WO2008033280A1

WO2008033280A1 - Liquid detergents with sustained release fragrance

Info

Publication number: WO2008033280A1
Application number: PCT/US2007/019583
Authority: WO
Inventors: Thorsten Bastigkeit; Jessica Lawshe; Michael Mathiesen
Original assignee: The Dial Corporation
Priority date: 2006-09-11
Filing date: 2007-09-07
Publication date: 2008-03-20

Abstract

Liquid detergent compositions and methods of their preparation are disclosed. In certain embodiments, liquid detergent compositions having at least 60 percent water, a hydrophobic fragrance delivery vehicle, and having an alkaline pH are provided, which may be useful in laundry applications and may also provide effective and/or long lasting fragrance delivery to the laundered articles.

Description

LIQUID DETERGENTS WITH SUSTAINED RELEASE FRAGRANCE

FIELD OF THE INVENTION

The invention relates to liquid detergent compositions and methods of their preparation. More particularly, the present invention relates to liquid detergent compositions having at least 60 percent water, a hydrophobic fragrance delivery vehicle, and having an alkaline pH, which may be useful in laundry applications and may also provide effective fragrance delivery to the laundered articles.

BACKGROUND OF THE INVENTION

The controlled release of ingredients in various preparations is a subject of interest in a wide range of consumer applications. In the field of detergents, the accelerated or delayed release of perfumes is of great importance in this field because both the product and the wash liquor and the articles treated therewith are desired to be controllably, preferably intensively and lastingly, perfumed. A number of techniques have been employed to extend the duration of fragrance emanation from detergents, wash liquors, and laundered articles, including, for example, applying perfumes to carrier materials and coating the perfumed carriers, or encapsulating perfumes, or incorporating them in complexes (such as cyclodextrin/perfume complexes). Perfumes may also be chemically bound to carrier media, where the chemical bond may be slowly broken and the perfume concurrently released. This principle has been put into practice, for example, in the esterification of perfume alcohols.

One manner of chemical bond breaking that has been disclosed utilizes siloxanes as slow release vehicles for perfume alcohols. In the presence of small amounts of moisture, the perfume alcohols are slowly released by hydrolysis of the siloxane esters. For example, monomelic orthosilicic acid esters having one to four covalently bound perfume alcohols, for example, bis(eugenoxy)diethoxysilane or bis(cinnamoyloxy)diethoxysilane, are described, in US 3,215,719 (Dan River Mills).

Also disclosed in GB 2007703 (Dow Corning) is the use of silicon compounds containing perfume alcohols in laundry care, but this disclosure is limited to powder-form or granular detergents).

Oligosilicic acid esters containing perfume or biocide alcohols have been disclosed for use in detergents, including aqueous detergents (WO 01/68037), the disclosure of which is hereby incorporated herein by reference, in its entirety. Acyclic siloxanes and related silicic acid esters incorporating perfume alcohols with the general formula M_aMVDbDVT_cTVQd where M and M' = RiR₂R₃SiOiZ₂, D and D' = R4RsSiθ2/2, T and T' = RgSiθ₃/2 and Q = Siθ4/2, where Ri to Rg independently of one another are selected from Ci-4oalkyl or alkoxy and Ci-4oaryl or aryloxy groups and the indices a, a' are positive and one or more of the indices b,b\c,c' and d are positive or 0, are described in GB 2319527 (General Electric). The use of those perfuming siloxanes in detergents was not mentioned in the application. Further, the disclosure underscored the problematic premature hydrolysis that occurred when water was allowed to come in contact with siloxanes or silicic acid esters.

The same hydrolysis activity of siloxanes generally allowing sustained delivery of perfume compounds has in the past contributed to their lack of use in liquid detergents. On one hand, many of the known siloxanes compounds cannot be used in water-containing detergents because they hydrolyze in the product itself, reducing or destroying altogether the compound's ability to delay release of the perfume alcohol. This hydrolysis is accelerated in conventional detergents that have alkaline pH values. Secondly, the introduction of large amounts of water both increases the rate of hydrolysis and makes the hydrophobic fragrance vehicles less soluble in the detergent. This causes these materials to separate and reduces both the consistency and the efficaciousness of fragrance delivery to the laundered article in the washing process. Accordingly, there is a need to provide perfumes in a manner which not only perfumes the laundry care product, the wash liquor, and the laundered articles, but which does so in a manner that creates persistent perfume on the laundered article, allowing the article to retain its impression of freshness. There is also a need to provide more effective hydrophobic fragrance delivery vehicles, preferably hydrolysis-resistant siloxane esters of perfume alcohols, which may be incorporated in water-containing detergents without showing excessive signs of hydrolysis in the laundry care product itself.

As mentioned above, there can be a tension created between solubility of hydrophobic fragrance vehicles and their stability in the product detergent. Applicants have surprisingly found that certain combinations of surfactants provide better solubility in product, and/or better stability of fragrance delivery vehicles in the laundry care product or during the laundering process. In some preferred embodiments, the detergent systems herein disclosed provide both enhanced solubility and improved stability of the fragrance delivery vehicle, leading to more effective delivery of fragrance onto the laundered article. The present invention is directed to these, as well as other important ends. SUMMARY OF THE INVENTION

The invention is directed, in certain embodiments, to liquid detergent compositions comprising water; an optional alkaline agent capable of adjusting the pH of the liquid detergent composition to a pH of from about 7 to about 12.5; from about 0.5 to about 10 percent of nonionic surfactant; from about 0.5 to about 14 percent of anionic surfactant composition comprising alcohol ether sulfate or mixture of alcohol ether sulfate and alkylbenzenesulfonate; and from about 0.05 to about 1.5 percent of hydrophobic fragrance delivery vehicle, each based on the weight of the liquid detergent composition; said detergent composition having a pH of from about 7 to about 12.5.

Other aspects of the invention relate to methods of preparing liquid detergent compositions of the invention comprising water; an optional alkaline agent capable of adjusting the pH of the liquid detergent composition to a pH of from about 7 to about 12.5; from about 0.5 to about 10 percent of nonionic surfactant; from about 0.5 to about 14 percent of anionic surfactant composition comprising alcohol ether sulfate or mixture of alcohol ether sulfate and alkylbenzenesulfonate; from about 0.05 to about 1.5 percent of hydrophobic fragrance delivery vehicle, each based on the weight of the liquid detergent composition; said detergent composition having a pH of from about 7 to about 12.5.

These and other embodiments of the invention will become more apparent from the following detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 describes the apparatus used to determine cloud point and inverse cloud point.

Figure 2 shows a series of Plots for the Solubility of SAE's in Surfactant Formulations.

Figure 3 illustrates the influence of surfactant on the solubility of the silicic acid ester perfume delivery vehicle in a series of photographic representations.

Figure 4 shows the results of a sensory panel test comparing fragrance emanation from towels laundered using liquid detergent compositions of the present invention with/without added hydrophobic fragrance delivery vehicles.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

As employed above and throughout the disclosure, the following terms, unless otherwise indicated, shall be understood to have the following meanings.

As used herein, the term "perfume alcohol" refers to any compound or mixture of compounds of formula R'-OH, known to be a perfume, wherein R' is the residual of an aroma chemical or fragrance component, that is capable of being physically or covalently bound to the hydrophobic delivery vehicle, irrespective of the further structure of the perfume compound. Non-limiting examples of perfume alcohols may be found in Steffan Arctander, "Perfume and Flavor Chemicals (Aroma Chemicals)", Volumes 1 and 2, (1969); Bauer, K. et al., "Common Fragrance and Flavor Materials", Wiley- VCH Publishers (1997); Guenther Ohloff, "Scent and Fragrances", Springer- Verlag Publishers (1994); and "Perfumes: Art, Science, and Technology", Mueller, P. M.l and Lamparsky, D, editors, Blackie Academic and Professional Publishers (1994), the disclosures of which are each hereby incorporated herein by reference, in their entireties. Preferred perfume alcohols include 10-undecen-l-ol, 2,6-dimethylheptan-2-ol, 2- methylbutanol, 2-methylpentanol, 2-phenoxyethanol, 2-phenylpropanol, 2-tert-huty\ cyclohexanol, 3,5,5-trimethylcyclohexanol, 3-hexanol, 3 -methyl-5 -phenyl pentanol, 3-octanol, 3-phenylpropanol, 4-heptenol, 4-isopropyl cyclohexanol, 4-tert-butyl cyclohexanol, 6,8- dimethyl-2-nonanol, 6-nonen-l-ol, 9-decen-l-ol, α-methyl benzyl alcohol, α-terpineol, amyl salicylate, benzyl alcohol, benzyl salicylate, β-terpineol, butyl salicylate, citronellol, cyclohexyl salicylate, decanol, dihydromyrcenol, dimethyl benzyl carbinol, dimethyl heptanol, dimethyl octanol, ethyl salicylate, ethyl vanillin, eugenol, farnesol, geraniol, heptanol, hexyl salicylate, isoborneol, isoeugenol, isopulegol, linalool, menthol, myrtenol, n-hexanol, nerol, nonanol, octanol, p-methan-7-ol, phenethyl alcohol, phenol, phenyl salicylate, tetrahydrogeraniol, tetrahydrolinalool, thymol, trans-2-m-6-nonadienol, trans-2-nonen-l-ol, _>--2M.s-2-octenol, undecanol, vanillin, tetrahydromyrcenol, the various natural and synthetic sandalwood alcohols, traMs-2-hexen-l-ol, cis-2-hexen-l-ol, l-octen-3-ol, and cinnamyl alcohol.

When employed herein, the term "biocide alcohol" refers to any compound of formula R' -OH, wherein R' is the residual of an biocide compound, that is capable of being physically or covalently bound to the hydrophobic delivery vehicle. Biocide alcohols in the context of the present invention are understood to be any compounds which contain at least one alcohol group and which at least inhibits germ growth, such as for example, phenoxyethanol, 1,2-propylene glycol, glycerol, citric acid and esters thereof, lactic acid and esters thereof, salicylic acid and esters thereof, 2-benzyl-4-chlorophenol and 2,2'-methylene-bis-(6-bromo-4-chlorophenol). In certain preferable embodiments, non-limiting examples of biocide alcohols may include alcohols which also act as perfume alcohols. Perfume alcohols additionally having biocidal properties include, for example, citronellol, eugenol, farnesol, thymol, and geraniol. The lower alkyl alcohols described in the prior art as typical residues of the silicic acid esters do not count as biocide alcohols in the context of the present invention. Explicitly, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-bwtyl alcohol are not regarded as biocide alcohols in the context of the present invention. By contrast, conventional biocides with alcohol functions are expressly regarded as biocide alcohols in the context of the invention even though their effect is attributable to other functional groups. Various bromphenols and biphenylol and quaternary ammonium compounds containing at least one long alkyl chain and at least one alkyl group bearing a hydroxy group are mentioned by way of example in this regard.

