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Title:
FABRIC SOFTENING COMPOSITIONS AND METHODS
Document Type and Number:
WIPO Patent Application WO/2002/040623
Kind Code:
A2
Abstract:
The present invention relates to stable, aqueous fabric softening compositions, fabric softening methods and articles of manufacture that use such fabric softening compositions comprising polyalkyleneoxy polysiloxanes selected from the group consisting of polyethyleneoxy polysiloxane, polyethyleneoxy/polypropyleneoxy polysiloxanes, and mixtures thereof. The composition is preferably applied as small particle size droplets, especially from spray containers. The present invention also relates to a method of identifying, selecting, and/or designing the preferred polyethyleneoxy polysiloxanes and/or polyethyleneoxy/polypropyleneoxy polysiloxanes that provide superior fabric softening performance in general, and especially for use in the fabric softening composition of the present invention.

Inventors:
TRINH TOAN
SCHNEIDERMAN EVA
STANTON DAVID THOMAS
SMITH JOHN WILLIAM
KRAMER MICHAEL LEE
TORDIL HELEN BERNARDO
FRANKENBACH GAYLE MARIE
LIU ZAIYOU
BARNABAS MARY VIJAYARANI
Application Number:
PCT/US2001/043285
Publication Date:
May 23, 2002
Filing Date:
November 20, 2001
Export Citation:
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Assignee:
PROCTER & GAMBLE (US)
International Classes:
C08F283/12; C08F291/00; G01N33/44; C08L51/00; C08L51/08; C08L53/00; C11D1/82; C11D3/00; C11D3/37; C11D17/00; G06F19/00; C11D17/04; G06F19/16; (IPC1-7): C11D3/00
Domestic Patent References:
WO2000024857A22000-05-04
Foreign References:
EP0544493A11993-06-02
US5955093A1999-09-21
US6001343A1999-12-14
US5880089A1999-03-09
EP1092803A12001-04-18
US3299112A1967-01-17
Attorney, Agent or Firm:
Reed, David T. (OH, US)
Download PDF:
Claims:
What is claimed is:
1. A fabric softening composition comprising: (A) an effective amount to soften fabric, of polyalkyleneoxy polysiloxane selected from the group consisting of polyethyleneoxy polysiloxane, polyethyleneoxy/polypropyleneoxy polysiloxanes, and mixtures thereof, having an average molecular weight of from about 3,000 to about 200,000, and being characterized by Correlation I : wherein t&num diSi is the average total number of the Si (CH3) 20 units in the molecule ; t#EO is the average total number of the ethyleneoxy CH2CH2O units in the molecule; % Si is the weight percent of all siloxane units in the molecule; and the softness index S is at least about 10; (B) optionally, an effective amount of fabric wrinkle control agent; (C) optionally, an effective amount to provide olfactory effects of perfume; (D) optionally, an effective amount to improve the performance of the composition, of surfactant; (E) optionally, an effective amount, to kill, or reduce the growth of microbes, of antimicrobial active; (F) optionally, an effective amount to assist in antimicrobial action of aminocarboxylatechelator; (G) optionally, an effective amount to control malodor, of odor controlling agent; (H) optionally, an effective amount of antimicrobial preservative; (I) optionally, an effective amount of adjunct quaternary ammonium fabric softeningagent; (J) optionally, adjunct material selected from the group consisting of chemical stabilizer including antioxidant, static control agent, suds suppressor, soil release agent, colorant, brightener, insect repelling agent, moth repelling agent, and mixtures thereof; and (K) aqueous carrier, wherein said composition contains at least one additional component selected from the group consisting of (B) through (J).
2. The composition of Claim 1, wherein said S has a value of at least about 20.
3. The composition of Claim 1, wherein said t&num diSi is from about 4 to about 600.
4. The composition of Claim 3, wherein said t&num diSi is from about 90 to about 510.
5. The composition of Claim 1, wherein said t#EO is from about 30 to about 2,200.
6. The composition of Claim 5, wherein said t#EO is from about 200 to about 1,200.
7. The composition of Claim 1, wherein said % Si is from about 3 to about 65.
8. The composition of Claim 7, wherein said % Si is from about 12 to about 60.
9. The composition of Claim 1, wherein said polyalkyleneoxy polysiloxane has a molecular weight of from about 7,500 to about 140,000.
10. The composition of Claim 9, wherein said polyalkyleneoxy polysiloxane has a molecular weight of from about 20,000 to about 40,000.
11. The composition of any one of Claims 110, wherein said polyalkyleneoxy polysiloxane is polyethyleneoxy polysiloxane.
12. The composition of any one of Claims 110, wherein said polyalkyleneoxy polysiloxane is polyethyleneoxy/polypropyleneoxy polysiloxane.
13. The composition of any one of Claims 112, wherein said polyalkyleneoxy polysiloxane is present at a level of from about 0.01% to about 10%, by weight of the composition.
14. The composition of any one of Claims 113, wherein said fabric wrinkle control agent is selected from the group consisting of fabric lubricant, shape retention polymer, fabric care polysaccharide, hydrophilic plasticizer, and mixtures thereof, and present at a level of from about 0.05% to about 5%.
15. The composition of any one of Claims 114, wherein said perfume is present at a level of from about 0.003% to about 0.5%, by weight of the composition, and wherein said perfume comprises at least about 25%, by weight of the perfume composition of substantive perfume ingredients that have a boiling point of at least about 250°C.
16. The composition of Claim 15, wherein said substantive perfume ingredients are selected from the group consisting of allyl cyclohexane propionate, ambrettolide, amyl benzoate, amyl cinnamate, amyl cinnamic aldehyde, amyl cinnamic aldehyde dimethyl acetal, isoamyl salicylate, hydroxycitronellalmethyl anthranilate, benzophenone, benzyl salicylate, isobutyl quinoline, betacaryophyllene, cadinene, cedrol, cedryl acetate, cedryl formate, cinnamyl cinnamate, cyclohexyl salicylate, cyclamen aldehyde, dihydro isojasmonate, diphenyl methane, diphenyl oxide, dodecalactone, 1 (1, 2,3,4,5,6,7,8 octahydro2,3,8,8tetramethyl2naphthalenyl)ethanone, ethylene brassylate, ethyl methyl phenyl glycidate, ethyl undecylenate, isoeugenol, 15hydroxypentadecanoic acid lactone, 1, 3,4,6,7,8hexahydro4,6,6,7,8,8hexamethylcyclopentagamma2benzopyran, geranyl anthranilate, hexadecanolide, hexenyl salicylate, hexyl cinnamic aldehyde, hexyl salicylate, paratertiarybutylalphamethyl hydrocinnamic aldehyde, linalyl benzoate, 2 methoxy naphthalene, methyl cinnamate, methyl dihydrojasmonate, betamethyl naphthyl ketone, musk indanone, musk ketone, musk tibetine, myristicin, deltanonalactone, oxahexadecanolide10, oxahexadecanolide11, patchouli alcohol, 5acetyl1, 1, 2,3,3,6 hexamethylindan, phenyl ethyl benzoate, phenylethylphenylacetate, phenyl heptanol, phenyl hexanol, alphasantalol, 15hydroxypentadecanoic acid, lactone, tonalid, delta undecalactone, gammaundecalactone, vetiveryl acetate, yarayara, allyl phenoxy acetate, cinnamic alcohol, cinnamic aldehyde, cinnamyl formate, coumarin, dimethyl benzyl carbinyl acetate, ethyl cinnamate, ethyl vanillin (3methoxy4ethoxy benzaldehyde), eugenol, eugenyl acetate, heliotropine, indol, isoeugenol, koavone, methylbetanaphthyl ketone, methyl cinnamate, methyl dihdrojasmonate, beta methyl naphthyl ketone, methyl nmethyl anthranilate, deltanonalactone, gammanonalactone, para methoxy acetophenone (acetanisole), phenoxy ethyl iso butyrate, phenoxy ethyl propionate, piperonal, triethyl citrate, vanillin, and mixtures thereof.
17. The composition of any one of Claims 116, wherein said surfactant is present at a level of from about 0.05% to about 5%, by weight of the composition, and selected from the group consisting of nonionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant, and mixtures thereof.
18. The composition of Claim 17, wherein said surfactant is nonionic surfactant present at a polyethyleneoxy polysiloxane/nonionic surfactant weight ratio of from about 4: 1 to about 1: 3.
19. The composition of any one of Claims 118, wherein said antimicrobial active is present at a level of from about 0.001% to about 0.8%, by weight of the composition.
20. The composition of any one of Claims 119, wherein said odor controlling agent is selected from the group consisting of uncomplexed cyclodextrins; zinc and copper salts; soluble carbonate and/or bicarbonate salts; water soluble ionic polymers; and mixtures thereof; and is present at a level of from about 0.01% to about 5%, by weight of the composition.
21. The composition of any one of Claims 120, wherein said adjunct quaternary ammonium fabric softening agent is present at a level of from about 0.05% to about 3%, by weight of the usage composition.
22. The composition of any one of Claims 121, wherein said aqueous carrier is water, said composition optionally containing from 0% to about 20%, by weight of the total composition, of low molecular weight water soluble organic solvent, selected from the group consisting of ethanol, isopropanol, propanol, and mixtures thereof.
23. The composition of any one of Claims 112, wherein said composition is a concentrated composition to be diluted for use, wherein: (A) the level of said polyalkyleneoxy polysiloxane is from about 1% to about 30%, by weight of the composition; (B) when present, the level of said optional fabric wrinkle control agent is of from about 1% to about 20%, by weight of the composition; (C) when present, the level of said optional perfume is from about 0.01% to about 5%, by weight of the composition; (D) when present, the level of said optional surfactant is from about 0.1% to about 15%, by weight of the composition; (E) when present, the level of said optional antimicrobial active is from about 0.003% to about 2%, by weight of the composition; and (G) when present, the level of said odor controlling agent is from about 1% to about 20%, by weight of the composition.
24. An article of manufacture comprising a fabric softening composition of any one of Claims 123 in a package in association with instructions for use which direct the consumer to apply at least an effective amount of said fabric softening composition and/or polyalkyleneoxy polysiloxane on fabric to provide a fabric softening benefit.
25. The article of Claim 24, wherein said composition additionally provides at least one of the following fabric care benefits: wrinkle removal, wrinkle reduction, wrinkle resistance, fabric wear reduction, fabric wear resistance, fabric pilling reduction, fabric color maintenance, fabric color fading reduction, fabric color restoration, fabric soiling reduction, fabric soil release, fabric shape retention, and/or fabric shrinkage reduction in a package in association with instructions for use which direct the consumer to apply at least an effective amount of said composition to provide at least one of said fabric care benefits.
26. The article of Claim 24 or 25, wherein said instructions for use direct the consumer to apply an amount of composition to provide from about 0.005% to about 5%, by weight of the fabric.
27. The article of any one of Claims 2426, wherein the composition is a concentrated composition and said instructions for use comprise an instruction which directs the consumer to dilute said composition to form a diluted fabric softening composition.
28. The article of any one of Claims 2427, wherein said instructions for use comprise text, pictures and/or icons.
29. The article of any one of Claims 2428, wherein said instructions for use comprise an instruction which directs the consumer to apply to apply at least an effective amount of said composition to said fabric during the drying step of a laundry process, to provide said fabric care benefits.
30. The article of manufacture comprising a composition according to any one of Claims 123 in a spray dispenser.
31. The article of Claim 30, wherein said spray dispenser comprises a manually activated sprayer selected from the group consisting of trigger sprayer, pump sprayer, nonaerosol selfpressurized sprayer, and aerosol sprayer, or a nonmanually operated, powered sprayer, selected from the group consisting of powered sprayer, air aspirated sprayer, liquid aspirated sprayer, electrostatic sprayer, and nebulizer sprayer.
32. A fabric having improved characteristics having an effective amount of a fabric softening composition of any one of Claims 123 applied thereto.
33. A method for providing a fabric with a fabric softening benefit wherein said method comprises applying an effective amount of a fabric softening composition of any one of Claims 123 to the fabric.
34. The method of Claim 33, wherein said method does not comprise a step wherein the fabric is ironed.
35. The method of Claim 33 or 34, wherein said method additionally provides at least one of the following fabric care benefits: wrinkle removal, wrinkle reduction, wrinkle resistance, fabric wear reduction, fabric wear resistance, fabric pilling reduction, fabric color maintenance, fabric color fading reduction, fabric color restoration, fabric soiling reduction.
36. The method of any one of Claims 3335, wherein said composition is applied to said fabric as droplets by using a spray dispenser.
37. The method of any one of Claims 3336, wherein said composition is applied to fabric prior to or during the drying step.
38. The method of any one of Claims 3337, wherein said fabric is wet.
39. A method for selecting and/or designing good performing polyalkyleneoxy silicones for use as fabric softening active in an aqueous fabric softening composition for direct application to fabric, and/or for use in fabric softening methods and/or articles of manufacture comprising said fabric softening compositions, said method comprises the step of using the Correlation I of Claim 1 to identify such a polyalkyleneoxy silicone.
40. The method of claim 39, wherein the identification of a polyalkyleneoxy silicone comprises the following steps: (a) Choose a desired S value, typically at least about 20; (b) Set a desired average molecular weight, MW, being typically from from about 7,500 to about 140,000; (c) Set a desired % EO (weight % of all ethyleneoxy EO units in the molecule), then derive t#EO (the average total number of ethyleneoxy units in the molecule) with t#EO being typically from about 100 to about 1,800; (d) Choose the type of polyalkyleneoxy polysiloxane selected from polyethyleneoxy polysiloxane or polyethyleneoxy/polypropyleneoxy polysiloxane, then set the desired % Si value; (e) Use the desired values for S, t#EO and % Si to calculate t&num diSi (the approximated total average number of dimethylsiloxane SiMe20 units in the molecule), using Correlation I, wherein t&num diSi is typically about from about 40 to about 530; (f) Calculate % diSi (weight % of total dimethylsiloxane units) and % triSi (weight % of the terminal trimethylsiloxane units); and (g) Calculate t&num linkSi (the average number of the polyalkyleneoxy pendant groups).
41. A polyalkyleneoxy polysiloxane selected from the group consisting of polyethyleneoxy polysiloxane, polyethyleneoxy/polypropyleneoxy polysiloxanes, and mixtures thereof, having an average molecular weight of from about 3,000 to about 200,000, and being characterized by Correlation I : wherein t&num diSi is the average total number of the Si (CH3) 20 units in the molecule; t#EO is the average total number of the ethyleneoxy CH2CH2O units in the molecule; % Si is the weight percent of all siloxane units in the molecule; and the softness index S is at least about 30.
42. A polyalkyleneoxy polysiloxane selected from the group consisting of polyethyleneoxy polysiloxane, polyethyleneoxy/polypropyleneoxy polysiloxanes, and mixtures thereof, having an average molecular weight of from about 3,000 to about 200,000, and being characterized by Correlation I : wherein t&num diSi is the average total number of the Si (CH3) 20 units in the molecule; t#EO is the average total number of the ethyleneoxy CH2CH20 units in the molecule; % Si is the weight percent of all siloxane units in the molecule; and the softness index S is at least about 15, excluding the following compounds: Silwet L77, Silwet L711, Silwet L720, Silwet L721, Silwet L7000, Silwet L7001, Silwet L7002, Silwet L7087, Silwet L 7200, Silwet L7210, Silwet L7220, Silwet L7230, Silwet L7280, Silwet L7600, Silwet L7602, Silwet L7604, Silwet L7605, Silwet L7607, Silwet L7608, Silwet L 7610,7614, Silwet L7622, Silwet L7644, Silwet L7650, Silwet L7657, Silwet L8500, Silwet L8600, Silwet L8610, Silwet L8620, Silwet FZ2104, Silwet FZ2120, Silwet FZ2161, Silwet FZ2162, Silwet FZ2163, Silwet FZ2164, Silwet FZ2165, Silwet FZ 2166, Silsoft 477, Silsoft 487, Silsoft 497, DC 190, DC 193, DC 2 5237, DC2 5573, DC 3225C, DC 5093, DC 5097, DC 5098, DC 5103, DC 5197, DC 5200, DC 5211, DC 5212, DC 5220, DC 5225C, DC 5237, DC 5247, DC 5329, DC5604, DC 8692, DC Q2 2511, DC Q25220, DC Q43667, FF 400, Sylgards 309, SH3771C, SH3772C, SH3773C, SH3746, SH3748, SH3749, SH8400, SF8410, SH8700, SF 1188A, SF 1288, SF 1388, SF 1488, SF 1328, SF 1528, TSF 4440, TSF 4441, TSF 4445, TSF 4446, TSF 4452, TSF 4450, OL 17, OL 31, OL 44, AC 3233, AI 3669, AI 3465, AI 3466, AI 3467, AI 3468, VP 3738, VP 3739, TP 3792, TP 3793, TP 3794, TP 3799, TP 3800, TP 3801, TP 3804, TP 3805, TP 3806, Abif B 8800, Abil B 8830, Abil B 8832, Abil B 8842, Abil B 8843, Abil B 8847, Abil B 8851, Abil B 8852, Abil B 8863, Abil B 8873, Abil EM 97, Abil EM90, Abil WE09, Abil B 88183, Abil B 88184, Abil 9950, Abil EM90, Abil EM97, Abil WE90, Abil Care 85, KF351, KF352, KF353, KF354, KF 355, KF615, KF618, KF625, KF857, KF862, KF888, KF945, KF8001, X223667, X223939A, X224741, X226008, X228645, Fancorsilo LIM 1, Fancorsil LIM 2, Fancorsil LIM 3, Alkasile NE 5850, Alkasil NEP 7370, Alkasil° NEPCA 250185, Rhodorsilo Oils 70646, Silbiones Oils 70646, Amersil DMC287, Amersil DMC357, Masilo 1066 D, Masil 280 LP, Masif SF 19, Masil SF 19A, Silicone Copolymer F754, Silicone Fluid VP, Belsil# DMC 6031, Belsil DMC 6032, Belsil DMC 6033, Belsil DMC 6035, Troysolo S366, Troysol 380W, and Forests G23.
43. Use of a polyalkyleneoxy polysiloxane of Claim 1 in an aqueous fabric softening composition for direct application to fabric.
Description:
FABRIC SOFTENING COMPOSITIONS AND METHODS

