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Rinse Added Fabric Treatment Composition

Abstract: An aqueous rinse-added fabric treatment composition with improved anti-redeposition and fragrance delivery benefits. Methods of improving soil anti-redeposition, fragrance delivery and fabric treatment by rinsing the fabrics in a rinse solution comprising the inventive compositions.

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Notices, Deadlines & Correspondence

Patent Information

Application #
Filing Date
17 October 2008
Publication Number
03/2009
Publication Type
INA
Invention Field
CHEMICAL
Status
Email
Parent Application
Patent Number
Legal Status
Grant Date
2017-10-11
Renewal Date

Applicants

HINDUSTAN UNILEVER LIMITED
HINDUSTAN LEVER HOUSE, 165-166 BACKBAY RECLAMATION, MUMBAI-400020,

Inventors

1. ZHU YUN-PENG
7-17 OAK STREET, FAIR LAWN, NEW JERSEY 07410, UNITED STATES OF AMERICA.
2. GU HONG
UNILEVER HOME & PERSONAL CARE USA, 40 MERRITT BOULEVARD, TRUMBULL, CONNECTICUT 06611, UNITED STATES OF AMERICA.
3. MURPHY DENNIS STEPHEN
1239 DEER TRAIL LANE, LIBERTYVILLE, ILLINOIS 60048, UNITED STATES OF AMERICA.

Specification

C6693/C
FORM - 2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See Section 10 and Rule 13)


RINSE-ADDED FABRIC TREATMENT COMPOSITION
HINDUSTAN UNILEVER LIMITED, a company incorporated under
the Indian Companies Act, 1913 and having its registered office
at 165/166, Backbay Reclamation, Mumbai -400 020, Maharashtra, India

The following specification particularly describes the invention and the manner in which it is to be performed


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RINSE-ADDED FABRIC TREATMENT COMPOSITION FIELD OF THE INVENTION
5 The invention relates to rinse-added fabric treatment
compositions, which have fabric treatment and additional
benefits, including anti-redeposition benefits, and to
methods of using compositions and achieving various benefits
from the use thereof.
10
BACKGROUND OF THE INVENTION
Laundry detergents provide excellent soil removal, but can often make fabric feel harsh after washing. To combat this
15 problem, a number of fabric conditioning technologies,
including rinse-added softeners, dryer sheets, and 2-in-l detergent softeners, have been developed. The majority of fabric softeners contain a cationic active, which is deposited on the fabric. Rinse-added liquid fabric
2 0 softeners are among the most popular forms of fabric softening products.
A consumer need exists for fabric softeners to deliver benefits in addition to fabric softening. The deposition of
25 functional actives in the rinse cycle is higher than in wash cycle, and it is desirable to have a functional ingredient to deliver in the rinse cycle for benefits thereafter. One drawback of fabric softener treatment is a gradual excess accumulation of a cationic fabric softener on the surface of
30 the fabric, especially after repeated use. The excess of cationic fabric softener on the fabric bears a positive charge and is hydrophobic, and tends to have a strong interaction with stain and soils that usually have a

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negative charge. This makes stains and soil more difficult to remove from fabrics and more easily re-deposited onto the fabric after being removed. Also, an excess build-up of conditioning agent on fabric might have a negative effect on 5 anti-redepostion efficacy of detergent in the next wash. As the result, fabric, especially white fabric, looks dull after repeated treatment with a cationic fabric softener.
Therefore, there is a need to minimize the negative effect 10 of fabric softener on anti-redeposition to keep fabric integrity.
Thus, there is a need to improve anti-redeposition in fabric softening treatment. Sodium carboxymethyl celluloses
15 (hereinafter "CMC") are known anti-redeposition agents.
Unfortunately, due to their anionic nature, CMC interacts with cationic fabric actives in liquid formulations, resulting in instability and precipitation, thus detracting from the performance and appearance of the commercial
2 0 product.
Various fabric treatment products containing fabric softening actives and CMC have been described. See for instance EP 257 861; WO 03/097781; Martens et al., US 25 2006/0030515; Ramachandran, US 4,203,851; EP 885 283; EP 123 400.
The present invention is based at least in part on the discovery that liquid fabric treatment compositions may be 30 manufactured which contain cationic fabric softeners and CMC

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(thus delivering fabric softening and additional benefits, including anti-redeposition), yet are physically stable.
SUMMARY OF THE INVENTION 5
The present invention includes in part an aqueous rinse-added fabric treatment composition, the composition comprising:
(a) from about 2.5% to about 30%, by weight of the
10 composition, of a cationic fabric softener, with
the provision that when the cationic fabric softener has Formula (I) wherein each R1 is methyl it is present in amount of at least about 10%;
(b) from about 0.0.5% to about 2%, by weight of the
15 composition, of a water-soluble sodium
carboxymethylcellulose having a molecular weight average from about 5,000 about 250,000 Da.
The invention also includes methods of improving anti-20 redeposition and fragrance delivery benefits of fabric treatment compositions.
DETAILED DESCRIPTION OF THE INVENTION ..
25 Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and/or use are to be understood as modified by the word "about". All amounts
30 are by weight of the final liquid composition, unless otherwise specified.

