GB2311296A - Perfumed particulate detergent compositions for hand dishwashing - Google Patents

Abstract

Disclosed are perfumed, dry particulate detergent and detergent/bleach compositions comprising anionic surfactant; solid builder and/or filler materials; and a blooming perfume composition. The components of the blooming perfume composition are defined by their boiling point and their octanol/water partition coefficient. Such compositions, which optionally contain a chlorine bleach, are useful for the hand washing of cooking and/or eating utensils. The perfume component utilized therein is ready noticeable to the user of the composition but does not spot or film surfaces washed using such compositions.

Description

Title :PERFUMED. PARTICULATE DETERGENT COMPOSITIONS FOR HAND DISHWASHING The present invention relates to particulate dry detergent compositions and detergent with bleach compositions which are useful for the hand washing of eating and cooking utensils and which have an especially desirable perfume composition incorporated there into.

In many parts of the world. granular detergent products, which contain relatively high levels of surfactants. builders and preferably bleaching agents, are used for the hand washing of eating and cooking utensils. Since dishwashing operations using such products involve the close proximity of the dishwasher to the dishwashing operation and to the detergent products used therein, it is desirable and commercially beneficial to add perfume materials to such products. PerfUmes provide an olfactory aesthetic benefit that can serve as a signal of cleanliness. Such perfumes should therefore be readily noticeable to the user of the particulate dishwashing products. Any perfumes that are used, however, should not leave residue or residual odor on surfaces that the washing solution formed from any such product has contacted. Residual perfumes on such surfaces, for example, on pots, pans, dishes and countertops, can cause undesirable spotting and filming.

Given the foregoing considerations, it is an object of the present invention to provide perfumed, dry particulate detergent compositions suitable for use in hand dishwashing operations for the cleaning of eating and cooking utensils.

It is a further object of this invention to provide in such perfumed hand dishwashing products selected tx pes of "blooming" perfume ingredients which impart a readily noticeable and desirable odor to the dishwashing products during use.

It is a further object of the present invention to provide such blooming perfumed detergent products that do not leave undesirable residual spotting or filming perfume materials on surfaces contacted with washing solutions formed from such products.

The present invention provides perfumed, dry particulate detergent compositions which are useful for the hand washing of eating and cooking utensils and which have an especially desirable and noticeable blooming perfume component. Such compositions comprise a) at least about 1% of an anionic surfactant; b) sufficient builder and filler to ensure a dry particulate composition; and c) from about 0.05% to 3% of a blooming perfume composition. The blooming perfurne composition is one which contains at least five different blooming perfume ingredients. A blooming perfume ingredient is one which has a boiling point of 260"C or lower and which has a calculated loglo of its octanoUwater partition coefficient, P, of about 3 or higher. Such compositions preferably also contain a chlorine bleach and have their blooming perfume compositions protected by combining the perfume composition with other materials to form moisture-activated, encapsulated perfume particles. When the blooming perfume composition is present in the form of cyclodextriniperfume complexes, particles of such complexes should be no more than about 12 microns in size.

Materials essentially and optionally incorporated in the detergent and bleach compositions of the present invention are described hereinafter. Unless otherwise specified. all concentrations and ratios are on a weight basis.

The compositions described herein are "dry particulate" products. For purposes of this invention, "dry particulate" compositions are not necessarily moisture-free, but are flowable powder or granular products which are essentially dry to the touch.

As used herein. "alkyl" means hydrocarbyl moieties which are straight or branched. saturated or unsaturated with one or more double bonds. Alkyl may be of single or mixed lengths. and are often mixed lengths and saturation derived from natural sources such as tallow. coconut oil. palm oil. etc.

Anionic Surfactants The compositions herein comprise at least about 1% preferably at least about 8%. also preferably at least about 18% anionic surfactant. more preferably from about 20% to about 40%. more preferably still from about 22% to about 36%, more preferably still from about 24% to about 32%. still more preferably from about 26% to about 30%.

Preferred anionic surfactant materials useful in the subject compositions include the water-soluble salts. preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 24 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Examples of such anionic surfactants are the salts of compatible cations, e.g., sodium, potassium, ammonium, monoethanolammonium. diethanolammonium, and triethanolammonium, with alkyl sulfates, alkylbenzene or alkyltoluene sulfonates, ethoxylated alkyl sulfates, and other surfactant anions disclosed hereinbelow.

Preferred alkylbenzene and alkyltoluene sulfonates include those with an alkyl portion which is straight chain or branched chain, preferably having from about 8 to 18 carbon atoms, more preferably from about 10 to about 16 carbon atoms. The alkyl chains of the alkylbenzene and alkyltoluene sulfonates preferably have an average chain length of from about 11 to about 14 carbon atoms.

Alkylbenzene sulfonates are preferred. Alkylbenzene sulfonate which includes branched chain alkyl is termed ABS. Alkylbenzene sulfonate which is all straight chain is preferred because it is more biodegradable; it is termed LAS and is the preferred anionic surfactant. Alkylberizene sulfonic acids useful as precursors for these surfactants include decyibenzene sulfonic acid, undecylbenzene sulfonic acid, dodecylbenzene sulfonic acid. tridecylbenzene sulfonic acid, tetrapropylenebenzene sulfonic acid, and mixtures thereof. Preferred sulfonic acids as precursors of the alkylbenzene sulfonates useful for compositions herein are those in which the alkyl chain is linear and averages from about 11 to about 13 carbon atoms in length.

Suitable cations for such alkylbenzene sulfonates include the alkali metals (lithium, sodium. and potassium), ammonium and/or alkanolammonium; preferred are potassium, and especially sodium.

Preferred alkyl sulfates include those with an alkyl portion which is straight chain or branched chain. preferably having from about 8 to about 24 carbon atoms, more preferably from about 10 to about 20 carbon atoms, more preferably still from about 12 to about 18 carbon atoms. The alkyl chains of the alkyl sulfates preferably have an average chain length of from about 14 to about 16 carbon atoms. The alkyl chains are preferably linear. Alkyl sulfates are typically obtained by sulfating fatty alcohols produced by reducing the glycerides of fats and/or oils from natural sources. especially from tallow or coconut oil. Preferred alkyl sulfates include lauryl sulfates, stearyl sulfates. palmityl sulfates. decyl sulfates, myristyl sulfates, tallow alkyl sulfates. coconut alkyl sulfates, C1 2-15 alkyl sulfates. and mixtures of these surfactants. Preferred cations for the alkyl sulfates include sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, and triethanolammonium; most preferred is sodium.

Other preferred anionic surfactants include alkylpolyethoxylate sulfates having the formula RO(C2H4O)XSO3M wherein R is alkanyl or alkenyl having from about 10 to about 20 carbon atoms, preferably from about 12 to about 16 or 18; X is from about 1/2 to about 20 on average, preferably from about 1 to about 10, more preferably from about 2 to about 6; and M is a water-soluble compatible cation such as those disclosed hereinabove. The alkylpolyethoxylate sulfates useful in the subject invention are typically condensation products of ethylene oxide and monohydric alcohols having from about 10 to about 20 carbon atoms. The alcohols can be derived from natural fats. e.g., coconut oil or tallow, or can be synthetic.

Preferred cations of such surfactants are potassium, and especially sodium. Specific examples of alkylpolyethyoxlate sulfates include sodium coconut alkylpolyethoxylate (3) ether sulfate. sodium C12-15 alkylpolyethoxylate (3) ether sulfate. sodium tallow alkylpolyethoxylate (6) ether sulfate, and potassium C12-13 alkylpolyethoxylate (1) ether sulfate.

Anionic surfactants include water-soluble salts of the higher fatty acids, or "soaps". This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, preferably from about 12 to about 18 carbon atoms.