TECHNICAL FIELD The present invention relates to stable, preferably translucent, more preferably clear, aqueous fabric softening compositions, articles of manufacture, and/or method of use, comprising selected polyalkyleneoxy polysiloxanes. This fabric softening composition is designed to be applied mainly on fabrics outside of the laundry processes, but can also be used during the laundry processes.

BACKGROUND OF THE INVENTION Fabric softening benefit obtained in the home is traditionally provided during the laundry cycle, either by using a rinse-added fabric softener that is added to the rinse cycle, or a dryer-added fabric softener, most commonly a dryer-added sheet, to be added to the dryer. Traditional rinse-added and dryer-added fabric softener products typically are used to treat a whole load of fabrics in the laundry cycle, e. g., in a washer or an automatic dryer. However, it is usually inconvenient and/or wasteful to soften a single or a few clothing items with this method. This is a frequent and common problem, when only one or two fabric items need to be washed. In such cases, the fabrics are usually washed by hand and line dried. Included to this category are delicate fabrics that need to be hand washed individually, and not to be dried in an automatic clothes dryer. The hand-washed and line-dried fabric items usually feel coarse and harsh, unlike the items that are machine washed and/or dried in an automatic clothes dryer.

Most consumer rinse-added fabric softener and dryer-added fabric softener compositions contain dialkyl and/or alkenyl quaternany ammonium salts as the main fabric softening active. Examples of quaternany ammonium fabric softening actives are

disclosed in U. S. Pat. Nos.: 3,861,870, Edwards et al.; 4,308,151, Cambre; 3,886, 075, Bernardino ; 4,233,164, Davis; 4,401,578, Verbruggen ; 3,974,076, Wiersema et al.; and 4,237,016, Rudkin et al. Some preferred quaternary ammonium fabric softening active systems are disclosed in U. S. Pat. Nos: 4,661,269, issued April 28, 1987, to T. Trinh et al.; U. S. Pat. No. 5,545,340, issued Aug. 13,1996, to Wahl et al.; 5,747,443 issued May 5,1998 to E. H. Wahl et al.; and 5,830,845 issued Nov. 3,1998 to T. Trinh et al.

Examples of dryer-added fabric softener actives are given in U. S. Pat. No. 6,046,154 issued Apr. 4,2000 to Trinh et al.; other dryer-added fabric softener actives can be found in US 4,327,133; US 4,421,792; US 4,426,299; US 4,460,485; US 3,644,203; US 4,661,269; U. S 4,439,335; U. S 3,861,870; US 4,308,151; US 3,886,075; US 4,233,164; US 4,401,578; US 3,974,076; US 4,237,016 and EP 472,17.

Alternative actives have been suggested, such as silicones, due to their lubricity.

Silicones can be used in liquid fabric softener compositions to provide additional fabric feel, as is disclosed in U. S. Pat. No. 4,855,072 issued Aug. 8,1989 to Trinh et al, said patent being incorporated herein by reference. The preferred silicones are polydimethylsiloxanes that can be incorporated into the softener compositions as a neat fluid, or can be added in a preemulsified form which is available from many suppliers.

Examples of these preemulsified silicones are a 60% emulsion of polydimethylsiloxane (350 cs) from Dow Coming Corporation under the trade name DOW CORNING 1157 Fluid, and a 50% emulsion of polydimethylsiloxane (10,000 cs) from General Electric Company under the trade name General Electric SM 2140 Silicones. In order to increase fabric substantivity of the silicones to improve fabric feel, the silicones can be derivatised with cationic groups, such as those disclosed in U. S. Pat. Nos. 5,098,979 issued Mar. 24,1992 and 5,196,499 issued Mar. 23,1993, both to O'Lenick, Jr., or the silicones can be derivatised with reactive, curable groups that can condense to form higher molecular weight silicones, such as those disclosed in U. S. Pat. No. 4,419,391 issued Dec. 6,1983 to Tanaka et al., all said patents are incorporated herein by reference.

It is well known that after treated several times with rinse-added fabric softener products and/or dryer-added fabric softener products, the cotton fabrics become somewhat waterproof, and become less water absorbent. This is because the common fabric softener actives are substantive to fabrics.

The silicones can also be derivatised with hydrophilic groups, to make them able to self-emulsify and/or to provide surface activity. The most common silicones of this class are the polyalkyleneoxy polysiloxanes. Commercial literature on polyalkyleneoxy polysiloxanes, such as"Silwets Surfactants", OS-144 6/94-1OM, published by OSi Specialties, Inc., discloses that some of the polyalkyleneoxy polysiloxanes add softness to

fabrics, and that the softness property increases with the percent silicone in the polyalkyleneoxy polysiloxanes.

Although many of the fabric softener actives have been disclosed as having softening activity, there has previously been means by which to determine softener actives are most effective and/or preferred in the context of a product which is sprayed onto the fabrics in contrast to actives that are deposited on fabric in the rinse and/or washing steps from a highly dilute aqueous bath. The art has not considered how to select optimum softener actives when there is no competition between the fabrics and the aqueous bath.

In one aspect, the present invention relates to stable, preferably translucent, more preferably clear, aqueous fabric softening compositions comprising polyalkyleneoxy polysiloxanes which comprise at least some ethyleneoxy units, articles of manufacture comprising said compositions and/or method for use of said compositions on fabrics, preferably by direct application of said compositions on fabrics. Preferably, the compositions are used by the consumer to spray onto fabrics, particularly clothes, one at a time, to conveniently provide fabric softening benefit, without having to treat the whole load of fabrics in a washer and/or dryer, and/or without having to iron the fabrics. Cotton fabrics treated with the composition of the present invention do not become waterproof and synthetic fabrics can become more water absorbent. The articles of manufacture of the present invention preferably are packaged in association with instructions for use to direct the consumer to use the composition to treat fabrics correctly, including, e. g., the manner and/or amount of composition to spray, e. g., to apply an effective amount of the fabric softening composition and/or polyethyleneoxy polysiloxane to the fabric, to provide the fabric softening benefit, without the need of using the traditional rinse-added or dryer-added softener products and/or ironing. The fabric softening actives of the present invention can readily be washed off the fabrics. The aqueous fabric softening compositions of the present invention contain polyalkyleneoxy polysiloxanes as a key softening actives. However, it is found that in the context of the aqueous fabric softening compositions of the present invention, that are designed for direct application on fabrics, contrary to the teaching in the Silwet@ Surfactants literature, the percent silicone alone correlates very poorly with the fabric softening performance of the spray compositions.

Instead, it is discovered, using a quantitative structure-activity relationship (QSAR) approach, that the fabric softening performance of the compositions of the present invention depends on a combination of several properties of the polyalkyleneoxy polysiloxanes including the average total number of SiMe2O units in the molecule, the

average total number of ethyleneoxy CH2CH2O units in the molecule, and the % silicone.

The compositions of the present invention can provide other fabric care benefits, such as, wrinkle removal, wrinkle reduction, fabric color restoration, and/or fabric color rejuvenation, and when optional ingredients are present, the compositions can optionally provide other fabric care benefits, such as malodor control, static control, antibacterial action, insect repellency, and the like, as well as a"scent signal"in the form of a pleasant odor, and combinations thereof.

SUMMARY OF THE INVENTION The present invention relates to stable, preferably translucent, more preferably clear, aqueous fabric softening compositions, fabric softening methods and articles of manufacture that use such fabric softening compositions, for use on fabrics, comprising: (A) an effective amount to soften fabric of polyalkyleneoxy polysiloxane selected from the group consisting of polyethyleneoxy polysiloxane, polyethyleneoxy/polypropyleneoxy polysiloxanes, and mixtures thereof, having a molecular weight of from about 1,200 to about 200,000 and being characterized by Correlation I : S = 3.246 (&num )-1. 880 (V% )-0. 9066&num EO+17. 70 (I) wherein t&num diSi is the average total number of the Si (CH3) 20 units in the molecule; % Si is the weight percent of total siloxane units in the molecule; t&num EO is the average total number of the ethyleneoxy CH2CH20 units in the molecule; and S is the Softness Index which is typically at least about 10; (B) optionally, an effective amount of fabric wrinkle control agent; (C) optionally, but preferably, an effective amount to provide olfactory effects of perfume; (D) optionally, an effective amount to clarify the composition and/or improve the performance of the composition of surfactant ; (E) optionally, an effective amount, to kill, or reduce the growth of microbes, of antimicrobial active; (F) optionally, an effective amount to assist in antimicrobial action of aminocarboxylate chelator; (G) optionally, an effective amount to control malodor of odor controlling agent; (H) optionally, an effective amount of antimicrobial preservative;

(I) optionally, an effective amount of adjunct quaternary ammonium fabric softening agent to provide additional fabric softening benefit; and (J) aqueous carrier ; said composition preferably containing at least one of (B) through (I).

The present invention also relates to concentrated compositions, wherein the level of polyethyleneoxy polysiloxane is from about 1% to about 40%, preferably from about 2% to about 20%, more preferably from about 3% to about 10%, by weight of the composition which are diluted to form compositions with the usage concentrations of polyethyleneoxy polysiloxane of, e. g., from about 0.1% to about 5%, by weight of the diluted composition, as given hereinabove, which are the"usage conditions".

The present invention also relates to the compositions incorporated into a spray dispenser (sprayer) to create an article of manufacture that can facilitate treatment of fabric articles and/or surfaces with said compositions containing polyethyleneoxy polysiloxane and other optional ingredients at a level that is effective, yet is not discernible when dried on the surfaces. The spray dispenser comprises manually activated and non-manual operated spray means and a container containing the fabric softening composition. The articles of manufacture preferably are in association with instructions for use to direct the consumer to apply an effective amount of the fabric softening composition and/or polyethyleneoxy polysiloxane to the fabric to provide the desired benefit.

The present invention also comprises the use of small particle diameter droplets of the compositions herein, to treat fabrics, to provide superior performance, e. g., the method of applying the compositions to fabrics, etc. as small particles (droplets) preferably having average particle sizes (diameters) of from about 10 llm to about 120 u m, more preferably from about 20 um to about 100 urn.

The present invention also relates to a method of using Correlation I to identify, select, and/or design the preferred polyethyleneoxy polysiloxanes and/or polyethyleneoxy/polypropyleneoxy polysiloxanes that provide superior fabric softening performance in general, and especially for use in the fabric softening composition of the present invention.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stable, preferably translucent, more preferably clear, aqueous fabric softening composition, fabric softening methods and articles of manufacture that use such fabric softening composition, for use on fabrics, comprising:

(A) an effective amount to soften fabric, typically from about 0.01% to about 10%, preferably from about 0.1% to about 5%, more preferably from about 0.2% to about 3%, and even more preferably from about 0.3% to about 2%, by weight of the composition of polyalkyleneoxy polysiloxane selected from the group consisting of polyethyleneoxy polysiloxane, polyethyleneoxy/polypropyleneoxy polysiloxanes, and mixtures thereof, having a molecular weight of at least about 1,200, preferably from about 2,000 to about 200,000, more preferably from about 4,000 to about 150,000, even more preferably from about 5,000 to about 120,000, and yet more preferably from about 6,000 to about 100,000, and being characterized by Correlation I : wherein t&num diSi is the average total number of the Si (CH3) 2O units in the molecule; % Si is the weight percent of total silicone (or siloxane) in the molecule; t#EO is the average total number of the ethyleneoxy CH2CH2O units in the molecule; and S is the Softness Index which is, typically at least about 10, preferably at least about 15, more preferably at least about 20, even more preferably at least about 25, yet more preferably at least about 30; typically t&num diSi is from about 4 to about 450, preferably at least about 15 to about 350, more preferably from about 30 to about 250, even more preferably from about 60 to about 250; typically % Si is from about 5 to about 90, preferably from about 8 to about 80, more preferably from about 10 to about 70, and even more preferably from about 12 to about 60; for ease of formulation in aqueous compositions, % Si is preferably equal or less than about 50%; and typically t#EO is from about 25 to about 2,000, preferably from about 40 to about 1,500, more preferably from about 60 to about 1,200, and even more preferably from about 100 to about 1,000.

