemicals are used like complex phosphates,
non-ionic surfactants, soap noodles, different inorganic salts and other additive those
used for optimizing detergency effect.
In detergent powder, main foaming component is anionic surfactant. According to
the present invention, when laundry detergent containing powder silicone antifoam is
dissolved in water, huge amount of foam generates due to anionic surfactant and no
interaction takes place between amino group of modified silicone fluid and anionic
surfactant due to the presence of high foam in the liquor. As soon as, the washing
fabric come across the said liquor in the washing cycle, modified amino silicone fluid
penetrates inside the fiber due to its high affinity towards the fabric but due to high
lather during washing cycle in machine wash or during rubbing the fabrics in hand
wash after soaking with amino silicone fluid penetrated into the said fabric, the
anionic surfactant can't come towards the amino group of modified silicone to
interact and form salt. Therefore, foaming nature of the detergent during prewash or
in post wash does not change. In rinsing cycle, residual detergent transfers into fresh
water from the fabric after squeezing the fabrics. Therefore, rinsing liquor foam
density reduces significantly due to less amount of detergent present in the liquor
and hence, anionic surfactant easily reacts with modified amino silicone penetrated
and attached to the fabric due to less foam in liquor to form water soluble silicone
salt that transfers immediately to rinsing liquor due to the formation of a neutral salt
with anionic surfactant. As a result, anionic surfactant thus transformed to a salt of

silicone and anionic surfactant thereby loses its foaming nature and hence, foams in
rinsing lather are eliminated in significant amounts. Specially, in case of hand wash,
no foam is observed after 1 to 2 rinsing.
It is thus observed according to the present invention, laundry detergent antifoam
powder not only saves water in rinsing cycles but also provides for good conditioning
effects on the fabric due to residual silicone adhered onto the fabric.
It is observed according to the present invention, modified amino silicone/
organopolysiloxane fluid directly incorporated in the liquid laundry detergent for the
purpose of saving water in rinsing cycles during fabric washing by hand or by
machine wash is also similar to the laundry powder detergents containing the said
novel powder based antifoam agent similarly serving the purpose of saving water.
According to the present invention that novel modified amino silicone or
organopolysiloxane fluid /powder can be used in personal care i.e. more particularly
in hair care application for conserving water during the hair rinsing.
It is also a fact according to the present invention that the modified amino silicone or
organopolysiloxane in powder or fluid form can be used in personal care i.e. more
particularly in hair care applications and body wash for conserving water during the
hair/body washing.
It is another possibility according to the present invention that the modified amino
silicone or organopolysiloxane in powder or fluid form can be used in different home
care applications like floor cleaner, wash room cleaners besides home laundry and
industrial laundry applications especially for the conservation of water
It is also made clear according to the present invention that modified amino silicone
or organopolysiloxane in powder or fluid form can be used in defoamers or antifoam
agents in textile processing or textile treatments/ pulp and paper papers and other
industrial applications where foaming due to anionic substances.
The details of the invention, its nature and objects are explained hereunder in
greater detail in relation to the following non-limiting examples.

EXAMPLES
Step -I
Detergent Formulation for hand wash: Example without antifoam powder
Linear Alkyl benzene sulfonate Salt = 14.00 part
Sodium tripolyphosphate = 26.40 part
Soda Ash = 47.55 part
Sodium Sulphate = 4.40 part
Sod.Perborate = 6.85 part
Tetra Acetyl Ethylene Diamine = 0.5 part
Perfume = 0.30 part
Example-1
Step -II : Polymer Synthesis
In the 10 lit reactor, transferred 5648 gm 80 mPa.s α,ω hydroxyl terminated
polydimethylsiloxane, 250 gm α,ω polyethyl glycol 10 EO terminated via propylene
spacing polydimethylsilicone having polymer MW approx 1800 having 38 mole %
polyoxyethylene groups G and 782 gm gamma amino ethyl amino propyl methyl
dimethoxy silane. Closed the reactor and purged with nitrogen for 30 min. Reactor
was equipped with stirring, heating/cooling having vertical condenser that could use
for stripping as well refluxing. Receiver was connected at the bottom of the
condenser. Reactor also had a facility to work under nitrogen atmosphere or under
vacuum or under pressure. An accurate temperature controlling system also installed
in the reactor so that reaction could be carried out at desire temperature. After 30
min nitrogen purging, increased the reactor material temperature to 130°C under
nitrogen purging. Added 1 gm 40% active alcoholic KOH solution and reaction was
carried out for 1 hr. Repeat the same catalyst addition twice and every time reaction
was carried out 1 hr. Then added 40 gm trimethylsiloxay terminated dimethyl
polysiloxane having viscosity 10 mPa.s and reaction was continued for 2. hr. Again
added 2 gm KOH solution and continued reaction for another 2 hr. neutralized the
fluid with 5.0 gm Silyl Phosphate. Stopped nitrogen purging and distillation was
carried out under -300 to -500 mm Hg vacuum at 150°C for removing all volatiles.

