AU9053891A - Granular detergent or bleaching compositions containing amidoperoxyacid bleach and perfume - Google Patents

Description

GRANULAR DETERGENT OR BLEACHING COMPOSITIONS CONTAINING AMIDOPEROXYACID BLEACH AND PERFUME

TECHNICAL FIELD This invention relates to granular detergent or bleaching compositions containing amidoperoxyacid bleach and selected perfume ingredients which have improved stability when in direct contact with the bleach. Preferably, a complete perfume containing the stable perfume ingredients is sprayed directly onto the granular detergent or bleaching composition containing the amidoperoxyacid bleach. The compositions are preferably used for cleaning laundry, but can also be used for cleaning or bleaching hard surfaces.

BACKGROUND OF THE INVENTION Perfumes are a desirable part of the laundry process. They are used to cover up the chemical odors of the cleaning ingre¬ dients and provide an aesthetic benefit to the wash process and, preferably, the cleaned fabrics. Perfumes are often added directly to laundry compositions, such as by spraying the perfume onto finished compositions. However, perfumes are, in general, volatile and many perfume ingredients can be destroyed or damaged by contact with cleaning ingredients, especially alkali and bleaches. To minimize direct contact between perfume and bleach components in laundry compositions, bleaches are sometimes admixed after perfume spray-on. Even this does not avoid oxidation of perfumes by bleaches, particularly when reactive bleaches such as peroxyacids are present, at least partly because of perfume mobility in granular detergent compositions.

One solution to this incompatibility problem is encapsulation of the perfume. This increases the expense and complexity of formulation and does not always provide sufficient protection.

European Patent Application 332,259, published September 13, 1989, discloses granular detergent or bleaching compositions containing peroxyacid bleach, including amidoperoxyacids, and perfumed silica particles which separate and protect the perfume from oxidation by the bleach.

U.S. Patents 4,634,551, Burns et al , issued January 6, 1987, 4,686,063, Burns, issued August 11, 1987, and 4,909,953, Sadlowski et al, issued March 20, 1990, disclose amidoperoxyacid bleaches useful in the present invention. These compositions can include other ingredients such as perfumes, but no specific perfume ingredients are mentioned.

U.S. Patent 4,023,631, Sims et al, issued May 8, 1990, discloses bleach and/or detergent compositions containing peracid bleach and perfume ingredients which do not contain alkenyl or ^•alkynyl groups and have peracid stability values of at least 65%.

Despite the above disclosures in the art, there is a continuing need for the development or identification of perfumes suitable for use in granular detergent or bleaching compositions containing amidoperoxyacid bleaches and which have improved stability when in direct contact with such bleaches.

SUMMARY OF THE INVENTION

The present invention relates to granular detergent or bleaching compositions comprising, by weight:

(a) from about 1% to about 75% of an amidoperoxyacid bleach of the formula:

R1-NH-C-R2-C-00H or R1-C-NH-R2-C-00H

II I! II II

0 0 0 0 wherein Rl is an alkyl group containing from about 6 to about 12 carbon atoms and R2 is an alkylene group containing from 1 to about 6 carbon atoms, and

(b) from about 0.1% to about 2% of a perfume comprising at least about 60% by weight of perfume ingredients selected from the group consisting of amyl salicy!ate, anisaldehyde, benzyl salicylate, butyl cinnamic aldehyde, citronellol, cyclohexyl salicylate, eugenol , Exaltex, tricyclodecenyl acetate, geraniol, Herbavert, ionone beta, ionone gamma methyl, keone, methyl cedrylone, Methyl cyclogeraniate, rose oxide DL, patchouli, phenyl ethyl alcohol, terpineol, Tonalid, Undecavertol, vanillin, Ylang Oliffac 765, Ambretone, Linacsol, Methanyl acetate T, Methyl sandeflor, Trepanol, Dihydroterpineol T, Grisalva, Mayol, Ambrox coeur, Parmantheme, coumarin, LRG 201, paramethoxy ' acetophenone, musk ketone, Galaxolide 50, tricyclo decenyl proprionate, Traseolide 70, Sinocitryl, dimethyl octanol, musk xylol, Cash eran, Clonal, Ca ekol DH, Sandalore, Rhubafuran V-9042, Cero el 3, Marenil (N), Corps rhubarb, clove oil, phenyl ethyl acetate, -^Q tonkalactone, Exaltolide, iso jasmone, a brettolide,

Dihydrofloralol, cedar english, Nardorosol, fenchyl alcohol, B napthyl methyl ether, and tridecene-2-nitrile; wherein said perfume is in direct contact with said

15 amidoperoxyacid bleach.