As used herein, the term "hydrophobic fragrance delivery vehicle" refers to any material, whose solubility is limited in aqueous environments, that is capable of binding aroma chemicals, or fragrance ingredients, especially those typically referred to as perfume alcohols. Also included are other such materials, such as the biocide alcohols, which are useful in fabric care, and may be similarly bound and released over time. The binding of these materials, such as aroma chemicals or fragrance ingredients, or biocide alcohols, to the fragrance delivery vehicle may be physical, covalent, or both, in its nature. Non-limiting examples include aluminates, titanates, cyclodextrins, silicates, and oligo- and polymeric forms thereof.

For example, silicon derivatives of perfume alcohols have been prepared, among other ways, by transesterification of the lower alcohol silicon esters (WO 01/68037; GB 2007703, GB 2319527; US 6,005,132; and US 2,547,944), the disclosures of which are each hereby incorporated herein by reference, in their entireties. Transesterifications may be carried out, for example, as described in H. Steinmann, et al., Z. Chem. 3, 1977, pp. 89-92, the disclosure of which is hereby incorporated herein by reference, in its entirety. Commercially available silicic acid esters are normally used as educts. For example, the ethanol ester is obtainable from Wacker Chemie, Burghausen, Germany. The transesterification reaction may be controlled solely by increasing the temperature and distilling off the readily volatile by-product lower alcohols. Often, however, catalysts are used for the transesterification. The catalysts typically include Lewis acids, preferably aluminum tetraisopropylate, titanium tetraisopropylate, or silicon tetrachloride, basic catalysts, or catalyst mixtures such as combinations of aluminum chloride with potassium fluoride. The oligomeric silicic acid esters thus formed incorporate at least one perfume alcohol, alcohol, or any combination of the two. If incompletely transesterified, the esters still contain residues of lower alcohols. Also, if small quantities of water or other H-acidic compounds are present during the production of the silicic acid esters, the perfume alcohol may be replaced by OH groups. Accordingly, the silicic acid ester mixtures according to the invention may also contain one or more hydrogens as R² substituents.

Oligosilicic acid esters of lower alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and ført-butanol, are commercially obtainable. The preparation of oligosilicic acid esters incompletely transesterified with perfume alcohols leads to silicic acid ester mixtures in which the substituents R are partly selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. Such compounds represent a preferred embodiment of the present invention.

The invention relates to liquid detergent compositions and methods of their preparation. In certain embodiments, liquid detergent compositions having at least 60 percent water, a hydrophobic fragrance delivery vehicle, and having an alkaline pH, are useful in laundry applications and provide effective fragrance delivery to the laundered articles. This invention is related by subject matter to recently granted U.S. application Serial No. 10/221,890, filed September 17, 2002, the disclosure of which is hereby incorporated herein by reference, in its entirety.

While not wishing to be bound by theory it is believed that one advantage of hydrophobic fragrance materials or their delivery vehicles is their preference to partition onto cloth relative to their propensity to stay in the wash waters. In part this may be due to solubility considerations. As such, there appears to be a need to balance the level of hydrophobicity required for effective partitioning onto cloth with the level of solubility required to keep the fragrance or its delivery vehicle from phase-separating in the liquid laundry care product over time. For example, as the amount of water in the detergent increases, hydrophobic materials become less soluble, all other things being equal. Improving the solubility to counter the effect of higher levels of water in the detergent would, in general, increase the risk of intimate contact between the fragrance and water. When hydrolysable fragrance delivery vehicles are employed, the increase in solubility will typically lead to an increased risk of non-productive hydrolysis.

Other factors to be considered include the pH of the liquid detergent, the impact of pH on other actives such as enzymes, and the water level in the final product. In many instances, liquid detergents are formulated based on the stability requirements of other ingredients in the detergent. For example, many enzymes used in detergents are unstable to alkaline pH. As a consequence, these types of detergents are formulated at lower pH to ensure the activity of the enzymes during the laundering process. Other types of liquid detergents, for example, nonenzyme containing detergents work more effectively at higher pH. In addition, manufacturers want to increase water levels while maintaining detergent effectiveness to minimize production costs. All of these changes may in some way affect the sustained release of fragrance materials, and, as a consequence, the impressions of a product's effectiveness by the retail consumer.

Accordingly, the present invention is directed, in part, to liquid detergent compositions comprising water; an optional alkaline agent capable of adjusting the pH of the liquid detergent composition to a pH of from about 7 to about 12.5; from about 0.5 to about 10 percent of nonionic surfactant; from about 0.5 to about 14 percent of anionic surfactant composition comprising alcohol ether sulfate or mixture of alcohol ether sulfate and alkylbenzenesulfonate; and from about 0.05 to about 1.5 percent of hydrophobic fragrance delivery vehicle, each liquid detergent composition component amount being based on the weight of the liquid detergent composition; said detergent composition having a pH of from about 7 to about 12.5.

In certain embodiments, the liquid detergent compositions comprise from about 60 to about 95 percent water, preferably from about 70 to about 95 percent water, with from about 80 to about 95 percent water being more preferred, based on the weight of the liquid detergent composition.

In other embodiments, the liquid detergent compositions comprise from about 0.5 to about 10 percent of nonionic surfactant, preferably from about 1 to about 5 percent, with from about 1 to about 3.75 percent being more preferred, based on the weight of the liquid detergent composition.

In some preferred aspects of the invention, the nonionic surfactant comprises alcohol ethoxylate, more preferably having the formula II;

R^O-(CH₂CH₂O)_P-H

(H) wherein R¹ is Cio-^alkyl, and p is an integer from 3 to 9.

In certain aspects of the invention, wherein the nonionic surfactant is an alcohol ethoxylate of formula II, R¹ preferably is Ci₂.i₈alkyl, more preferably Ci₄-i₅alkyl.

In other preferred embodiments, p is the integer 5, 6, 7, or 8, more preferably 7.

In some aspects of the invention, the liquid detergent compositions comprise from about 0.5 to about 14 percent of anionic surfactant composition, preferably from about 0.5 to about 10 percent, more preferably from about 1 to about 7.5 percent, still more preferably from about 2 to about 7.5 percent, based on the weight of the liquid detergent composition. In certain preferred embodiments, the anionic surfactant composition comprises alcohol ether sulfate. In other preferred embodiments, it comprises a mixture of alcohol ether sulfate and alkylbenzenesulfonate. In embodiments where alkylbenzenesulfonate is a liquid detergent composition component, the alkyl substituent of said alkylbenzenesulfonate is preferably C₉- oalkyl, even more preferably n-C^nalkyl.

Preferable alcohol ether sulfate anionic surfactant include compounds of the formula I:

R-O-(CH₂CH₂O)₄₁-SO₃H

(D wherein R is Cu-isalkyl, and q is an integer from 1 to 9. In some preferred embodiments, q is an integer from 2 to 8. Alcohol ether sulfate anionic surfactant may preferably be incorporated into the liquid detergent composition at levels from about 0.5 to about 10 percent, more preferably 1 to about 7.5 percent, still more preferably from about 1 to about 3.75 percent, based on the weight of the liquid detergent composition.

In other aspects of the invention directed to liquid detergent compositions comprising a mixture of alcohol ether sulfate and alkylbenzenesulfonate, the alcohol ether sulfate is present at a level of from about 0.5 to about 10 percent, preferably 1.0 to about 3.75 percent, and/or the alkylbenzenesulfonate is present at a level of from about 0.5 to about 4 percent, preferably 1.0 to about 3.75 percent, based on the weight of the liquid detergent composition.

The invention is also directed, in part, to liquid detergent compositions comprising an optional alkaline agent capable of adjusting the pH of the liquid detergent composition to a pH of from about 7 to about 12.5. The alkaline agent may be added in any convenient alkaline form, such as a completely alkaline or partially neutralized form, so long as it contributes a degree of alkalinity to the liquid detergent composition when added. By way of non-limiting example where a carbonate, silicate, borate, or phosphate is used as the alkaline agent, the carbonate may be added as CO₃ ^2", HCO₃ ^", or sesquicarbonate, or any combination thereof; phosphate as PO4^3' or HPO4^2", or any combination thereof; silicate as SiCU^"4 or XSiO₂ :Na₂O, or any combination thereof; or borate as B4O7^2", or B(OH)₄ ^", or any mixture thereof. In certain embodiments the alkaline agent is a silicate, borate, phosphate, carbonate, bicarbonate, or any combination thereof, preferably carbonate or bicarbonate, or alternatively preferred carbonate or silicate, or any combination thereof, more preferably carbonate. In some embodiments, and/or by way of non- limiting example, when an alkaline agent, preferably carbonate or bicarbonate, is added to the liquid detergent composition to adjust the pH, typically from about 1 to about 4 percent, preferably from about 1.5 to about 2.5 percent, based on the weight of the liquid detergent composition of the alkaline agent is added to bring the pH within the preferred range of from about 7 to about 12.5. In some embodiments, the alkaline agent may favorably modify the viscosity of the liquid detergent composition to between about 200 and about 800 centipoise (cps).

Although the carbonate or bicarbonate preferred in some embodiments of the invention may be any carbonate that would be recognized by one of ordinary skill in the art as appropriate in liquid detergent compositions, the carbonate or bicarbonate preferably comprises ammonium carbonate, sodium carbonate, sodium bicarbonate, or potassium carbonate, or any mixture thereof. More preferably, the carbonate comprises sodium carbonate.