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It should be noted that in specifying any range of concentration, any particular upper concentration can be associated with any particular lower concentration. 5
For the avoidance of doubt the word "comprising" is intended to mean "including" but not necessarily "consisting of" or "composed of". In other words, the listed steps or options need not be exhaustive.
10
"Liquid" as used herein means that a continuous phase or predominant part of the composition is liquid and that a composition is flowable at 15°C and above (i.e., suspended solids may be included). Concentrated liquids and gels are
15 included in the definition of liquid compositions as used herein.
CATIONIC FABRIC SOFTENERS
20 The fabric conditioning composition of the present invention comprises one or more cationic softening materials.
It is especially preferred if the cationic compound is a substantially water insoluble quaternary ammonium material 25 which comprises a compound having two C12-22 alkyl or alkenyl groups connected to the nitrogen head group via at least one ester link. It is more preferred if the quaternary ammonium material has two ester links present.
30 A first group of preferred cationic materials for use in the invention is represented by formula (I):

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5 Formula (I)
wherein each R1 group is independently selected from C1-4 10 alkyl, hydroxyalkyl or C2-4 alkenyl groups; and wherein each R2 group is independently selected from C8-28 alkyl or alkenyl groups;
15
T is
X~ is any anion compatible with the cationic surfactant, such as halides or alkyl sulphates, e.g. chloride, methyl 20 sulphate or ethyl sulphate and n is 0 or an integer from 1-5.
Especially preferred materials within this formula are di-alkenyl esters of triethanol ammonium methyl sulphate and N-
25 N-di(tallowoyloxy ethyl) N,N-dimethyl ammonium chloride. Commercial examples of compounds within this formula are Tetranyl AOT-1 (di-oleic ester of triethanol ammonium methyl sulphate 80% active), AO-1(di-oleic ester of triethanol ammonium methyl sulphate 90% active), Ll/90 (partially
30 hardened tallow ester of triethanol ammonium methyl sulphate

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90% active), L5/90 (palm ester of triethanol ammonium methyl sulphate 90% active (supplied by Kao corporation); Rewoquat WE15 (C10-C20 and C16-C18 unsaturated fatty acid reaction products with triethanolamine dimethyl sulphate quaternised 5 90 % active), ex Witco Corporation, Stepantex VK-90, Stepantex VQ-90, Stepantex PH90, StepanUL9O (Stepan); Armosoft TEQ-E and Armosoft HT-TEQ (Akzo Nobel); Varisoft WE18, Varisoft WE20 Varisoft WE HV, RewoquatWE20,Varisoft WE21CP (Degussa), and Armosoft DEQ (di-tfrllowylethyl ester 10 dimethyl ammonium salt) from Akzo.
A second preferred type of quaternary ammonium material is represented by formula (II):
15
Formula (II)
20
wherein R1, R2, n and X" are as defined above.
Preferred materials of this class such as 1,2
bis[tallowoyloxy]-3- trimethylammonium propane chloride and 25 1,2-bis[oleyloxy]-3-trimethylammonium propane chloride and their method of preparation are, for example, described in US 4137180 (Lever Brothers), the contents of which are incorporated herein. Preferably these materials also comprise small amounts of the corresponding monoester, as 30 described in US 4137180.

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A third preferred type of quaternary ammonium material is represented by formula (III) :
5
Formula (III)
10 where R1 and R2 are C3-28 alkyl or alkenyl groups; R3 and R4 are C1-4 alkyl or C2-4 alkenyl groups and X~ is as defined above.
Examples of compounds within this formula include di(hard 15 tallow alkyl)dimethyl ammonium chloride, di(hard tallow alkyl) dimethyl ammonium methyl sulphate, di(tallow alkyl)dimethyl ammonium chloride, di(tallow alkyl) dimethyl ammonium methyl sulphate, dihexadecyl dimethyl ammonium chloride, dioctadecyl dimethyl ammonium chloride and 20 di(coconut alkyl) dimethyl ammonium chloride. Commercially avialble sources of compounds within Formula III include Arquad2HT-75, Arquad HC, Arquad HTL8 MS (Akzo Nobel); Varisoft 137(Degussa).
25 Another preferred cationic softening agent is diamido quaternary ammonium salt of formula (IV):

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wherein Rl is an acyolic aliphatic C15-C22 hydrocarbon group, R2 is a divalent alkylene group having 1 to 3 carbon atoms, R5 and R8 are C1-C4 saturated alkyl or hydroxyalkyl group and A is anion.
Also suitable are diamido alkoxylated quaternary ammonium salts having Formula (V):
10


15
20

wherein n is equal to from about 1 to about 5, and R1, R2, R5
and A are as defined above.
Commercial sources of fabric softeners within Formula
IV/Formula V include but are not limited to Stepan's Accosoft 460HC, Accosoft 501, Accosoft 550-L90, Accosoft 550-75, Accosoft 550-90 HHV, Accosoft 440-75; Dialkyl quat-90 (Rhodia); Varisoft 222LM90%, Varisoft 110, Rewoquat W222LM (Degussa), Incrosoft 100 pastilles (Croda).
Optionally, fatty acids may be used, as a coactive softening ingredient, to enhance deposition and to reduce cost.

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Suitably, fatty acids include those containing from about 12 to 25, preferably from about 13 to about 22, more preferably from about 16 to about 20, total carbon atoms, with the fatty chain having from about 10 to about 22, preferably 5 from about 10 to 20, more preferably from about 12 to about 18 total carbon atoms. Fatty acids can have straight and branched saturated and unsaturated alkyl chains. Fatty acids are present in the product at a level of from 0% to about 5%, preferably from about 0.25% to about 2.5%. 10
It is advantageous for environmental reasons if the quaternary ammonium material is biologically degradable.
Generally, the cationic softeners are present in the 15 composition in amount from 2.5% to 30%, more preferably 5 to 27%, most preferably 5 to 25%.
If it is desired to provide the composition as a concentrate, then the cationic softeners are preferably 20 present in an amount of 10-50%, more preferably 10-45% by weight, most preferably 10-30% by weight.
Preferred cationic compounds are substantially water insoluble. 25
CMC
The second essential ingredient is selected from specific group of CMC. By virtue of employing specific CMC, 30 stability of liquid fabric softening compositions is
maintained (i,e., no co-precipitation), without detriment to