Cooled the fluid to room temperature under vacuum after completion of distillation. A
clear α,ω-glycol terminated amino polydimethyl siloxane was obtained having
viscosity 1000 mPa.s at 25°C and amine no 1.24 and having 3.3 mol %
polyoxyethylen groups G. On average 50 mol% of the radical X, i.e. the terminal
groups of the amino polydimethyl siloxane according to formula (I), are
polyoxyethylen groups G and 50 mol% of the radical X are radicals R = methyl
radicals.
Step -III: Antifoam Compound Formulation
Equipment used: 10 litre volume, Stainless steel plough shear mixer, with one side
entry high speed dispersing tool, suitability jacketed for nominal pressure hot-
water/cold water, heating and cooling. All shaft glands N2 purged. Suitable dust
separator installed at loading hopper and standard bottom drain provision.
a. Take 3.5 kg of commercial grade Sodium Carbonate powder having particle size
125 micron into above mixer.
b. Stir and heat to 130°C under N2 purge to dry the powder.
c. After the drying powder for about an hour, start adding Amino Silicone Fluid
(capped with PEG-dimethyl siloxy group having amine no 1.24 and viscosity 1000
mPa.s), by metering pump. Ensure dispensing is uniform into the stirred mass.
4. Addition of 1.5 kgs of above fluid is done in about 3 hour, while temperature is
maintained at 130°C.
5. Continue mixing for another 1 hr after fluid addition.
6. Cool the powder to 40°C before draining.
Step - IV: Detergent Formulation for hand wash: Example with antifoam
powder
Linear Alkyl benzene sulfonate Salt = 14.00 part
Sodium tripolyphosphate = 26.40 part

Soda Ash = 47.05 part
Sodium Sulphate = 4.40 part
Sod.Perborate = 6.85 part
Tetra Acetyl Ethylene Diamine = 0.5 part
Perfume = 0.30 part
Antifoam powder (produced step..) = 0.5 part
Step -V: Detergent Formulation for machine wash: Example without
antifoam powder of the invention
Linear Alkyl benzene sulfonate Salt = 10.00 part
Soap = 1.25 part
Lauryl alcohol 7 EO = 2.00 part
Sodium tripolyphosphate = 26.40 part
Soda Ash = 47.9 part
Sodium Sulphate = 4.40 part
Enzyme Protease = 0.40 part
Sod.Perborate = 6.85 part
Tetra Acetyl Ethylene Diamine = 0.5 part
Perfume = 0.30part
Step -VI: Detergent Formulation for machine wash: Example with antifoam
powder of the invention
Linear Alkyl benzene sulfonate Salt = 10.00 part
Soap = 1.25 part
Lauryl alcohol 7 EO = 2.00 part
Sodium tripolyphosphate = 26.40 part
Soda Ash = 47.40 part
Sodium Sulphate = 4.40 part
Enzyme Protease = 0.40 part
Sod.Perborate = 6.85 part
Tetra Acetyl Ethylene Diamine = 0.5 part
Perfume = 0.30part
Antifoam powder (produced in step IV) = 0.5 part