Other anionic surfactants useful in the subject invention compositions include sodium alkyl glycerol ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates: sodium or potassium salts of alkylphenol ethylene oxide ether sulfates containing from about 1 to about 12 units of ethylene oxide per molecule. and wherein the alkyl group contains from about 8 to about 12 carbon atoms; and secondary alcohol sulfates containing from about 14 to about 18 carbon atoms.

Other anionic surfactants useful in the subject invention compositions include the water-soluble salts of esters of a-sulfonated fatty acids containing from about 8 to about 20 carbon atoms in the fatty acid group and from about I to about 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxyalkane-l- sulfonic acids containing from about 2 to about 9 carbon atoms in the acyl group and tirom about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin and paraffin sulfonates containing from about 10 to about 20 carbon atoms; - alkoxyalkane sulfonates containing from about 1 to about 3 carbon atoms in the alkyl group and from 8 to about 20 carbon atoms in the alkane moiety; alkylphenol polyethylene oxide ether sulfates. with from about I to about 10 units of ethylene oxide per molecule on the average, in which the alkyl radicals contain from about 8 to about 12 carbon atoms; the reaction products of fatty acids esterified with isethionic acid, where fatty acids are derived from synthetic or natural sources; fatty acid amides of a methyl tauride in which the fatty acids are derived from synthetic or natural sources; and 13-acetoxy- or -acetamido-alkane sulfonates, where the alkane has from about 8 to about 22 carbon atoms.

Solid Materials The subject dry particulate compositions necessarily comprise sufficient solid materials for the compositions to be in their dry particulate state. To achieve this the subject compositions comprise high levels of solid builders or solid fillers or mixtures thereof. Excluding the surfactants, perfume compositions, optional chlorine bleach material, and moisture discussed herein, the remainder of the subject compositions preferably comprises at least about 80%, more preferably from about 90% to about 100%, more preferably still from about 95% to about 99%, materials selected from such builders and fillers.

Builders The compositions herein also preferably comprise at least about 1% phosphorus-containing builder, also preferably from about 2% to about 40%, more preferably from about 3% to about 20%, more preferably still from about 5% to about 12%.

Preferred phosphorus-containing builder materials are inorganic phosphate, pyrophosphate, or polyphosphate materials which have the ability to remove metal ions other than alkali metal ions from wash solutions by sequestration, including by chelation or by precipitation reactions. Preferred phosphorus-contairiing builders include trisodium phosphate, tetrasodium pyrophosphate, sodium tripolyphosphate, and sodium hexametaphosphate; sodium tripolyphosphate is the most preferred phosphorous-containing builder.

The compositions of the present invention also preferably comprise from about 1% to about 20% silicate builder, also preferably from about 3% to about 17%. more preferably from about 5% to about 15%.

The silicate builder materials are water-soluble silicates which are a mixture of SiO2 and M2O (M=Na or K). having a ratio of SiO2:M2O of from about 1:1 to about 3.6:1. preferably from about 1.6:1 to about 3.2:1. Such silicates help provide the desired alkalinity for the products herein during use.

Blooming Perfume Composition The detergent compositions herein also comprise from about 0.05% to 3% of a blooming perfume composition. More preferably, the blooming perfume composition comprises from about 0.1% to 2% of the detergent compositions herein, even more preferably from about 0.2% to 1.2%. Most preferably, the detergent compositions herein contain from about 0.4% to 0.8% of the blooming perfume composition.

A blooming perfume composition is one which comprises blooming perfume ingredients. A blooming perfume ingredient is characterized by its boiling point (B.P.) and its octanol/water partition coefficient (P). The octanol/water partition coefficient of a perfume ingredient is the ratio between its equilibrium concentrations in octanol and in water. The preferred perfume ingredients of this invention have a B.P., determined at the normal, standard pressure of about 760 mm Hg, of about 260"C or lower, preferably less than about 255"C; and more preferably less than about 250"C, and an octanoilwater partition coefficient P of about 1,000 or higher. Since the partition coefficients of the preferred perfume ingredients of this invention have high values, they are more conveniently given in the form of their logarithm to the base 10, logP. Thus the preferred perfume ingredients of this invention have logP of about 3 or higher, preferably more than about 3.1, and even more preferably more than about 3.2.

The boiling points of many perfume ingredients are given in, e.g., "Perfume and Flavor Chemicals (Aroma Chemicals)," Steffen Arctander, published by the author. 1969, incorporated herein by reference.

The logP of many perfume ingredients has been reported; for example, the Pomona92 database. available from Daylight Chemical Information Systems, Inc.

(Daylight CIS), Irvine. California. contains many, along with citations to the original literature. However. the logP alues are most conveniently calculated by the "CLOGP" program. also available from Daylight CIS. This program also lists experimental logP values when they are available in the Pomona92 database. The "calculated logP" (ClogP) is determined by the fragment approach of Hansch and Leo ( cf.. A. Leo. in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G.

Sammens. J. B. Tavlor and C. A. Ramsden. Eds., p. 295, Pergamon Press, 1990, incorporated herein by reference). The fragment approach is based on the chemical structure of each perfume ingredient. and takes into account the numbers and types of atoms. the atom connectivity. and chemical bonding. The ClogP values, which are the most reliable and widely used estimates for this physicochemical property, are preferably used instead of the experimental logP values in the selection of perfume ingredients which are useful in the present invention.

Thus. when a perfume composition which is composed of ingredients having a B.P. of about 260"C or lower and a ClogP. or an experimental logP, of about 3 or higher, is used in a hand dish particulate cleaning composition, the perfume is very effusive and very noticeable when the product is used.

Table 1 gives some non-limiting examples of blooming perfume ingredients, useful in hand dish particulate cleaning compositions of the present invention. The blooming perfume compositions used in the present invention contain at least 5 different blooming perfume ingredients, preferably at least 6 different blooming perfume ingredients, more preferably at least 7 different blooming perfume ingredients, and even more preferably at least 8 different blooming perfume ingredients. Most common perfume ingredients which are derived from natural sources are composed of a multitude of components. For example, orange terpenes contain about 90% to about 95% d-limonene, but also contain many other minor ingredients. When each such material is used in the formulation of blooming perfume compositions of the present invention, it is counted as one single ingredient, for the purpose of defining the invention. Furthermore, the blooming perfume compositions of the present invention contain at least about 50 wt.% of blooming perfume ingredients. preferably at least about 55 wt.% of blooming perfume ingredients, more preferably at least about 60 wt.% of blooming perfume ingredients, and even more preferably at least about 70 wt.% of blooming perfume ingredients. The bloorning perfume compositions herein should not contain any single ingredient at a level of more than about 60 %, by weight of the composition, preferably not more than about 50 %, by weight of the composition, and even more preferably not more than about 40 %* by weight of the composition.

Some of the blooming perfume ingredients used in the present invention can optionally be replaced b! "delayed blooming" perfume ingredients. The optional delayed blooming perfume ingredients of this invention have a B.P., measured at the normal, standard pressure. of about 260"C or lower, preferably less than about 255"C; and more preferably less than about 250"C, and a logP or ClogP of less than about 3. Thus, when a perfume composition is composed of some preferred blooming ingredients and some delayed blooming ingredients, the perfume effect is longer lasting when the product is used. Table 2 gives some non-limiting examples of optional delayed blooming perfume ingredients. useful in the hand dish particulate cleaning compositions of the present invention. Delayed blooming perfume ingredients are used primarily in applications where the water will evaporate. thus liberating the perfume.

When delayed blooming perfume ingredients are used in combination with the blooming perfume ingredients in the blooming perfume compositions employed in the present invention. the weight ratio of blooming perfume ingredients to delayed blooming perfume ingredients is typically at least about 1, preferably at least about 1.3, more preferably about 1.5. and even more preferably about 2. The blooming perfume compositions contain at least about 50 wt.% of the combined blooming perfume ingredients and delayed blooming perfume ingredients, preferably at least about 55 wt.% of the combined perfume ingredients, more preferably at least about 60 wt.% of the combined perfume ingredients, and even more preferably at least about 70 wt.% of the combined perfume ingredients. When some optional delayed blooming perfume ingredients are used in combination with the blooming perfume ingredients in the blooming perfume compositions, the blooming perfume compositions of the present invention contain at least 4 different blooming perfume ingredients and 2 different delayed blooming perfume ingredients, preferably at least 5 different blooming perfume ingredients and 3 different delayed blooming perfume ingredients, and more preferably at least 6 different blooming perfume ingredients and 4 different delayed blooming perfume ingredients.