The present invention is also directed, in part, to liquid detergent compositions comprising at least one hydrophobic fragrance or biocide delivery vehicle. Typically, this is present at a level of from about 0.05 to about 1.5 percent, based on the weight of the liquid detergent composition. These levels, as one of ordinary skill in the art would recognize, may be modified upward or downward accordingly, to account for the properties of the particular fragrance, biocide, mixture of fragrance and/or bio cide, or fragrance component being delivered to the laundered article. In certain preferred embodiments, the hydrophobic fragrance delivery vehicle(s) is or are present at a level from about 0.05 to about 0.5 percent based on the weight of the liquid detergent composition. In other preferred embodiments, the liquid detergent composition further comprises one or more fragrance or biocide components, one or more fragrances, or any mixture thereof, that is/are not covalently bound to the hydrophobic delivery vehicle.

The added fragrance may be present as synthetic or naturally occurring individual perfume compounds, their mixtures, including those containing ester, ether, aldehyde, ketone, or alcohol functional groups, as well as hydrocarbon-type molecules. Non-limiting examples of perfume compounds of the ester type include benzyl acetate, phenoxyethyl isobutyrate, p-tert- butyl cyclohexyl acetate, Iinalyl acetate, dimethyl benzyl carbinyl acetate (DMBCA), phenyl ethyl acetate, benzyl acetate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate, benzyl salicylate, cyclohexyl salicylate, fϊoramat, melusate and jasmacyclate. The ethers include, for example, benzyl ethyl ether and Ambroxan; the aldehydes include, for example, linear alkanals containing 8 to 18 carbon atoms, citral, citronellal, citronellyloxy acetaldehyde, cyclamen aldehyde, lilial and bourgepnal; the ketones include, for example, ionones, α-isomethyl ionone and methyl cedryl ketone; the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenyl ethyl alcohol and the various terpineols, while the hydrocarbons include, above all, terpenes, such as limonene and pinene. However, mixtures of perfume compounds which together produce an attractive perfume note are preferably used.

Fragrance mixtures may also contain natural perfume mixtures obtainable from vegetable sources, for example pine, citrus, jasmine, patchouli, rose, or ylang-ylang oil. Also suitable are clary oil, camomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, ladanum oil,orange blossom oil, neroli oil, orange peel oil, sandalwood oil, and others.

In addition to the impact that one or more functional groups, or a particular compound's overall structure may have on a perfume compound's odor impression, certain physical characteristics are also important to odor impression, such as volatility and intensity. For example, to be perceived by the receptors in the nose, perfume compounds require a certain minimum level of volatility. This volatility is controlled by, among other things, the molecular weight of the compound. Thus, most perfumes have molecular weights of up to about 200 dalton, molecular weights of 300 dalton and higher being less typical.

Intensity is usually expressed in terms of the minimum level of compound required at the odor receptor to trigger a recognition of the odorant. In view of the differences in volatility and intensity of perfumes, the odor of a perfume or fragrance composed of several perfume compounds changes during the evaporation process. Odor impressions are usually divided into the three aspects of top note, middle note (or body), and end note (or dry out). Relative to the overall perfume composition, the more volatile components are enriched in the initial phases (commonly referred to as "top note") of fragrance emanation from the product or laundered article. In the latter phases of fragrance emanation (commonly referred to as "end note or dry out"), the more volatile components fall to non-detectible limits, and the less volatile compounds predominate. In the composition of perfumes, more readily volatile perfumes may be fixed, for example, to certain "fixatives", which prevents them from volatilizing too rapidly. The hydrophobic fragrance delivery vehicles disclosed herein represent an effective method to fix certain fragrance compounds in the laundry care compositions of the present invention and extend their impression in the overall character of the perceived fragrance over time.

Firmly adhering perfumes suitable for use in accordance with the present invention are, ^' for example, the essential oils, such as angelica root oil, aniseed oil, arnica flowers oil, basil oil, bay oil, champax blossom oil, silver fir oil, silver fir cone oil, elemi oil, eucalyptus oil, fennel oil, pine needle oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, Indian wood oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, sweet flag oil, camomile oil, camphor oil, canaga oil, cardamom oil, cassia oil, Scotch fir oil, copaiba balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemon grass oil, limette oil, mandarin oil, melissa oil, amber seed oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, orange oil, origanum oil, palmarosa oil, patchouli oil, Peru balsam oil, petit grain oil, pepper oil, peppermint oil, pimento oil, pine oil, rose oil, rosemary oil, sandalwood oil, celery seed oil, lavender spike oil, Japanese anise oil, turpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, ysop oil, cinnamon oil, cinnamon leaf oil, citronella oil, citrus oil and cypress oil. However, relatively high-boiling or solid perfumes of natural or synthetic origin may also be used in accordance with the invention as firmly adhering perfumes or perfume mixtures. These compounds include those mentioned in the following and mixtures thereof: ambrettolide, α-amyl cinnamaldehyde, anethole, anisaldehyde, anise alcohol, anisole, methyl anthranilate, acetophenone, benzyl acetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, W 2

borneol, bornyl acetate, Boisambrene forte, α-bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formiate, heliotropin, methyl heptyne carboxylate, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, irone, isoeugenol, isoeugenol methyl ether, isosafirol, jasmone, camphor, carvacrol, carvone, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl-n-amyl ketone, methyl anthranilic acid methyl ester, p-methyl acetophenone, methyl chavicol, para-meihyl quinoline, methyl-β-naphthyl ketone, methyl-n-nonyl acetaldehyde, methyl-n-nonyl ketone, muskone, β-naphthol ethyl ether, β- naphthol methyl ether, nerol, n-nonyl aldehyde, nonyl alcohol, n-octyl aldehyde, p- oxyacetophenone, peπtadecanolide, β-phenyl ethyl alcohol, phenyl acetaldehyde dimethyl acetal, phenyl acetic acid, pulegone, safrol, isoamyl salicylate, methyl salicylate, hexyl salicylate, cyclohexyl salicylate, santalol, sandelice, scatol, terpineol, thymene, thymol, troenan, γ- undecalactone, vanillin, veratrum aldehyde, cinnamaldehyde, cinnamyl alcohol, cinnamic acid, ethyl cinnamate, benzyl cinnamate.

The more readily volatile perfumes include, in particular, the relatively low-boiling perfumes of natural or synthetic origin which may be used either individually or in the form of mixtures. Examples of more readily volatile perfumes are diphenyl oxide, limonene, linalool, linalyl acetate and propionate, melusate, menthol, menthone, methyl-n-heptenone, pinene, phenyl acetaldehyde, terpinyl acetate, citral, citronellal.

The lower alcohol silicic acid esters used for the production of the hydrophobic fragrance delivery vehicles present in some preferred aspects of the invention, may, for economic or other reasons, not be pure compounds, but instead may be technical mixtures of oligosilicic acid esters of lower alcohols with different degrees of oligomerization. The distribution of the degree of oligomerization may correspond directly to the degree of oligomerization present in the starting material or may be modified by the reaction conditions used to prepare the fragrance delivery vehicles. Thusly, a distribution of oligomerization, arising from use of starting materials or from use of certain reaction conditions, may be found in the fragrance delivery vehicles, preferably the perfume alcohol containing silicic acid esters according to the invention that may be used in conjunction with the laundry care compositions of the present invention.

In some preferred embodiments, one or more hydrophobic fragrance delivery vehicles comprise at least one cyclic silicic acid ester, acyclic silicic acid ester, or mixture thereof, more preferably a plurality of cyclic silicic acid esters, acyclic silicic acid esters, or mixtures thereof, with mixture or mixtures thereof being more preferred. In certain preferred embodiments, at least one cyclic silicic acid ester has the formula III:

in wherein each R² is independently is H, Ci-βalkyl, Ci-βalkenyl, Ci-βalkynyl, or the residual of perfume alcohol or biocide alcohol, provided that at least one of R² is the residual of perfume alcohol or biocide alcohol; and m is an integer from 1 to 20, preferably 2 to 10.

In certain more preferred aspects of the invention, the silicic acid ester has the formula:

or mixture thereof. hi other preferred embodiments, at least one acyclic silicic acid ester has the formula IV:

IV wherein each R² is independently is H, Ci^alkyl, Cuβalkenyl, Ci-βalkynyl, or the residual of perfume alcohol or biocide alcohol, provided that at least one of R² is the residual of perfume alcohol or biocide alcohol; and n is an integer from 2 to 100, preferably 2 to 50, more preferably 2 to 20, still more preferably 2 to 10, with 4, 5, 6, 7, or 8 being even more preferred.

In any of the embodiments hereinabove disclosed pertaining to cyclic or acyclic silicic acid esters, preferably at least about 75 percent, more preferably at least about 90 percent of the total R² substituents in the silicic acid esters, more preferably still, substantially all of the total R² substituents in the silicic acid esters are each independently the residual of perfume alcohol or biocide alcohol. Although cyclic and acyclic oligosilicic acid esters have been disclosed for use in aqueous media, such as certain liquid detergents, the stability of those esters is lessened when significant amounts of water are present. This effect is further compounded when the aqueous environment is at alkaline pH. Both water and base promote the hydrolysis of these silicic acid esters. Applicants have surprisingly found that the use of certain mixtures of surfactants enhances the solubility of the oligosilicic acid esters while protecting the esters from accelerated hydrolysis typically found under aqueous alkaline conditions. Improved solubility leads to more consistent performance in end use liquid detergent compositions. Enhanced stability results in delivery of more fragrance to the laundered article rather than being lost to wash/rinse effluents during the laundering process.

The invention includes, in part, liquid detergent compositions comprising from about 85 to about 95 percent water; from about 1.0 to about 3.75 percent of nonionic surfactant, preferably having the formula C₁₄-_ISaIlCyI-O-(CH₂CH₂O)₇-H; from about 1.0 to about 3.75 percent of alcohol ether sulfate, preferably having the formula IaUTyI-O-(CH₂CH₂O)₇-SO₃H; from about 1.0 to about 3.75 percent of linear alkylbenzenesulfonate, preferably C9-i3linear alkylbenzenesulfonate, more preferably Ci₃linear alkylbenzenesulfonate; from about 1.5 to about 2.5 percent carbonate, preferably sodium carbonate; and from about 0.05 to about 1.5 percent, preferably from about 0.05 to about 0.3 percent, of a hydrophobic fragrance delivery vehicle, said hydrophobic fragrance delivery vehicle preferably comprising at least one cyclic silicic acid ester, acyclic silicic acid ester, or mixture thereof; each liquid detergent composition component amount being based on the weight of the liquid detergent composition; said detergent composition having a pH of from about 7 to about 12.5.