Preferably % EO, the weight percent of all of the ethyleneoxy CH2CH2O units in the molecule, is less than about 80, preferably from about 10 to about 75, more preferably from about 15 to about 70, and even more preferably from about 25 to about 50; and EO/tail, the average number of ethyleneoxy CH2CH2O units per pendant group, is typically less than about 100, preferably less than about 75, more preferably less than about 50, and even more preferably less than about 40.

(B) optionally, an effective amount of fabric wrinkle control agent, preferably selected from the group consisting of fabric lubricant, shape retention polymer, fabric care polysaccharide, hydrophilic plasticizer, and mixtures thereof, preferably from about 0.05% to about 5%, more preferably from about 0.2% to about 3%, even more preferably from about 0.3% to about 2% by weight of the usage composition (with concentrated compositions having a level of from about 1% to about 20%, preferably from about 2% to about 15%, more preferably from about 3% to about 10%, by weight of the composition, of fabric wrinkle control agent); (C) optionally, but preferably, an effective amount to provide olfactory effects of perfume, preferably from about 0.003% to about 0.5%, more preferably from about 0.01% to about 0.3%, and even more more preferably from about 0.05% to about 0.2%, by weight of the composition of perfume (with concentrated compositions having a level of from about 0.01% to about 5%, preferably from about 0.1% to about 2%, more preferably from about 0.3% to about 1%, by weight of the composition, of perfume), preferably a perfume containing at least about 25%, preferably at least about 40%, more preferably at least about 60%, even more preferably at least about 75%, by weight of the perfume composition of substantive perfume ingredients that have a boiling point of at least about 240°C ; and optionally, a minor amount of perfume ingredients selected from the group consisting of allyl amyl glycolate, ambrox, anethole, bacdanol, benzyl acetone, benzyl salicylate, butyl anthranilate, calone, cetalox, cinnamic alcohol, coumarin, cyclogalbanate, Cyclal C, cymal, damascenone, alpha- damascone, 4-decenal, dihydro isojasmonate, gamma-dodecalactone, ebanol, ethyl anthranilate, ethyl-2-methyl butyrate, ethyl methylphenyl glycidate, ethyl vanillin, eugenol, flor acetate, florhydral, fructone, frutene, heliotropin, herbavert, cis-3-hexenyl salicylate, indole, alpha-ionone, beta- ionone, iso cyclo citral, isoeugenol, alpha-isomethylionone, keone, lilial, linalool, lyral, methyl anthranilate, methyl dihydrojasmonate, methyl heptine carbonate, methyl isobutenyl tetrahydropyran, methyl beta naphthyl ketone, methyl nonyl ketone, beta naphthol methyl ether, nerol, para-anisic aldehyde, para hydroxy phenyl butanone, phenyl acetaldehyde, gamma-undecalactone, undecylenic aldehyde, vanillin, and mixtures thereof;

(D) optionally, an effective amount to clarify the composition and/or improve the performance of the composition, preferably from about 0.05% to about 5%, more preferably from about 0.1% to about 3%, and even more preferably from about 0.2% to about 1.5%, by weight of the usage composition, of surfactant, preferably nonionic surfactant (with concentrated compositions having a level of from about 0.1% to about 15%, preferably from about 0.2% to about 8%, more preferably from about 0.3% to about 5%, by weight of the composition, of surfactant); (E) optionally, an effective amount, to kill, or reduce the growth of microbes, of antimicrobial active, preferably from about 0.001% to about 0.8%, more preferably from about 0.002% to about 0.3%, even more preferably from about 0.003% to about 0.2%, by weight of the composition, and preferably selected from the group consisting of halogenated compounds, cyclic nitrogen compounds, quaternary compounds, and phenolic compounds (with concentrated compositions having a level of from about 0.003% to about 2%, preferably from about 0.01% to about 1.2%, more preferably from about 0.1% to about 0.8%, by weight of the composition, of antimicrobial active); (F) optionally, an effective amount to assist in antimicrobial action of aminocarboxylate chelator; preferably from about 0.001% to about 0.3%, preferably from about 0.01% to about 0.1%, more preferably from about 0.02% to about 0.05%, by weight of the usage composition; (G) optionally, an effective amount to control malodor, typically present at a level of from about 0.01% to about 5%, preferably from about 0.1% to about 4%, more preferably from about 0.2% to about 3%, and even more preferably from about 0.3% to about 2%, by weight of the composition (with concentrated compositions which are meant to be diluted, containing from about 1% to about 20%, preferably from about 1% to about 10%, more preferably from about 2% to about 5%, by weight of the composition), of odor controlling agent, preferably selected from the group consisting of uncomplexed cyclodextrins; zinc and copper salts; soluble carbonate and/or bicarbonate salts; water soluble ionic polymers; and mixtures thereof; more preferably uncomplexed cyclodextrin; water soluble zinc salts; water soluble anionic polymers, and mixtures thereof; (H) optionally, an effective amount of antimicrobial preservative, preferably from about 0.0001% to about 0.5%, more preferably from about 0.0002%

to about 0.2%, most preferably from about 0.0003% to about 0.1%, by weight of the composition; (I) optionally, an effective amount of adjunct quaternary ammonium fabric softening agent to provide additional fabric softening benefit, typically present at a level of from about 0.05% to about 3%, preferably from about 0.1% to about 2%, more preferably from about 0.3% to about 1%, by weight of the usage composition; and (J) aqueous carrier; said composition preferably containing at least one of (B) through (I), and wherein said methods of using said compositions preferably does not comprise an ironing step.

The present invention also relates to the compositions incorporated into a spray dispenser (sprayer) to create an article of manufacture that can facilitate treatment of fabric articles and/or surfaces with said compositions containing polyethyleneoxy polysiloxane and other optional ingredients at a level that is effective, yet is not discernible. when dried on the surfaces. The spray dispenser comprises both manually activated and non-manual operated spray means and a container containing the fabric softening composition. The articles of manufacture preferably are packaged in association with instructions for use to direct the consumer to use the composition to treat fabrics correctly, including, e. g., the manner and/or amount of composition to spray, e. g., to apply an effective amount of the fabric softening composition and/orpolyethyleneoxy polysiloxane to the fabric, to provide the desired benefit. As used herein, the phrase"in association with"means the instructions are either directly printed on the container itself or presented in a different manner including, but not limited to, a brochure, print advertisement, electronic advertisement, and/or verbal communication, so as to communicate the set of instructions to a consumer of the article of manufacture. It is important that the instructions be as simple and clear, so that using pictures and/or icons may be desirable.

Preferably, the fabric softening composition of the present invention is clear. The term"clear"as defined herein means transparent or translucent, preferably transparent, as in"water clear,"when observed through a layer having a thickness of less than about 10 cm.

The present invention also relates to concentrated compositions, wherein the level of of polyethyleneoxy polysiloxane is from about 1% to about 40%, preferably from about 2% to about 20%, more preferably from about 3% to about 10%, by weight of the composition. The concentrated composition is typically diluted to form compositions with the usage concentrations of polyethyleneoxy polysiloxane of, e. g., from about 0.1%

to about 5%, by weight of the diluted composition, as given hereinabove, which are the "usage conditions". Specific levels of other optional ingredients in the concentrated composition can readily be determined from the desired usage composition and the desired degree of concentration. These concentrated compositions can be used in a process for preparing large volumes of treatment composition in which water is added, either in a separate container, or in the container of the article of manufacture comprising the spray means.

Alternatively, a relatively concentrated composition can be applied directly on wet fabrics, e. g., fabrics that have been just washed and not yet dried, so that the polyethyleneoxy polysiloxane can be diluted in situ on the wet fabrics. Compositions for use to apply on wet fabrics typically comprises polyethyleneoxy polysiloxane at a level of from about 0.1% to about 20%, preferably from about 0.2% to about 5%, and more preferably from about 0.3% to about 3%, by weight of the composition.

Also preferred are fabric softening compositions for treating fabric in the drying step, comprising an effective amount of polyethyleneoxy polysiloxane, and optionally, adjunct ingredients, e. g., fabric wrinkle control agent, perfume, odor controlling agent, and mixtures thereof. The dryer-added fabric care composition is preferably provided as part of an article of manufacture in combination with a dispensing means such as a flexible substrate or a sprayer which effectively releases the fabric care composition in an automatic tumble clothes dryer.

The fabric softening composition of the present invention can optionally provide one of other fabric care benefits: wrinkle removal, wrinkle reduction, fabric color restoration, and/or static control. The fabric softening composition of the present invention can also contain optional ingredients to additionally provide at least one of the following fabric care benefits: wrinkle removal, wrinkle reduction, wrinkle resistance, fabric wear reduction, fabric wear resistance, fabric pilling reduction, fabric color maintenance, fabric color fading reduction, fabric color restoration, fabric soiling reduction, fabric soil release, fabric shape retention, and/or fabric shrinkage reduction, in a package in association with instructions for use which direct the consumer to apply at least an effective amount of said composition to provide at least one of said fabric care benefits. Many optional ingredients are given hereinabove and/or of the types disclosed in U. S. Pat. Nos. 5,968,404; 5,997,759; and 6,001,343; issued Oct. 19, 1999; Dec. 7,1999; and Dec. 14, 1999, respectively, to Trinh et al., and U. S. Pat. No. 6,033,679 issued Mar. 7, 2000 to Woo et al., all of said patents are incorporated herein by reference.

The present invention also relates to a method of using Correlation I to (a) estimate and/or predict the fabric softening performance of a polyalkyleneoxy silicone,

(b) select or identify the preferred polyalkyleneoxy silicones, and/or (c) design preferred polyalkyleneoxy silicones that provide superior fabric softening performance in fabric care compositions in general, and especially for use in the fabric softening composition of the present invention, as well as fabric care methods and/or articles of manufacture that use such fabric care compositions. Thus the present invention relates to a method using Correlation I hereinabove to design novel polyalkyleneoxy polysiloxanes to provide superior fabric softening benefit via aqueous compositions for direct application, by setting the S value at 15 or higher, preferably at 20 or higher, more preferably at 25 or higher, and even more preferably at 30 or higher; and wherein t&num diSi is set at from about 4 to about 450, preferably from about 15 to about 350, more preferably from about 30 to about 250, and even more preferably from about 60 to about 250; wherein % Si is set from about 5 to about 90, preferably from about 8 to about 80, more preferably from about 10 to about 70, and even more preferably from aboutl2 to about60; wherein t#EO is set from about 25 to about 2,000, preferably from about 40 to about 1,500, more preferably from about 60 to about 1,200, and even more preferably from about 100 to about 1,000; and wherein the molecular weight of at least about 1,200, preferably from about 2,000 to about 200,000, more preferably from about 4,000 to about 150,000, even more preferably from about 5,000 to about 120,000, and yet more preferably from about 6,000 to about 100,000.

The present invention further includes the novel polyalkyleneoxy polysiloxanes that are derived from the method disclosed above using Correlation I, comprising the polyalkyleneoxy polysiloxanes that do not currently exist and/or commercially available.

The present invention also relates to the use of said novel polyalkyleneoxy polysiloxanes to provide fabric softening benefit using aqueous compositions. The present invention further relates to the use of said polyalkyleneoxy polysiloxanes to provide one of other fabric care benefits : wrinkle removal, wrinkle reduction, fabric color restoration, fabric color rejuvenation and/or static control.

All of the patents, patent applications, and references referred to herein are incorporated, either wholly, or in relevant part, by reference. All parts, ratios, and percentages herein are by weight and all numerical limits are used with the normal degree of accuracy afforded by the art unless otherwise specified.

I. COMPOSITION

(A) POLYALKYLENEOXY POLYSILOXANES Polyalkyleneoxy polysiloxanes are also known by other names, including silicone copolyols, silicone glycol copolymers, silicone glycol surfactants, silicone polyoxyalkylene copolymers, silicone poly (oxyalkylene) copolymers, siloxane polyethers, polyalkylene oxide polysiloxanes, polyalkylene oxide silicone copolymers, and dimethicone copolyols.

Polyalkyleneoxy polysiloxanes useful as fabric softening active in the composition of the present invention comprise a polysiloxane polymer backbone and one or more polyalkyleneoxy side chains, and having the general formula: RlhCH3) 2SiO [(CH3) 2SiO] a [(CH3) (RI) SiO] bSi (CH3) --R' wherein each Ri is the same or different and is selected from the group consisting of Cl-C4 alkyl group, preferably methyl; phenyl; polyethyleneoxy/polypropyleneoxy group; optionally C2 to C8 alkenyl group, especially an allyl group; and mixtures thereof; with at least one RI being a polyethyleneoxy/polypropyleneoxy group, wherein the polyethyleneoxy/polypropyleneoxy group has the general formula: - (CH2) n 0 (C2H40) c (C3H6°) d R2 wherein n is 3 or 4, and each R2 is the same or different and is selected from the group consisting of hydrogen, C1-C4 alkyl group, and/or acetyl group, preferably hydrogen and/or methyl group; said polyalkyleneoxy polysiloxane is selected from the group consisting of polyethyleneoxy polysiloxanes (c is not 0 and d = 0), polyethyleneoxy/ polypropyleneoxy polysiloxanes (both c and d are not 0), and mixtures thereof; said polyalkyleneoxy polysiloxane has a molecular weight of at least about 1,200, preferably from about 2,000 to about 200,000, more preferably from about 4,000 to about 150,000, even more preferably from about 5,000 to about 120,000, and yet more preferably from about 6,000 to about 100,000; and said polyalkyleneoxy polysiloxane is characterized by Correlation I : wherein t&num diSi is the average total number of the Si (CH3) 20 units in the molecule; % Si is the weight percent of total silicone (or siloxane) in the molecule; t#EO is the average total number of the ethyleneoxy CH2CH2O units in the molecule; and S is the Softness Index which is typically at least about 10, preferably at least about 15, more preferably at least about 20, even more preferably at least about 25, yet more

preferably at least about 30; typically t&num diSi is from about 4 to about 450, preferably at least about 15 to about 350, more preferably from about 30 to about 250, even more preferably from about 60 to about 250; typically % Si is from about 5 to about 90, preferably from about 8 to about 80, more preferably from about 10 to about 70, and even more preferably from about 12 to about 60; for ease of formulation in aqueous compositions, % Si is preferably equal or less than about 50%; and typically t#EO is from about 25 to about 2,000, preferably from about 40 to about 1,500, more preferably from about 60 to about 1,200, and even more preferably from about 100 to about 1,000. Typical % EO, the weight percent of all of the ethyleneoxy CH2CH2O units in the molecule, is less than about 80, preferably from about 10 to about 75, more preferably from about 15 to about 70, and even more preferably from about 25 to about 50; and EO/tail, the average number of ethyleneoxy CH2CH2O units per pendant group, is typically less than about 100, preferably less than about 75, more preferably less than about 50, and even more preferably less than about 40.

Correlation I is identified using an quantitative structure-activity relationship (QSAR) method as is described in Applicants'copending U. S. Serial No., entitled "Predictive Method For Polymers", filed November 20,2001, in the name of Schneiderman, et al., said application being incorporated herein by reference.