In the perfume art. some auxiliary materials having no odor, or a low odor, are used. e.g., as solvents. diluents. extenders or fixatives. Non-limiting examples of these materials are ethyl alcohol. carbitol. diethylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate. isopropyl myristate. and benzyl benzoate. These materials are used for. e.g., solubilizing or diluting some solid or viscous perfume ingredients to, e.g., improve handling and/or formulating. These materials are useful in the blooming perfume compositions. but are not counted in the calculation of the limits for the definitioniformulation of the blooming perfume compositions of the present invention.

Non-blooming perfume ingredients. which should be minimized in hand dish particulate cleaning compositions of the present invention, are those having a B.P. of more than about 260"C. Table 3 gives some non-limiting examples of nonblooming perfume ingredients. In some particular hand dish particulate cleaning compositions, some non-blooming perfume ingredients can be used in small amounts. e.g., to improve product odor.

It can be desirable to use blooming and delayed blooming perfume ingredients and even other ingredients. preferably in small amounts, in the blooming perfume compositions of the present invention. that have low odor detection threshold values. The odor detection threshold of an odorous material is the lowest x-apor concentration of that material which can be detected. The odor detection threshold and some odor detection threshold values are discussed in, e.g., "Standardized Human Olfactory Thresholds". M. Demos et al. IRL Press at Oxford University Press. 1990. and "Compilation of Odor and Taste Threshold Values Data". F. A. Fazzalari. editor. ASTM Data Series DS 48A. American Society for Testing and Materials. 1978 both of said publications being incorporated by reference. The use of small amounts of non-blooming perfume ingredients that have low odor detection threshold values can improve perfume odor character, without the potential negatives normally associated with such ingredients, e.g., spotting and/or filming on, e.g., dish surfaces. Non-limiting examples of perfume ingredients that have low odor detection threshold values useful in the present invention include coumarin, vanillin, ethyl vanillin, methyl dihydro isojasmonate, 3-hexenyl salicylate, isoeugenol, lyral, gamma-undecalactone, gamma-dodecalactone, methyl beta naphthyl ketone, and mixtures thereof These materials are preferably present at low levels in addition to the blooming and delayed blooming ingredients, typically less than about 5%, preferably less than about 3%, more preferably less than about 2%, by weight of the blooming perfume compositions of the present invention.

Table 1 Examples of "Blooming" Perfume Ingredients Approx. Approx.

Perfume Ingredients BP ( C) ClogP allo-Ocimene 192 4.362 Allyl Heptoate 210 3.301 Anethol 236 3.314 Benzyl Butyrate 240 3.698 Camphene 159 4.192 Carvacrol 238 3.401 beta-Caryophyllene 256 6.333 cis-3-Hexenyl Tiglate 101 3.700 Citral (Neral) 228 3.120 Citronellol 225 3.193 Citronellyl Acetate 229 3.670 Citronellyl Isobutyrate 249 4.937 Citronellyl Nitrile 225 3.094 Citronellyl Propionate 242 4.628 Cyclohexyl Ethyl Acetate 187 3.321 Decyl Aldehyde 209 4.008 Dihydro Myrcenol 208 3.030 Dihydromyrcenyl Acetate 225 3.879 Dimethyl Octanol 213 3.737 Diphenyl Oxide 252 4.240 Dodecalactone 258 4.359 Ethyl Methyl Phenyl Glycidate 260 3.165 Fenchyl Acetate 220 3.485 gamma Methyl Ionone 230 4.089 gamma-n-Methyl lonone 252 4.309 gamma-Nonalactone 243 3.140 Geranyl Acetate 245 3.715 Geranyl Formate 216 3.269 Geranyl Isobutyrate 245 4.393 Geranyl Nitrile 222 3.139 Hexenyl Isobutyrate 182 3.181 Hexyl Neopentanoate 224 4.374 Hexyl Tiglate 231 3.800 alpha-lonone 237 3.381 beta-Ionone 239 3.960 gamma-Ionone 240 3.780 alpha-Irone 250 3.820 Isobomyl Acetate 227 3.485 Isobutyl Benzoate 242 3.028 Isononyl Acetate 200 3.984 Isononyl Alcohol 194 3.078 Isobutyl Quinoline 252 4.193 Isomenthol 219 3.030 para-Isopropyl Phenylacetaldehyde 243 3.211 Isopulegol 212 3.330 Lauric Aldehvde (Dodecanal) 249 5.066 Lilial (p-t-Bucinal) 258 3.858 d-Limonene 177 4.232 Linalyl Acetate 220 3.500 Methyl Acetate 227 3.210 Methyl Chavicol 216 3.074 alpha-iso "gamma" Methyl Ionone 230 4.209 Methyl Nonvl Acetaldehyde 232 4.846 Methyl Octvl Acetaldehyde 228 4.317 Mvrcene 167 4 272 Neral 228 3.120 Neryl Acetate 231 3.555 Nonyl Acetate 212 4.374 Nonyl Aldehyde 212 3.479 Octyl Aldehvde 223 3.845 Orange Terpenes td-Limonene) 177 4.232 para-Cymene 179 4.068 Phenyl Heptanol 261 3.478 Phenyl Hexanol 258 3.299 alpha-Pinene 157 4.122 beta-Pinene 166 4.182 alpha-Terpinene 176 4.412 gamma-Terpinene 183 4.232 Terpinolene 184 4.232 Terpinyl acetate 220 3.475 Tetrahydro Linalool 191 3.517 Tetrahydro Myrcenol 208 3.517 Tonalid 246 6.247 Undecenal 223 4.053 Veratrol 206 3.140 Verdox 221 4.059 Vertenex 232 4.060 Table 2 Examples of "Delayed Blooming" Perfume Ingredients Approx Approx.