Apart from the perfumes and biocides, the liquid detergent compositions may also contain ingredients typical of such compositions, such as for example, surfactants, builders, bleaching agents, enzymes and other active substances.

In certain embodiments of the present invention, additional anionic and non-ionic surfactants, cationic surfactants, and/or amphoteric surfactants may be added to the composition. In some embodiments, the composition may comprise anionic surfactant components in addition to the alkyl ethoxysulfate discussed above. In an exemplary embodiment, the additional anionic surfactant may be present in the composition in a range from about 0.1 percent to about 10 percent by weight of the composition, preferably 0.1 percent to 2 percent by weight of composition.

In accordance with one aspect of an exemplary embodiment of the invention, the composition comprises sodium linear alkylbenzenesulfonate, available from Klaven Chemicals, Ltd. Other useful anionic surfactants include, but are not limited to, those of the sulfonate type and of the sulfate type. Other preferred surfactants of the sulfonate type include C9_i3alkylbenzenesulfonates, alkenesulfonates (or mixtures thereof), hydroxyalkanesulfonates, and disulfonates, as are obtained, for example, from Ci₂-i₈monoolefms having a terminal or internal double bond by sulfonating with gaseous sulfur trioxide followed by alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates, which are obtained from Ci2-i8alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, respectively. Likewise suitable, in addition, are the esters of α-sulfo fatty acids (ester sulfonates), e.g. the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters which are the monoesters, diesters and triesters, and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with from 1 to 3 mol of fatty acid or in the transesterification of triglycerides with from 0.3 to 2 mol of glycerol. Preferred sulfated fatty acid glyceryl esters are sulfation products of saturated fatty acids of 6 to 22 carbon atoms, e.g., of capric acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Preferred alkenyl sulfates are the alkali metal salts, and especially the sodium salts, of the sulfuric monoesters of Cn-Cisfatty alcohols, examples being those of coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or of C₁0-C₂0OXO alcohols, and those monoesters of secondary alcohols of this chain length. Preference is also given to alk(en)yl sulfates of said chain length which contain a synthetic straight-chain alkyl radical prepared on a petrochemical basis, these sulfates possessing degradation properties similar to those of the corresponding compounds based on fatty-chemical raw materials. From a detergents standpoint, Ci2-Ciealkylsulfates and Ci₂-Ci₅alkylsulfates, and also Ci-rC^alkylsulfates, are preferred. In addition, secondary alkyl sulfates, which may for example be obtained as commercial products from Shell Oil Company under the name DAN^®, are suitable anionic surfactants (see US 5,075,041 for example).

Also suitable are the sulfuric monoesters of the straight-chain or branched C7-₂1 alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C9.11 alcohols containing on average 3.5 mol of ethylene oxide (EO) or Ci₂-isfatty alcohols containing from 1 to 4 EO which are known as fatty alcohol ether sulfates.

Anionic surfactants further include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic esters and which constitute the monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates comprise Cs-isfatty alcohol radicals or mixtures thereof. Especially preferred sulfosuccinates contain a fatty alcohol radical derived from ethoxylated fatty alcohols which themselves represent nonionic surfactants. Particular preference is given in turn to sulfosuccinates whose fatty alcohol radicals are derived from ethoxylated fatty alcohols having a narrowed homolog distribution. Similarly, it is also possible to use alk(en)ylsuccinic acid containing preferably 8 to 18 carbon atoms in the alk(en)yl chain, or salts thereof.

Further suitable anionic surfactants are, in particular, soaps. Suitable soaps include saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and, in particular, mixtures of soaps derived from natural fatty acids, e.g., coconut, palm kernel, or tallow fatty acids.

The anionic surfactants, including the soaps, may be present in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. Preferably, the anionic surfactants are in the form of their sodium or potassium salts, in particular in the form of the sodium salts. The non-aqueous liquid laundry detergent compositions of the present invention, however, preferably utilize the ammonium salts, especially the salts of organic bases, as for example of isopropylamine.

A further class of anionic surfactants is the class of ether carboxylic acids which is obtainable by reacting fatty alcohol ethoxylates with sodium chloroacetate in the presence of basic catalysts. Ether carboxylic acids have the general formula: Rio 0-(CH₂-CH₂-O)_P-CH₂- COOH where Ri₀ = Ci_-Ig and/? = 0.1 to 20. Ether carboxylic acids are water hardness insensitive and have excellent surfactant properties.

Other suitable nonionic surfactants include, but are not limited to, alkoxylated amines, advantageously ethoxylated and/or propoxylated, especially primary and secondary amines having preferably 1 to 18 carbon atoms per alkyl chain and on average 1 to 12 mol of ethylene oxide (EO) and/or 1 to 10 mol of propylene oxide (PO) per mole of amine.

Capped alkoxylated fatty amines and fatty alcohols will be found particularly advantageous, especially for use in the present invention's non-aqueous formulations. In capped fatty alcohol alkoxylates and fatty amine alkoxylates, the terminal hydroxyl groups of the fatty alcohol alkoxylates and fatty amine alkoxylates are etherified with Q^oalkyl groups, preferably methyl or ethyl groups.

Useful nonionic surfactants further include alkyl glycosides of the general formula RO(G)_x, for example as compounds, particularly with anionic surfactants, where R is a primary straight-chain or methyl-branched (in the 2-position especially) aliphatic radical having 8 to about 22 and preferably about 12 to about 18 carbon atoms and G represents a glycose unit having 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any desired number between 1 and 10; preferably, x is in the range from about 1.2 to about 1.4.

Other nonionic surfactants which may be added include alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.

Further suitable surfactants include those known as "gernini surfactants". This term is used generally to refer to those compounds which possess two hydrophilic and two hydrophobic groups per molecule. These groups are generally separated from one another by what is known as a spacer. This spacer is generally a carbon chain, which should be long enough to keep the hydrophilic groups at a distance sufficient to allow them to act independently of one another. Surfactants of this kind are generally notable for an unusually low critical micelle concentration and the ability to reduce greatly the surface tension of water. In exceptional cases, however, the expression gemini surfactants is used to embrace not only dimeric but also trimeric surfactants.

Examples of suitable gemini surfactants are sulfated hydroxy mixed ethers, dimer alcohol bis- and trimer alcohol tris-sulfates and ether sulfates. Tipped dimeric and trimeric mixed ethers are notable in particular for their bi- and multifunctionality. These capped surfactants possess good wetting properties and are low-sudsing, making them particularly suitable for use in machine washing or cleaning processes. However, it is also possible to use gemini-polyhydroxy fatty acid amides or polypolyhydroxy fatty acid amides.

Further suitable non-ionic surfactants are polyhydroxy fatty acid amides of the formula

R⁵

I R-CO-N-JZl where RCO is an aliphatic acyl radical having 6 to 22 carbon atoms, R⁵ is hydrogen or an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms, and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known materials, typically obtainable by reduction amination of a reducing sugar with ammonia, an alkylamine or an alkanol amine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of the polyhydroxy fatty acid amides also includes compounds of the formula R⁶-O-R⁷

I

R-CO-N-[Z] where R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R⁶ is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R⁷ is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, preference being given to C^-allcyl radicals or phenyl radicals, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of said radical.

[Z] is preferably obtained by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose, or xylose. The N-alkoxy- or N-aryloxy-substituted compounds may then be converted to the desired polyhydroxy fatty acid amides, for example, in accordance with the teaching of international patent application WO 95/07331 by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

In a preferred embodiment, the laundry detergent composition comprises alkoxylated fatty alcohols, more preferably ethoxylated and/or propoxylated fatty alcohols.

Mild-action laundry detergent compositions advantageously utilize nonionic surfactants selected from the group of alkoxylated fatty alcohols and/or alkyl glycosides, especially mixtures of alkoxylated fatty alcohols and alkylglycosides.

In another embodiment, cationic surfactants may be added to the detergent composition. Cationic surfactants are any agent that functions as detergency booster. If cationic surfactants are used, they are present in the detergents in small quantities of preferably on the order of about 0.01 to about 10 percent by weight, and more preferably in quantities of about 0.1 to about 3.0 percent by weight.

Optionally, the detergent composition of the present invention may additionally comprise amphoteric surfactants. Amphoteric surfactants may be present in an amount of from about 0.5 percent to about 5 percent by weight of the composition.

Preferred amphoteric surfactants are the alkylbetaines of the formula (Ia), the alkylamidobetaines of the formula (Ib), the sulfobetaines of the formula (Ic) and the amidosulfobetaines of the formula (Id),

R^N⁺(CHs)₂-CH₂COO- (Ia)

R¹-CO-NH-(CH2)3-N⁺(CH₃)2-CH₂COO- (Ib)

R^N⁺(CHa)₂-CH₂CH(OH)CH₂SO₃- (Ic)

R¹-CO-NH-(CH2)3-N⁺(CH3)2-CH₂CH(OH)CH₂Sθ₃- (Id) . in which R¹ is a saturated or unsaturated C6-22-alkyl radical, preferably Cg-is-alkyl radical, in particular a saturated Cio-i₆-alkyl radical, for example, a saturated C 12-14-alkyl radical.

Particularly preferred amphoteric surfactants are the carbobetaines, in particular the carbobetaines of the formula (Ia) and (Ib), more preferably the alkylamidobetaines of the formula (Ib).