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fabric softening, yet anti-redeposition and other favourable properties (enhanced fragrance deposition, improved shape retention) are attained.
5 In order to achieve these benefits, CMC included in the
inventive compositions is selected from CMC with a molecular weight average in a range of from 15,000 to 250,000 Da (Daltons), more preferably in a range of from 20,000 to 90,000 Da. It has been found that CMC with the molecular
10 weight average in the claimed ranges can be co-present with a cationic softener, despite the anionic nature of CMC without disturbing the physical stability of the composition, i.e. without causing precipitation and phase separation. The degree of substitution of CMC is also
15 important: suitable CMC has a degree of substitution in the range of 0.5 to 1.5, preferably in the range of from 0.5 to 1. The most preferred CMC has a molecular weight of 90,000 and the degree of substitution of 0.7. The molecular weight is measured by use of size exclusion chromatography and is a
20 weight average molecular weight. The degree of substitution (DS) describes the average number of carboxymethyl groups attached to each anhydroglucose unit. There are 3 hydroxyl groups per anhydroglucose unit on cellulose, and so the DS can range from 0 to 3. The DS of CMCs is determined by use
25 of Near Infrared Adsorption Spectrum. In general, the DS can also be determined by the following method. Weigh accurately about 200 mg of the sample, previously dried at 105° to constant weight, and transfer it into a 250 ml, glass-stoppered Erlenmeyer flask. Add 75 ml of glacial
30 acetic acid, and connect the flask with a water-cooled
condenser, and reflux gently on a hot plate for 2 hours.

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Cool, transfer the solution to a 250-ml beaker with the aid of 50 ml of glacial acetic acid, and titrate with 0.1 N perchloric acid in dioxane while stirring with a magnetic stirrer. Determine the endpoint potentiometrically with a 5 pH meter equipped with a standard glass electrode and a
calomel electrode modified as follows: Discard the aqueous potassium chloride solution, rinse and fill with the supernatant liquid obtained by shaking thoroughly 2 g each of potassium chloride and silver chloride (or silver oxide)
10 with 100 ml of methanol, then add a few crystals of
potassium chloride and silver chloride (or silver oxide) to the electrode. Record the ml of 0.1 N perchloric acid versus mV (0 to 700 mV range), and continue the titration to a few ml beyond the endpoint. Plot the titration curve, and
15 read the volume (A), in ml, of 0.1 N perchloric acid at the inflection point. Calculate the degree of substitution (DS) by the formula
(16.2A/G)/[1.000 - (8.0 A/G)3, 20
where
A = the volume of 0.1 N perchloric acid required (ml) G = weight of the sample taken (mg) 25 16.2 = one-tenth of the formula weight of one anhydroglucose unit
8.0 = one-tenth of the formula weight of one sodium carboxymethyl group
30 CMC is included in the. inventive compositions in an amount of from 0.05 to 2%, preferably in an amount of from 0.3 to 2%, most preferably in an amount of from 0.5 to 2%. It has been found that relatively higher amounts of CMC within the

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included ranges produce soil anti-redeposition benefits after the first rinse, whereas lower (i.e. below 0.3%) amounts may need a repeated treatment with inventive compositions to deliver improved anti-redeposition benefits. 5
WATER
The compositions are aqueous, that is, the inventive compositions comprise generally from 20% to 96.5%, 10 preferably from 40% to 90% of water, most preferably from 50% to 80% to achieve optimum cost and ease of manufacturing, of water. Other liquid components, such as solvents, liquid organic matters including organic bases, and their mixtures can be present.
15
pH
The pH of the inventive liquid compositions is generally in the range of from 2.5 to 4.5. If the pH is too high, trace
20 amounts of amine salts from fabric softener may precipitate, affecting product stability Also,depending on the chemical properties of cationic softening agents, the pH affects the stability of the composition such as discoloration, degradation.
25

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PROCESS OF MAKING COMPOSITIONS
CMC is added slowly while stirring into water to get an even dispersion. The mixture then is heated to around 65°C to 5 ensure CMC is fully dissolved. To this solution at around 65°C, pre-melted cationic softening agent(s) is/are added slowly while maintaining mixing. A salt solution may be added at approximately halfway to the mixture through the addition of cationic softening agents as needed to avoid the
10 formation of a gel or a thick dispersion. After the mixture is cooled down below 45°C, perfume and other ingredients may be added while keeping mixing. A salt solution may be added to the mixture to get the desirable viscosity. Also, the pH of the mixture is adjusted to pH 2.5 to 4.5 by use of
15 inorganic or organic acid as needed.
SURFACTANT
Inventive compositions are preferably substantially free of 20 detergent surfactant in order to maximize the performance from fabric softener. The cationic softeners included in the compositions interact unfavourably with anionic surfactants, thus detracting from the performance of the compositions. The presence of non-ionic and other 25 surfactants is also preferably minimized since a surfactant removes compounds from the fabric, whereas the cationic softener and the CMC included in the inventive compositions seek to be deposited onto the fabric. Thus, the inventive compositions generally contain less than 2% of detergent 30 surfactants, preferably less than 1%, most preferably less