Perfume Ingredients BP(0C) ClogP Allyl Caproate 185 2.772 Amyl Acetate 142 2.258 Amyl Propionate 161 2.657 Anisic Aldehyde 248 1.779 Anisole 154 2.061 Benaaldehyde 179 1.480 Benznl Acetate 215 1.960 Benzvl Acetone 235 1.739 Benzvl Alcohol 205 1.100 Benzvl Formate 202 1.414 Benzvl Iso Valerate 246 2.887 Benz'I Propionate 222 2.489 Beta Gamma Hexenol 157 1.337 Camphor Gum 208 2.117 laevo-Carveo 1 227 2.265 d-Canone 231 2.010 laevo-Carvone 230 2.203 Cinnamic Alcohol 258 1.950 Cinnamyl Formate 250 1.908 cis-Jasmone 248 2.712 cis-3-Hexenyl Acetate 169 2.243 Cuminic alcohol 248 2.531 Curninic aldehyde 236 2.780 CyclalC 180 2.301 Dimethyl Benzyl Carbinol 215 1.891 Dimethyl Benzyl Carbinyl Acetate 250 2.797 Ethyl Acetate 77 0.730 Ethyl Aceto Acetate 181 0.333 Ethyl Amyl Ketone 167 2.307 Ethyl Benzoate 212 2.640 Ethyl Butyrate 121 1.729 Ethyl Hexyl Ketone 190 2.916 Ethyl Phenyl Acetate 229 2.489 Eucalyptol 176 2.756 Eugenol 253 2.307 Fenchyl Alcohol 200 2.579 Flor Acetate (tricyclo Decenyl Acetate) 175 2.357 Frutene (tricyclo Decenyl Propionate) 200 2.260 Geraniol 230 2.649 Hexenol 159 1.397 Hexenyl Acetate 168 2.343 Hexyl Acetate 172 2.787 Hexyl Formate 155 2.381 Hydratropic Alcohol 219 1.582 Hydroxycitronellal 241 1.541 Indole 254 2.132 Isoamvl Alcohol 132 1.222 I somenthone 210 2.831 Isopulegyl Acetate 239 2.100 Isoquinoiine 243 2.080 Ligustral 177 2.301 Linalool 198 2.429 Linalool Oxide 188 1.575 Linalyl Format 202 2.929 Menthone 207 2.650 Methyl Acetophenone 228 2.080 Methyl Amyl Ketone 152 1.848 Methyl Anthranilate 237 2.024 Methyl Benzoate 200 2.111 Methyl Benzyl Acetate 213 2.300 Methyl Eugenol 249 2.783 Methyl Heptenone 174 1.703 Methyl Heptine Carbonate 217 2.528 Methyl Heptyl Ketone 194 1.823 Methyl Hexyl Ketone 173 2.377 Methyl Phenyl Carbinyl Acetate 214 2.269 Methyl Salicylate 223 1.960 Methyl-N-Methyl Anthranilate 256 2.791 Nerol 227 2.649 Octalactone 230 2.203 Octyl Alcohol (Octanol-2) 179 2.719 para-Cresol 202 1.000 para-Cresyl Methyl Ether 176 2.560 para-Methoxy Acetophenone 260 1.801 para-Methyl Acetophenone 228 2.080 Phenoxy Ethanol 245 1.188 Phenyl Acetaldehyde 195 1.780 Phenyl Ethyl Acetate 232 2.129 Phenyl Ethyl Alcohol 220 1.183 Phenyl Ethyl Dimethyl Carbinol 238 2.420 Prenyl Acetate 155 1.684 Propyl Butyrate 143 2.210 Pulegone 224 2.350 Rose Oxide 182 2.896 Safrole 234 1.870 4-Terpinenol 212 2.749 alpha-Terpineo 1 219 2.569 Viridine 221 1.293 Table 3 Examples of Non-Blooming Perfume Ingredients Approximate Approx.

Perfume Inaredients B.P. ( C) ClogP Allyl Cyclohexane Propiona Amyl Benzoate 262 3.417 Amyl Cinnamate 310 3.771 Amyl Cinnamic Aldehyde 285 4.324 Amyl Cinnamic Aldehyde Dimethyl Acetal 300 4.033 iso-Amyl Salicylate 277 4.601 Aurantiol 450 4.216 Benzophenone 306 3.120 Benzyl Salicylate 300 4.383 Cadinene 275 7.346 Cedrol 291 4.530 Cedryl Acetate 303 5.436 Cinnamyl Cinnamate 370 5.480 Coumarin 291 1.412 Cyclohexyl Salicylate 304 5.265 Cyclamen Aldehvde 270 3.680 Dihydroisojasmonate +300 3.009 Diphenyl Methane 262 4.059 Ethylene Brassylate 332 4.554 Ethyl Methyl Phenyl Glycidate 260 3.165 Ethyl Undecylenate 264 4.888 iso-Eugenol 266 2.547 Exaltolide 280 5.346 Galaxolide +260 5.482 Geranyl Anthranilate 312 4.216 Hexadecanolide 294 6.805 Hexenyl Salicvlate 271 4.716 Hexyl Cinnamic Aldehvde 305 5.473 Hexyl Salicylate 290 5.260 Linalvl Benzoate 263 5.233 2-Methoxy Naphthalene 274 3.235 Methyl Cinnamate 263 2.620 Methyl Dihydrojasmonate 300 '.275 beta-Methyl Naphthyl ketone 300 2.275 Musk Indanone +250 5.458 Musk Ketone MP = 137"C 3.014 Musk Tibetine MP=1360C 3.831 Myristicin 276 3.200 delta-Nonalactone 280 2.760 Oxahexadecanolide-10 +300 4.336 Oxahexadecanolide-11 MP = 35"C 4.336 Patchouli Alcohol 285 4.530 Phantolide 288 5.977 Phenyl Ethyl Benzoate 300 4.058 Phenylethylphenylacetate 325 3.767 alpha-Santalol 301 3.800 Thibetolide 280 6.246 delta-Undecalactone 290 3.830 gamma-Undecalactone 297 4.140 Vanillin 285 1.580 Vetiveryl Acetate 285 4.882 Yara-Yara 274 3.235 (a) M.P. is melting point: these ingredients have a B.P. higher than about 260"C.

The perfumes suitable for use in the hand dish particulate cleaning compositions herein can be formulated from known fragrance ingredients and for purposes of enhancing environmental compatibility, the perfume compositions used herein are preferably substantially free of halogenated fragrance materials and nitromusks.

The blooming perfume compositions hereinbefore described are preferably incorporated into moisture-activated. complexed or encapsulated perfume particles for use in the particulate hand dish cleaning compositions of this invention. Such perfume particles include. for example. cyclodextrin/perfume inclusion complexes, polysaccharide cellular matrix perfume microcapsules, and the like. Encapsulation of the blooming perfume compositions minimizes the depletion of the volatile blooming perfume ingredients when the product box is opened and during storage.

Perfume is released when products are dissolved in washing solution to thereby provide a pleasant odor signal in use. Furthermore. the water-activated perfume carrier protects the perfume from chemical degradation caused by the different -bleach systems which are commonly present in the particulate hand dishwashing detergent compositions of this invention.

It is also preferable to use both free perfume and encapsulated perfume in the same particulate hand dishwashing detergent composition. with the two perfumes being either the same. or two different perfumes. Normally, the free perfume mainly provides the product (or box) perfume odor, and covers any base product odor, while the encapsulated perfume mainly provides the in-use perfume odor when the detergent composition is diluted into the wash water.

Due to the minimized loss of the volatile ingredients of the blooming perfume compositions as a result of encapsulating said compositions in the water-activated protective perfume carriers, the blooming perfume compositions which are used in the encapsulated form can contain less blooming perfume ingredients than those used in the free, unencapsulated form. The encapsulated and/or complexed blooming perfume compositions can typically contain at least about 20%, preferably at least about 30%, and more preferably at least 40%, of blooming perfume ingredients. Higher levels of blooming perfume ingredients and delayed blooming perfume ingredients are also preferred.

Especially preferred perfume particulates comprise cyclodextrin inclusion complexes of the blooming perfume compositions herein with a particle size of less than about 12 microns. As used herein, the term "cyclodextrin" includes any of the known cyclodextrins such as unsubstituted cyclodextrins containing from six to twelve glucose units. especially, alpha-. beta-, and gamma-cyclodextrins, and/or their derivatives, andlor mixtures thereof. The alpha-cyclodextrin consists of 6, the beta-cyclodextrin 7. and the gamma-cyclodextrin 8, glucose units arranged in a donut-shaped ring. The specific coupling and conformation of the glucose units give the cyclodextrins a rigid. conical molecular structure with a hollow interior of a specific volume. The "lining" of the internal cavity is formed by hydrogen atoms and glycosidic bridging oxygen atoms, therefore this surface is fairly hydrophobic.

These cavities can be filled with all or a portion of an organic molecule with suitable size to form an "inclusion complex." Alpha-. beta-, and gamma-cyclodextrins can be obtained from. among others. American Maize-Products Company (Amaizo), Hammond, Indiana.