Examples of suitable betaines and sulfobetaines are the following compounds named according to INCI: Almondamidopropyl Betaine, Apricotamidopropyl Betaine, Avocadamidopropyl Betaine, Babassuamidopropyl Betaine, Behenamidopropyl Betaine, Behenyl Betaine, Betaine, Canolamidopropyl Betaine, Capryl/Capramidopropyl Betaine, Carnitine, Cetyl Betaine, Cocamidoethyl Betaine, Cocamidopropyl Betaine, Cocamidopropyl Hydroxysultaine, Coco-Betaine, Coco-Hydroxysultaine, Coco/Oleamidopropyl Betaine, Coco- Sultaine, Decyl Betaine, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallow Glycinate, Dimethicone Propyl PG-Betaine, Erucamidopropyl Hydroxysultaine, Hydrogenated Tallow Betaine, Isostearamidopropyl Betaine, Lauramidopropyl Betaine, Lauryl Betaine, Lauryl Hydroxysultaine, Lauryl Sultaine, Milkamidopropyl Betaine, Minkamidopropyl Betaine, Myristamidopropyl Betaine, Myristyl Betaine, Oleamidopropyl Betaine, Oleamidopropyl Hydroxysultaine, Oleyl Betaine, Olivamidopropyl Betaine, Palmamidopropyl Betaine, Palmitamidopropyl Betaine, Palmitoyl Carnitine, Palm Kernelamiodopropyl Betaine, Polytetrafluoroethylene Acetoxypropyl Betaine, Ricinoleamidopropyl Betaine, Sesamidopropyl Betaine, Soyamidopropyl Betaine, Stearamidopropyl Betaine, Stearyl Betaine, Tallow- amidopropyl Betaine, Tallowamidopropyl Hydroxysultaine, Tallow Betaine, Tallow Dihydroxyethyl Betaine, Undecylenamidopropyl Betaine and Wheat Germamidopropyl Betaine. Other suitable amphoteric surfactants may also be employed.

Another significant group of detergent ingredients which may be included within the invention are the builders. This class of substances is understood to encompass both organic and inorganic builders. These are compounds which may both perform a carrier function in the granules according to the invention and act as a water-softening substance in use.

Useful organic builders are, for example, the polycarboxylic acids usable, for example, in the form of their sodium salts (polycarboxylic acids in this context being understood to be carboxylic acids carrying more than one acid function). Examples include citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), providing its use is not ecologically unsafe, and mixtures thereof. Preferred salts are the salts of the polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

The acids per se may also be used. Besides their builder effect, the acids typically have the property of an acidifying component and, accordingly, are also used to establish a lower and more mild pH value in laundry or dishwashing detergents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and mixtures thereof are particularly mentioned in this regard.

Other suitable builders are polymeric polycarboxylates such as, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular weight of 500 to 70,000 g/mole. This class of substances is described in detail in the foregoing. The co-polymeric polycarboxylates may be used either in powder form or as an aqueous solution. The content of co-polymeriσ polycarboxylates in the granules is preferably 0.5 to 20 percent by weight and more particularly 3 to 10 percent by weight.

In order to improve their solubility in water, the polymers may also contain allylsulfonic acids, for example allyloxybenzenesulfonic acid and methallylsulfonic acid (see, for example, EP-B-O 727448), as monomer. Biodegradable polymers of more than two different monomer units are also particularly preferred, examples including those which contain salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives as monomers (DE- A-43 00772) or those which contain salts of acrylic acid and 2-alkylallylsuIfonic acid and sugar derivatives as monomers (DE-C-42 21 381). Other preferred copolymers are those described in German patent applications DE- A-43 03 320 and DE-A-44 17734 which preferably contain acrolein and acrylic acid/acrylic acid salts or acrolein and vinyl acetate as monomers. Other preferred builders are polymeric aminodicarboxylic acids, salts, or precursors thereof. Polyaspartic acids or salts and derivatives thereof, which, according to German patent application DE-A- 195 40086, have a bleach-stabilizing effect in addition to their co-builder properties are particularly preferred.

Other suitable builders include polyacetals which may be obtained by reaction of dialdehydes with polyol carboxylic acids containing 5 to 7 carbon atoms and at least three hydroxyl groups, for example as described in European patent application EP-A-O 280 223. Preferred polyacetals are obtained from dialdehydes, such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids, such as gluconic acid and/or glucoheptonic acid.

Other suitable organic builders include dextrins, which are oligomers or polymers of carbohydrates that may be obtained by partial hydrolysis of starches. The hydrolysis may be carried out by standard methods, for example acid- or enzyme-catalyzed methods. The end products are preferably hydrolysis products with average molecular weights of 400 to 500,000 g/mol. A polysaccharide with a dextrose equivalent of 0.5 to 40 and, more particularly, 2 to 30 is preferred, the dextrose equivalent being an accepted measure of the reducing effect of a polysaccharide by comparison with dextrose which has a dextrose equivalent of 100. Both maltodextrins with a dextrose equivalent of 3 to 20 and dry glucose syrups with a dextrose equivalent of 20 to 37 and also so-called yellow dextrins and white dextrins with relatively high molecular weights of 2,000 to 30,000 g/mol may be used. A preferred dextrin is described in British patent application 94 19 091. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Dextrins thus oxidized and processes for their production are known, for example, from EP-A-O 232202, EP-A-O 427 349, EP-A-O 472 042 and EP-A-O 542496 and from WO 92/18542, WO-A-93/08251, WO-A-93/16110, WO-A- 94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A-95/20608. An oxidized oligosaccharide according to German patent application DE-A- 19600 018 is also suitable for use as a builder. A product oxidized at Ce of the saccharide ring can be particularly advantageous.

Other suitable co-builders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Ethylenediamine-N₅N'-di succinate (EDDS), for which the synthesis is described in US 3,158,615, is preferably used in the form of its sodium or magnesium salt. Glycerol disuccinates and glycerol trisuccinates as described, for example, in US 4,524,009 and US 4,639,325, in EP-A-O 150930, and in JP 93/339896, are also particularly preferred in this connection. The quantities used in zeolite-containing and/or silicate-containing formulations are from 3 to 15 percent by weight.

Other useful organic co-builders are, for example, acetylated hydroxycarboxylic acids and salts thereof which may optionally be present in lactone form and which contain at least 4 carbon atoms, at least one hydroxy group and at most two acid groups. Co-builders such as these are described, for example, in WO-A-95/20029.

Another class of substances with co-builder properties are the phosphonates, more particularly hydroxyalkane and aminoalkane phosphonates. Among the hydroxyalkane phosphonates, l-hydroxyethane-l,l-diphosphonate (HEDP) is particularly important as a co- builder. It is preferably used in the form of a sodium salt, the disodium salt showing a neutral reaction and the tetrasodium salt an alkaline reaction (pH 9). Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and higher homologs thereof. They are preferably used in the form of the neutrally reacting sodium salts, for example as the hexasodium salt of EDTMP and as the hepta- and octasodium salt of DTPMP. Within the class of phosphonates, HEDP is preferably used as builder. The aminoalkane phosphonates also show a pronounced heavy metal binding capacity. Accordingly, it can be of advantage, particularly where the detergents also contain bleaching agents, to use aminoalkane phosphonates, more especially DTPMP, or mixtures of the phosphonates mentioned.

In addition, any compounds capable of forming complexes with alkaline earth metal ions may be used as co-builders.

A- preferred inorganic builder is finely crystalline, synthetic zeolite containing bound water, preferably zeolite A, X, and/or P. A particularly preferred zeolite P is, for example, zeolite MAP (for example Doucil® A24, a product of Crosfield). Also suitable, however, are zeolite X and mixtures of A, X and/or P. VEGOBOND AX® (by Condea Augusta S.p.A.), a co-crystallizate of zeolite A and zeolite X is one such example. Any suitable zeolite may be used as a spray-dried powder or even as an undried stabilized suspension still moist from its production. Where the zeolite is used in the form of a suspension, the suspension may contain small additions of nonionic surfactants as stabilizers, for example 1 to 3 percent by weight, based on zeolite, of ethoxylated Ci_2-18fatty alcohols containing 2 to 5 ethylene oxide groups, Ci₂-i₄fatty alcohols containing 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have a mean particle size of less than 10 μm (volume distribution, as measured by the Coulter Counter method) and contain preferably 18 to 22 percent by weight and, more preferably, 20 to 22 percent by weight of bound water.

Suitable substitutes or partial substitutes for the zeolite are layer silicates of natural and synthetic origin. Layer silicates such as these are known, for example, from patent applications DE-A-23 34 899, EP-A-O 026 529 and DE-A-35 36 405. Their suitability is not confined to a particular composition or structural formula, although smectites and especially bentonites are preferred. Crystalline layer-form sodium silicates corresponding to the general formula NaMSi_xO_2x+i -yBbO, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x being 2, 3 or 4, are also suitable substitutes for zeolites and phosphates. Crystalline layer silicates such as these are described, for example, in European patent application EP-A-O 164 514. Preferred crystalline layer silicates corresponding to the above formula are those in which M is sodium and x assumes the value 2 or 3. Both β- and δ- sodium disilicates Na₂Si₂O_S yH₂O are particularly preferred.

Other preferred builders are amorphous sodium silicates with a modulus (Na₂OrSiO₂ ratio) of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and more preferably 1:2 to 1:2.6 which dissolve with delay and exhibit multiple wash cycle properties. The delay in dissolution in relation to conventional amorphous sodium silicates can have been obtained in various ways, for example by surface treatment, compounding, compacting or by overdrying. Li the context of the invention, the term 'amorphous' is also understood to encompass 'X-ray amorphous'. Li other words, the silicates do not produce any of the sharp X-ray reflexes typical of crystalline substances in X-ray diffraction experiments, but at best one or more maxima of the scattered X- radiation which have a width of several degrees of the diffraction angle. Particularly good builder properties may even be achieved where the silicate particles produce crooked or even sharp diffraction maxima in electron diffraction experiments. This may be interpreted to mean that the products have microcrystalline regions between 10 and a few hundred ran in size, values of up to at most 50 nm and, more particularly, up to at most 20 run being preferred. So-called X-ray amorphous silicates such as these, which also dissolve with delay in relation to conventional waterglasses, are described for example in German patent application DE-A-4400 024. Compacted amorphous silicates, compounded amorphous silicates and overdried X-ray- amorphous silicates are particularly preferred, the overdried silicates in particular preferably also occurring as carriers in the granules according to the invention or being used as carriers in the process according to the invention.

The generally known phosphates may of course also be used as builders providing their use is not ecologically problematical. The sodium salts of orthophosphates, pyrophosphates and, in particular, tripolyphosphates are particularly suitable. Their content is generally no more than 25 percent by weight and preferably no more than 20 percent by weight, based on the final detergent. In some cases, it has been found that tripolyphosphates in particular, even in small quantities of up to at most 10 percent by weight, based on the final detergent, produce a synergistic improvement in multiple wash cycle performance in combination with other builders.