The most common molecular structures for polyalkyleneoxy polysiloxanes include the graft copolymers (also called the rake-type or comb copolymers, or the alkyl-pendant copolymers) and the ABA copolymers. The graft copolymers have the general structure: (CH3)3SiO-[(CH3)2SiO]a-[(CH3)(R1)SiO]b-Si (CH3) 3 wherein the polyalkyleneoxy groups (Rl) are attached along a linear polysiloxane backbone through a series of hydrolytically stable Si-C bonds. A special type of graft copolymers are the"trisiloxanes"wherein a = 0 and b = 1.

The ABA copolymers are linear and have the general structure: Rl-- (CH3) 2SiO- [ (CH3) 2SiOJa-Si (CH3) z-R'.

Methods for Structural Characterization and Generation of Structural Descriptors for Polyalkyleneoxy Polysiloxanes 29Si-NMR and l3C-NMR methods, and hydroiodic acid sample hydrolysis followed by the quantitative GC analysis of the resulting alkyliodides are used to structurally characterize polyalkyleneoxy polysiloxanes of the graft type and the ABA type.

The 29Si-NMR spectra are obtained at 59.70MHz using a Fourier transform spectrometer. Chromium (1, 3-pentanedione) 3 is added to speed up the relaxation and suppress the nuclear Overhauser effect, caused by proton decoupling, on the silicon spectra. The 29Si-NMR spectra can differentiate and help to quantitatively yield the average number of Si atoms of different siloxane units, viz., the trimethylsiloxane (CH3) 3SiO units, the dimethylsiloxane Si (CH3) 2-O units, and/or the methyl (alkylene) siloxane Si (CH3) (CnH2n) O units that link with the poly (alkyleneoxy) groups wherein n is typically 3.

The 13C-NMR spectra are obtained at 75.57MHz using a Fourier transform spectrometer. The chromium (1, 3-pentanedione) 3 added to aid acquiring the silicon spectra, does not cause excessive broadening of the'3C spectra. The'3C-NMR spectra yield structural information of all of the carbon groups and are used to determine the average number of pendant groups, the type of pendant groups, the capping groups, and the average number of unreacted allyl groups, if present.

Polyalkyleneoxy polysiloxanes are hydrolyzed by hydroiodic acid, a reaction catalyzed by adipic acid, to produce iodoethane, 1-iodopropane and 2-iodopropane. The hydrolyzed samples (hydrolysates) comprising iodoethane, 1-iodopropane and 2- iodopropane, are analyzed by gas chromatography with the FID detection against an internal standard (octane) and an external standard calibration with iodoalkanes to obtain the mass ratio of the ethyleneoxy units (designated as WEO) and the mass ratio of the propyleneoxy units (designated as wpO) in the polyalkyleneoxy polysiloxane molecules.

Sum of mass ratio of all siloxane units (designated as ws ;), ethyleneoxy units and propyleneoxy units is equal to 1: Wsi + Wso + Wpo = 1 Molecular weight of all siloxane units is determined from the average number of individual siloxane units determined from 29Si-and'3C-NMR and the respective molecular weight of the individual units according to the equation: MW of all siloxane units = 2*89 + (t#diSi) *74 + # linking units* 101 wherein 74 is the molecular weight of each dimethylsiloxane unit, 89 is the molecular weight of each trimethylsiloxane unit, and 101 is the molecular weight of each linking siloxane SiMe (CH2CH2CH2) O unit. When the linking groups are different from CH2CH2CH2, or when the molecule has only one or none SiMe30 unit, or when some unreacted allyl groups are present, the calculation can be modified accordingly.

Molecular weight of each polyalkyleneoxy polysiloxane molecule, designated as MW, is estimated from the mass ratio of all siloxane units, wSi, (with wSi = 1-wEO-wPO) and the corresponding molecular weight of all siloxane units by the following equation: MW = MW of all siloxane units/ws ; The average total number of ethyleneoxy units,-CH2CH2O-, designated as t#EO, and the average total number of propyleneoxy units,-CH (CH3) CH20-, designated as t#PO, are derived from the molecular weight MW of the polyalkyleneoxy polysiloxane, the mass ratio WEO of the ethyleneoxy units and the mass ratio wPO of the propyleneoxy units, respectively, by the following equations: t#EO = MW*WEO/44 and t#PO = MW *wpo/58 wherein 44 is the molecular weight of one ethyleneoxy unit-CH2CH2O-, and 58 is the molecular weight of one propyleneoxy unit-CH (CH3) CH2O-.

Weight % of all EO units (% EO), weight % of all PO units (% PO), and weight % of all siloxane units (% Si), are obtained by the following equations: % EO = 100 wEO = 100*t#EO*44/MW % PO = 100 wpo = 100*t&num EO*58/MW, and % Si = 100WSi = 100 - % EO-% PO The average number of ethyleneoxy units and the average number of propyleneoxy units, respectively, per polyalkyleneoxy group are calculated by dividing the average total number of these units by the sum of the average number of methyl (alkylene) siloxane Si (CH3) (CnH2n) O units and the average number of unreacted allyl groups according to the following equation: #EO/group = t#EO/(#Si(CH3)(CnH2n)O+ average # of unreacted allyl groups) The weight % of silicon is calculated by the ratio of the total number of all siloxane groups multiplied by the molecular weight of silicon and divided by the MW: % Si atom = 100*total # of all siloxane groups * 28/MW For the structural description of the polyalkyleneoxy polysiloxanes, several linear transforms of the structural parameters, such as log (t#Si), #(t&num Si), 1/t&num Si, #(t&num diSi), # (% Si), log (t#EO), log (t&num PO), #(t&num EO), #(t&num PO), #(&num EO/tail), #(#PO/tail) have also been found useful.

Preferred polyalkyleneoxy polysiloxanes of the present invention are water soluble or water dispersible. This property is controlled by the average number of

ethyleneoxy units in the polyether chain (R1), with higher content (percent by weight in the composition) of ethyleneoxy units corresponds to higher water solubility.

Polyalkyleneoxy polysiloxanes which are water insoluble or not readily dispersible in water can be incorporated into the compositions of the present invention by using a suitable emulsifier, preferably nonionic surfactant. Polyalkyleneoxy polysiloxanes comprising only propyleneoxy units, and without ethyleneoxy units are not preferred to use alone, but can be used in mixtures with other emulsifiers and/or suitable polyalkyleneoxy polysiloxanes, preferably polyethyleneoxy polysiloxanes which can serve as emulsifiers in the composition.

Typical levels of polyalkyleneoxy polysiloxane in usage compositions for usage conditions are from about 0.01% to about 10%, preferably from about 0.1% to about 5%, more preferably from about 0.2% to about 3%, and even more preferably from about 0.3% to about 2%, by weight of the usage composition. Typical levels of polyalkyleneoxy polysiloxane in concentrated compositions, to be diluted with water to form compositions with the usage concentrations, are from about 1% to about 40%, preferably from about 2% to about 20%, more preferably from about 3% to about 10%, by weight of the concentrated compositions.

Nonlimiting examples of polyalkyleneoxy polysiloxanes suitable for use in the compositions of the present invention are, e. g., the Silwet surfactants which are available from OSi Specialties, Inc., Danbury, Connecticut; DC silicone copolyols which are available from Dow Coming Corporation, Midland, Michigan; GE Silicones, Waterford, New York; and Goldschmidt Chemical Corp., Hopewell, Virginia. Nonlimiting examples of suitable polyalkyleneoxy polysiloxanes that are commercially available, are as follows: Name t#diSi(a) t#EO(b) %Si(c) S Value(d) DC-2 5573 194 754 19 26 DC-190 116 411 20 26 Silwet L-7230 68 151 24 19 Silwet L-7001 82 254 20 28 Silwet L-7622 90 107 62 27 Silwet L-7087 75 263 18 24 DC Q2 5220 137 854 15 22 Silwet-L-7220 40 91 17 19 Silwet L-7200 62 333 21 18 Silwet L-7210 17 71 12 14 Silwet L-7002 25 127 17 22 Silwet L-7602 24 42 56 19 Silwet L-7644 21 54 48 13 Silwet L-7604 20 61 48 11 Silwet L-7657 18 66.4 45 12 Silwet L-8620 13 20 57 13 Silwet L-8600 8 25 42 13

(a) Approximated total average number of the Si (CH3) 20 units in the molecule.

(b) Approximated total average number of the ethyleneoxy CH2CH2O units in the molecule.

(c) Approximated percent siloxane in the molecule.

(d) Softness Index as derived from Correlation I.

Comparative Polyethyleneoxy Polysiloxanes: The following comparative polyalkyleneoxy polysiloxanes represent silicones that have an S value of less than about 10, and thus are not suitable for use as fabric softener actives of the present invention. Name t#diSi t#EO %Si S Value DC 2 5237 11 233 10 9 Silwet L-7600 6. 5 70 32 4 Silwet L-7605 19 117 30 8 Silwet L-7280 0 9 29 5 Silwet L-77 0 10 37 3 Silwet L-7607 0 17 32 3 Silwet L-7608 0 8 44 3

Trisiloxane polymers such as Silwet L-77 and L-7608 are not suitable for use as fabric softener actives in the compositions of the present invention, but they can be useful to help distribute and spread the composition on certain fabrics, so they are preferred for their wetting property. When Silwet@ L-77 and/or L-7608 are present, the pH of the compositions is preferred to be maintained from about 6.0 to about 8. 0, preferably from about 6.5 to about 7.5, and more preferably from about 6.7 to about 7.3.

The present invention also relates to a method of using Correlation I to (a) estimate and/or predict the fabric softening performance of a polyalkyleneoxy polysiloxane, (b) select or identify the preferred polyalkyleneoxy polysiloxanes, and/or (c) design preferred polyalkyleneoxy polysiloxanes that provide superior fabric softening performance in fabric care compositions in general, and especially for use in the fabric softening composition of the present invention, as well as fabric care methods and/or articles of manufacture that use such fabric care compositions.

Procedure to Estimate and/or Predict Fabric Softening Performance of a polyalkyleneoxy polysiloxane: This is done by first determining the structural parameters required by Correlation I, and then calculate the S value using Correlation I: (a) Determine the approximated average total number of the SiMe2O units in the molecule (t#diSi), the number of methyl (alkylene) siloxane Si (CH3) (CnH2n) O units, and total average number of siloxane units t#Si by 29Si-NMR and l3C-NMR methods as described hereinabove.

(b) Determine the approximated average molecular weight (MW) of the polyalkyleneoxy polysiloxane by a combination of 29Si-NMR method and GC analysis of the hydrolysate of the polyalkyleneoxy polysiloxane as described hereinabove.

(c) Determine the approximated weight percent of all siloxane units (% Si) from the mass balance equation % Si = 100-% EO-% PO

(d) Determine the approximated average total number of ethyleneoxy EO units (t#EO), and the approximated average total number of propyleneoxy PO units (t#PO) by the GC method as described hereinabove. The approximated weight percent total EO (% EO) and the weight percent total PO (% PO) are derived from t#EO and t#PO by the equations: % EO = 100 x (t#EO x 44)/MW % PO = 100 x (t#PO x 58)/MW t (e) Calculate the estimated/predicted S value from Correlation I by using the above values for t&num diSi, t#EO, and % Si.

Procedure to Design Preferred Novel Polyalkyleneoxy Polysiloxanes : Correlation I provides a method for designing novel polyalkyleneoxy polysiloxanes that have not been prepared before that can provide superior fabric softening performance in the fabric softening compositions of the present invention. The method allows some flexible choices in designing new molecules, including, but not limited to, (i) choice of preferred type of molecules, e. g., polyethyleneoxy polysiloxane or polyethyleneoxy/ polypropyleneoxy polysiloxane; (ii) choice of preferred molecular weight range; and/or (iii) choice of degree of hydrophicity/water compatibility by setting the preferred weight % of all ethyleneoxy EO units and the weight % of all siloxane units. A typical procedure includes the following steps to design a polyalkyleneoxy polysiloxane (wherein the polyalkyleneoxy groups are linked to the silicone backbone by the CH2CH2CH2 linking groups, with no unreacted allyl groups, and the molecule has two terminal SiMe30 siloxane units): (a) Set a desired S value, typically at least about 15, preferably at least about 25, more preferably at least about 30, still more preferably at least about 32 and yet more preferably at least about 34.

(b) Set a desired average molecular weight, MW, typically at least from about 1,200, preferably from about 2,000 to about 200,000, more preferably from about 4,000 to about 150,000, even more preferably from about 5,000 to about 120,000, and yet more preferably from about 6,000 to about 100,000.

(c) Set a desired weight % of all ethyleneoxy EO units (% EO) for the molecule, typically less than about 80, preferably from about 10 to about 75, more preferably from about 15 to about 70, and even more preferably from about 25 to about 50.

The average total number of the ethyleneoxy units in the molecule (t#EO) is then derived from the equation % EO = 100 x (t#EO x 44)/MW

wherein t#EO is typically from about 25 to about 2,000, preferably from about 40 to about 1,500, more preferably from about 60 to about 1,200, and even more preferably from about 100 to about 1,000.

(d) Choose the type of polyalkyleneoxy polysiloxane, viz., polyethyleneoxy polysiloxane or polyethyleneoxy/polypropyleneoxy polysiloxane, then set the desired % Si, that is the weight % of all siloxane units (which include the terminal trimethylsiloxane Me3SiO units, the dimethylsiloxane SiMe2O units, and/or the linking siloxane SiMe (CH2CH2CH2) O units that link to the polyalkyleneoxy groups). For polyethyleneoxy polysiloxane % EO + % Si = 100, while for polyethyleneoxy/polypropyleneoxy polysiloxane % EO + % PO + % Si = 100.

(e) Use the desired values for S, t#EO and % Si to calculate t&num diSi (the approximated average total number of dimethylsiloxane SiMe2O units in the molecule), using Correlation I, wherein t&num diSi is typically from about 4 to about 450, preferably at least about 15 to about 350, more preferably from about 30 to about 250, even more preferably from about 60 to about 250; (f) Calculate the average total number of all siloxane groups according to the following equation t#Si=1.119*t#diSi+3.788 (g) The average number of the polyalkyleneoxy pendant groups are t&num linkSi = t&num Si-t&num diSi-2 for branched graft copolymers.

When the molecule has only one or none SiMe30 unit, the calculation can be modified accordingly.