Cyclodextrin derivatives are disclosed in U.S. Pat. Nos: 3,426,011, Parmerter et al.. issued Feb. 4. 1969:3.453.257, 3,453.258, 3,453,259, and 3,453,260, all in the names of Parmerter et al.. and all also issued July 1. 1969. 3.459.731, Gramera et al., issued Aug. 5. 1969: .553.191. Parmerter et al.. issued Jan. 5, 1971; 3,565,887, Parmerter et al.. issued Feb. 33. 1971:4,535.152, Szejtli et al.. issued Aug. 13, 1985; 4.616.008, Hirai et al.. issued Oct. 7. 1986: 4.638.058. Brandt et al.. issued Jan. 20, 1987: 4.746.734. Tsuchisama et al.. issued May 24. 1988; and 4.678,598, Ogino et al.. issued Jul. 7. 1987. all of said patents being incorporated herein by reference.

Examples of cyclodextrin derivatives suitable for use herein are methyl-beta cx clodextrin. hvdroxn ethx l-beta-cvclodextrin. and hydroxypropyl-beta-cyclodextrin of different degrees of substitution (D.S.). available from Amaizo; Wacker Chemicals (USA). Inc.: and Aldrich Chemical Company. Water-soluble derivatives are also highlv desirable.

The individual cyclodextrins can also be linked together, e.g., using multifunctional agents to form oligomers, polymers, etc. Examples of such materials are available commercially from Amaizo and from Aldrich Chemical Company (beta-cyclodextrin/epichlorohydrin copolymers). The preferred cyclodextrin for use in forming the perfume inclusion complexes is betacyclodextrin. It is also desirable to use mixtures of cyclodextrins. Preferably at least a major portion of the cyclodextrins are alpha-, beta- and/or gamma-cyclodextrins, more preferably alpha- and beta-cyclodextrins. Some cyclodextrin mixtures are commercially available from, e.g., Ensuiko Sugar Refining Company, Yokohama, Japan.

The cyclodextrin/perfume inclusion complexes useful herein are formed in any of the ways known in the art. Typically, the complexes are formed either by bringing the blooming perfume composition and the cyclodextrin together in a suitable solvent, e.g., water. or, preferably, by kneading/slurrying the ingredients together in the presence of a suitable, preferably minimal, amount of solvent, preferably water. The kneading/slurrying method is particularly desirable because it produces smaller complex particles and requires the use of less solvent, eliminating or reducing the need to further reduce particle size and separate excess solvent.

Disclosures of complex formation can be found in Atwood, J.L., J.E.D. Davies & D.D. MacNichol, (Ed.): Inclusion Compounds. Vol. III, Academic Press (1984), especially Chapter 11, Atwood. J.L. and J.E.D. Davies (Ed.): Proceedings of the Second International Symposium of Cvclodextnns Tokyo, Japan, (July, 1984), and J. Szejtli, Cvclodextnn Technologv, Kluwer Academic Publishers (1988), said publications incorporated herein by reference.

In general, perfume/cyclodextrin complexes have a molar ratio of perfume ingredients to cyclodextrin of about 1:1. However, the molar ratio can be either higher or lower, depending on the size of the perfume molecules and the identity of the cyclodextrin compound. The molar ratio can be determined by forming a saturated solution of the cyclodextrin and adding the perfume to form the complex. In general the complex will precipitate readily. If not. the complex can usually be precipitated by the addition of electrolyte, change of pH, cooling, etc. The complex can then be analyzed to determine the ratio of perfume to cyclodextrin.

As stated hereinbefore. the actual complexes are determined by the size of the cavity in the cyclodextrin and the size of the perfume molecules. Desirable complexes can be formed using mixtures of cyclodextrins since the blooming perfumes are mixtures of materials that vary widely in size. It is usually desirable that at least a majority of the material be alpha-, beta-, and/or gamma-cyclodextrin, more preferably beta-cyclodextrin. The content of the perfume in the beta cyclodextrin complex is typically from about 5% to about 15%, more normally from about 8% to about 13%. The particulate hand dishwashing detergent compositions of this invention preferably will comprise of from 0% to about 15%, preferably from about 1% to about 10%, more preferably from about 2% to about 8% of cyclodextriniperfume complex.

Continuous complexation operation usually involves the use of supersaturated solutions, kneading/slurrying method, and/or temperature manipulation, e.g., heating and then either cooling, freeze-drying, etc. The complexes are dried to a dry powder to make the desired composition. In general, the fewest possible process steps are preferred to avoid loss of perfume.

Cyclodextrin/perfume complexes used in this invention having a particle size of less than about 12 microns, preferably less than about 10 microns, more preferably less than about 8 microns, and even more preferably less than about 5 microns. improve the release, especially the speed of release of the perfume when the complexes are wetted.

The particle size is typically between about 0.001 and 10 microns, preferably between about 0.05 and 5 microns. It is highly desirable that at least an effective amount of the blooming perfume be in complexes having the said particle sizes. It is desirable that at least about 75%. preferably at least about 80%, more preferably at least about 90%, and even more preferably at least about 100%, of the complex that is present have these particle sizes.

These small particles of the invention are conveniently prepared by kneading methods and/or grinding techniques. Cyclodextrin complexes with large particle sizes can be pulverized to obtain the desired smaller particles of less than about 12 microns by using, e.g.. a fluid energy mill. Examples of fluid energy mills are the Trost Air Impact Pulverizers. sold by Garlock Inc., Plastomer Products, Newtown, Pennsylvania: the Micronizer fluid energy mills sold by Sturtevant, Inc., Boston, Massachusetts; and the Spiral Jet Mill sold by Alpine Division, MicroPul Corporation (Hosokawa Micron International. Inc.). Summit. New Jersey.

As used herein. the particle size refers to the largest dimension of the particle and to the ultimate (or primary) particles. The size of these primary particles can be directly determined with optical or scanning electron microscopes. The slides must be carefully prepared so that each contains a representative sample of the bulk cyclodextrin complexes. The particles sizes can also be measured by any of the other well-l:nown methods. e.g., wet sieving (non-aqueous), sedimentation. light scattering. etc. A convenient instrument that can be used to determine the particle size distribution of the dry complex powder directly (without having to make a liquid suspension or dispersion) is the Malvem Particle and Droplet Sizer, Model 2600C, sold by Malvem Instruments, Inc., Southborough, Massachusetts. Some caution should be observed in that some of the dry particles may remain agglomerated. The presence of agglomerates can be further determined by microscopic analysis. Some other suitable methods for particle size analysis are described in the article "Selecting a particle size analyzer: Factors to consider," by Michael Pohl, published in Powder and Bulk Engineering, Volume 4 (1990), pp. 26-29, incorporated herein by reference. It is recognized that the very small particles can readily aggregate to form loose agglomerates that are easily broken apart by either some mechanical action or by the action of water. Accordingly, particles should be measured after they are broken apart, e.g., by agitation or sonication. The method, of course, should be selected to accommodate the particle size and maintain the integrity of the complex particles, with iterative measurements being made if the original method selected proves to be inappropriate.

The blooming perfume compositions added to the detergent products herein as perfume particles may also be protected by incorporating them into matrix perfume microcapsules. Water-soluble cellular matrix perfume microcapsules are solid particles containing the blooming perfume ingredients stably held in the cells. The water-soluble matrix material comprises mainly polysaccharide and polyhydroxy compounds. The polysaccharides are preferably higher polysaccharides of the nonsweet, colloidally-soluble types, such as natural gums, e.g., gum arabic, starch derivatives, dextrinized and hydrolyzed starches, and the like. The polyhydroxy compounds are preferably alcohols, plant-type sugars, lactones, monoethers, and acetals. The cellular matrix microcapsules useful in the present invention are prepared by, e.g., (I) forming an aqueous phase of the polysaccharide and polyhydroxy compound in proper proportions, with added emulsifier if necessary or desirable; (2) emulsifying the blooming perfume compositions in the aqueous phase; and (3) removing moisture while the mass is plastic or flowable, e.g., by spray drying droplets of the emulsion. The matrix materials and process details are disclosed in. e.g., U.S. Pat. No. 3,971,852, Brenner et al., issued July27, 1976, which is incorporated herein by reference.