DETAILED DESCRIPTION OF THE INVENTION The granular detergent or bleaching compositions of the present invention comprise amidoperoxyacid bleach and selected perfume ingredients which have improved stability when in direct 0 contact with the bleach, such as happens when a complete perfume containing the stable perfume ingredients is sprayed directly onto the composition containing the bleach or prior to the addition of the bleach. In addition to improved perfume stability, the present compositions have improved amidoperoxyacid bleach ⁵ stability due to the low reactivity with perfume ingredients.

The granular detergent or bleaching compositions of the present invention comprise from about 1% to about 75%, preferably from about 2% to about 60%, more preferably from about 3% to about 50%, by weight of an amidoperoxyacid bleach of the formula ⁰ Rl - NH - C - R2 - C - 00H or R1-C-NH-R2-C-00H

II II II II o o o o wherein Rl is an alkyl group containing from about 6 to about 12 carbon atoms, and R is an alkylene containing from 1 to about 6 ^ carbon atoms. Preferably, R¹ is an alkyl group containing from about 8 to about 10 carbon atoms, and R is an alkylene group containing from about 2 to about 4. Bleach granules for use by themselves or as an additive for granular detergent compositions preferably contain from about 20% to about 70%, more preferably from about 30% to about 60%, by weight of the amidoperoxyacid bleach. Fully formulated granular detergents preferably contain from about 2% to about 10%, more preferably from about 3% to about 6%, by weight of the amidoperoxyacid bleach.

A preferred amidoperoxyacid herein is the monononyl^ ide of p_eroxysuccinic acid ("NAPSA"). Most preferred is the mononony- lamide of βeroxyadipic acid ("NAPAA"). Another name for NAPAA is 6-(nonyl mino)-6-oxo-caproic acid. The chemical formula for NAPAA is:

H O 0 i I II

CH3(CH2)δN C (CH2)4C00H The molecular weight of NAPAA is 287.4.

Example I of U.S. Patent 4,686,063 contains a description of the synthesis of NAPSA, from column 8, line 40 to Column 9, line 5, and NAPAA, from column 9, line 15 to column 9, line 65. At the end of the .amidoperoxyacid synthesis, the reaction is quenched with water, filtered, washed with water to remove some excess sulfuric acid (or other strong acid with which the peroxyacid was made), and filtered again.

The amidoperoxyacid wet cake thus obtained is contacted with a phosphate buffer solution at a pH between about 3.5 and 6, preferably between about 4 and 5. It has been found that if the pH of the amidoperoxyacid wet cake is raised too high, the amidoperoxyacid is dissolved, but if the pH is too low, the amidoperoxyacid is unstable. Without meaning to be bound by theory, it is believed that to stabilize the amidoperoxyacid, the strong acidity remaining from the sulfuric acid (or other strong acid) with which the peroxyacid is made must be neutralized without at the same time destroying the weak acid which is the peroxyacid. A buffer accomplishes this purpose. It has been determined that phosphate buffer, but not acetate or water washing, stabilizes the amidoperoxyacid. Since water washing to the same pH does not achieve the same effect as the phosphate buffer wash, it is theorized that some of the phosphate remains in the wet cake after contact with the phosphate buffer, which also helps storage stability. This is further borne out by the fact that phosphate buffer washing followed by water washing results in the peroxyacid having less stability than phosphate buffer washing alone.

The phosphate buffer is preferably orthophosphate or pyrophosphate in a concentration range of from about 0.01 M (moles/liter) to about 1 M. Most preferred is a 0.10 M solution of orthophosphates. These can be selected from the group consisting of H3PO4 (phosphoric acid), NaH2Pθ4 (monobasic sodium phosphate), Na2HPθ4 (dibasic sodium phosphate), and Na3P04 (tribasic sodium phosphate), so that the final solution has a pH of between about 3.5 and 6, preferably between about 4 and 5. Other salts such as potassium can be employed. Examples of phosphate buffer solution compositions can be found in Buffers for pH and Metal Ion Control by D.D. Perrin and Boyd Dempsey (Chapman & Hall, 1974).