Step VII: Performance Evaluation (hand wash)
Protocol used for the evaluation of detergent in bucket by hand washing was as
below
a. used 24°fH hard water
b. fabric to liquor ratio was 1:10
c. used 4 gpl detergent (gpl = grams per liter)
d. lathering was done for 20 sec and immerged the fabrics in bucket
water.
e. washing cycle maintained 15 min or 30 min and measured lather
height in every 5 min or 10 min intervals.
f. squeezed fabrics at 50% weight pick up
g. rinsing was done in each case in fresh 24°fH hard water in ratio of
rinse water 1 part and 7part fresh water and then 5 see whisking;
squeezed fabrics at 50% weight pick up and measured the foam height
in bucket.
Step VIII: Performance Evaluation ( Machine wash)
Protocol used for the evaluation of detergent in top load automatic machine
a. used 24°fH hard water
b. fabric to liquor ratio was 1:10
c. used 4 gpl detergent (gpl = grams per liter)
d. washing cycle maintained 15 min or 30 min. Open the top lid of
washing machine just before discharged the washing liquor(as soon as
top lid opened, m/c stopped in operation automatically) and took out
fabrics by squeezing so that fabric retained 50% wash liquor. After
taking out the fabric, measure the foam height.
f. Closed the top lid and ran machine. As soon as machine discharged the
washing liquor, opened top lid of the machine and transferred the
fabrics in the machine. Closed the top lid of machine and immediately
machine was in operation for rinsing cycle. Open the top lid of washing
machine just before discharged the 1st rinsing liquor. Took out fabrics
by squeezing so that fabrics were 50% washed liquor. After taking out
the fabric, measure the foam height and noted as 1st rinsing foam
height.
g. Closed the top lid and followed step 'f' for foam height measurement of
2nd, 3rd & 4th rinsing.

Above Table I and II shows the application result of the detergent produced in step
IV of experiment in step II clearly directs to the fact that detergent IV containing
0.5% of the delay antifoam compound of the present invention performed extremely
well in comparison to conventional Detergent in step I in rinsing cycle and in washing
cycle, where there was comparable preferred foam height in detergent of step IV and
detergent made in step I.
From Table I and II, it is also clear that delay antifoam powder produced in the
experiment showed preferred foaming natures in washing cycle and at dilution stage
of rinsing, due to less foam, anionic surfactant penetrates faster in the fabric and
reacted with amino group of the silicone in fabric. Therefore, anionic surfactant loses
the foaming character and passes on to the aqueous phase. On the other hand, in
the washing cycle, anionic surfactant cannot penetrate enough due to high foam to
attach itself to the amino of silicone polymer and therefore no difference in foam is
observed during washing cycle either in hand wash or in machine wash. Similar
result from machine wash is also observed in table II when detergents are used from
those made in steps V and VI.
Therefore, according to the present invention, modification of silicone molecule and
use of such modified molecules such as the modified amino silicone/
organopolysiloxane in detergent formulation is acceptable to all users globally with a
consideration of different washing habit from one person to another person, from
one region to another region, from one country to another country. Again, we
observed from experiment, newly developed delay antifoam powder according to
present invention worked at 0.5% dosage which obviously does not put much impact
on the cost of detergent formulation that most importantly helps detergent
manufacturer to pass-on the benefits towards whole detergent consumers without
increasing the product cost.
It is thus possible by way of the present invention to provide for detergent
formulations and the like to favour both washing and rinsing cycles and make
washing of clothes/fabrics more convenient and user friendly apart from taking care
of avoiding unnecessary wastage of valuable water and saving the environment from
unnecessarily wastage of water in hand wash and/or machine washing and the like.