Thus, in some embodiments of the invention, the liquid detergent compositions may, for example, further comprise at least one of surfactant, optical brightener, coloring agent, fragrance, enzyme, builder, electrolyte, UV absorber, pH adjuster, bleach, crease control agent, fabric softener, pearl luster agent, chelating agent, preservative, redeposition inhibitor, odor absorber, dye transfer inhibitor, and thickener, or any mixture thereof.

Among the compounds yielding H₂O₂ in water which serve as bleaching agents, sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate are particularly important. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and HbCVyielding peracidic salts or peracids, such as perbenzoates, peroxophthalates. diperazelaic acid, phthaloiminoperacid or diperdodecane dioic acid. Even where bleaching agents are used, it is possible to leave out surfactants and/or builders so that pure bleach tablets can be produced. If such bleach tablets are to be used for washing laundry, a combination of sodium percarbonate with sodium sesquicarbonate is preferably used irrespective of what other ingredients the tablets contain. Typical organic bleaching agents are diacyl peroxides, such as dibenzoyl peroxide for example. Other typical organic bleaching agents are the peroxy acids, of which alkyl peroxy acids and aryl peroxy acids are particularly mentioned as examples. Preferred representatives are (a) peroxybenzoic acid and ring-substituted derivatives thereof, such as alkyl peroxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N- nonenylamidopersuccinates and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, diperoxyphthalic acids, 2-decyldiperoxybutane-l,4-dioic acid, N,N-terephthaloyl-di(6- aminopercaproic acid).

Other suitable bleaching agents in dishwashing detergents are chlorine- and bromine- releasing substances. Suitable chlorine- or bromine-releasing materials are, for example, heterocyclic N-bromamides and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and/or dichloroisocyanuric acid (DICA) and/or salts thereof with cations, such as potassium and sodium. Hydantoin compounds, such as l,3-dichloro-5,5-dimethyl hydantoin, are also suitable.

In order to obtain an improved bleaching effect where washing is carried out at temperatures of 60⁰C or lower, bleach activators may be incorporated in detergents according to the invention. The bleach activators may be compounds which form aliphatic peroxocarboxylic acids containing preferably 1 to 10 carbon atoms and more preferably 2 to 4 carbon atoms and/or optionally substituted perbenzoic acid under perhydrolysis conditions. Substances bearing O- and/or N-acyl groups with the number of carbon atoms mentioned and/or optionally substituted benzoyl groups are suitable. Preferred bleach activators are polyacylated alkylenediamines, more particularly tetraacetyl ethylenediamine (TAED), acylated triazine derivatives, more particularly l,5-diacetyl-2,4-dioxohexahydro-l,3,5-triazine (DADHT), acylated glycolurils, more particularly tetraacetyl glycoluril (TAGU), N-acylimides, more particularly N-nonanoyl succinimide (NOSI), acylated phenolsulfonates, more particularly n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, more particularly phthalic anhydride, acylated polyhydric alcohols, more particularly triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran. In addition to or instead of the conventional bleach activators mentioned above, so-called bleach catalysts may also be present. Bleach catalysts are bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and cobalt-, iron-, copper- and ruthenium-ammine complexes may also be used as bleach catalysts.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus, are particularly suitable. Proteases of the subtilisin type are preferred, proteases obtained from Bacillus lentus being particularly preferred. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or of protease, lipase and cellulase, but especially cellulase-containing mixtures, are of particular interest. Peroxidases or oxidases have also proved to be suitable in some cases. The enzymes may be adsorbed to supports and/or encapsulated in membrane materials to protect them against premature decomposition. The percentage content of enzymes, enzyme mixtures or enzyme granules in the tablets according to the invention may be, for example, from about 0.1 to 5 percent by weight and is preferably from 0.1 to about 2 percent by weight. The most commonly used enzymes include lipases, amylases, cellulases and proteases. Preferred proteases are, for example BLAP^® 140 (Biozym), Optimase^®-M-440 and Opticlean^®-M-250 (Solvay Enzymes); Maxacal^® CX and Maxapem^® or Esperase^® (Gist Brocades) or even Savinase^® (Novo). Particularly suitable cellulases and lipases are Celluzym^® 0.7 T and Lipolase^® 30 T (Novo Nordisk) while particularly suitable amylases are Duramyl^® and Termamyl^® 60 T and Termamyl^® 90 T (Novo), Amylase- LT^® (Solvay Enzymes) or Maxamyl^® P5000 (Gist Brocades). Other enzymes may also be used.

In addition, the detergents according to the invention may also contain components with a positive effect on the removability of oil and fats from textiles by washing (so-called soil repellents). This effect becomes particularly clear when a textile which has already been repeatedly washed with a detergent according to the invention containing this oil- and fat- dissolving component is soiled. Preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers, such as methyl cellulose and methyl hydroxypropyl cellulose containing 15 to 30 percent by weight of methoxyl groups and 1 to 15 percent by weight of hydroxypropoxyl groups, based on the nonionic cellulose ether, and the polymers of phthalic acid and/or terephthalic acid known from the prior art or derivatives thereof, more particularly polymers of ethylene terephthalates and/or polyethylene glycol terephthalates or anionically and/or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

The detergents may contain derivatives of diaminostilbenedisulfonic acid or alkali metal salts thereof as optical brighteners. Suitable optical brighteners are, for example, salts of 4,4'- bis-(2-anilino-4-morpholino-l,3,5-triazinyl-6-amino)-stilbene-2,2'-disulfonic acid or compounds of similar composition which contain a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group. Brighteners of the substituted diphenyl styryl type, for example alkali metal salts of 4,4'-bis-(2-sulfostyryl)- diphenyl, 4,4'-bis-(4-chloro-3-sulfostyryl)-diphenyl or 4-(4-chlorostyryl)-4'-(2-sύlfostyryl)- diphenyl, may also be present. Mixtures of the brighteners mentioned above may also be used.

In order to improve their aesthetic impression, the detergents according to the invention may be colored with suitable dyes. Preferred dyes, which are not difficult for the expert to choose, have high stability in storage, are not affected by the other ingredients of the detergents or by light and do not have any pronounced substantivity for textile fibers so as not to color them.

The present invention is also directed, in part, to methods of preparing a liquid detergent composition comprising combining from about 60 to about 95 percent, preferably from about 85 to about 95 percent water; from about 0.5 to about 10 percent of nonionic surfactant, preferably from about 1.0 to about 3.75 percent of nonionic surfactant; from about 0.5 to about 14 percent of an anionic surfactant comprising alcohol ether sulfate, or mixture of alcohol ether sulfate, preferably from about 1.0 to about 3.75 percent alcohol ether sulfate, and alkylbenzenesulfonate preferably from about 1.0 to about 3.75 percent alkylbenzenesulfonate; from about 1 to about 4 percent, preferably from about 1.5 to about 2.5 percent, carbonate; from about 0.05 to about 1.5 percent, preferably from about 0.05 to about 0.3 percent, of a hydrophobic fragrance delivery vehicle, said hydrophobic fragrance delivery vehicle preferably comprising at least one cyclic silicic acid ester, acyclic silicic acid ester, or mixture thereof; the level of each liquid detergent composition component amount being based on the weight of the liquid detergent composition; and optionally modifying the pH, if required, to bring the pH of the composition to within the range of about 7 to about 12.5.

EXAMPLES

Examples detailed below were carried out using the following standard laboratory equipment and supplies. Materials used included C 14-₁₅ alcohol ethoxylate 7 EO (Shell Neodol W

45-7, NI), Ci ₃ linear alkylbenzenesulfonate (LAS), sodium laureth sulfate 7 Mole (AES), softened water, sodium carbonate, and perfume containing silicic acid ester component (SAE). Testing equipment included a compact digital overhead stirrer, Mettler digital balance, Glass graduated beakers (600 ml), an ASTM Partial Immersion Thermometer having a range of 32-180° F, digital camera for record keeping, and Design Expert 6.0.1 computer software.

Three separate experiments were carried out to assess the stability of silicic acid esters in a typical low-surfactant-containing laboratory detergent formulation. A typical low-surfactant- containing laboratory formulation was prepared with water (60 - 97.95 percent), AES (0.5 — 10 percent), NI (0.5 - 10 percent), LAS (0.5 - 4 percent), carbonate (1 - 4 percent), and SAE (0.05 - 0.3 percent), all on a weight percent of total formulation basis. The composition had a pH of (or was subsequently adjusted by the addition of more carbonate or silicate to a pH of) 6-12.5.

General Procedure and Equipment for High (Inverse) Cloud Point

General/Description of Method

The solubility inversion temperature or "cloud point" of the each of the nonionic surfactants and/or detergent systems utilized was measured because, in general, these surfactants are less soluble in water at higher temperatures than at lower temperatures. A solubility inversion temperature of 14O⁰F is commonly required to ensure proper appearance and stability in the final consumer product.

Procedure

Each liquid surfactant or detergent sample was stirred thoroughly during the heating process. While stirring, care was taken not to whip air into the sample to avoid obscuring the cloud point. A hot water bath was prepared by heating a beaker 1/2 filled with softened water to at least 180° for use in testing.

While holding the test tube at an angle, the sample was poured down the inside wall of the test tube until the tube was half-filled with sample. Care was taken to avoid wetting the stopper area of the tube and so that no bubbles were formed. While holding the test tube at a 45° angle, the stirrer-thermometer assembly (thermometer and brazing rod) was slowly inserted taking care that no bubbles were formed. The stopper was tightened and the stirrer-thermometer assembly was lowered to the bottom of the test tube. The thermometer was then raised so that the bottom of the bulb projected 1 — 2 mm below the stirrer. The sample level was typically at or within 1/2" above the thermometer immersion line. If not, the level line on the test tube was adjusted accordingly. The assembly (Figure 1^*) was placed in the hot water bath and allowed to stand with occasional stirring until the sample became cloudy. Then it was removed and stirred continuously at a rate of about one stroke per second. The temperature at which the sample cleared was the approximate cloud point. Then the sample was allowed to cool 1-2 degrees. The assembly was returned to the bath and stirring was continued. The sample was visually inspected at each temperature rise of 1° while stirring. When the sample was uniformly cloudy it was removed from the hot water bath. With continued slow stirring, the test solution was allowed to cool slowly until it became clear. The temperature at which is became clear was recorded as its Inverse Cloud Point.