Moisture-activated perfume microcapsules can be obtained commercially, e.g., as IN-CAPt) from Polak's Frutal Works, Inc., Middletown, New York; and as Optilok System g) encapsulated perfumes from Encapsulated Technology, Inc., Nyack, New York.

The particulate hand dishwashing detergent compositions of this invention will preferably comprise of from 0% to about 6%, preferably from about 0.2% to about 4%. more preferably from about 0.4% to about 2% of water-activated matrix perfume microcapsules. Water-soluble matrix perfume microcapsules preferably have size of from about 0.5 micron to about 300 microns, more preferably from about 1 micron to about 200 microns, most preferably from about 2 microns to about 100 microns.

Optional Ingredients Optional ingredients which may be incorporated in the particulate hand dish cleaning compositions of the present invention include, but are not limited to, the following: The detergent compositions of the present invention may optionally contain a chlorine bleach material which provides from about 0.003% to about 4% available chlorine based on the weight of the composition, preferably from about 0.01% to about 2%, more preferably from about 0.05% to about 1%, more preferably still from about 0.1% to about 0.5%.

Methods for determining "available chlorine" of compositions incorporating chlorine bleach materials are well known in the art. Available chlorine is the chlorine which can be liberated by acidification of an aqueous solution of hypochiorite ions (or a material that can form hypochlorite ions in aqueous solution) and at least a molar equivalent amount of chloride ions. Numerous materials are known which provide available chlorine.

A conventional analvtical method for determining available chlorine is by addition of an excess of an iodide salt and titration of the liberated free iodine with a reducing agent. such as sodium thiosulfate. Samples of the detergent compositions are typically dissolved in a water-chloroform mixture to extract any interfering organics. prior to analyzing for available chlorine. An aqueous solution containing about 1% of the subject composition is used to determine available chlorine of the composition.

Many chlorine bleach materials are known, such as disclosed in Mizuno. W.G., "Dishwashing", Detergencv: Theorv and Test Methods, Surfactant Science Series. Volume 5. Part III. pages 872-878. Chlorine bleach materials useful in the subject invention compositions include alkali metal hypochlorites, hypochlorite addition products. and N-chloro compounds usually containing an organic radical. N-chloro compounds are usually characterized by a double bond on the atom adjacent to a trivalent nitrogen and a chlorine (Cl+) attached to the nitrogen which is readily exchanges with H+ or M+ (where Mt is a common metal ion such as Na+. I(-. etc.). so as to release HOCI or OCI- on hvdrolvsis.

Preferred alkali metal hypochorite compounds useful in the detergent compositions herein include sodium hypochlorite. potassium hypochlorite, and lithium hypochlorite. Although known as chlorine bleach materials. alkaline earth metal hypochlorites. such as calcium hypochlorite and magnesium hypochlorite, are not preferred for the present compositions due to poor compatibility of the alkaline earth metal cations with the anionic surfactants.

A preferred hypochlorite addition product useful in the detergent compositions of this invention is chlorinated trisodium phosphate which is a crystalline hydrated double salt of trisodium phosphate and sodium hypochlorite, which is prepared by crystallizing from an aqueous blend of sodium hypochlorite, castic soda, trisodium phosphate, and disodium phosphate. Chlorinated trisodium phosphate is typically commercially available as chlorinated trisodium phosphate dodecahydrate.

Examples of N-chloro compounds useful as chlorine bleach materials in the subject compositions include trichlorolisocyanuric acid, dichloroisocynauric acid, monochloroisocyanuric acid, 1,3-dichloro-5,5-dimethylhydantoin, 1-chloro-5,5- dimethylhydantoin, N-chlorosuccinimide, N-chlorosulfamate, N-chloro-p- nitroacetanilide, N-chioro-o-nitroacetanilide, N-chloro-m-nitroacetanilide, N-mdichloroacetanilide, N-p-dichloroacetanilide, Dichlorarnine-T, N-chloropropionanilide, N-chlorobutyranilide, N-chloroacetanilide, N-o-dichloroacetanilide, N-chloro-p-acetotoluide, N-chloro-m-acetotoluide, N-chloroformanilide, N-chloroo-acetotoluide, Chloramine-T, ammonia monochloramine, albuniinoid chloramines, N-chlorosulfamide, Chloramine B, Dichloramine B, Di-Halo (bromochlorodimethylhydantoin), N,N'-dichlorobenzoylene urea, p-toluene sulfodichloroamide, trichloromelamine, N-chloroammeline, dichloroazodicarbonamide, N-chloroacetyl urea, N,N'-dichlorobiuret, chlorinated dicyandiamide, and alkali metal salts of the above acids, and stable hydrates of the above compounds.

Particularly preferred chlorine bleach materials useful in the detergent compositions herein are chloroisocynanuric acids and alkali metal salts thereof, preferably potassium. and especially sodium salts thereof. Examples of such compounds include trichloroisocyananuric acid, dichloroisocyanuric acid, sodium dichloroisocyanurate. potassium dichloroisocyanurate, and trichloro-potassium dichloroisocynanurate complex. The most preferred chlorine bleach material is sodium dichloroisocyanurate; the dihydrate of this material is particularly preferred due to its excellent stability.

The compositions of the present invention may also comprise, as an optional builder. from 0% to about 30% alkali metal carbonate. preferably sodium carbonate.

preferably from about 5% to about 20%.

The compositions of the present invention may also comprise from 0% to about 98% filler materials such as sodium sulfate, sodium chloride, sucrose, sucrose esters. etc.. preferably from about 5% to about 75%, also preferably from about 10% to about 60%. more preferably from about 20% to about 50%. The preferred filler material is sodium sulfate.

The compositions of the present invention may also comprise from 0% to about 2% antiredeposition materials such as carboxymethylcellulose, polyethyleneglycol, polyvinylpyrrolidone, poivvinylalchols, etc., preferably from about 0.5% to about 1%. Carboxymethylcellulose is the preferred antiredeposition material.

The compositions of the present invention may also comprise from 0% to about 5% minor ingredients including, but not limited to, brighteners, dyes, etc., preferably from about 0.5% to about 2%.

The compositions of the subject invention comprise from 0% to about 10% moisture, preferably from about 1% to about 8%. more preferably from about 3% to about 7%.

Process for Preparation/Method of Use The dry particulate compositions of the present invention can be made by a variety of processes. including dry blending of particulate ingredients and addition of liquid ingredients by spraying on and blending in. Preferred processes for making the detergent compositions herein are well-known processes for making spray-dried detergent products. Typically, surfactant is blended with builders, filler materials, other non-volatile and non-heat sensitive components. and sufficient water to form a slurry which is spray-dried using a standard tower operation. To the dry particulate product thus produced is added the chlorine bleach material and minors via dry blending, spray on, or a combination thereof.

Other preferred processes for making the detergent compositions herein are processes for making agglomerated materials in various mixers. Suitable mixers include high-speed. high-shear mixers such as the Loedige CUB8, the Shugi Granulator. and the Drais K-TTP(!). and moderate-speed mixers including plowshare mixers, such as the Loedige Kh48 and the Drais K-Tt). The dry components of the subject compositions are ted to such mixers and intimately mixed. Liquid components can be sprayed into such mixers and be mixed with the dry components therein. or can be sprayed on the mixtures after discharge from the mixer. preferably with an additional blending step.

The present invention also involves methods of cleaning cooking or eating utensils by washing them bv hand in an aqueous solution or dispersion of cleaning compositions of the tepe herein described. In fact. for the hand dishwashing methods herein, the stashing solution can be formed from a composition containing onlv 1% of an anionic surfactant and from about 0.005% to 3% of one or more blooming perfume ingredients. Preferred solutions or dispersions of the compositions herein for cleaning cooking or eating utensils are aqueous-based comprising from about 1% to about 8%, preferably from about 2% to about 6%, of the compositions hereinbefore described, and the balance water.

Examples The following non-limiting examples exemplify perfume compositions, moisture-activated perfume particles and detergent compositions using such perfumes and perfume particles.