Nonlimiting examples of the preferred polyethyleneoxy polysiloxanes which are derived from Correlation I and useful in the compositions of the present invention includes: Ex. No. of Predicted No. MW % EO % PO % Si t#diSi Tails(a) t#EO t#PO S 1 37, 400 43 6 51 217 28 366 39 35 2 32,100 42 0 58 212 27 306 0 35 3 40,000 42 12 46 212 27 382 83 34 4 57,200 39 27 34 219 28 507 266 34 5 47, 400 36 26 38 205 26 388 212 35 6 33,300 34 16 50 190 24 257 92 35 7 78, 300 30 46 24 212 27 534 621 35 8 36,200 30 26 44 181 23 247 162 35 9 27,300 28 14 58 180 23 174 66 35 10 32,700 26 29 45 168 22 193 164 35 11 89,800 22 59 19 190 24 449 913 35 12 63, 500 10 73 17 121 16 144 799 35 13 48,300 10 69 21 116 16 110 575 35 14 16900 16 0 84 161 21 61 0 35 15 31500 43 0 57 205 26 306 0 34 16 21100 26 0 74 177 23 127 0 35 17 43,000 51 4 45 220 28 498 30 33 18 58,900 46 21 33 220 28 616 213 33 19 51,500 40 26 34 202 26 468 231 33 20 41,700 33 32 35 168 22 313 230 33 21 62,500 33 41 26 184 24 469 442 33 22 23,100 31 6 63 166 22 163 24 33 23 32,300 25 34 41 151 20 184 189 33 24 22,900 23 19 58 150 20 120 75 33 25 23,900 22 23 55 147 19 120 95 33 26 87,600 21 63 16 158 21 418 952 32 27 69, 900 19 63 18 141 19 302 759 33 28 33300 47 0 53 203 26 352 0 33 29 19900 28 0 72 162 21 128 0 33 30 26300 39 0 61 182 23 234 0 33 31 49, 100 59 4 37 206 26 658 34 30 32 50, 000 54 11 35 197 25 614 95 30 33 66,400 54 17 29 219 28 815 195 30 34 30,400 48 4 48 165 21 332 21 30 35 26,300 42 5 53 166 21 251 23 31 36 21,400 40 0 60 146 19 195 0 30 37 32,200 40 19 41 150 20 293 105 30 38 25,000 32 23 45 128 17 182 99 30 39 22, 700 31 19 50 127 17 160 74 30 40 34,100 28 38 34 132 17 217 223 31 41 19,600 19 34 47 104 14 85 115 30 42 16,100 15 29 56 101 14 55 81 30 43 41,000 12 70 18 82 11 112 495 29 44 15300 23 0 77 132 17 81 0 30 45 26200 44 0 56 170 22 261 0 31 46 43700 58 0 42 208 27 577 0 31 47 33,400 63 0 37 140 18 478 0 25 48 55,900 63 11 26 168 22 800 106 25 49 39,200 62 6 32 144 19 552 41 25 50 50,400 60 12 28 160 21 687 104 25 51 29, 100 49 15 36 118 16 324 75 25 52 23,400 46 14 40 104 14 245 56 25 53 16,400 36 16 48 88 12 134 45 25 54 12,900 34 0 66 94 13 100 0 25 55 22,000 32 35 33 81 11 160 133 25 56 25,800 20 57 23 64 9 117 254 25 57 17,800 19 49 32 62 9 77 150 25 58 15,300 16 48 36 60 9 56 127 25 59 8700 15 0 85 82 12 29 0 25 60 12300 33 0 67 91 13 93 0 25 61 20400 52 0 48 110 15 239 0 25 (a) The average number of tails is t&num linkSi, i. e., the average number of polyalkyleneoxy polysiloxane groups in the molecule.

Besides fabric softening, polyalkyleneoxy polysiloxanes can also provide other benefits, such as color restoration, wrinkle reduction, and lubricity to fabrics.

The preparation of polyalkyleneoxy polysiloxanes is well known in the art.

Polyalkyleneoxy polysiloxanes of the present invention can be prepared according to the procedure set forth in U. S. Pat. No. 3,299,112, incorporated herein by reference.

Typically, polyalkyleneoxy polysiloxanes of the present invention are readily prepared by an addition reaction between a hydrosiloxane (i. e., a siloxane containing silicon-bonded hydrogen) and an alkenyl ether (e. g., a vinyl, allyl, or methallyl ether) of an alkoxy or hydroxy end-blocked polyalkyleneoxy). The reaction conditions employed in addition reactions of this type are well known in the art and in general involve heating the reactants (e. g., at a temperature of from about 85°C to 110°C) in the presence of a platinum catalyst (e. g., chloroplatinic acid) and a solvent (e. g., toluene). Additional disclosures of preparation methods for polyalkyleneoxy polysiloxanes can be found in Silicone Surfactants, R. M. Hill (Ed.), Marcel Dekker, Inc. (1999), Chapter 2, said publication being incorporated herein by reference.

Although some polyalkyleneoxy polysiloxanes have been prepared and commercially available, and may even have been disclosed generically with a fabric softening benefit, there has been no appreciation that specific polyalkyleneoxy polysiloxanes within the defined parameters herein have highly desirable softening benefit when applied, e. g :, as an aqueous spray. The incidental disclosure of the existing polyalkyleneoxy polysiloxanes or commercially available polyalkyleneoxy polysiloxanes does not suggest any reason for preparing other closely related polyalkyleneoxy polysiloxanes. Presently, there is no means for accurately predicting or guiding the preparation of other polyalkyleneoxy polysiloxanes that provide good softness performance in the context of an aqueous spray product. Therefore, the present invention relates to all novel polyalkyleneoxy polysiloxanes capable of providing fabric softening benefit selected from the group consisting of polyethyleneoxy polysiloxane, polyethyleneoxy/polypropyleneoxy polysiloxanes, and mixtures thereof, having an average molecular weight of from about 3,000 to about 200,000, and being characterized by Correlation I : wherein the softness index S is at least about 15, preferably at least about 20, and more preferably at least about 25, excluding the incidentally disclosed polyethyleneoxy polysiloxanes, said incidentally disclosed polyethyleneoxy polysiloxanes include: Silwet L-77, Silwet L-711, Silwet L-720, Silwet L-721, Silwet L-7000, Silwet L-7001, Silwet L- 7002, Silwet L-7087, Silwet L-7200, Silwet L-7210, Silwet L-7220, Silwet L-7230,

Silwet L-7280, Silwet L-7600, Silwet L-7602, Silwet L-7604, Silwet L-7605, Silwet L- 7607, Silwet L-7608, Silwet L-7610,7614, Silwet L-7622, Silwet L-7644, Silwet L-7650, Silwet L-7657, Silwet L-8500, Silwet L-8600, Silwet L-8610, Silwet L-8620, Silwet FZ- 2104, Silwet FZ-2120, Silwet FZ-2161, Silwet FZ-2162, Silwet FZ-2163, Silwet FZ- 2164, Silwet FZ-2165, Silwet FZ-2166, Silsoft@ 477, Silsoft 487, Silsoft 497, DC 190, DC 193, DC 2 5237, DC-2 5573, DC 3225C, DC 5093, DC 5097, DC 5098, DC 5103, DC 5197, DC 5200, DC 5211, DC 5212, DC 5220, DC 5225C, DC 5237, DC 5247, DC 5329, DC5604, DC 8692, DC Q2-2511, DC Q2-5220, DC Q4-3667, FF 400, Sylgard° 309, SH3771C, SH3772C, SH3773C, SH3746, SH3748, SH3749, SH8400, SF8410, SH8700, SF 1188A, SF 1288, SF 1388, SF 1488, SF 1328, SF 1528, TSF 4440, TSF 4441, TSF 4445, TSF 4446, TSF 4452, TSF 4450, OL 17, OL 31, OL 44, AC 3233, AI 3669, AI 3465, AI 3466, AI 3467, AI 3468, VP 3738, VP 3739, TP 3792, TP 3793, TP 3794, TP 3799, TP 3800, TP 3801, TP 3804, TP 3805, TP 3806, Abil'D B 8800, Abil B 8830, Abil B 8832, Abil B 8842, Abil B 8843, Abil B 8847, Abil B 8851, Abil B 8852, Abil B 8863, Abil B 8873, Abil EM 97, Abil EM-90, Abil WE-09, Abil B 88183, Abil B 88184, Abil 9950, Abil EM-90, Abil EM-97, Abil WE-90, Abil Care 85, KF351, KF352, KF353, KF354, KF 355, KF615, KF618, KF 625, KF 857, KF 862, KF-888, KF945, KF-8001, X-22-3667, X-22-3939A, X-22-4741, X-22-6008, X-22-8645, Fancorsil'LIM 1, Fancorsil LIM 2, Fancorsil LIM 3, Alkasil@ NE 58-50, Alkasil NEP 73-70, Alkasil NEPCA 250-185, Rhodorsil'Oils 70646, Silbionee Oils 70646, Amersil' DMC-287, Amersil DMC-357, Masilo 1066 D, Masil"280 LP, Masil@ SF 19, Masil@ SF 19A, Silicone Copolymer F-754, Silicone Fluid VP, Belsil@ DMC 6031, Belsil DMC 6032, Belsil DMC 6033, Belsil DMC 6035, Troysol@ S366, Troysol 380W, and Forest" G-23. Silwet polyethyleneoxy polysiloxanes are available from CK Witco Corporation, Greenwich, Connecticut, Silsoft polyethyleneoxy polysiloxanes were available from OSi Specialties, Inc. Danbury, Connecticut, DC polymers, FF 400, and Sylgard 309 are available from Dow Coming Corporation, Midland, Michigan, SH polymers are available from Dow Corning-Toray, SF polymers are available from GE-Silicones, TSF polymers are available from GE-Toshiba, OL, AC, AI, VP, and TP polymers are available from GE-Bayer, Abil polymers are available from Th. Goldschmidt AG, Hopewell, Virginia, KF and X polymers are available from Shin-Etsu, Fancorsil polymers are available from

Fancor, Alkasil, Rhodorsil, and Silbione polymers are available from Rhodia, Inc., Cranbury, New Jersey, Amersil polymers are available from Amerchol Corp., Edison, New Jersey, Masil polymers are vailable from PPG/Mazer, Silicone Copolymer F-754, Silicone Fluid VP, and Belsil polymers are available from Wacker, Forbest polymer is available from Lucas Meyer GmbH, Hamburg, Germany, and Troysol polymers are available from Troy Corp., Florham Park, New Jersey.

(B) WRINKLE CONTROL AGENT The composition can optionally contain an effective amount fabric wrinkle control agent, preferably selected from the group consisting of : fiber lubricants, shape retention polymers, polysaccharides, hydrophilic plasticizers, and mixtures thereof. Effective amount of wrinkle control agent is from about 0.05% to about 5%, preferably from about 0.2% to about 3%, more preferably from about 0.3% to about 2% by weight of the usage composition (with concentrated compositions having a level of from about 1% to about 20%, preferably from about 2% to about 15%, more preferably from about 3% to about 10%, by weight of the concentrated solution).

(1) Fiber Lubricants The fabric softening composition of the present invention can comprise optional fiber lubricant to impart a lubricating property or increased gliding ability to fibers in fabric, particularly clothing. Preferred fiber lubricants include silicones.

(a) Silicones The present invention can use silicone to impart a lubricating property or increased gliding ability to fibers in fabric, particularly clothing. Nonlimiting examples of useful silicones include noncurable silicones such as polydimethylsilicone and volatile silicones, and curable silicones such as aminosilicones and hydroxysilicones.

Suitable and preferred silicones that are useful in the compositions of the present invention are disclosed in WO 99/55953 published Nov. 4,1999 to Trinh et al., said publication is incorporated herein by reference.

When silicone is present, it is present at least an effective amount to provide lubrication of the fibers, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3%, more preferably from about 0.3% to about 2%, by weight of the usage composition.

(b) Synthetic solid particles

Solid polymeric particles of average particle size smaller than about 10 microns, preferably smaller than 5 microns, more preferably smaller than about 1 micron, e. g., Velustrol P-40 oxidized polyethylene emulsion available from Clariant, can be used as a lubricant, since they can provide a"roller-bearing"action. When solid polymeric particles are present, they are present at an effective amount to provide lubrication of the fibers, typically from about 0.01% to about 3%, preferably from about 0.05% to about 1%, more preferably from about 0.1% to about 0.5%, by weight of the usage composition.

(2) Shape Retention Polymer These polymers can be natural, or synthetic, and can act by forming a film, and/or by providing adhesive properties. Suitable and preferred shape retention polymers that are useful in the compositions of the present invention are disclosed in WO 99/55953 published Nov. 4,1999 to Trinh et al., said publication is incorporated herein by reference.

The optional film-forming and/or adhesive polymer of the present invention is present at least an effective amount to provide shape retention, typically from about 0.05% to about 5%, preferably from about 0.1% to about 3%, more preferably from about 0.2% to about 2%, even more preferably from about 0.3% to about 1%, by weight of the usage composition.

The adhesive polymer is present in the composition in a sufficient amount to result in an amount of from about 0.001% to about 1%, preferably from about 0.01% to about 0.5%, more preferably from about 0.02% to about 0.4% by weight of polymer per weight of dry fabrics.

Concentrated compositions can also be used in order to provide a less expensive product. When a concentrated product is used, i. e., when the wrinkle reducing active is from about 5% to about 50%, by weight of the concentrated composition, it is preferable to dilute the composition before treating fabric. Preferably, the wrinkle reducing active is diluted with about 50% to about 10,000%, more preferably from about 50% to about 8,000%, and even more preferably from about 50% to about 5,000%, by weight of the composition, of water.

Optional silicones and film-forming polymers can be combined to produce preferred wrinkle reducing actives. Typically the weight ratio of silicone to film-forming polymer is from about 10: 1 to about 1: 10, preferably from about 5: 1 to about 1: 5, and more preferably from about 2: 1 to about 1: 2. Typically, the preferred wrinkle reducing active of silicone plus polymer is present at a level of from about 0.1% to about 8%,

preferably from about 0.3% to about 5%, more preferably from about 0.5% to about 3%, by weight of the composition.

Optional but preferred adhesive and/or film forming polymers that are useful in the composition of the present invention actually contain silicone moieties in the polymers themselves. These preferred polymers, excluding the silicone copolyols, include graft and block copolymers of silicone with moieties containing hydrophilic and/or hydrophobic monomers. The silicone-containing copolymers in the spray composition of the present invention provide shape retention, body, and/or good, soft fabric feel. The useful copolymers are described in WO 99/55953 published Nov. 4, 1999 to Trinh et al., said publication is incorporated herein by reference.

(3) Fabric Care Polysaccharides Suitable optional fabric care polysaccharides for use in the composition of the present invention are those which have a globular conformation in dilute aqueous solution, via a random coiling structure. Said polysaccharides include homo-and/or hetero-polysaccharides with simple helical structure with or without branching, e. g., with 1,4-a-linked backbone structure (e. g., 1,4-a-glucan, 1,4-a-xylan) with or without branching, 1,3-p-linked backbone with or without branching (e. g., galactan), and all 1,6- linked backbones with or without branching (e. g., dextran, pullulan, pustulan), and with a weight-average molecular weight of from about 5,000 to about 500,000, preferably from about 8,000 to about 250,000, more preferably from about 10,000 to about 150,000, typically with sizes ranging from about 2 nm to about 300 nm, preferably from about 3 nm to about 100 nm, more preferably from about 4 nm to about 30 nm. The size is defined as the gyration length occupied by the molecule in dilute aqueous solutions. The useful fabric care polysaccharides are described with more details in WO 00/24856 published May 4,2000 to Barnabas et al., said publication is incorporated herein by reference.

Typical composition to be dispensed from a sprayer contains a level of fabric care polysaccharide with globular structure of from about 0.01% to about 5%, preferably from about 0.05% to about 2%, more preferably from about 0.1% to about 1%, by weight of the usage composition.

(4) Hydrophilic Plasticizer Optionally, the composition can contain a hydrophilic plasticizer to soften both the fabric fibers, especially cotton fibers, and the adhesive and/or film-forming shape retention polymers. Examples of the preferred hydrophilic plasticizers are low molecular weight polyhydric alcohols, such as is glycerol, ethylene glycol, propylene glycol,

diethylene glycol, dipropylene glycol, sorbitol, erythritol, and mixtures thereof, more preferably diethylene glycol, dipropylene glycol, ethylene glycol, propylene glycol and mixtures thereof.