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than 0.5% and optimally are entirely free of detergent surfactants.
OPTIONAL INGREDIENTS 5
Suitable optional ingredients include but are not limited to optical brighteners, UV inhibitors, dye-transfer inhibitors, dye fixative, malodour reducer, bactericides, chelating agents, silicones as a cosoftener and chemicals
10 conventionally used in textile treatment dispersion
compositions for example, preservatives, anti-shrinkage agents, fabric crisping agents, antioxidants, perfumes and the like. Preferably, dye-transfer inhibitor, and optical brighter, cyclodextrin, and profragrance. Particularly,
15 dye-transfer inhibitor, and optical brighter can be incorporated from 0.05% to 0.3%. Perfumes also are preferred, since the inventive compositions enhance perfume deposition.
2 0 PRODUCT FORM
The composition is a liquid, preferably colored composition, packaged in the opaque plastic container.
25 The container of the present invention may be of any form or size suitable for storing and packaging liquids for household use. For example, the container may have any size but usually the container will have a maximal capacity of 0.05 to 15 L, preferably, 0.1 to 5 L, more preferably from
30 0.2 to 2.5 L. Preferably, the container is suitable for
easy handling. For example the container may have handle or

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a part with such dimensions to allow easy lifting or carrying the container with one hand. The container preferably has a means suitable for pouring the liquid detergent composition and means for reclosing the container. 5 The pouring means may be of any size of form but, preferably will be wide enough for convenient dosing the liquid detergent composition. The closing means may be of any form or size but usually will be screwed or clicked on the container to close the container. The closing means may be 10 cap which can be detached from the container.
Alternatively, the cap can still be attached to the container, whether the container is open or closed. The closing means may also be incorporated in the container.
15 METHOD OF USING COMPOSITIONS
The compositions are used for the rinsing of fabrics, preferably in the rinse cycle of the automatic washing machine. In use, the indicated quantity of the composition
20 (generally in the range from 30 to 200 ml or 30 g to 200grams) depending on the actives of the composition depending on the size of the laundry load, the size and type of the washing machine, is added to the washing machine which also contains water and the soiled laundry.
25
BENEFITS
The compositions of this invention are intended to confer conditioning benefits to garments, home textiles, carpets 30 and other fibrous or fiber-derived articles. These

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formulations are not to be limited to conditioning benefits, however, and will often be multi-functional.
The primary treatment benefit afforded by these products is 5 softening. Softening includes, but is not limited to, an improvement in the handling of a garment treated with the compositions of this invention relative to that of an article laundered under identical conditions but without the use of this invention. Consumers will often describe an 10 article that is softened as "silky" or "fluffy", and
generally prefer the feel of treated garments to those that are unsoftened.
The conditioning benefits of these compositions are not 15 limited to softening, however. They may, depending on the particular embodiment of the invention selected, also provide an antistatic benefit. In addition to softening, the inclusion of CMC into the inventive compositions is believed to provide anti-redeposition benefits, enhanced 20 fragrance deposition and enhanced shape-retention benefit.
The following specific examples further illustrate the invention, but the invention is not limited thereto.
25 Armosoft DEQ — a cationic softening agent from Akzo Nobel. The sodium carboxymethylcelluloses (CMC) are from Aqualon. Ambergum 3021 —a sodium carboxymethylcellulose with a molecular weight average of approximately 15,000 and an average degree of substitution (DS) of about 1.3.

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CMC-T 7LT is a technical grade sodium carboxymethylcellulose with a molecular weight average of 90,000Da with a DS of 0.7.
CMC- 7L2 has a DS of 0.84 with a molecular weight average of 5 about 90,OOODa.
CMC-7H4XF is a sodium carboxymethylcellulose with a molecular weight average around 700,000 with an average DS of 0.7.
10 EXAMPLES
These examples investigated the compatibility of various fabric softening actives with various tMC. The compositions were prepared by a method described above under Process of 15 Making Compositions. The compositions that were prepared and the results that were obtained are summarized in Tables 1-8 below. The actives of the ingredients listed are 100% as it is.

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TABLE 1

1 2 3 4 5 6 A |B |C
Ingredients weight %
Lactic acid 0.15 0.15 0.15 0.15 0.15 0.15 0.15
Ambergum302 1 0.13 0.13 0.13 0.13
CMC-T 7LT 0.13 0.13 0.13 0.13
CM07H4xF 0.13
Armosoft DEQ 10.00 21.0 17.0 17.0 17.0 10 5.5 5.5 10
Fragrance qs qs qs qs qs qs qs qs qs
Presevative qs qs qs qs qs qs qs qs qs
AlK(S04)2.1 2H20 0.05 0.13 0.16 0.06 0.01 0.01 0.02
CaC12.2H20 0.0 0.13 0.13
Water to 100% to 100% to 100% to 100% to 100% to 100% to
100% to 100% to 100%
Stability, overnight good good good good good good phase
separa
tion phase separ ation phase
separa tion
Stability, 1 month good good good good good good N/A N/A N/A

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TABLE 2

7 8 9 10 11
Ingredients weight %
Lactic acid 0.10 0.10
Ambergum3021 0.13 0.13
CMC-T 7LT 0.80 0.13
CMC-7L2 0.80
Armosoft DEQ 17.0 17.0
Ditallow dimethyl ammonium chloride 5.5 9.5 9.5
methyl
bis (tallowam
idoethyl)-2-
hydroxyethyl
ammonium
methyl
sulfate 6.0 6.0
dye qs qs qs qs qs
Fragrance qs qs qs qs qs
Preservative qs qs qs qs qs
A1K(S04)2.12 H20 0.13
CaC12.2H20 0.001 0.12 0.13 0.15
Water to 100% to 100% to 100% to 100% to 100%
Stability, overnight good good good good good
Stability, 1 month good good good good good

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TABLE 3
Fabric softening evaluation