General Procedure and Equipment for Low Cloud Point

General/Description of Method

This method is intended for use on nonionic and anionic surfactants. The cloud point of a liquid is the temperature at which solid substance begins to separate from solution as a sample is cooled. A temperature of 32°F is specified for liquid detergents to ensure proper appearance stability. Because the high viscosity of liquid detergents interferes with heat transfer, it is necessary to stir the sample very thoroughly during the cooling process. While stirring, air must not be whipped into the sample, as it will completely obscure the cloud point. The apparatus described in this procedure is designed to meet these requirements.

Procedure

A cooling bath was prepared by adding crushed ice, ethyl alcohol and water to a 600ml. beaker. To avoid condensation in the upper part of the test tube, the bath level was adjusted to match the sample height. To ensure that the temperature of the bath was uniform during the test, the bath was stirred.

Holding the test tube on an angle, the sample was poured down the inside wall of the test tube to a pre-marked fill level. Care was taken to avoid wetting the stopper area of the test tube and no bubbles were formed in the sample during pouring. While holding the test tube at a 45° angle, the stirrer-thermometer assembly (thermometer and brazing rod) was slowly inserted taking care that no bubbles were formed. The stopper was tightened and the stirrer-thermometer assembly was lowered to the bottom of the test tube. The thermometer was then raised so that the bottom of the bulb projected 1 - 2 mm below the stirrer. The sample level was typically at or within 1/2" above the thermometer immersion line. If not, the level line on the test tube was adjusted accordingly. The test tube with stirrer-thermometer assembly (Figure 1) was placed in the cooling bath, allowing the sample to cool with occasional stirring of the sample until the sample became cloudy. The temperature at which the sample first became cloudy was recorded as the cloud point temperature of the sample.

Example 1

In the first experiment the solubility of the silicic acid esters was evaluated at low surfactant ranges. The experiment was conducted using three surfactants and one builder in the following levels: C13 linear alkylbenzenesulfonate (LAS) 1 — 3.75 percent, sodium laureth sulfate 7 Mole (AES) 1 - 3.75 percent, C₁4-₁₅ alcohol ethoxylate 7 EO, 1 - 3.75 percent (under the trade name Shell Neodol 45-7), carbonate 1.57 - 2.47 percent, all on a weight percent of total formulation basis.

Starting with these ranges, an experimental design was developed using the Design Expert computer software program to develop a D-optimal mixture design of experiments. The design program used a quadratic model to estimate points in the experimental design. The resultant design consisted of seventeen experiments that were analyzed for solubility using three responses: appearance done by visual assessment, high cloud point (also know as inverse cloud point), and low cloud point. The high (inverse) and low cloud point methods that were followed are recognized common practices.

The results of this design made it possible to narrow down the low range of the combination of surfactants and carbonate needed to achieve acceptable stability for the detergent formulation containing silicic acid esters. The results showed the influence of the nonionic surfactant, anionic surfactant, and carbonate on solubilizing silicic acid esters (See Figure 2). The experiment also showed the influence of increased carbonate on low surfactant detergent formulation to obtain acceptable stability of silicic acid esters in a formulation.

Example 2

The influence of individual surfactants and/or combinations of surfactants on the stability of silicic acid esters in a detergent mixture was analyzed. For this experiment, the same surfactants and builder listed in the Experiment 1 were used. Single surfactants were added to the water/SAE mixture to determine individual surfactant influence on solubility of the SAE as well as the minimum level of surfactant required to maximize SAE solubility. Each surfactant (or each surfactant in a surfactant combination) was individually step-wise to the water/SAE mixture until reasonable solubility was visually observed. Order of addition of surfactants W 2

appeared to have little, if any significant influence on solubility of silicic acid esters. However, the comparative tests showed that a combination of a nonionic surfactant and alcohol ether sulfate surfactant effectively solubilized the silicic acid esters with/without added carbonate. The pictures shown in Figure 3 summarize the results of this experiment. The first and second pictures in the series show the effect of two different alcohol ether sulfate surfactants on the solubility of a silicic acid ester in water. The third picture depicts the impact of using a mixture of alcohol ether sulfate surfactant and a C_B linear alkylbenzenesulfonate surfactant on the solubility of a silicic acid ester in water. The fourth picture shows the enhanced solubility of a silicic acid ester in water when a mixture of alcohol ether sulfate surfactant and nonionic surfactant are employed.

Example 3

The stability of silicic acid esters in a finished detergent formulation was analyzed using direct liquid injection gas chromatography mass spectrometry (GCMS). For this experiment, the silicic acid esters and fragrance were added to Purex Free & Clear™ liquid detergent. The stability of silicic acid esters in the formula was analyzed using analytical extraction methods. Experiments were conducted in the laboratory to determine the amount of free alcohols (cis-3- hexenol, citronellol, and geraniol) in detergent formulated with silica acid ester analogues of cis- 3-hexenol, citronellol, and geraniol. These experiments were conducted with two different extraction solvents, methanol and methylene chloride, in order to show the amounts of free alcohol and derivatized alcohol (as the corresponding silica acid ester) present with time in both the detergent and the fabric softener.

Equipment

Gas Chromatograph-Mass Spectrometry was performed using an Agilent 6890N/5973 inert GCMS. A Hewlett-Packard Innowax capillary GC column (- 3OM x 0.25mm x 0.25μ film) was used to perform the chromatographic separation.

Chemicals and Reagents:

Methylene chloride, methanol, c/_?-3~hexenol, citronellol, and geraniol were used as received. cw-3-Hexenol silicic acid ester, citronellol silicic acid ester, and geraniol silicic acid ester were prepared by the procedure outlined in US 7,098,178 B2, issued August 29, 2006. Purex Free & Clear™ liquid detergent was used as purchased. Procedure

Separate analytical standards containing a mixture of cis-3-hexenol, citronellol, and geraniol were prepared in methanol and in methylene chloride solvents. For methanol solutions, aliquots were transferred to autosampler vials for analysis. For methylene chloride solutions, an aliquot of the methylene chloride layer was carefully transferred to a scintillation vial where it was dried over anhydrous sodium sulfate for one hour. A portion of the dried solution was then transferred to an autosampler vial for analysis.

Separate analytical standards containing a mixture of cis-3-hexenol SAE, citronellol SAE, and geraniol SAE were prepared in methanol and in methylene chloride solvents. Aliquots were transferred to autosampler vials for analysis.

Separate samples of the detergents and fabric softeners were prepared in methanol and in methylene chloride solvents by accurately weighing each sample into a separate volumetric flask and diluting to volume with the appropriate solvent. A stir bar was added and the solution is mixed at high speed on a magnetic stirrer for one hour.

Standards and samples were sequentially analyzed by GC-MS. The weight percent of free alcohols was calculated for all samples. Recoveries can be calculated for detergents and fabric softeners prepared using the free alcohols. The results for the SAE-containing samples prepared in methylene chloride provided a measure of the free alcohols currently present in the detergent and fabric softeners. The level of free alcohols measured in SAE-containing samples prepared in methanol provided an estimate of the total alcohols present in a sample. The methanol solvent converted the SAE's to the corresponding free alcohols. Subtracting the amount of free alcohols measured in the methylene chloride sample from the total alcohols found in the corresponding methanol sample gave a measure of the residual perfume alcohol still contained in the silicic acid ester.

The results showed that the silicic acid esters had acceptable stability in the finished product. A sensory evaluation by sensory panel members confirmed the extended release (directly caused by improved stability of the SAE in the detergent or fabric softener formulation) of the perfume alcohol in end product "sniff-testing". The panel smell ed towels that were laundered using the silicic-acid-esters-containing detergent and towels washed in pure fragrance alcohol containing (non-SAE-containing) detergent. Three days after washing the towels, the towels washed with detergent or fabric softener containing silicic acid esters showed higher fragrance intensity than towels washed with detergent containing only free fragrance alcohols (Figure 4). When ranges are used herein for physical properties, such as weight percent of compositions, or pH values, or chemical properties, such as chemical formulae (for example, carbon chain length or number of ethylene oxide repeating units in a compound), all combinations and subcombinations of ranges and specific embodiments therein are intended to be included.

The disclosures of each patent, patent application and publication cited or described in this document are hereby incorporated herein by reference, in their entirety.

Those skilled in the art will appreciate that numerous changes and modifications can be made to the preferred embodiments of the invention and that such changes and modifications can be made without departing from the spirit of the invention. It is, therefore, intended that the appended claims cover all such equivalent variations as fall within the true spirit and scope of the invention.

Claims

What is Claimed:

1. A liquid detergent composition comprising: water; an optional alkaline agent capable of adjusting the pH of the liquid detergent composition to apH of from about 7 to about 12.5; from about 0.5 to about 10 percent of nonionic surfactant, based on the weight of the liquid detergent composition; from about 0.5 to about 14 percent of anionic surfactant composition comprising alcohol ether sulfate or mixture of alcohol ether sulfate and alkylbenzenesulfonate, based on the weight of the liquid detergent composition; and from about 0.05 to about 1.5 percent of hydrophobic fragrance delivery vehicle based on the weight of the liquid detergent composition; said detergent composition having a pH of from about 7 to about 12.5.

2. The liquid detergent composition of claim 1, wherein the anionic surfactant composition comprises: from about 0.5 to about 10 percent of alcohol ether sulfate based on the weight of the liquid detergent composition; and from about 0.5 to about 4 percent of linear alkylbenzenesulfonate based on the weight of the liquid detergent composition.

3. The liquid detergent composition of claim 2, wherein the anionic surfactant composition comprises: from about 1.0 to about 3.75 percent of alcohol ether sulfate based on the weight of the liquid detergent composition; and from about 1.0 to about 3.75 percent of linear alkylbenzenesulfonate based on the weight of the liquid detergent composition.

4. The liquid detergent composition of claim 2, wherein the nonionic surfactant comprises: from about 1.0 to about 3.75 percent alcohol ethoxylate based on the weight of the liquid detergent composition.