The aqueous compositions containing these plasticizers also tend to provide a slower drying profile for clothing/fabrics, to allow time for any wrinkles to disappear when the clothing/fabrics are hung to dry. This is balanced by the desire by most consumer to have the garments to dry faster. Therefore, when needed, the plasticizers should be used at an effective, but as low as possible, level in the composition. When a hydrophilic plasticizer is used, it is present in the at a level of from 0.01% to 5%, preferably from 0. 05% to 2%, more preferably from 0.1% to 1% by weight of the usage composition.

(C) PERFUME The fabric softening composition of the present invention can also optionally provide a"scent signal"in the form of a pleasant odor which provides a freshness impression to the treated fabrics. The scent signal can be designed to provide a fleeting perfume scent. When perfume is added as a scent signal, it is added only at very low levels, e. g., from about 0.001% to about 1%, preferably from about 0.003% to about 0.3%, more preferably from about 0.005% to about 0.2%, by weight of the usage composition.

Perfume can also be added as a more intense odor in product and on fabrics.

When stronger levels of perfume are preferred, relatively higher levels of perfume can be added.

Any type of perfume can be incorporated into the composition of the present invention. The preferred perfume ingredients are those suitable for use to apply on fabrics and garments. Typical examples of such preferred ingredients are given in U. S.

Pat. 5,445,747, issued Aug. 29,1995 to Kvietok et al., 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, those materials disclosed in said patents.

The perfumes useful in the present invention compositions are preferably 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.

Concentrated fabric softening composition of the present invention can contain higher levels of perfume, up to about 3%, preferably from about 0.01% to about 1%, and more preferably from about 0.1% to about 0.5%, by weight of the finished fabric softening composition.

Preferably, the fabric softening composition herein comprises a perfume comprising substantive perfume ingredients to provide a long lasting perfume odor benefit. It is preferable that at least about 25%, preferably at least about 40%, more preferably at least about 60%, and even more preferably at least about 75%, by weight of the perfume is composed of substantive perfume ingredients; and optionally some perfume ingredients having low odor detection threshold.

Substantive perfume ingredients are characterized by their boiling points (B. P.).

The substantive perfume ingredients of this invention have a B. P, measured at the normal, standard pressure of 760 mm Hg, of about 240°C or higher, and preferably of about 250°C or higher.

The boiling points of many perfume ingredients are given in, e. g.,"Perfume and Flavor Chemicals (Aroma Chemicals),"Steffen Arctander, published by the author, 1969, incorporated herein by reference. Other boiling point values can be obtained from different chemistry handbooks and data bases, such as the Beilstein Handbook, Lange's Handbook of Chemistry, and the CRC Handbook of Chemistry and Physics. When a boiling point is given only at a different pressure, usually lower pressure than the normal pressure of 760 mm Hg, the boiling point at normal pressure can be approximately estimated by using boiling point-pressure nomographs, such as those given in"The Chemist's Companion,"A. J. Gordon and R. A. Ford, John Wiley & Sons Publishers, 1972, pp. 30-36. The boiling point values can also be estimated via a computer program that is described in"Development of a Quantitative Structure-Property Relationship Model for Estimating Normal Boiling Points of Small Multifunctional Organic Molecules", David T. Stanton, Journal of Chemical Information and Computer Sciences,

Vol. 40, No. 1,2000, pp. 81-90, incorporated herein by reference. Thus, when a perfume composition is composed of substantive perfume ingredients having a B. P. of about 240°C or higher, they appreciably remain on fabrics after the drying step.

Non-limiting examples of the preferred substantive perfume ingredients of the present invention include: allyl cyclohexane propionate, ambrettolide, amyl benzoate, amyl cinnamate, amyl cinnamic aldehyde, amyl cinnamic aldehyde dimethyl acetal, iso- amyl salicylate, aurantiol (trade name for hydroxycitronellal-methyl anthranilate), benzophenone, benzyl salicylate, iso-butyl quinoline, beta-caryophyllene, cadinene, cedrol, cedryl acetate, cedryl formate, cinnamyl cinnamate, cyclohexyl salicylate, cyclamen aldehyde, dihydro isojasmonate, diphenyl methane, diphenyl oxide, dodecalactone, iso E super (trade name for 1- (1, 2,3,4,5,6,7,8-octahydro-2,3,8,8- tetramethyl-2-naphthalenyl)-ethanone), ethylene brassylate, ethyl methyl phenyl glycidate, ethyl undecylenate, iso-eugenol, exaltolide (trade name for 15- hydroxypentadecanoic acid, lactone), galaxolide (trade name for 1,3,4,6,7,8-hexahydro- 4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyran), geranyl anthranilate, hexadecanolide, hexenyl salicylate, hexyl cinnamic aldehyde, hexyl salicylate, lilial (trade name for para-tertiary-butyl-alpha-methyl hydrocinnamic aldehyde), linalyl benzoate, 2-methoxy naphthalene, methyl cinnamate, methyl dihydrojasmonate, beta- methyl naphthyl ketone, musk indanone, musk ketone, musk tibetine, myristicin, delta- nonalactone, oxahexadecanolide-10, oxahexadecanolide-11, patchouli alcohol, phantolide (trade name for 5-acetyl-1, 1, 2,3,3,6-hexamethylindan), phenyl ethyl benzoate, phenylethylphenylacetate, phenyl heptanol, phenyl hexanol, alpha-santalol, thibetolide (trade name for 15-hydroxypentadecanoic acid, lactone), tonalid, delta-undecalactone, gamma-undecalactone, vetiveryl acetate, yara-yara, allyl phenoxy acetate, cinnamic alcohol, cinnamic aldehyde, cinnamyl formate, coumarin, dimethyl benzyl carbinyl acetate, ethyl cinnamate, ethyl vanillin (3-methoxy-4-ethoxy benzaldehyde), eugenol, eugenyl acetate, heliotropine, indol, isoeugenol, koavone, methyl-beta-naphthyl ketone, methyl cinnamate, methyl dihdrojasmonate, beta methyl naphthyl ketone, methyl-n- methyl anthranilate, delta-nonalactone, gamma-nonalactone, para methoxy acetophenone (acetanisole), phenoxy ethyl iso butyrate, phenoxy ethyl propionate, piperonal, triethyl citrate, vanillin, and mixtures thereof. Other substantive perfume ingredients useful in the present invention include methyl-N-methyl anthranilate, benzyl butyrate, benzyl iso valerate, citronellyl isobutyrate, citronellyl propionate, delta-nonalactone, dimethyl benzyl carbinyl acetate, dodecanal, geranyl acetate, geranyl isobutyrate, gamma-ionone, para-isopropyl phenylacetaldehyde, cis-jasmone, methyl eugenol, hydroxycitronellal,

phenoxy ethanol, benzyl iso valerate, anisic aldehyde, cuminic alcohol, cis-jasmone, methyl eugenol, and mixtures thereof.

The preferred perfume compositions used in the present invention contain at least 4 different substantive perfume ingredients, preferably at least 5 substantive perfume ingredients, more preferably at least 6 different substantive perfume ingredients, and even more preferably at least 7 different substantive perfume ingredients. Most common perfume ingredients which are derived from natural sources are composed of a multitude of components. When each such material is used in the formulation of the preferred perfume compositions of the present invention, it is counted as one single ingredient, for the purpose of defining the invention.

In the perfume art, some materials having no odor or very faint odor are used as diluents or extenders. Non-limiting examples of these materials are dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate, and benzyl benzoate. These materials are used for, e. g., diluting and stabilizing some other perfume ingredients.

These materials are not counted in the formulation of the substantive perfume compositions of the present invention.

Low Odor Detection Threshold Perfume Ingredients The substantive perfume compositions of the present invention can also comprise some low odor detection threshold perfume ingredients. The odor detection threshold of an odorous material is the lowest vapor concentration of that material which can be olfactorily detected. The odor detection threshold and some odor detection threshold values are discussed in, e. g.,"Standardized Human Olfactory Thresholds", M. Devos et al, IRL Press at Oxford University Press, 1990, and"Compilation of Odor and Taste Threshold Values Data", F. A. Fazzalari, editor, ASTM Data Series DS 48A, American Society for Testing and Materials, 1978, both of said publications being incorporated by reference. The use of small amounts of perfume ingredients that have low odor detection threshold values can improve perfume odor character, even though they are not as materially substantive as the substantive perfume ingredients disclosed hereinabove.

Perfume ingredients having a significantly low detection threshold, useful in the substantive perfume composition of the present invention, are selected from the group consisting of allyl amyl glycolate, ambrox, anethole, bacdanol, benzyl acetone, benzyl salicylate, butyl anthranilate, calone, cetalox, cinnamic alcohol, coumarin, cyclogalbanate, Cyclal C, cymal, damascenone, alpha-damascone, 4-decenal, dihydro isojasmonate, gamma-dodecalactone, ebanol, ethyl anthranilate, ethyl-2-methyl butyrate, ethyl methylphenyl glycidate, ethyl vanillin, eugenol, flor acetate, florhydral, fructone, frutene, heliotropin, herbavert, cis-3-hexenyl salicylate, indole, alpha-ionone, beta-

ionone, iso cyclo citral, isoeugenol, alpha-isomethylionone, keone, lilial, linalool, lyral, methyl anthranilate, methyl dihydrojasmonate, methyl heptine carbonate, methyl isobutenyl tetrahydropyran, methyl beta naphthyl ketone, methyl nonyl ketone, beta naphthol methyl ether, nerol, para-anisic aldehyde, para hydroxy phenyl butanone, phenyl acetaldehyde, gamma-undecalactone, undecylenic aldehyde, vanillin, and mixtures thereof. These materials are preferably present at low levels in addition to the substantive perfume ingredients, typically less than about 40%, preferably less than about 30%, more preferably less than about 20%, by weight of the total perfume compositions of the present invention. However, only low levels are required to provide a perfume odor effect. Some substantive perfume ingredients also have low odor detection threshold.

These materials are counted as substantive perfume ingredients in the formulation of the substantive perfume compositions of the present invention The compositions of the present invention can also comprise a perfume delivery system that can slowly release perfume ingredients after the fabric is treated by the fabric care composition of this invention. Said comprises one or more pro-fragrances, pro-perfumes, pro-accords, and mixtures thereof hereinafter known collectively as"pro-perfumes". The pro-perfumes of the present invention can exhibit varying release rates depending upon the pro-perfume chosen. In addition, the pro-perfumes of the present invention can be admixed with the perfume materials which are released therefrom to present the user with an initial fragrance, scent, accord, or bouquet. Non-limiting examples of pro-perfumes according to the present invention are ester and polyester pro-perfumes, p-ketoester pro-perfumes, acetal and ketal pro-perfumes, orthoester pro-perfumes, and mixtures thereof.

Pro-perfumes are suitably described in the following: U. S. 5,378,468 Suffis et al., issued January 3,1995; U. S. Pat. 5,531,910, Severns et al., issued July 2,1996, U. S.

5,626,852 Suffis et al., issued May 6,1997; U. S. 5,710,122 Sivik et al., issued January 20,1998; U. S. 5,716,918 Sivik et al., issued February 10,1998; U. S. 5,721,202 Waite et al., issued February 24,1998; U. S. 5,744,435 Hartman et al., issued April 25,1998; U. S.

5,756,827 Sivik, issued May 26,1998; U. S. 5,830,835 Severns et al., issued November 3, 1998; U. S. 5,919,752 Morelli et al., issued July 6,1999 all of which are incorporated herein by reference.

When cyclodextrin is present for odor control benefit, it is essential that the perfume be added at a level wherein even if all of the perfume in the composition were to complex with the cyclodextrin molecules when cyclodextrin is present, there will still be an effective level of uncomplexed cyclodextrin molecules present in the solution to provide adequate odor control. In order to reserve an effective amount of cyclodextrin molecules for odor control when cyclodextrin is present, perfume is typically present at a

level wherein less than about 90% of the cyclodextrin complexes with the perfume, preferably less than about 50% of the cyclodextrin complexes with the perfume, more preferably, less than about 30% of the cyclodextrin complexes with the perfume, and most preferably, less than about 10% of the cyclodextrin complexes with the perfume.

The cyclodextrin to perfume weight ratio should be greater than about 8: 1, preferably greater than about 10: 1, more preferably greater than about 20: 1, even more preferably greater than 40: 1 and most preferably greater than about 70: 1.

Preferably the perfume for use in presence of cyclodextrin is hydrophilic and is composed of hydrophilic perfume ingredients having a ClogP of less than about 3.2, more preferably equal to or less than about 3.0. Said perfume comprises at least about 25% hydrophilic perfume ingredients, preferably at least about 50%, more preferably at least about 75%, by weight of the perfume composition.

Nonlimiting suitable and preferred hydrophilic perfume ingredients and methods to determine ClogP, the calculated logP, are given in U. S. Pat. No. 6,001,343, issued Dec.

14,1999 to Trinh et al., said patent is incorporated herein by reference.

(D) SURFACTANT Surfactant is an optional but preferred ingredient of the present invention.

Surfactant is useful in the composition to facilitate the dispersion and/or solubilization of, e. g., polyalkyleneoxy polysiloxanes, wrinkle control agents such as silicones, and/or certain relatively water insoluble adjunct shape retention polymers. Some surfactants, e. g., some nonionic surfactants are especially useful to clarify compositions (make the compositions clear) that comprise polyalkyleneoxy polysiloxanes that are not soluble in water at preferred levels in the compositions. Surfactant is also preferably included when the composition is used in a spray dispenser in order to enhance the spray characteristics of the composition and allow the composition to distribute more evenly, and to prevent clogging of the spray apparatus. The spreading of the composition can also allow it to dry faster, so that the treated material is ready to use sooner. For concentrated compositions, the surfactant facilitates the dispersion of many actives such as antimicrobial actives and perfumes in the concentrated aqueous compositions. Suitable surfactant useful in the present invention is nonionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant, and mixtures thereof.

When surfactant is used in the composition of the present invention, it is added at an effective amount to provide one, or more of the benefits described herein, typically from about 0.05% to about 5%, preferably from about 0.1% to about 3%, more preferably from about 0.2% to about 1.5%, and even more preferably, from about 0.2% to about 1%,

by weight of the usage composition. Concentrated compositions to be diluted for use comprise higher levels of surfactants, typically from about 0.1% to about 15%, preferably from about 0.2% to about 8%, more preferably from about 0.3% to about 5%, by weight of the concentrated composition.

A preferred type of surfactant is ethoxylated surfactant, such as addition products of ethylene oxide with fatty alcohols, fatty acids, fatty amines, etc. Optionally, addition products of mixtures of ethylene oxide and propylene oxide with fatty alcohols, fatty acids, fatty amines can be used. Suitable ethoxylated surfactants for use in the compositions, articles, and method of present invention is given in WO 99/55953 published Nov. 4,1999 to Trinh et al., said publication is incorporated herein by reference.

Other useful surfactants are those having a hydrophobic moiety and hydrophilic ionic groups, including, e. g., anionic, cationic, and amphoteric groups. Examples of suitable nonionic, anionic, cationic, ampholytic, zwitterionic and semi-polar nonionic surfactants are disclosed in U. S. Pat. Nos. 5,707,950 and 5,576,282, incorporated herein by reference.