D 12 13 14 E
Ingredients weight % weight %
Lactic acid 0.15 0.15 0.15
Ambergum302 1 0.13 0.13
CMC-T 7LT 0.13
CMC-7H4xF
ArmosoftDEQ 19.0 17.0 17.0
Ditallowdim ethyl ammonium chloride 5.5 5.5
dye qs qs qs qs qs
Fragrance qs qs qs qs qs
Presevative qs qs qs qs qs
A1K(S04)2.1 2H20 0.13
CaCl2.2H20 0.13 0.13 0.001 0.006
Water to 100% to 100% to 100% to 100% to 100%
Dosage (g) 26.5 29.6 29.6 72.0 72.0
Active (g) 5.04 5.03 5.03 3.96 3.96
Softening score 3.25 4.04 3.00 5.83 6.17
5
Compositions D and E were used as control in evaluation of
softening performance. Both D and E did not contain CMC. A
multiple comparison method was used to evaluate the
softening performance. The dosages and actives are listed
10 in Table 3 above. Composition were added in the rinse-cycle at the amount of dosage. A total 2.7 kg of fabrics including 2 harshened towels were washed with 98.6 g of Tide® original scent detergent in 82.3 liters of water at 120ppm hardness. At the rinse cycle, a certain amount of fabric softener was
15 added, and the water hardness was adjusted. After rinse
cycle, the fabrics were tumble dried. Next day, the towels

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were evaluated by panelists. A duplicate test with different wash machines and dryer was carried out. When compositions D, 12 and 13 were evaluated, twenty-eight observation of towel softness were made for each 5 composition. When compositions 14 and E were evaluated,
twenty-four observation of towel softness were made for each composition. The softness was scored from 1 to 10, 1 was the least soft and 10 was the most soft. The score was an average of scores from the observation. It can be seen that 10 all tested compositions delivered softening benefit, i.e. the addition of CMC did not deleteriously affect the softening benefit.
The compositions in Table 4 below were used in examination 15 of softening performance of the composition having CMC
against composition D without CMC. Thirty-six observation of towel softness were made for each composition. It can be seen again that the addition of CMC did not detract from softening performance. 20

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TABLE 4
Softening Evaluation

D 15 16
Ingredients
weight %
Water to 100% to 100% to 100%
Lactic acid 0.15 0.10 0.10
Ambergum302 1
CMC-T 7LT 0.80
CMC-7L2 0.8
ArmosoftDEQ 19.0 17.0 17.0
dye qs qs qs
Fragrance qs qs qs
Presevative qs qs qs
A1K(S04)2.1 2H20 0.13
CaCl2.2H20 0.13 0.13

Dosage (g) 26.5 29.6 29.6
Active (g) 5.04 5.03 5.03
Softening score 5.61 6.08 5.64
5
Antiredeposition test
The antiredeposition performance of compositions D, 4, 15, and 16 was evaluated. A Terg-O-Tometer was used to examine the anti-redeposition property. Fabric was first treated with each composition having the same actives in one liter of water with water hardness adjusted to 120 ppm. After
dryxng, two pieces of the treated fabrics were washed by use

® of "all free clear detergent" in Terg-O-Tometer in the
presence of stain-clothes and soil in 1 liter water with hardness of 120 ppm. After drying, the fabrics were read with a Hunter UltraScan Prospectrophotometer. The used

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stain-cloth and soil were EMPA106, a particulate oil stain and a carbon black or a dispersion of carbon black, a
particulate soil.
5 Cotton Fabrics (4x 6 inches) were used. TIC429 is weaved and TIC460 is double-knitted cotton. Six pieces of TIC429 were treated in each pot and four pieces of TIC4 60 were treated in each pot by adding the fabrics to 1000 ml of 0.050% of a tested softening (as it is 100%). The water hardness was
10 adjusted to 120ppm hardness. The bath was agitated at
100rpm at 24oC for 12 min. The fabrics were taken out from the fabric softener solution and squeezed to remove the extra water. The fabric softener-treated fabrics were then dried.
15
In antiredeposition test, two fabric softener-treated fabrics were added to 1000 ml of a 0.17% all free clear detergent aqueous solution with donor stain-clothes and soils. The water hardness was adjusted to 120ppm hardness.
20 The wash bath was agitated at lOOrpm at 32°C for 12 min. along with stain-donors clothes. The washed fabrics were taken out from the detergent solution. After rinsed in running water, the fabric were dried and then read by use of Hunter UltraScan Prospectrophotometer to evaluate the
25 antiredepostion effect.
The TIC429 fabrics were treated with the fabric softener and
® washed with "all free clear" twice in the presence of 0.05g
® carbon black in one liter of 0.17% wall free clear"
30 detergent solution. L* is the lightness of fabric and dE is

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the difference in color against the original standard fabric. The smaller the dE, the less color change the fabric has after wash, indicating better antiredeposition. The results are in Table below. The fabric treated with 5 composition 4 having 0.13% CMC T7LT gave better whiteness than composing D having no CMC.

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TABLE 5
Antiredeposition of particulate soils

Sample L* dE
D 71.71 15.91
4 73.04 14.58
5 The TIC4 60 fabrics were treated with the fabric softener and
® washed with "all free clear" one time with 25 g of 0.2%
carbon black dispersion in one liter of 0.17% ""all free
® clear" detergent solution. The fabric treated with
Composition 15 having 0.8% CMC-T 7LT gave better whiteness 0 than Composition D having no CMC (see Table 6). Actually, it was easy to visually notice the difference between the two fabrics.
TABLE 6 5 Antiredeposition of particulate soils

Sample L* dE
D 76.02 16.24
15 79.43 12.82
The TIC4 60 fabric was treated with the fabric softener and
® washed with "all free clear" with 3 pieces of EMPA106 as a
0 stain donor-cloth and 25 g of 0.2% carbon black dispersion
® in 1000 ml of 0.17% "all free clear" detergent aqueous
solution. The fabric treated with compositions 15 and 16 that had 0.8% CMC gave better whiteness than composition D without CMC. Actually, it was easy to visually notice the 5 difference among the three fabrics. The fabric treated with Composition 15 with CMC T 7LT was slightly whiter than the fabrics treated with Composition 16 with CMC 7L2, and both