The following perfume compositions are prepared: PERFUME A - Citrus Floral Type Perfume Ingredients Wt.% Blooming Ingredients Citral 4 Citronellol 5 Citronellyl Nitrile 3 para Cymene 2 Decyl Aldehyde 1 Dihydro Myrcenol 15 Geranyl Nitrile 3 alpha-Ionone 2 Linalyl Acetate 5 gamma-Methyl Ionone 3 Myrcene 1.5 Orange Terpenes 15 beta-Pinene 3 Delayed Blooming Ingredients Anisic Aldehyde 1 beta gamma Hexenol 0.3 cis-3-Hexenyl Acetate 0.2 cis-Jasmone 1 Linalool 8 Nerol 3 alpha-Terpineol 4 Other Ingredients Amyl Salicylate 1 Hexyl Cinnamic Aldehyde 5 Hexyl Salicylate 3 P.T. Bucinal 5 Patchouli 1 Phenyl Hexanol 5 Total 100 PERFUME B - Rose Floral Type Perfume Ingredients Wt.% Blooming Ingredients Citronellol 15 Citronellyl Nitrile 3 Decyl Aldehyde 1 Dihydro Myrcenol 5 Dimethyl Octanol 5 Diphenyl Oxide 1 Geranyl Acetate 3 Geranyl Formate 3 alpha-lonone 3 Isobomyl Acetate 4 gamma-Methyl Ionone 4 P. T. Bucinal 10 Delaved Blooming Ingredients Geraniol 7 Phenyi Ethyl Alcohol 15 Terpineol 5 Other Ingredients Aurantiol 3 Benzophenone 3 Hexyl Cinnamic Aldehyde Total 100 PERFUME C - Natural Lime Type Perfume Ingredients Wt.% Blooming Ingredients Camphene 1 Caryophyllene 1 para-C'rnene 1 Geranyl Acetate 2 d-Limonene 49 Myrcene alpha-Pinene 1.5 beta-Pinene 2 Terpinolene 20 Delayed Blooming Ingredients Eucalyptol 1.5 Fenchyl alcohol 1 Linalool 3 Terpinene4-ol 2 Terpineol 10 Other Ingredients Bisabolene Total 100 PERFUME D - Natural Lemon Type Perfume Ingredients Wt.% Blooming Ingredients Citral 4 Frutene 15 d-Limonene 50 Linalyl Acetate 6 alpha-Pinene 4 beta-Pinene 3 Other Ingredients Methyl Dihydrojasmonate Total 100 PERFUME E - Fruity Lemon Type Perfume Ingredients Wt.% Blooming Ingredients Dihydro Myrcenol 1 Dihydro Terpineol 2.5 para-Cyrnene 0.5 Isononvl Alcohol 0.5 Tetrahvdro Linalool 45 Tetrahvdro Mvrcenol 44 Verdox 1 Delaved Blooming Ingredients Camphor gum 0.5 Dimethyl Benzyl Carbinol 1 Eucalypto I Fenchyl Alcohol 1.5 Other Ingredients Dimethyl 1.5 Total 100 PERFUME F - Citrus Lime Type Perfume Ingredients Wt.% Blooming Ingredients Citral 3 Citronellyl Nitrile 2 Decyl Aldehyde 0.5 Dihydro Myrcinol 10 Frutene S Geranyl Nitrile 3 Linalyl Acetate 5 Octyl Aldehyde 0.5 Orange Terpenes 30 para-Cymene 1.5 Phenyl Hexanol 5 alpha-Pinene 2.5 Terpinyl Acetate 2 Tetrahydro Linalool 3 Verdox 1 Delaved Blooming Ingredients Benzyl Propionate 2 Eucalyptol 2 Fenchyl Alcohol 0.5 Flor Acetate 7 beta gamma Hexenol 0.5 Linalool 7 alpha-Terpineol 2 Other Ingredients Methyl Dihydro Jasmonate Total 100 PERFUME G - Fruity Lemon (Bleach Stable) Perfume Ingredients Wt.% Blooming Ingredients Dihydro Myrcenol 1 Dihydro Terpineol 2.5 para-Cvmene 0.5 Isononvl Alcohol 0.5 Tetrahydro Linalool 45 Tetrahvdro Mvrcenol 44 Verdox 1 Delaved Blooming Ingredients Camphor gum Eucalyptol 1 Fenchyl Alcohol 1.5 Other Ingredients Dimetol U Total 100 Following are non-limiting examples of moisture-activated encapsulated perfumes, e.g., cyclodextrin/perfume inclusion complexes and matrix perfume microcapsules, that can be incorporated into the compositions of this invention.

Cvclodextrinmerfume Complex.

A mobile slurry is prepared by mixing about 1 Kg of beta-cyclodextrin and about 1 liter of water in a stainless steel mixing bowl of a Kitchen Aid mixer using a plastic coated heavy-duty mixing blade. Mixing is continued while about 175 g of the perfume is slowly added. The liquid-like slurry immediately starts to thicken and becomes a creamy paste. Stirring is continued for about 30 minutes. About 0.5 liter of water is then added to the paste and blended well. Stirring is resumed for about an additional 30 minutes. During this time the complex again thickens, although not to the same degree as before the additional water is added. The resulting creamy complex is spread in a thin layer on a tray and allowed to air dry.

This produces about 1.1 keg of granular solid which is ground to a fine powder.

Matrix Perfume Microcapsules.

An example of water-activated matrix perfume microcapsules is made according to Example 1 of U.S. Pat No. 3,971,852, except that a blooming perfume composition is used instead of orange oil.

Using the blooming perfume compositions and/or encapsulated blooming perfume compositions. as described hereinbefore. the following dry particulate hand dish detergent compositions are prepared: Example 1

Ingredient Weight Percent LAS 25 Sodium triphosphate 40 Sodium silicate (ratio 1.6) 7.5 Perfume A 1.2 Sodium sulfate 18 Carboxymethylcellulose 1 Moisture balance Example 2

Ingredient Weight Percent LAS 20 Sodium tripolyphosphate 15 Sodium silicate (ratio 2.0) 10 Perfilme B 0.8 Sodium sulfate 30 Sodium carbonate 20 Moisture balance Example3

Ingredient Weight LPerat Coconut fatty alcohol sulfate 24 Sodium tripolyphosphate 20 Sodium silicate (ratio 1.6) 3 Chlorinated trisodium phosphate 5 Sodium carbonate 15 Sodium sulfate 28 Perfilme G 0.8 Moisture balance Example 4

Ingredient 7 WeightPerceet LAS 28 Sodium tripolyphosphate 5 Sodium silicate (ratio 2.35) 14 Sodium dichloroisocyanurate dihydrate 0.5 Sodium sulfate 45 Perfume C 0.6 Moisture balance Example 5

Ingredient Weight Percent LAS 25 Sodium tripolyphosphate 10 Sodium silicate (ratio 2.0) 6 Sodium dichloroisocyanurate 0.3 Sodium sulfate 43

Sodium carbonate 10 Perfume G 0.7 Moisture balance Example6

Ingredient Weight Percent ABS 18 Sodium tripolyphosphate 15 Sodium silicate (ratio 2.0) Perfume D 1 Sodium carbonate 9 Sodium sulphate 45 Moisture balance Example 7

Ingredient Weight Percent ABS 18 Sodium tripolyphosphate 15 Sodium silicate (ratio 2.0) 8 Perfume 1 Sodium carbonate 9 Sodium sulphate 45 Perfilme G 0.8 Moisture balance Example 8

Ingredient Weight Perecit LAS 24 Sodium triphosphate 38 Sodium silicate (ratio 1.6) 8 beta-Cyclodextrin/Perfume C complex 6 powder Sodium sulfate 17 Carboxymethylcellulose I Moisture balance Example 9