(E) ANTIMICROBIAL ACTIVE Optionally, the fabric softening composition of the present invention comprise an effective amount, to kill, or reduce the growth of microbes, of antimicrobial active; preferably from about 0.001% to about 0.8%, more preferably from about 0.002% to about 0.3%, even more preferably from about 0.003% to about 0.2%, by weight of the usage composition. The effective antimicrobial active can function as disinfectants/sanitizers, and is useful in providing protection against organisms that become attached to the fabrics.

Nonlimiting examples of antimicrobial actives which are useful in the present invention are given in WO 99/55953 published Nov. 4,1999 to Trinh et al., said publication is incorporated herein by reference.

(F) AMINOCARBOXYLATE CHELATOR Chelators, e. g., ethylenediaminetetraacetic acid (EDTA), hydroxyethylene- diaminetriacetic acid, diethylenetriaminepentaacetic acid, and other aminocarboxylate chelators, and mixtures thereof, and their salts, and mixtures thereof, can optionally be used to increase antimicrobial and preservative effectiveness against Gram-negative bacteria, especially Pseudomonas species. Nonlimiting examples of suitable aminocarboxylate chelators and information of their usage are given in U. S. Pat. No.

6,001,343 cited hereinabove, and incorporated herein by reference.

The optional chelators are present in the compositions of this invention at levels of, typically, from about 0.001% to about 0.3%, more preferably from about 0.01% to about 0.1%, most preferably from about 0.02% to about 0.05% by weight of the usage compositions to provide antimicrobial efficacy in this invention.

(G) ODOR CONTROL AGENT Fabric softening compositions of the present invention can optionally contain odor control agent, preferably uncomplexed cyclodextrins, water soluble zinc salts, soluble carbonate and/or bicarbonate salts, water soluble ionic polymers, and mixtures thereof.

Nonlimiting examples of preferred odor control agents are given in U. S. Pat. No.

5,997,759, issued Dec. 7,1999 to Trinh et al., said patent is incorporated herein by reference. Typical levels of odor control agent in compositions for usage conditions are from about 0.01% to about 5%, preferably from about 0.1% to about 4%, more preferably from about 0.2% to about 3%, and even more preferably from about 0.3% to about 2%, by weight of the composition.

(a) Cyclodextrin Suitable cyclodextrin for use in the compositions, articles, and method of present invention is given in WO 99/55953 published Nov. 4,1999 to Trinh et al., said publication is incorporated herein by reference. Typical levels of cyclodextrin in usage compositions for usage conditions are from about 0.01% to about 5%, preferably from about 0.1% to about 4%, more preferably from about 0.2% to about 3%, and even more preferably from about 0.3% to about 2%, by weight of the composition. It is preferable that the treated fabric contains a level of less than about 5 mg of cyclodextrin per gram of fabric, more preferably less than about 2 mg of cyclodextrin per gram of fabric.

Low Molecular Weight Polyols Some low molecular weight polyols with relatively high boiling points, as compared to water, are preferred optional ingredients for improving odor control performance of the composition of the present invention when cyclodextrin is present.

The mechanism of odor control of low MW polyols, and preferred levels of said polyols, are discussed in U. S. Pat. No. 5,997,759 cited hereinabove, and incorporated herein by reference. Preferably the glycol used is ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol or mixtures thereof, more preferably ethylene glycol and/or propylene glycol. Cyclodextrins prepared by processes that result in a level of such polyols are highly desirable, since they can be used without removal of the polyols.

(b) Metal Salts

Optionally, but preferably, the present invention can include metallic salts for odor control and/or antimicrobial benefits. The metallic salts are selected from the group consisting of copper salts, zinc salts, and mixtures thereof. These benefits and other benefits are given in U. S. Pat. No. 5,997,759 cited hereinabove, and incorporated herein by reference. Preferably the metallic salts are water-soluble zinc salts, copper salts or mixtures thereof, and more preferably zinc salts, especially ZnCI.

When metallic salts are added to the composition of the present invention they are typically present at a level of from about 0.1% to about 10%, preferably from about 0.2% to about 8%, more preferably from about 0.3% to about 5% by weight of the usage composition. When zinc salts are used as the metallic salt, and a clear solution is desired, it is preferable that the pH of the solution is adjusted to less than about 7, more preferably less than about 6, most preferably, less than about 5, in order to keep the solution clear.

(c) Soluble Carbonate and/or Bicarbonate Salts Water-soluble alkali metal carbonate and/or bicarbonate salts, such as sodium bicarbonate, potassium bicarbonate, potassium carbonate, cesium carbonate, sodium carbonate, and mixtures thereof can be added to the composition of the present invention in order to help to control certain acid-type odors. Preferred salts are sodium carbonate monohydrate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, and mixtures thereof. When these salts are added to the composition of the present invention, they are typically present at a level of from about 0.1% to about 5%, preferably from about 0.2% to about 3%, more preferably from about 0.3% to about 2%, by weight of the composition. When these salts are added to the composition of the present invention it is preferably that incompatible metal salts not be present in the invention. Preferably, when these salts are used the composition should be essentially free of zinc and other incompatible metal ions, e. g., Ca, Fe, Ba, etc. which form water- insoluble salts.

(d) Water-Soluble Ionic Polymers Some water-soluble polymers, e. g., water-soluble cationic polymer and water-soluble anionic polymers can be used in the composition of the present invention to provide additional odor control benefits. Nonlimiting examples of such polymers that are useful in the present invention are given in U. S. Pat. No. 5,997,759 cited hereinabove, and incorporated herein by reference.

Water-soluble anionic polymers, e. g., polyacrylic acids and their water-soluble salts are useful in the present invention to control certain amine-type odors. Preferred polyacrylic acids and their alkali metal salts have an average molecular weight of less than about 20,000, more preferably less than 5,000. Polymers containing sulfonic acid groups, phosphoric acid groups,

phosphonic acid groups, and their water-soluble salts, and mixtures thereof, and mixtures with carboxylic acid and carboxylate groups, are also suitable.

When a water-soluble polymer is used it is typically present at a level of from about 0.001% to about 3%, preferably from about 0.005% to about 2%, more preferably from about 0.01% to about 1%, and even more preferably from about 0.05% to about 0.5%, by weight of the usage composition.

(e) Mixtures Thereof Mixtures of the above materials are desirable, especially when the mixture provides control over a broader range of odors.

(H) PRESERVATIVE Optionally, solubilized, water-soluble, antimicrobial preservative can be added to the composition of the present invention if the antimicrobial active (E) is not sufficient, or is not present, especially when cyclodextrin and/or polysaccharide molecules are present in the fabric softening compositions.

Suitable antimicrobial preservative for use in the compositions, articles, and method of present invention is given in WO 99/55953 published Nov. 4,1999 to Trinh et al., said publication is incorporated herein by reference.

Preferred levels of preservative are from about 0.0001% to about 0.5%, more preferably from about 0.0002% to about 0.2%, most preferably from about 0.0003% to about 0.1%, by weight of the usage composition.

(I) ADJUNCT FABRIC SOFTENING AGENTS The composition of the present invention can optionally contain adjunct quaternary ammonium fabric softening agent to provide additional fabric softening benefit. Examples of quaternany ammonium fabric softening actives are disclosed in U. S.

Pat. Nos.: 3,861,870, Edwards et al.; 4,308,151, Cambre; 3,886,075, Bernardino ; 4,233,164, Davis; 4,401,578, Verbruggen; 3,974,076, Wiersema et al.; and 4,237,016, Rudkin et al.; said patents being incorporated by reference herein. Some preferred quaternany ammonium fabric softening actives are disclosed in U. S. Pat. Nos: 4,661,269, issued April 28,1987, to T. Trinh et al; U. S. Pat. No. 5,545,340, issued Aug. 13,1996, to Wahl et al.; 5,747,443 issued May 5,1998 to E. H. Wahl et al; and 5,830,845 issued Nov.

3,1998 to T. Trinh et al; all said patents are incorporated herein by reference.

When the adjunct fabric softening agent is used, it is typically present at a level of from about 0.05% to about 3%, preferably from about 0.1% to about 2%, more preferably from about 0.3% to about 1%, by weight of the usage composition.

(J) AQUEOUS CARRIER

The preferred carrier of the present invention is water. The water which is used can be distilled, deionized, or tap water. Water is the main liquid carrier due to its low cost, availability, safety, and environmental compatibility.

Water is also very useful for fabric wrinkle removal or reduction. Not to be bound by theory, it is believed that water breaks many intrafiber and interfiber hydrogen bonds that keep the fabric in a wrinkle state. It also swells, lubricates and relaxes the fibers to help the wrinkle removal process.

The level of liquid carrier in the compositions of the present invention is typically greater than about 80%, preferably greater than about 90%, more preferably greater than about 95%, by weight of the composition.

Optionally, in addition to water, the carrier can contain a low molecular weight organic solvent that is highly soluble in water, e. g., ethanol, propanol, isopropanol, and the like, and mixtures thereof. Low molecular weight alcohols can help the treated fabric to dry faster. The optional solvent is also useful in the solubilization of some shape retention polymers described hereinbefore. The optional water soluble low molecular weight solvent can be used at a level of up to about 50%, typically from about 1% to about 20%, preferably from about 2% to about 15%, more preferably from about 5% to about 10%, by weight of the total composition. Factors that need to consider when a high level of solvent is used in the composition are odor, flammability, and environment impact; in such cases the optional water soluble low molecular weight solvent can be preferably used at a level of up to about 5%.

(K) OTHER OPTIONAL INGREDIENTS The composition of the present invention can optionally antistatic agents, insect and moth repelling agents, colorants, especially bluing agents, chemical stabilizers including antioxidants, anti-clogging agents, suds suppressors, brighteners, soil release agents, and mixtures thereof. Suitable optional ingredients for use in the compositions, articles, and method of present invention is given in WO 99/55953 published Nov. 4, 1999 to Trinh et al., said publication is incorporated herein by reference. The total level of optional ingredients is low, preferably less than about 5%, more preferably less than about 3%, and even more preferably less than about 2%, by weight of the usage composition. These optional ingredients exclude the other ingredients specifically mentioned hereinbefore.

II. ARTICLE OF MANUFACTURE

The fabric softening composition of the present invention can also be used in an article of manufacture comprising said composition plus a spray dispenser. The present invention also relates to an article of manufacture comprising the fabric softening composition in a package, in association with instructions for how to use the composition to treat fabrics correctly, in order to obtain the desirable fabric fabric softening and other optional fabric care results, viz, wrinkle removal and/or reduction, wrinkle resistance, fiber strengthening/anti-wear, fabric wear reduction, fabric color maintenance, fabric color restoration, fabric color fading reduction, soiling prevention and/or reduction, and/or fabric shape retention, and mixtures thereof. A preferred article of manufacture comprises said composition in a spray dispenser, in association with instructions for how to use the composition to treat fabrics correctly, including, e. g., the manner and/or amount of composition to spray, as will be described with more detailed herein below.

The instructions for use can also direct the consumer to apply the composition to the fabric in combination with stretching and/or smoothing of fabric, to provide effective fabric softening and/or wrinkle removal. It is important that the instructions be simple and clear, such that using text, pictures and/or icons may be desirable. Said instructions may include instructions that direct the consumer to apply the composition to fabric in the manner and in amounts as describe hereinafter.

The present invention also relates to an article of manufacture comprising a concentrated fabric softening composition comprising polyalkyleneoxy polysiloxane at a level of from about 1% to about 40%, by weight of the concentrated composition, in a package, in association with instructions for how to dilute said concentrated composition to form compositions with the usage concentrations of polyethyleneoxy polysiloxane of, e. g., from about 0.1% to about 5%, by weight of the diluted composition.

SPRAY DISPENSER The article of manufacture herein comprises a spray dispenser. The fabric softening composition is placed into a spray dispenser in order to be distributed onto the fabric. Said spray dispenser for producing a spray of liquid droplets can be any of the manually activated means as is known in the art, e. g. trigger sprayer, pump sprayer, non- aerosol self-pressurized sprayer, and aerosol-type sprayer, for treating fabric softening composition to small fabric surface areas and/or small number of fabric articles, as well as non-manually operated, powered sprayers for conveniently treating the odor-absorbing composition to large fabric surface areas and/or a large number of garments and/or articles. The spray dispenser herein does not normally include those that will substantially foam the aqueous fabric softening composition. To efficiently provide softness performance it is preferable to treat fabrics with the fabric softening composition

in the form of small droplet particles. Desirably, the Sauter mean particle diameter is from about 10 um to about 120 um, more preferably, from about 20, um to about 100 p m.

The manually activated spray dispensers include, but are not limited to, aerosol dispenser; self-pressurized non-aerosol container having a convoluted liner and an elastomeric sleeve; non-aerosol, manually activated, pump-spray dispenser; and manually activated trigger-spray dispenser. Non-manually operated spray dispeners include, but are not limited to, powered sprayers, air aspirated sprayers, liquid aspirated sprayers, electrostatic sprayers, and nebulizer sprayers. Detailed descriptions of spray dispensers that are suitable for use in the present invention are given in U. S. Pat. No. 6,001,343, incorporated hereinbefore by reference.

The preferred trigger sprayers are the blue inserted Gala ! sprayer, available from Berry Plastics Corp., or the Calmar TS800-1A@, Tus1300', and Tus-800-20, available from Calmar Inc., because of the fine uniform spray characteristics, spray volume, and pattern size. More preferred are sprayers with precompression features and finer spray characteristics and even distribution, such as Yoshino sprayers from Japan. Any suitable bottle or container can be used with the trigger sprayer, the preferred bottle is a 17 fl-oz. bottle (about 500 ml) of good ergonomics similar in shape to the CinchX bottle. It can be made of any materials such as high density polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyethylene terephthalate, glass, or any other material that forms bottles. Preferably, it is made of high density polyethylene or clear polyethylene terephthalate.

For smaller fluid ounce sizes (such as 1 to 8 ounces), a finger pump can be used with canister or cylindrical bottle. The preferred pump for this application is the cylindrical Euromist 11 from Seaquest Dispensing. More preferred are those with precompression features.

III. METHOD OF USE The fabric softening composition of the present invention can be used by distributing, e. g., by placing, an effective amount of the aqueous solution onto the fabric article to be treated. Distribution can be achieved by using a spray device, a roller, a pad, etc., preferably a spray dispenser. For fabric softening, an effective amount, as defined herein, means an amount sufficient to make the fabric feels softer than the fabric treated with water alone. Preferably, the amount of solution is not so much as to saturate or create a pool of liquid on said fabric article or surface and so that when dry there is no visual deposit readily discernible.

An effective amount of the liquid composition of the present invention is preferably sprayed onto fabrics, particularly clothing. The composition can be applied to dry or wet fabrics, preferably dry fabrics. The composition can also be applied onto fabrics in the drying step of a laundry process. When the composition is sprayed onto fabric, an effective amount should be deposited onto the fabric, with the fabric becoming damp or totally saturated with the composition, typically from about 5% to about 150%, preferably from about 10% to about 100%, more preferably from about 20% to about 75%, by weight of the dry fabric. The amount of polyalkyleneoxy polysiloxane fabric softening active typically sprayed onto the fabric is from about 0.005% to about 5%, preferably from about 0.01% to about 2%, more preferably from about 0.03% to about 1%, and even more preferably from about 0.1% to about 1 %, by weight of the dry fabric.