WO 2007/118732

PCT/EP2007/051993


of them were much whiter than the fabrics treated by with Composition D having no CMC.
TABLE 7 5 Antiredeposition of mixed soils of particulate soils and oil particulate soil

Sample L* dE
D 74.91 17.19
15 7 8.92 13.20
16 77.23 14.89
The TIC460 fabric was treated with the fabric softener and
® 10 washed with "all free clear" with 3 pieces of EMPA106 as a
stain donor-cloth in 1000 ml of 0.17% "all free clear"
detergent aqueous solution. The fabric treated with
Compositions 15 and 16 that have 0.8% CMC gave better
whiteness than Composition D without CMC.
15
TABLE 8
Antiredeposition of oil particulate soils

Sample L* dE
D 87.51 4.45
15 88.62 3.37
16 88.29 3.70

WO 2007/118732 PCT/EP2007/051993
AMENDED CLAIMS
received by the International Bureau on 02 October 2007
(02.10.2007)

1. An aqueous rinse-added fabric treatment composition, the
composition comprising; 5 (a) from about 2.5% to about 30%, by weight of the
composition, of a cationic fabric softener, with the provision that when the cationic fabric softener has Formula (I)
15
10
wherein each R1 group is independently selected from Ci_^ alkyl, hydroxyalkyl or Cz-4 alkenyl groups; and-wherein each R2 group is independently selected from Ce-ze alkyl or alkenyl groups;
20

25
X" is any anion compatible with the cationic surfactant, such as halides or alkyl sulphates, e.g. chloride, methyl sulphate or ethyl sulphate and n is 0 or an integer from
AMENDED SHEET (ARTICLE 19)

WO 2007/118732

PCT/EP2007/051993

1-5 and when each R1 is methyl group/ it is present in amount of at least about 10%;
(b) from about 0.05% to about 2%, by weight of the
5 composition, of a water-soluble sodium
carboxymethy1cellulose having a molecular weight average from about 5,000 to below about 100,000 Da.
2. The composition of claim 1, wherein the composition
10 comprises less than 2% detergent surfactants selected from the group consisting of anionic and nonionic surfactants.
3. The composition of claim lf wherein the carfooxymethyl
cellulose has a degree of substitution of from about 0.5 to
15 about 1.5.
4. The composition of claim 1, wherein the pH of the
composition is in the range of from about 2,5 to about 4.5.
20 5. The composition of claim 1 further comprising a fatty
acid.
6. The composition of claim 17 wherein the caxboxymethyl
cellulose is present in an amount of at least about 0.3% by
25 weight of the composition.
7. The composition of claim 1 wherein the composition is in
the form of a stable dispersion.
30 8. The composition of claim 7 wherein the composition is stable for at least a year at room temperature.
AMENDED SHEET (ARTICLE 19)

WO 2007/118732

PCT/EP2007/051993

10. The composition of claim 1 wherein the molecular weight
average of the carboxymethyl cellulose is from about 10,000
to about 90,000 Da.
5
11. The composition of claim 1 wherein the carboxymethyl
cellulose has a molecular weight average of about 90,000 Da
and the degree of substitution of about 0.7.
10 12, The composition of claim 1 wherein the composition further comprises an ingredient selected, from the group consisting of optical brighters, dye transfer inhibitors, cyclotfextrins, profragrances, silicones, dye-fixativess, UV absorbers, and mixtures thereof.
15
13. A method of soil anti-redeposition during laundering of fabrics, the method comprising rinsing the fabrics with a rinse solution comprising the composition of claim 1.
20 14. A method of delivering fabric treatment benefits to fabrics by rinsing the fabrics with a rinse solution comprising the composition of claim 1.
15- A method of improving the fragrance deposition onto the
25 fabrics, the method comprising rinsing the fabrics with a rinse solution comprising the composition of claim 1.
Dated this 17th day of october 2008
HINDUSTAN UNILEVER LIMITED
(S. Venkatramani) Senior Patents Manager
AMENDED SHEET (ARTICLE 19)