Ingredient | Weight Percent LAS 20 Sodium tripolyphosphate 14 Sodium silicate (ratio 2.0) 10 Perfume A 0.4 beta-Cyclodextrin/Perfume C complex 4 -, powder Sodium sulfate 28 Sodium carbonate 19 Moisture balance Example 10

Ingredient Weight Percent Coconut fatty alcohol sulfate 23 Sodium tripolyphosphate 20 Sodium silicate (ratio 1.6) 3 Chlorinated trisodium phosphate 5 Sodium carbonate 14 Sodium sulfate 26 Perfume G 0.4 beta-Cyclodextrin/Perfume E complex 4 powder Moisture balance Example 11

Ingredient Weight Percent LAS 28 Sodium tripolyphosphate 5 Sodium silicate (ratio 2.35) 14 Sodium dichloroisocyanurate dihydrate 0.5 Sodium sulfate 45 beta-Cyclodextrin/Perfume F complex 6 powder Moisture balance Example 12

Ingredient Weight Percent LAS 25 Sodium tripolyphosphate 10 Sodium silicate (ratio 2.0) 6 Sodium dichioroisocyanurate 0.3 Sodium sulfate 42 Sodium carbonate 10 Matrix microcapsules of Perfume F 1.4 Moisture balance Example 13

Ingredient Weigtt Percent ABS 18 Sodium tripolyphosphate 15 Sodium silicate (ratio 2.0) 8 Perfume A 0.5 Matrix microcapsules of Perfume E 1 Sodium carbonate 9 Sodium sulphate 45 Moisture balance Example 14

Ingredient Weit Percent ABS 18 Sodium tripolyphosphate 15 Sodium silicate (ratio 2.0) 8 Perfume 1 Sodium carbonate 9 Sodium sulphate 45 Perfume E 0.3 Matrix microcapsules of Perfume B 1.2 Moisture balance Example 15

Ingredient Weight Percent LAS 28 Sodium tripolyphosphate 5

Sodium silicate (ratio 1.6) 13.2 Perfume A 0.6 Sodium Sulfate 47.4 Moisture 5.5 Misc. 0.3 In the composition of Example 15, Perfume A can be replaced by Perfume C, Perfume F, or Perfume G.

While particular embodiments of the subject invention have been described, it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. It is intended to cover, in the appended claims, all such modifications that are within the scope ofthis invention.

Claims (10)

CLAIMS:

1. A perfumed, dry particulate detergent composition useful for hand washing eating and cooking utensils, which composition comprises: (a) at least 1%, preferably at least 18%, by weight of an anionic surfactant; (b) from 0.5% to 3% by weight of a blooming perfume composition that contains at least five different blooming perfume ingredients, each of which ingredients has a boiling point of 260"C or lower and a calculated logl0 of its octanol/water partition coefficient, P, of 3 or higher, with the proviso that when said blooming perfume composition is present as part of a cyclodextrin/perfume complex, the particles of said complex are less than 12 microns in size; (c) optionally a chlorine bleach material which provides from 0% to 4% available chlorine; (d) from 0% to 10% moisture; and (e) a remainder being all components of the composition other than (a) through (d), the remainder comprising at least 80%, preferably at least 90%, solid materials selected from builders, fillers, and mixtures thereof.

2. A perfumed, dry particulate detergent composition useful for hand washing eating and cooking utensils, which composition comprises: (a) at least 1% by weight of an anionic surfactant; (b) at least 1 % by weight of a phosphorous-containing builder; (c) from 1% to 20% by weight of a silicate builder: and (d) from 0.5% to 3% by weight of a blooming perfume composition that contains at least five different blooming perfume ingredients. each of which ingredients has a boiling point of 260"C or lower and a calculated log10 of its octanol/water partition coefficient. P, of 3 or higher, with the proviso that when said blooming perfume composition is present as part of a cyclodextriivperfume complex. the particles of said complex are less than 12 microns in size.

3. A perfumed, particulate detergent and bleach composition useful for hand washing eating and cooking utensils, which composition comprises: (a) at least 18% by weight of an anionic surfactant; (b) from 0.5% to 3% by weight of a blooming perfume composition that contains i) at least four different blooming perfume ingredients, each of which ingredients has a boiling point of 260"C or lower and a calculated loglO of its octanol/water partition coefficient, P, of 3 or higher; and ii) at least two different delayed blooming perfume ingredients, each of which ingredients has a boiling point of 260"C or lower and a logl0 of its octanol/water partition coefficient, P, of less than 3; with the proviso that when said blooming perfume composition is present as part of a cyclodextrinlperfume complex, the particles of said complex are less than 12 microns in size; (c) optionally a chlorine bleach material which provides from 0% to 4% available chlorine; (d) from 0% to 10% moisture; and (e) a remainder being all components of the composition other than (a) through (d), the remainder comprising at least 80%, preferably at least 90%, solid materials selected from builders, fillers, and mixtures thereof.

4. A perfumed, dry particulate detergent composition useful for hand washing eating and cooking utensils, which composition comprises: (a) from 10% to 40% by weight of an anionic surfactant selected from alkylbenzene sulfonates, alkyl sulfates and alkylpolyethoxylate sulfates; (b) from 2% to 40% by weight of a phosphorous-containing builder selected from trisodium phosphate. tetrasodium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate; (c) from 5% to 15% by weight of a silicate builder having an SiO2:Na2O ratio offrom 1.6:1 to 3.2:1; and (d) from 0.1% to 2% of a blooming perfume composition that contains at least five blooming perfume ingredients selected from the perfume materials set forth in Table 1 in the specification, with the proviso that when said blooming perfume composition is present as part of a cyclodextrin/perfume complex, the particles of said complex are less than 12 microns in size.

5. A perfumed, dry particulate detergent composition useful for hand washing eating and cooking utensils, which composition comprises: (a) from 10% to 40% by weight of an anionic surfactant selected from alkylbenzene sulfonates, alkyl sulfates and alkylpolyethoxylate sulfates; (b) from 2% to 40% by weight of a phosphorous-containing builder selected from trisodium phosphate, tetrasodium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate; (c) from 5% to 15% by weight of a silicate builder having an SiO2:Na2O ratio of from 1.6:1 to 3.2:1; and (d) from 0.1% to 2% of a blooming perfume composition that contains i) at least four blooming perfume ingredients selected from the perfume materials set forth in Table 1 of the specification; and ii) at least two delayed blooming perfume ingredients selected from the perfume materials set forth in Table 2 of the specification; with the proviso that when said blooming perfume composition is present as part of a cyclodextrin/perfume complex, the particles of said complex are less than 12 microns in size.

6. A composition according to any of Claims 1-5 wherein (a) the blooming perfume composition comprises at least 8 different blooming perfume ingredients; (b) each of the blooming perfume ingredients used in the blooming perfume compositions has a boiling point of 250"C or lower and a log1o of its octanol/water partition coefficient. P, of 3.2 or higher; and (c) the blooming perfume composition comprises at least 50% by weight of said blooming perfume composition of said blooming perfume ingredients.

7. A composition according to any of Claims 1-6 wherein said blooming perfiune composition is incorporated into said detergent composition in the form of moisture-activated, encapsulated perfume particles, preferably said moisture activated, encapsulated perfume particles being in the form of cyciodextrin/perfume complexes or water-soluble cellular matrix perfume microcapsules.

8. A composition according to any of Claims 1-7 wherein (a) the blooming perfume composition also comprises at least three different delayed blooming perfume ingredients; and (b) the weight ratio of blooming perfimie ingredients to delayed blooming perfume ingredients is at least 1.

9. A composition according to any of Claims 1-8 which additionally contains a chlorine bleach material which provides from 0.05% to 1% available chlorine.

10. A method for hand washing eating and cooking utensils using a perfumed dishwashing detergent composition, which method comprises manually contacting the utensils to be washed with an aqueous washing solution formed from a perfumed particulate detergent composition of any of Claims 1-9.