There are several ways that the amidoperoxyacid can be contacted with the phosphate buffer solution. Preferably, the amidoperoxyacid wet cake is placed in enough of the phosphate buffer to cover it, and the combination is slowly stirred for a period of time sufficient to assure thorough contact with the wet cake. Approximately one hour for 20.0 g of wet cake in 400 ml of phosphate buffer (0.10 M, pH=4.75), for example, is an appropriate amount of time. Suction filtration is then preferably applied to remove the solution. The wet cake can then be air dried overnight. Conceivably, less phosphate buffer solution of a stronger concentration could be used. A 0.1 M phosphate buffer solution is preferred since it provides more volume and, when mixed with the wet cake, thorough contact and easier stirring, than, for example, a 0.5 M solution.

Another preferred way of contacting the wet cake with the buffer is to pour the buffer over the wet cake and then apply vacuum filtration. In a plant, the filtered wet cake could be placed on a fluid bed for final drying before it is incorporated into the final detergent composition or bleaching agent.

The phosphate buffer wash should be done before the amidoperoxyacid has decomposed. The product has decomposed when there is so little amidoperoxyacid remaining that it is no longer an effective bleach. The activity of the amidoperoxyacid can be measured by the available oxygen. Generally, the higher the AvO is, the better the peroxyacid will bleach.

Other agents for storage stabilization or exotherm control can be added to the amidoperoxyacid before incorporation into the final product. For example, boric acid, an exotherm control agent disclosed in U.S. Patent 4,686,063, Burns, issued August 11, 1987 and incorporated herein, can be mixed with the amidoperoxyacid (which has been washed in phosphate buffer) in about a 2:1 peracid:boric acid ratio. The phosphate buffer washed amidoperoxyacid can also be mixed with appropriate amounts of dipicolinic acid and tetrasodium pyrophosphate,^' a chelating stabilization system.

It is preferred that the phosphate buffer washed amidoperoxyacid be formed into granules, dried, and used either separately or as part of a granular detergent composition. The granules can be comprised of from about 1% to about 75% of the phosphate buffer washed amidoperoxyacid, preferably from about 20% to about 70%, more preferably from about 30% to about 60% of NAPSA or NAPAA; from 0% to about 25% of an exotherm control agent, preferably from about 5% to about 15% of boric acid if present; from 0 to about 10% of Cπ-13 linear alkylbenzene sulfonate or Ci4_i5 alkyl sulfate, preferably from about 2% to about 7% of Cll-13 linear alkylbenzene sulfonate; from about 20% to about 70%, preferably from about 30% to about 60%, sulfate; and from 0 to about 20% of a chelating agent, preferably from about 0.02% to about. 0.10% tetrasodium pyrophosphate and from about 0.05% to about 0.20% of dipicolinic acid if present.

Chelants can optionally be included in the phosphate buffer before contact with the wet cake. Without wishing to be bound by theory, it is believed that adding the chelants in this way improves their effectiveness by more evenly distributing the chelants throughout the wet cake.

Examples of suitable chelants for use herein are: carboxylates, such as ethylene diamine tetraacetate (EDTA) and diethylene triamine pentaacetate (DTPA); polyphosphates, such as sodium acid pyrophosphate (SAPP), tetrasodium pyrophosphate (TSPP), and sodium tripolyphosphate (STPP) ; phosphonates, such as ethylhydroxydiphosphonate (Dequest^® 2010) and other sequestering agents sold under the Dequest^® trade name; and combinations of the above. Other sequestering agents for use herein are dipicolinic acid, picolinic acid, and 8-hydroxyquinoline, and combinations thereof.

The amidoperoxyacid herein can be used in a granular detergent composition or in a separate granular bleaching composition. It is more preferred that the amidoperoxyacid be incorporated into a granular laundry detergent composition. It is most preferred that the amidoperoxyacid be NAPSA or NAPAA and be formed into granules (after the phosphate buffer wash and drying) which are then incorporated into a granular laundry detergent composition.

Particulary preferred herein are bleach granules comprising three ingredients: NAPAA, bleach-stable surfactant, and a hydratable, NAPAA-compatible material.

NAPAA can be prepared by, for example, first reacting NAAA

( onononyl amide of adipic acid), sulfuric acid, and hydrogen peroxide. The reaction product is quenched by addition to ice water followed by filtration, washing with distilled water, and final suction filtration to recover the wet cake. Washing can be continued until the pH of the filtrate is neutral.