Documents

Orders

Section Controller Decision Date

Application Documents

# Name Date
1 2223-MUMNP-2008-CORRESPONDENCE(23-09-2010).pdf 2010-09-23
1 2223-MUMNP-2008-FORM-27 [28-08-2024(online)].pdf 2024-08-28
2 2223-MUMNP-2008-FORM 3(10-12-2013).pdf 2013-12-10
2 2223-MUMNP-2008-RELEVANT DOCUMENTS [29-09-2023(online)].pdf 2023-09-29
3 2223-MUMNP-2008-RELEVANT DOCUMENTS [14-09-2022(online)].pdf 2022-09-14
3 2223-MUMNP-2008-FORM 3(10-11-2014).pdf 2014-11-10
4 2223-MUMNP-2008-SPECIFICATION(AMENDED)-(12-02-2016).pdf 2016-02-12
4 2223-MUMNP-2008-RELEVANT DOCUMENTS [09-09-2021(online)].pdf 2021-09-09
5 2223-MUMNP-2008-REPLY TO EXAMINATION REPORT-(12-02-2016).pdf 2016-02-12
5 2223-mumnp-2008-assignment.pdf 2018-08-09
6 2223-MUMNP-2008-POWER OF ATTORNEY-(12-02-2016).pdf 2016-02-12
6 2223-mumnp-2008-claims.doc 2018-08-09
7 2223-MUMNP-2008-FORM 3-(12-02-2016).pdf 2016-02-12
7 2223-mumnp-2008-claims.pdf 2018-08-09
8 2223-MUMNP-2008-CORRESPONDENCE(21-1-2010).pdf 2018-08-09
8 2223-MUMNP-2008-CLAIMS(MARKED COPY)-(12-02-2016).pdf 2016-02-12
9 2223-MUMNP-2008-CLAIMS (AMENDED)-(12-02-2016).pdf 2016-02-12
9 2223-MUMNP-2008-CORRESPONDENCE(25-2-2014).pdf 2018-08-09
10 2223-MUMNP-2008-ABSTRACT-(12-02-2016).pdf 2016-02-12
10 2223-MUMNP-2008-CORRESPONDENCE-280115.pdf 2018-08-09
11 2223-mumnp-2008-correspondence.pdf 2018-08-09
11 2223-MUMNP-2008-FORM 3-(19-03-2016).pdf 2016-03-19
12 Other Document [05-05-2017(online)].pdf 2017-05-05
13 2223-mumnp-2008-description(complete).pdf 2018-08-09
13 Form 26 [05-05-2017(online)].pdf 2017-05-05
14 2223-MUMNP-2008-Examination Report Reply Recieved-210915.pdf 2018-08-09
14 Form 13 [05-05-2017(online)].pdf 2017-05-05
15 2223-mumnp-2008-form 1.pdf 2018-08-09
15 2223-MUMNP-2008-ORIGINAL UNDER RULE 6(1A)-11-05-2017.pdf 2017-05-11
16 2223-MUMNP-2008-FORM 13(7-2-2012).pdf 2018-08-09
16 2223-MUMNP-2008-Written submissions and relevant documents (MANDATORY) [02-08-2017(online)].pdf 2017-08-02
17 2223-MUMNP-2008-PETITION UNDER RULE 137 [02-08-2017(online)].pdf_15.pdf 2017-08-02
17 2223-MUMNP-2008-FORM 18(21-1-2010).pdf 2018-08-09
18 2223-MUMNP-2008-PETITION UNDER RULE 137 [02-08-2017(online)].pdf 2017-08-02
18 2223-mumnp-2008-form 2(title page).pdf 2018-08-09
19 2223-MUMNP-2008-PatentCertificate11-10-2017.pdf 2017-10-11
20 2223-mumnp-2008-form 2.pdf 2018-08-09
20 2223-MUMNP-2008-IntimationOfGrant11-10-2017.pdf 2017-10-11
21 2223-MUMNP-2008-FORM 3(12-8-2011).pdf 2018-08-09
21 2223-MUMNP-2008_EXAMREPORT.pdf 2018-08-09
22 2223-MUMNP-2008-FORM 3(15-2-2011).pdf 2018-08-09
22 2223-mumnp-2008-wo international publication report a1.pdf 2018-08-09
23 2223-MUMNP-2008-FORM 3(15-2-2012).pdf 2018-08-09
23 2223-mumnp-2008-pct-isa-237.pdf 2018-08-09
24 2223-mumnp-2008-pct-isa-210.pdf 2018-08-09
24 2223-MUMNP-2008-FORM 3(22-5-2014).pdf 2018-08-09
25 2223-MUMNP-2008-OTHERS-210915.pdf 2018-08-09
25 2223-MUMNP-2008-FORM 3(22-6-2013).pdf 2018-08-09
26 2223-MUMNP-2008-FORM 3(23-1-2013).pdf 2018-08-09
26 2223-MUMNP-2008-Original Under Rule 6(1 A)Form 3-270117.pdf 2018-08-09
27 2223-MUMNP-2008-FORM 3(24-2-2010).pdf 2018-08-09
27 2223-MUMNP-2008-ORIGINAL UNDER RULE 6 (1A)-070817.pdf 2018-08-09
28 2223-MUMNP-2008-FORM 3(25-4-2015).pdf 2018-08-09
28 2223-MUMNP-2008-HearingNoticeLetter.pdf 2018-08-09
29 2223-MUMNP-2008-FORM 3(4-8-2010).pdf 2018-08-09
29 2223-mumnp-2008-form 5.pdf 2018-08-09
30 2223-MUMNP-2008-FORM 3(8-8-2012).pdf 2018-08-09
30 2223-mumnp-2008-form 3.pdf 2018-08-09
31 2223-MUMNP-2008-Form 3-091015.pdf 2018-08-09
31 2223-MUMNP-2008-Form 3-160816.pdf 2018-08-09
32 2223-MUMNP-2008-Form 3-140717.pdf 2018-08-09
33 2223-MUMNP-2008-Form 3-091015.pdf 2018-08-09
33 2223-MUMNP-2008-Form 3-160816.pdf 2018-08-09
34 2223-MUMNP-2008-FORM 3(8-8-2012).pdf 2018-08-09
34 2223-mumnp-2008-form 3.pdf 2018-08-09
35 2223-MUMNP-2008-FORM 3(4-8-2010).pdf 2018-08-09
35 2223-mumnp-2008-form 5.pdf 2018-08-09
36 2223-MUMNP-2008-HearingNoticeLetter.pdf 2018-08-09
36 2223-MUMNP-2008-FORM 3(25-4-2015).pdf 2018-08-09
37 2223-MUMNP-2008-ORIGINAL UNDER RULE 6 (1A)-070817.pdf 2018-08-09
37 2223-MUMNP-2008-FORM 3(24-2-2010).pdf 2018-08-09
38 2223-MUMNP-2008-FORM 3(23-1-2013).pdf 2018-08-09
38 2223-MUMNP-2008-Original Under Rule 6(1 A)Form 3-270117.pdf 2018-08-09
39 2223-MUMNP-2008-FORM 3(22-6-2013).pdf 2018-08-09
39 2223-MUMNP-2008-OTHERS-210915.pdf 2018-08-09
40 2223-MUMNP-2008-FORM 3(22-5-2014).pdf 2018-08-09
40 2223-mumnp-2008-pct-isa-210.pdf 2018-08-09
41 2223-MUMNP-2008-FORM 3(15-2-2012).pdf 2018-08-09
41 2223-mumnp-2008-pct-isa-237.pdf 2018-08-09
42 2223-MUMNP-2008-FORM 3(15-2-2011).pdf 2018-08-09
42 2223-mumnp-2008-wo international publication report a1.pdf 2018-08-09
43 2223-MUMNP-2008-FORM 3(12-8-2011).pdf 2018-08-09
43 2223-MUMNP-2008_EXAMREPORT.pdf 2018-08-09
44 2223-mumnp-2008-form 2.pdf 2018-08-09
44 2223-MUMNP-2008-IntimationOfGrant11-10-2017.pdf 2017-10-11
45 2223-MUMNP-2008-PatentCertificate11-10-2017.pdf 2017-10-11
46 2223-MUMNP-2008-PETITION UNDER RULE 137 [02-08-2017(online)].pdf 2017-08-02
46 2223-mumnp-2008-form 2(title page).pdf 2018-08-09
47 2223-MUMNP-2008-PETITION UNDER RULE 137 [02-08-2017(online)].pdf_15.pdf 2017-08-02
47 2223-MUMNP-2008-FORM 18(21-1-2010).pdf 2018-08-09
48 2223-MUMNP-2008-FORM 13(7-2-2012).pdf 2018-08-09
48 2223-MUMNP-2008-Written submissions and relevant documents (MANDATORY) [02-08-2017(online)].pdf 2017-08-02
49 2223-mumnp-2008-form 1.pdf 2018-08-09
49 2223-MUMNP-2008-ORIGINAL UNDER RULE 6(1A)-11-05-2017.pdf 2017-05-11
50 2223-MUMNP-2008-Examination Report Reply Recieved-210915.pdf 2018-08-09
50 Form 13 [05-05-2017(online)].pdf 2017-05-05
51 2223-mumnp-2008-description(complete).pdf 2018-08-09
51 Form 26 [05-05-2017(online)].pdf 2017-05-05
52 Other Document [05-05-2017(online)].pdf 2017-05-05
53 2223-mumnp-2008-correspondence.pdf 2018-08-09
53 2223-MUMNP-2008-FORM 3-(19-03-2016).pdf 2016-03-19
54 2223-MUMNP-2008-ABSTRACT-(12-02-2016).pdf 2016-02-12
54 2223-MUMNP-2008-CORRESPONDENCE-280115.pdf 2018-08-09
55 2223-MUMNP-2008-CLAIMS (AMENDED)-(12-02-2016).pdf 2016-02-12
55 2223-MUMNP-2008-CORRESPONDENCE(25-2-2014).pdf 2018-08-09
56 2223-MUMNP-2008-CORRESPONDENCE(21-1-2010).pdf 2018-08-09
56 2223-MUMNP-2008-CLAIMS(MARKED COPY)-(12-02-2016).pdf 2016-02-12
57 2223-MUMNP-2008-FORM 3-(12-02-2016).pdf 2016-02-12
57 2223-mumnp-2008-claims.pdf 2018-08-09
58 2223-MUMNP-2008-POWER OF ATTORNEY-(12-02-2016).pdf 2016-02-12
59 2223-MUMNP-2008-REPLY TO EXAMINATION REPORT-(12-02-2016).pdf 2016-02-12
59 2223-mumnp-2008-assignment.pdf 2018-08-09
60 2223-MUMNP-2008-RELEVANT DOCUMENTS [09-09-2021(online)].pdf 2021-09-09
60 2223-MUMNP-2008-SPECIFICATION(AMENDED)-(12-02-2016).pdf 2016-02-12
61 2223-MUMNP-2008-FORM 3(10-11-2014).pdf 2014-11-10
61 2223-MUMNP-2008-RELEVANT DOCUMENTS [14-09-2022(online)].pdf 2022-09-14
62 2223-MUMNP-2008-FORM 3(10-12-2013).pdf 2013-12-10
62 2223-MUMNP-2008-RELEVANT DOCUMENTS [29-09-2023(online)].pdf 2023-09-29
63 2223-MUMNP-2008-CORRESPONDENCE(23-09-2010).pdf 2010-09-23
63 2223-MUMNP-2008-FORM-27 [28-08-2024(online)].pdf 2024-08-28