It is highly preferable to use the preferred particles sizes described hereinbefore, since the areas that receive too much liquid will be slow to dry. Once the fabric has been sprayed, it is air dried or dried in an automatic clothes dryer.

The fabric softening composition can be applied to fabrics made of fibers selected from the group consisting of natural fibers, synthetic fibers, and mixtures thereof; preferably fibers selected from the group consisting of : cellulosic fibers, proteinaceous fibers; synthetic fibers; long vegetable fibers; and mixtures thereof; more preferably selected from the group consisting of cotton, rayon, linen, Tencel, silk, wool and related mammalian fibers, polyester, acrylic, nylon, jute, flax, ramie, coir, kapok, sisal, henequen, abaca, hemp, sunn,, and mixtures thereof; and even more preferably selected from the group consisting of cotton, rayon, linen, polyester/cotton blends, silk, wool, polyester, acrylic, nylon, and mixtures thereof. The composition is particularly effective on fabrics made of cotton and cotton blends.

In a still further process aspect of the invention, the composition can be sprayed onto fabrics by in an in-home de-wrinkling chamber containing the fabric to be softened, thereby providing ease of operation. Conventional personal as well as industrial deodorizing and/or de-wrinkling apparatuses are suitable for use herein. Examples of home dewrinkling chambers include shower stalls. The spraying of the composition or compounds onto the fabrics can then occur within the chamber of the apparatus or before placing the fabrics into the chamber. Again, the spraying means should preferably be capable of providing droplets with a weight average diameter of from about 8 to about 100 um, preferably from about 10 to about 50 um. Preferably, the loading of moisture on fabrics made of natural and synthetic fibers is from about 5 to about 40%, more preferably from about 5 to about 20% by weight of the dried fabric.

The present invention encompasses the method of spraying a mist of an effective amount of fabric softening solution onto fabric and/or fabric articles. Preferably, said fabric and/or fabric articles include, but are not limited to, clothes, upholstered furniture, carpeting, bed linens, bath linens, tablecloths, sleeping bags, etc.

Textile fabrics can be treated in the mills with compositions containing the various softener actives described herein to provide the desired initial fabric feel and antistatic property. Such compositions to be used in the mills are not typically provided with elements that are important for home use, such as perfume and or detailed instructions for home use that are useful to the consumer. The preferred compositions herein comprise perfume and are suitable for home use, such as spraying fabrics outside of a conventional laundry process.

In situations where one, or very few, fabric items require cleaning, the items are usually washed by hand and line dried. The hand-washed and line-dried fabric items usually feel coarse and harsh, unlike the items that are machine washed and dried in an automatic clothes dryer. Sometimes the hand-washed, line-dried fabric roughness may be remedied by ironing with steam and/or with an ironing spray solution that may smooth out the fabric surface. The compositions herein, however, are capable of providing fabric softeness in such situations without the need for an ironing step (e. g. just by spraying the composition onto the fabric item).

A relatively concentrated composition can also be applied directly on wet fabrics, e. g., fabrics that have been just washed and not yet dried, so that the polyethyleneoxy polysiloxane can be diluted in situ on the wet fabrics. Compositions for use to apply on wet fabrics typically comprises polyethyleneoxy polysiloxane at a level of from about 0.1% to about 20%, preferably from about 0.2% to about 5%, and more preferably from about 0.3% to about 3%, by weight of the composition.

All percentages, ratios, and parts herein, in the Specification, Examples, and Claims are by weight and are the normal approximations unless otherwise stated.

The following are non-limiting examples of the instant composition. Perfume compositions that are used herein are as follows: Perfume ABC Perfume Ingredients Wt. % Wt. % Wt. % Anisic aldehyde--2 Benzophenone 3 5- Benzyl acetate 10 15 5 Benzyl salicylate 5 20 5 Cedrol 2 Citronellol 10-5 Coumarin--5 Cymal--3 Dihydromyrcenol 10-5 Flor acetate 5-5 Galaxolide 10 Lilial 10 15 20 Linalyl acetate 4-5 Linalool 6 15 5 Methyl dihydrojasmonate 3 10 5 Phenylethyl acetate 251 Phenyl ethyl alcohol 15 10 20 alpha-Terpineol 5-8 Vanillin--1 Total 100 100 100 Perfume D E Perfume Material Wt. % Wt. % Amyl salicylate 8 Benzyl acetate 8 8 Benzyl Salicylate-2 Citronellol 7 27 Dihydromyrcenol 2 - Eugenol 4 - Flor acetate 8 - Galaxolide 1- Geraniol 5 - Hexyl cinnamic aldehyde 2 - Hydroxycitronellal 3 - Lilial 2 - Linalool 12 13 Linalyl acetate 5 - Lyral 3 Methyl dihydrojasmonate 3 Nerol 2 Phenoxy ethyl propionate-3 Phenylethyl acetate 5 17 Phenylethyl alcohol 8 17 alpha-Terpineol 5 13 alpha-Terpinene 5 Tetrahydromyrcenol 2 100 100 Total Perfume F Perfume Ingredients Wt. % Benzophenone 0. 50 Benzyl acetate 3.00 Benzyl propionate 1.00 beta gamma Hexenol 0.20 Cetalox 0.10 cis 3 Hexenyl acetate 0.15 cis Jasmone 0.10 cis-3-Hexenyl salicylate 1 00 Citral 0. 50 Citronellal nitrile 0.70 Citronellol 3.65 Coumarin 0.70 Cyclal C 0.30 Cyclo galbanate 0.40 beta Damascone 0.05 Dihydro myrcenol 1.00 Ebanol 0.50 Flor acetate 5.00 Florhydral 0.70 Fructone 8.50 Frutene 3.00 Geranyl nitrile 0.40 Heliotropin 0.70 Hydroxycitronellal 2.50 Linalool 2.00 Linalyl acetate 1.50 Methyl dihydro jasmonate 5.00 Methyl heptine carbonate 0.05 Methyl iso butenyl tetrahydro pyran 0.15 Methyl phenyl carbinyl acetate 0.50 Nonalactone 1.50 P. T. Bucinal 8.40 para Hydroxy phenyl butanone 1.30 Phenoxy ethanol 28.55 Phenyl ethyl acetate 0.80 Phenyl ethyl alcohol 10.00 Prenyl acetate 1.50 Terpineol 1.50 Verdox 2.10 Vanillin 0.50 Total 100.00 Perfume G Perfume Ingredients Wt. % Anisic aldehyde 2.80 Benzyl acetone 1.00 cis 3 Hexenyl acetate 0.30 Citronellal nitrile 1.30 Citronellol 6.90 Coumarin 1.30 Cyclal C 0. 30 Cyclo galbanate 0. 70 Cymal 1.05 delta Damascone 0.05 Dihydro myrcenol 1.30 Dipropylene glycol 10.20 Dodecalactone 0.50 Ebanol 0.10 Ethyl vanillin 0.10 Flor acetate 8.00 Florhydral 1.30 Fructone 6.00 Galaxolide (50% in isopropyl myristate) 4.00 gamma Methyl ionone 1.00 Geranyl nitrile 0.30 Helional 1.50 Hydroxycitronellal 2.00 Iso bornyl acetate 1.80 Ligustral 0.10 Linalool 2.50 Methyl dihydrojasmonate 6. 20 Methyl heptine carbonate 0. 10 Methyl iso butenyl tetrahydro pyran 0.30 Methyl phenyl carbinyl acetate 1.00 Orange terpenes 2.00 P. T. Bucinal 10.00 Phenyl ethyl alcohol 20.00 Prenyl acetate 1.50

Verdox 2.50 Total 100.00 Perfume H I Perfume Material Wt. % Wt. % Ambrettolide 17.0 20.0 Ambroxan 0.5 3.0 Aurantiol 2.0 2.0 1-Cyclohexadecenone 1.0 1.0 Ebanol 0.5 1.0 Ethylene brassylate 7.0 4.0 Hexyl cinnamic aldehyde 4.0 10.0 Hydroxyambran 0.5 0.5 Indolene 50% 0.5 0.5 Gamma methyl ionone 1.0 1.0 Iso E Super 5.0 5.0 Tonalid 5.0 5.0 Okoumal 24.0 15.0 Vetivert acetate 3.0 3.0 4-Tertiary butyl cyclohexyl acetate 6.0 6.0 Alpha damascone 1.0 1.0 Citronellal nitrile 2.0 2.0 Alpha ionone 4.0 4.0 Frutene 8.0 8. 0 Verdox 8.0 8.0 Total 100.0 100.0 Perfumes H and I comprise about 80% of substantive perfume ingredients.

The following non-limiting fabric care compositions are prepared by mixing and dissolving the ingredients into clear or translucent solutions,. in accord with the present invention: Examples I Examples la Ib Ic Id Ie Ingredients Wt% Wt% Wt% Wt% Wt% <BR> <BR> Silwet L-7001 (a) 1. 4--<BR> <BR> <BR> <BR> <BR> <BR> Silwet L-7002--1. 0------<BR> <BR> <BR> <BR> <BR> <BR> Silwet L-7087----1. 0----<BR> <BR> <BR> <BR> <BR> Silwet L-7200------1. 3-- Silwet 1-7230 -- -- -- -- 1. 0 Substantive Perfume (b) 0.1 0.1 0.04 0.05 0.1 Kathon 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm Distilled water Bal. Bal. Bal. Bal. Bal.

(a) 75% active.

(b) Containing at least about 25% of substantive perfume ingredients, by weight of the total perfume composition.

Examples 11 Examples IIa lib lie IId lie IIf Ingredients Wt% Wt% Wt% Wt% Wt% Wt% DC 190 1. 2 -- -- -- -- -- <BR> <BR> <BR> DC 2 5093--1. 0--------<BR> <BR> <BR> <BR> <BR> DC 2 5573----1. 0------ DC 5247------1. 3---- DC Q2 5220 -- -- -- -- 1. 0-- Tegopren 5863 (a)----------1. 0 Substantive 0. 1 0.1 0.04 0.05 0.1 0.04 Perfume (b) Kathon 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm Distilled water Bal. Bal. Bal. Bal. Bal. Bal.

(a) Available from Goldschmidt Chemical Corporation, Hopewell, Virginia.

(b) Containing at least about 25% of substantive perfume ingredients, by weight of the total perfume composition.

Examples III Examples IIIa IIIb IIIc Hid Ingredients Wt% Wt% Wt% Wt% Silwet 7220 1. 2 -- -- -- <BR> <BR> <BR> Silwet 7602--1. 0----<BR> <BR> <BR> <BR> <BR> Silwet 7622----1. 0-- Silwet 7650------1. 3 Tween 20 (a) 1.2 1.0 1.0 1.3 Substantive Perfume 0.1 0.1 0.04 0.05 Kathon 3 ppm 3 ppm 3 ppm 3 ppm Distilled water Bal. Bal. Bal. Bal.

(a) A polyoxyethylene (20) sorbitan monolaurate, available from ICI Americas, Inc.

Wilmington, Delaware.

Examples III Examples IIIa IIIb IIIc nid Ingredients Wt% Wt% Wt% Wt% Silwet 7220 1. 2 -- -- -- Silwet 7602--1. 0----

Silwet 7622----1. 0-- Silwet 7650------1. 3 Tween 20 (a) 1.2 1.0 1.0 1.3 Substantive Perfume 0. 1 0.1 0.04 0.05 Kathon 3 ppm 3 ppm 3 ppm 3 ppm Distilled water Bal. Bal. Bal. Bal.

(a) A polyoxyethylene (20) sorbitan monolaurate, available from ICI Americas, Inc.

Wilmington, Delaware.

Examples IV Examples IVa IVb IVc IVd Ingredients Wt% Wt% Wt% Wt% Silicone of Example 1 1.2------ Silicone of Example 5--1.0---- Silicone of Example 9----1. 0-- Silicone of Example 11------1.1 Tween 20 1.2 1.0 1.0 1.1 Substantive Perfume 0.05 0.05 0.05 0.05 Kathon 3 ppm 3 ppm 3 ppm 3 ppm Distilled water Bal. Bal. Bal. Bal.

Examples V

Examples Va Vb Vc Vd Ingredients Wt% Wt% Wt% Wt% Silicone of Example 15 1.2------ Silicone of Example 18--1. 0---- Silicone of Example 20----1. 0-- Silicone of Example 25------1.1 Tween 20 1.2 1.0 1.0 1. 1 Perfume 0.05 0.05 0.05 0.05 Kathon 3 ppm 3 ppm 3 ppm 3 ppm Distilled water Bal. Bal. Bal. Bal.

Concentrated compositions of Examples VI-VIII are diluted with water to obtain usage compositions for, e. g., spraying, soaking and/or dipping fabric articles. They can also be used undiluted to treat fabric as rinse additive compositions.

Examples VI Examples VIa VIb Vie VId VIe Ingredients Wt% Wt% Wt% Wt% Wt% Silwet L-7200 10-------- Silwet L-7230--10------ DC 190----5----

DC 2 5573------10-- DC 5247-------5 Tween 20 Perfume 0.5 0.5 0.4 0.5 0.3 Kathon 6 ppm 6 ppm 6 ppm 6 ppm 6 ppm Distilled water Bal. Bal. Bal. Bal. Bal.

Examples VII Examples VIIa VIIb VIIc VIM Ingredients Wt% Wt% Wt% Wt% <BR> <BR> Silwet L-7001 15------<BR> <BR> <BR> <BR> <BR> Silwet L-7087--10----<BR> <BR> <BR> <BR> <BR> Silwet L-7622----5-- Silwet L-7650------10 Tween 20 10 10 5 10 Perfume 0.5 0.4 0.2 0.5 Kathon 6ppm 6ppm 6ppm 6ppm Distilled water Bal. Bal. Bal. Bal.

Examples VIII Examples Villa VIIIb VIIIc VIIId Ingredients Wt% Wt% Wt% Wt% Silicone of Example 5 10------ Silicone of Example 11--5---- Silicone of Example 15---10-- Silicone of Example 25------15 Tween 20 10 5 10 15 Substantive Perfume 0.5 0.3 0.4 0.7 Kathon 6ppm 6ppm 6ppm 6ppm Distilled water Bal. Bal. Bal. Bal.

The compositions of Examples I to VIII (diluted when appropriate) are sprayed onto clothing using, e. g., the TS-800 sprayer from Calmar, and allowed to evaporate off of the clothing.

The compositions of Examples I to VIII (diluted when appropriate) are sprayed onto clothing, using a blue inserted Guala trigger sprayer, available from Berry Plastics Corp. and a cylindrical Euromist II pump sprayer available from Seaquest Dispensing, respectively, and allowed to evaporate off of the clothing.

The compositions of Examples I to VIII (diluted when appropriate) contained in rechargeable battery-operated Solo Spraystar sprayers are sprayed onto large surfaces of fabric, such as several pieces of clothing, and allowed to evaporate off of these surfaces.

The compositions of Examples I to VIII (diluted when appropriate) are used for soaking or dipping of fabrics which are then optionally wrung or squeezed to remove excess liquid and subsequently dried.