Small particle size NAPAA agglomerates are desired herein to increase the amount of effective bleach which is in the wash solution and thereby improve bleaching/cleaning of fabrics in the wash. This is particularly useful in a hard water wash, i.e. wash water with more than about 6 grains of hardness, because hardness, specifically calcium ions, has been seen to interfere with available oxygen (AvO) from NAPAA with larger particle size. While not meaning to be bound by theory, it is believed that the calcium ions in the hard water surround large NAPAA particles, i.e. greater than about 300 microns, and interfere with the dissolution of the NAPAA, and that the smaller (about 0.1-260 microns) NAPAA particles dissolve rapidly in the wash water with minimal interference from the hardness ions. Small NAPAA particles are preferably recovered by quenching in water with high shear applied, e.g. rapid stirring, during addition of the NAPAA solution to water. Other known means of achieving small particle size may be used as appropriate. The NAPAA is then rinsed with water to remove excess sulfuric acid. The average particle size of the NAPAA herein is 0.1 to 260 microns and is in large part a function of the amount of shear applied. Even better solubility in harder water can be achieved, though, with a NAPAA average particle size of between about 1 and 160 microns. The average particle size is preferably from about 5 to 100 microns, and most preferably from about 5 to about 40 microns. It is believed that the present smaller particle size would improve NAPAA solubility in most aqueous applications in addition to a laundry application. It is surprising that a benefit in hard water is seen even where these small NAPAA particles are incorporated into a larger bleach granule. These bleach granules are added to a bleaching composition or detergent composition which is added to the wash water in a laundering application. NAPAA filter cake herein is preferably washed twice in phosphate buffer. It has been found that two successive phosphate buffer, washes lend optimal stability to NAPAA. It is also highly preferred that the NAPAA pH (10% solids in water) be between about 4.2 and 4.75. Surprisingly, this pH results in more thermally stable particles.

The bleach granules of this invention also include from about 1 to 40 weight % bleach-stable detergent surfactant selected from the group consisting of anionics, nonionics, zwitterionics and ampholytics and combinations thereof. From about 2 to 25 weight % bleach-stable detergent surfactant is preferred and about 2 to 7 weight % is most preferred. Anionic surfactant is preferred and salts of Cπ-13 linear alkyl benzene sulfonate and/or C12-I6 alkyl sulfate are more preferred. Sodium Cχ2-13 linear alkyl benzene sulfonate is most preferred.

Detergent surfactants useful herein are listed in U.S. Patents 3,664,961, Norris, issued May 23, 1972, and 3,919,678, Laughlin et al , issued December 30, 1975, both incorporated herein by reference. The following are representative examples of detergent surfactants useful in the present compositions.

Water-soluble salts of the higher fatty acids, i.e., "soaps", are useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.

Useful anionic surfactants also 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 10 to about.20 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 this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (Cg-Cis carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383. Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C11-13LAS.

Other anionic surfactants herein are the sodium alkyl glyceryl 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 alkyl phenol ethylene oxide- ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.

Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxyalkane-l-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin and paraffin sulfonates containing from about 12 to 20 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.

Water-soluble nonionic surfactants are also useful in the compositions of the invention. Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 15 carbon atoms, in either a straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of al yl phenol .

Preferred nonionics are the water-soluble and water-dispersible condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to 15 carbon atoms with from about 4 to 8 moles of ethylene oxide per mole of alcohol .

Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and two moieties selected from the group of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms; water-soluble phosphi.ne oxides containing one alkyl moiety of about 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl. and hydroxyalkyl moieties of from about 1 to 3 carbon atoms. Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.

Zwitterionic surfactants include derivatives of aliphatic, quaternary, ammonium, phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms.

The bleach granules herein also comprise from about 10 to 95 weight % hydratable, NAPAA-compatible material. The material preferably has a pH below about 8.0, most preferably below about 7.0. These can be selected from the group consisting of sodium sulfate, sodium acetate, sodium perborate, sodium phosphate, sodium acid phosphite, lithium formate, lithium sulfate, zinc nitrate, and combinations thereof.

Preferred are sodium sulfate (most preferred) and hydratable phosphate, e.g. the monobasic salt of phosphate. It is also preferred that the bleach granules comprise from about 20 to 70, most preferably 30 to 50, weight % of the above hydratable, NAPAA-compatible material. Materials to be avoided contain heavy metals such as iron and ha!ides.