ERegister / Renewals

3rd: 21 Dec 2017

From 02/03/2009 - To 02/03/2010

4th: 21 Dec 2017

From 02/03/2010 - To 02/03/2011

5th: 21 Dec 2017

From 02/03/2011 - To 02/03/2012

6th: 21 Dec 2017

From 02/03/2012 - To 02/03/2013

7th: 21 Dec 2017

From 02/03/2013 - To 02/03/2014

8th: 21 Dec 2017

From 02/03/2014 - To 02/03/2015

9th: 21 Dec 2017

From 02/03/2015 - To 02/03/2016

10th: 21 Dec 2017

From 02/03/2016 - To 02/03/2017

11th: 21 Dec 2017

From 02/03/2017 - To 02/03/2018

12th: 20 Feb 2018

From 02/03/2018 - To 02/03/2019

13th: 27 Feb 2019

From 02/03/2019 - To 02/03/2020

14th: 28 Feb 2020

From 02/03/2020 - To 02/03/2021

15th: 03 Feb 2021

From 02/03/2021 - To 02/03/2022

16th: 01 Mar 2022

From 02/03/2022 - To 02/03/2023

17th: 02 Mar 2023

From 02/03/2023 - To 02/03/2024

18th: 01 Mar 2024

From 02/03/2024 - To 02/03/2025