We Claim:
1. Laundry detergent composition for machine or hand washing comprising:
a modified amino silicone antifoam fluid of the Formula
XR2Si(OSiAR)n(OSiR2)mOSiR2X (I)
where
A is a radical of the formula
X is R or a polyoxyalkylen group G of the formula
-R4-(O-R5)γ-O-R6
R is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms,
R1 is a divalent C1-C10-alkylen radical, preferably a radical of the formula -
CH2CH2CH2-,
R2 is a hydrogen atom or a C1-C4-alkyl radical, preferably a hydrogen atom,
R3 is a divalent C1-C10-alkylen radical, preferably a radical of the formula -
CH2CH2-,
R4 is a divalent C1-C10-alkylen, preferably a radical of the formula -CH2CH2CH2-,
R5 is a C1-C4-alkylen radical, preferably a radical of the formula -CH2CH2- or -
CH2CH2(CH3)- or mixtures of them,
R6 is a hydrogen atom or an C1-C4-alkyl radical, preferably a hydrogen atom or a
methyl radical, more preferably a hydrogen atom,
n is an integer from 1 to 6, preferably from 1 to 3,
m is an integer from 1 to 200, preferably from 1 to 80,
x is 0 or 1 and
y is an integer from 5 to 20, preferably from 5 to 12,
with the provision that on average from 30 to 60 Mol%, preferably 50 Mol%, of
radicals X are polyoxyalkylen groups G;
and
a usual laundry detergent formulation for machine or hand washing.

2. Laundry detergent composition for machine or hand washing as claimed in claim 1
in powder form comprising:
(A) an antifoam powder in an amount of 0.3 to 2.5 % by weight relating to the
total amount of the laundry detergent composition comprising of i) 10 to 35 % by
weight of the modified amino silicone antifoam fluid of Formula (I) and ii) 65 to 90 %
by weight of a carrier filler selected from the group consisting of sodium carbonate,
sodium sulphate, aluminium silicate, potassium carbonate, potassium sulphate,
sodium bicarbonate, potassium bicarbonate and zeolite; and
(B) a usual laundry detergent formulation for machine or hand washing.
3. An antifoam powder comprising of
(1) 10 to 35 % by weight of a modified amino silicone antifoam fluid of the
formula
XR2Si(OSiAR)n(OSiR2)mOSiR2X (I)
where
A is a radical of the formula
X is R or a polyoxyalkylen group G of the formula
-R4-(O-R5)γ-O-R6
R is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms,
R1 is a divalent C1-C10-alkylen radical, preferably a radical of the formula -
CH2CH2CH2-,
R2 is a hydrogen atom or a C1-C4-alkyl radical, preferably a hydrogen atom,
R3 is a divalent C1-C10-alkylen radical, preferably a radical of the formula -
CH2CH2-,
R4 is a divalent C1-C10-alkylen, preferably a radical of the formula -CH2CH2CH2-,
R5 is a C1-C4-alkylen radical, preferably a radical of the formula -CH2CH2- or -
CH2CH2(CH3)- or mixtures of them,
R6 is a hydrogen atom or an C1-C4-alkyl radical, preferably a hydrogen atom or a
methyl, more preferably a hydrogen atom,

n is an integer from 1 to 6, preferably from 1 to 3,
m is an integer from 1 to 200, preferably from 1 to 80,
x is 0 or 1 and
y is an integer from 5 to 20, preferably from 5 to 12,
with the provision that on average from 30 to 60 Mol%, preferably 50 Mol%, of
radicals X are polyoxyalkylen groups G; and
(2) 65 to 90 % by weight of a carrier filler selected from the group comprising of
sodium carbonate, sodium sulphate, aluminium silicate, potassium carbonate,
potassium sulphate, sodium bicarbonate, potassium bicarbonate and zeolite.
4. Process for preparing the antifoam powder as claimed in 3 comprising the steps of
(i) stirring and drying the carrier filler at a temperature from 100°C to 150 °C, (ii)
mixing the dried carrier filler with the antifoam silicone fluid of Formula (I) at a
temperature from 100°C to 150°C and (iii) cooling and obtaining therefrom the said
antifoam powder.
5. An antifoam silicone fluid adapted for use in fluid/ powder based detergent
formulations comprising of formula
XR2Si(OSiAR)n(OSiR2)mOSiR2X (I)
where
A is a radical of the formula
-R1-[NR2-R3-]xNR22
X is R or a polyoxyalkylen group G of the formula
-R4-(O-R5)y-O-R6
R is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms,
R1 is a divalent C1-C10-alkylen radical, preferably a radical of the formula -
CH2CH2CH2-,
R2 is a hydrogen atom or a C1-C4-alkyl radical, preferably a hydrogen atom,