The approximate hydration temperatures of some of these materials are given below:

Sodium acetate 136*F

Sodium phosphate 94

Sodium perborate 104

Sodium acid phosphite 108

Sodium sulfate 90

These hydratable materials are useful in processing the bleach granules of this invention and they add integrity to the final bleach granule. An appropriate method for forming these bleach granules is described in U.S. Patent 4,091,544, Hutchins, issued May 30, 1978, incorporated herein. That process involves allowing the mixture to be formed into spherical particles, flakes, ribbons or other desired configuration. The chosen forms are then cooled to a temperature sufficiently low so that the hydratable material is hydrated. To remove the unwanted waters of hydration and free water the material is heated to a temperature which allows the water to be driven off but will not cause the forms to soften and stick together. This process allows for the elimination of the need for further size reduction and the associated dust. Other known methods of forming granules or agglomerates may be used as appropriate. An additional surprising discovery is that boric acid, an exotherm control agent, should not be added to the NAPAA before addition to the bleach granule if improved thermal stability is desired. It was found in U.S. Patent 4,686,063, Burns, issued August 11, 1987, incorporated herein, that peroxygen bleaching compounds can be stabilized by addition of exotherm control agents, particularly boric acid. When the present NAPAA-contain- ing bleach granules are incorporated in a granular detergent composition, leaving out boric acid results in improved thermal stability when compared to the same granules containing boric acid. This difference in stability is marked in bleach granules comprising about 25 weight % NAPAA. It is therefore preferred herein not to include boric acid in the NAPAA bleach granules.

It has also been found that the present bleach granules are stable in detergent compositions even without the addition of chelants (other than the residual phosphate which may remain from the preferred buffer wash). Chelants are known to combine with metal ions present and thus help to prevent decomposition of peroxyacids which* can be catalyzed by heavy metals. Chelants have been described in, for example, U.S. Patent 4,909,953, Sadlowski et al, issued March 20, 1990, incorporated herein. Examples of such chelants, which are optionally not included herein, are: carboxylates, such as ethylene diamine tetraacetate (EDTA) and diethylene triamine pentaacetate (DTPA); polyphosphates, such as sodium acid pyrophosphate (SAPP), tetrasodium pyrophosphate (TSPP), and sodium tripolyphosphate (STPP); phosphonates, such as ethylhydroxydiphosphonate (Dequest^® 2010) and other sequestering agents sold under the Dequest® trade name; dipicolinic acid, picolinic acid, and 8-hydroxyqu noline, and combinations thereof.

The bleach granules herein are effective bleaching agents and are stable in solution and in product, expecially in preferred form, i.e. without boric acid or additional chelants, and where

NAPAA has been phosphate buffer washed and brought to a pH between about 3.5 and 6 before addition to the bleach granule. Perfume Ingredients

The compositions of the-present invention also comprise from about 0.1% to about 2%, preferably from about 0.2% to about 1%, preferably from about 0.25% to about 0.75%, by weight of a perfume comprising at least about 60% by weight of perfume ingredients selected from the group consisting of amyl salicylate, anisaldehyde, benzyl salicylate, butyl cinnamic aldehyde, citronellol, cyclohexyl salicylate, eugenol , Exaltex, tricyclo- decenyl acetate, geraniol, Herbavert, ionone beta, ionone gamma methyl, keone, methyl cedrylone, Methyl cyclogeraniate, rose oxide DL, patchouli, phenyl ethyl alcohol, terpineol, Tonalid, Unde- cavertol, vanillin, Ylang Oliffac 765, Ambretone, Linacsol, Methanyl acetate T, Methyl sandeflor, Trepanol , Dihydroterpineol T, Grisalva, Mayol , Ambrox coeur, Parmantheme, coumarin, LRG 201, paramethoxy acetophenone, musk ketone, Galaxolide 50, tricyclo decenyl proprionate, Traseolide 70, Sinocitryl, dimethyl octanol, musk xylol, Cashmeran, Clonal, Camekol DH, Sandalore, Rhubafuran V-9042, Ceromel.3, Marenil (N), Corps rhubarb, clove oil, phenyl ethyl acetate, tonka!actone, Exaltolide, iso jas one, a bret- tolide, Dihydrofloralol, cedar english, Nardorosol, fenchyl alcohol, B napthyl methyl ether, and tridecene-2-nitrile. The above perfume ingredients have a stability grade of 7B or higher after three months, as described in Example I.