5. The liquid detergent composition of claim 1, wherein the alkyl moiety of the alkylbenzenesulfonate is n-Cp-πalkyl.

6. The liquid detergent composition of claim 1 , wherein the alcohol ether sulfate has the formula I:

R-O-(CH₂CH₂O)_C-SO₃H

(I) wherein R is Ci₂-i₈alkyl, and q is an integer from 1 to 9.

7. The liquid detergent composition of claim 6, wherein q is an integer from 2 to 8.

8. The liquid detergent composition of claim 1, wherein the nonionic surfactant is alcohol ethoxylate.

9. The liquid detergent composition of claim 8, wherein alcohol ethoxylate has the formula II:

R^O-(CH₂CH₂O)_P-H

. (H) wherein R¹ is Cio-isalkyl, and p is an integer from 3 to 9.

10. .The liquid detergent composition of claim 9, wherein p is the integer 5, 6, 7, or 8.

11. The liquid detergent composition of claim 10, wherein p is the integer 7.

12. The liquid detergent composition of claim 9, wherein R¹ is

13. The liquid detergent composition of claim 12, wherein R¹ is C₁₄.₁₅a.kyl.

14. The liquid detergent composition of claim 13, wherein p is 7.

15. The liquid detergent composition of claim 1, comprising from about 70 to about 95 percent water based on the weight of the liquid detergent composition.

16. The liquid detergent composition of claim 15, comprising from about 80 to about 95 percent water based on the weight of the liquid detergent composition.

17. The liquid detergent composition of claim 1, wherein the anionic surfactant composition comprises from about 1 to about 3.75 percent of alcohol ether sulfate based on the weight of the liquid detergent composition.

18. The liquid detergent composition of claim 2, wherein the anionic surfactant composition comprises from about 1 to about 3.75 percent of alkylbenzenesulfonate based on the weight of the liquid detergent composition.

19. The liquid detergent composition of claim 1 , wherein the nonionic surfactant comprises from about 1 to about 3.75 percent based on the weight of the liquid detergent composition.

20. The liquid detergent composition of claim 1, wherein the alkaline agent is carbonate or silicate, or any combination thereof.

21. The liquid detergent composition of claim 20, wherein the alkaline agent is a carbonate or bicarbonate.

22. The liquid detergent composition of claim 1, wherein the carbonate or bicarbonate comprises ammonium carbonate, sodium carbonate, sodium bicarbonate, or potassium carbonate, or any combination thereof.

23. The liquid detergent composition of claim 22, wherein the carbonate comprises sodium carbonate.

24. The liquid detergent composition of claim 22, wherein the carbonate is present at a level of from about 1.5 to about 2.5 percent based on the weight of the liquid detergent composition.

25. The liquid detergent composition of claim 1 further comprising at least one of: surfactant, optical brightener, coloring agent, fragrance, enzyme, builder, electrolyte,

UV absorber, pH adjustor, bleach, crease control agent, fabric softener, pearl luster agent, chelating agent, preservative, redeposition inhibitor, odor absorber, dye transfer inhibitor, and thickener, or any mixture thereof.

26. The liquid detergent composition of claim 1, wherein the hydrophobic fragrance delivery vehicle comprises about 0.05 to about 0.5 percent based on the weight of the liquid detergent composition.

27. The liquid detergent composition of claim 1, wherein the hydrophobic fragrance delivery vehicle comprises at least one cyclic silicic acid ester, acyclic silicic acid ester, or mixture thereof.

28. The liquid detergent composition of claim 1, wherein the hydrophobic fragrance delivery vehicle comprises a plurality of cyclic silicic acid esters, acyclic silicic acid esters, or mixture thereof.

29. The liquid detergent composition of claim 27, further comprising a fragrance that is not covalently bound to the hydrophobic delivery vehicle.

30. The liquid detergent composition of claim 27, wherein at least one cyclic silicic acid ester has the formula III:

in or at least one acyclic silicic acid ester has the formula IV:

rv wherein each R² is independently is H, Ci-βalkyl, Ci-βalkenyl, C^alkynyl, or the residual of perfume alcohol or biocide alcohol, provided that at least one of R² is the residual of perfume alcohol or biocide alcohol; m is an integer from 1 to 20; and n is an integer from 2 to 100.

31. The liquid detergent composition of claim 30, wherein residual of perfume alcohol or biocide alcohol is 10-undecen-l-ol, 2,6-dimethylheptan-2-ol, 2-methylbutanol, 2-methylpentanol, 2-phenoxyethanol, 2-phenylpropanol, 2-ter/-butyl cyclohexanol, 3,5,5-trimethylcyclohexanol, 3-hexanol, 3-methyl-5-phenyl pentanol, 3-octanol, 3-phenylpropanol, 4-heptenol, 4-isopropyl cyclohexanol, 4-tert-butyl cyclohexanol, 6,8- dimethyl-2-nonanol, 6-nonen-l-ol, 9-decen-l-ol, α-methyl benzyl alcohol, α-terpineol, amyl salicylate, benzyl alcohol, benzyl salicylate, β-terpineol, butyl salicylate, citronellol, cyclohexyl salicylate, decanol, dihydromyrcenol, dimethyl benzyl carbinol, dimethyl heptanol, dimethyl octanol, ethyl salicylate, ethyl vanillin, eugenol, farnesol, geraniol, heptanol, hexyl salicylate, isoborneol, isoeugenol, isopulegol, linalool, menthol, myrtenol, n-hexanol, nerol, nonanol, octanol, p-methan-7-ol, phenethyl alcohol, phenol, phenyl salicylate, tetrahydrόgeraniol, tetrahydro linalool, thymol, trans-2-cts-6-nonadienol, trans-2-nonen-l-ol, ft-αw.s-2-octenol, undecanol, vanillin, tetrahydromyrcenol, the various natural and synthetic sandalwood alcohols, *rα«_?-2-hexen-l-ol, cw-2-hexen-l-ol, l-octen-3-ol, and cinnamyl alcohol.

32. The liquid detergent composition of claim 30, wherein m is an integer from 2 to 10.

33. The liquid detergent composition of claim 30, wherein n is 4, 5, 6, 7, or 8.

34. The liquid detergent composition of claim 30, wherein the cyclic silicic acid ester has the formula:

or mixture thereof.

35. The liquid detergent composition of claim 30, wherein at least about 75 percent of the total R² substituents in the silicic acid esters are each independently the residual of perfume alcohol or biocide alcohol.

36. The liquid detergent composition of claim 35, wherein at least about 90 percent of the possible R² substituents in the silicic acid esters are each independently the residual of perfume alcohol or biocide alcohol.

37. The liquid detergent composition of claim 1, comprising: from about 85 to about 95 percent water by weight of the liquid detergent composition; from about 1.0 to about 3.75 percent of nonionic surfactant based on the weight of the liquid detergent composition; from about 1.0 to about 3.75 percent of alcohol ether sulfate based on the weight of the liquid detergent composition; from about 1.0 to about 3.75 percent of linear alkylbenzenesulfonate based on the weight of the liquid detergent composition; from about 1.5 to about 2.5 percent carbonate based on the weight of the liquid detergent composition; and from about 0.05 to about 1.5 percent of a hydrophobic fragrance delivery vehicle based on the weight of the liquid detergent composition; said detergent composition having a pH of from about 7 to about 12.5.

38. The liquid detergent composition of claim 37, wherein the hydrophobic fragrance delivery vehicle comprises at least one cyclic silicic acid ester, acyclic silicic acid ester, or mixture thereof.

39. The liquid detergent composition of claim 1, wherein the hydrophobic fragrance delivery vehicle is present at about 0.05 to about 0.3 percent based on the weight of the liquid detergent composition.

40. The liquid detergent composition of claim 38 comprising: from about 85 to about 95 percent water by weight of the liquid detergent composition; from about 1.0 to about 3.75 percent of nonionic surfactant having the formula:

Ci4-i₅alkyl-O-(CH₂CH₂O)7-H based on the weight of the liquid detergent composition; from about 1.0 to about 3.75 percent of alcohol ether sulfate having the formula:

IaUTyI-O-(CH₂CH₂O)₇-SO₃H; based on the weight of the liquid detergent composition; from about 1.0 to about 3.75 percent of linear C₁₃alkylbenzenesulfonate based on the weight of the liquid detergent composition; from about 1.5 to about 2.5 percent sodium carbonate based on the weight of the liquid detergent composition; and from about 0.05 to about 0.3 percent of a hydrophobic fragrance delivery vehicle based on the weight of the liquid detergent composition; said detergent composition having a pH of from about 7 to about 12.5.

41. The method of preparing a liquid detergent composition of claim 1, comprising combining: from about 60 to about 95 percent water by weight of the liquid detergent composition; from about 0.5 to about 10 percent of nonionic surfactant based on the weight of the liquid detergent composition; from about 0.5 to about 14 percent of an anionic surfactant comprising alcohol ether sulfate or mixture of alcohol ether sulfate and alkylbenzenesulfonate based on the weight of the liquid detergent composition; from about 1 to about 4 percent carbonate based on the weight of the liquid detergent composition; from about 0.05 to about 1.5 percent of a hydrophobic fragrance delivery vehicle based on the weight of the liquid detergent composition; and optionally modifying the pH, if required, to bring the pH of the composition to within the range of about 7 to about 12.5.

42. The method of claim 41, wherein the hydrophobic fragrance delivery vehicle comprises at least one cyclic silicic acid ester, acyclic silicic acid ester, or mixture thereof.

43. The method of claim 41 , comprising combining: from about 85 to about 95 percent water by weight of the liquid detergent composition; from about 1.0 to about 3.75 percent of nonionic surfactant based on the weight of the liquid detergent composition; from about 1.0 to about 3.75 percent of alcohol ether sulfate based on the weight of the liquid detergent composition; from about 1.0 to about 3.75 percent of linear alkylbenzenesulfonate based on the weight of the liquid detergent composition; from about 1.5 to about 2.5 percent carbonate based on the weight of the liquid detergent composition; and from about 0.05 to about 0.3 percent of a hydrophobic fragrance delivery vehicle based on the weight of the liquid detergent composition; and optionally modifying the pH, if required, to bring the pH of the composition to within the range of about 7 to about 12.5.

44. The liquid detergent composition of claim 1 , having a viscosity of from about 200 to about 800 cps.