R3 is a divalent C1-C10-alkylen radical, preferably a radical of the formula -
CH2CH2-,
R4 is a divalent C1-C10-alkylen, preferably a radical of the formula -CH2CH2CH2-,
R5 is a C1-C4-alkylen radical, preferably a radical of the formula -CH2CH2- or -
CH2CH2(CH3)- or mixtures of them,
R6 is a hydrogen atom or an C1-C4-alkyl radical, preferably a hydrogen atom or a
methyl radical, more preferably a hydrogen atom,
n is an integer from 1 to 6, preferably from 1 to 3,
m is an integer from 1 to 200, preferably from 1 to 80,
x is 0 or 1 and
y is an integer from 5 to 20, preferably from 5 to 12,
with the provision that on average from 30 to 60 Mol%, preferably 50 Mol%, of
radicals X are polyoxyalkylen groups G
6. Process for preparing the antifoam silicone fluid as claimed in claim 5 comprising
(I) reacting in a first step
(a) an α,ω-dihydrogen-diorganopolysiloxane of the formula
HR2SiO-(R2SiO)p-SiR2H
with
(b) a polyoxyalkylen compound of the formula
R4'-(O-R5)γ-O-R6
in the presence of
(c) a hydrosilylation catalyst, preferably a platinum catalyst,
(II) reacting in a second step
(d) the resulting hydrosilylation product obtained from step (I) of the formula
XR2SiO-(R2SiO)p-SiR2X
and
(e) a diorganopolysiloxane of the formula
HOR2SiO-(R2SiO)s-SiR2OH

with
(f) an aminoalkyl silane of the formula
ASiR(OR7)3
in the presence of
(g) a basic catalyst, preferably potassium methoxide and potassium ethoxide,
and in the presence of
(h) a chain-terminating organopolysiloxane of the formula
R3SiO-(R2SiO)z-SiR3
at a temperature of from 80°C to 150°C,
and then, after the reaction (II)
(III) neutralizing the basic catalyst (g),
by addition of a neutralizing agent (k), preferably a triorganosilyl phosphate, more
preferably a trimethylsilyl phosphate,
where
A is a radical of the formula
-R1-[NR2-R3-]XNR22
X is R or a polyoxyalkylen group G of the formula
-R4-(O-R5)γ-O-R6
R is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms,
R1 is a divalent C1-C10-alkylen radical, preferably a radical of the formula -
CH2CH2CH2-,
R2 is a hydrogen atom or a C1-C4-alkyl radical, preferably a hydrogen atom,
R3 is a divalent C1-C10-alkylen radical, preferably a radical of the formula -
CH2CH2-,
R4 is a divalent C1-C10-alkylen, preferably a radical of the formula -CH2CH2CH2-,
R4' is a monovalent C1-C10-alkenyl radical having a terminal carbon-carbon
double bond,

R5 is a C1-C4-alkylen radical, preferably a radical of the formula -CH2CH2- or -
CH2CH2(CH3)- and mixtures of them,
R6 is a hydrogen atom or an C1-C4-alkyl radical, preferably a hydrogen atom or a
methyl, more preferably a hydrogen atom,
R7 is a monovalent C1-C4-alkyl radical,
p is an integer from 10 to 25,
s is an integer from 20 to 60,
x is 0 or 1,
y is an integer from 5 to 20 and
z is an integer from 0 to 10.
7. A silicone based antifoaming agent/ modified amino silicone in fluid and powder
form, laundry detergent composition involving the same and its process of
manufacture thereof substantially as hereindescribed and illustrated with reference
to the accompanying examples.

Laundry detergent formulation for machine or hand wash comprising an antifoam
powder involving delay antifoam composition and preparation of the said antifoam
powder comprising modified anti foam amino silicone/ organopolysiloxane fluid
absorbed in carrier filler, its preparation and use in laundry detergent formulation
especially in fabric wash adapted for excellent antifoaming effect in rinsing cycle. The
process of synthesis of the said modified amino silicone/ organopolysiloxane based
delay antifoam compound/ agent present in the said antifoam powder or antifoam
fluid for use in detergent formulation is also illustrated having diverse applications
such as in personnel care, specially hair care, textile, release and alike.