Particularly preferred perfumes herein comprise at least about 60% by weight of perfume ingredients selected from the group consisting of a yl salicylate, anisaldehyde, benzyl salicylate, cyclohexyl salicylate, eugenol, Exaltex, Herbavert, ionone beta, keone, Methyl cyclogeraniate, Tonalid, vanillin, Ylang Oliffac 765, Linacsol, Trepanol , Dihydroterpineol T, Mayol, A brox coeur, Parmantheme, LRG 201, paramethoxy acetophenone, musk ketone^', Galaxolide 50, Sinocitryl, dimethyl octanol, musk xylol, Cash eran, Clonal, Camekol DH, Rhubafuran V-9042, Marenil (N), tonkalactone, iso jasmone, Dihydrofloralol, Nardorosol, fenchyl alcohol, B napthyl methyl ether, and tridecene-2-nitrile. These ingredients have a stability grade of 8B or higher after three months, as described in Example I.

Of the above, particularly preferred perfume ingredients include Exaltex, Methyl cyclogeraniate, vanillin, Ylang Oliffac 765, Trepanol, Ambrox coeur, paramethoxy acetophenone, Sinocitryl, Clonal, Camekol DH, iso jasmone, Dihydrofloralol, Nardorosol, fenchyl alcohol, and tridecene-2-nitrile. These ingredients have a stability grade of 9B or higher after three months. ^'

Preferred perfume ingredients for use herein are those having a stability grade of 7B or higher after six months, as described in Example I. These include amyl salicylate, anisaldehyde, benzyl salicylate, citronellol, cyclohexyl salicylate, eugenol, Exaltex, ionone beta, methyl cedrylone, patchouli, Tonalid, vanillin, Trepanol, Grisalva, Ambrox coeur, Parmantheme, coumarin, LRG 201, paramethoxy acetophenone, musk ketone, Galaxolide 50, Traseolide 70, Sinocitryl, musk xylol, Clonal, Sandalore, Marenil (N), clove oil, Exaltolide, iso jasmone, Nardorosol, fenchyl alcohol, B napthyl methyl ether, and tridecene-2-nitrile.

Of the above, the more preferred ingredients have a stability grade of 8B or higher after six months. These include benzyl salicylate, cyclohexyl salicylate, ionone beta, vanillin, Ambrox coeur, LRG 201, paramethoxy acetophenone, musk ketone, Sinocitryl, Marenil (N), Nardorosol, fenchyl alcohol, and tridecene-2-nitrile.

The most preferred ingredients have a stability grade of 9B or higher after six months. These are vanillin, paramethoxy acetophenone, Sinocitryl, and tridecene-2-nitrile.

Other particularly preferred perfume materials herein are those which are generally considered unstable in the presence of peroxyacid bleaches, yet have stability grades of 7B or higher after three months, as reported in Example I. These include amyl salicylate, benzyl salicylate, citronellol, eugenol, tricyclodecenyl acetate, methyl cedrylone, and tricyclo decenyl propionate.

Particularly perfumes herein comprise at least about 65%, preferably at least about 70%, and more preferably at least about 75% by weight of the above stable perfume ingredients.

The bleach granules herein are preferably included in a granular detergent composition or bleaching composition. The preferred granular detergent composition comprises from about 2 to 50, preferably about 5 to 25, weight % bleach granules according to the above description, from about 5 to 50 weight % detergent surfactant, which is described above, and from about 10 to 60 weight % detergency builder. The bleaching composition preferably comprises from about 10 to 100 weight % of the present bleach granules.

Water-soluble inorganic or organic electrolytes are suitable detergency builders. The builder can also be water-insoluble calcium ion exchange materials; non-limiting examples of suitable water-soluble, inorganic detergent builders include: alkali metal carbonates, borates, phosphates, bicarbonates and silicates. Specific examples of such salts include sodium and potassium tetraborates, bicarbonates, carbonates, orthophosphates, pyrophosphates, tripolyphosphates and metaphosphates. Examples of suitable organic alkaline detergency builders include: (1) water-soluble amino carboxylates and aminopolyacetates, for example, nitrilotriacetates, glycinates, ethylenediaminetetraacetates, N-(2-hydroxyethyl)nitri1odiacetates and diethylenetriaminepentaacetates; (2) water-soluble salts of phytic acid, for example, sodium and potassium phytates; (3) water-soluble polyphosphonates, including sodium, potassium and lithium salts of ethane-1-hydroxy-l, 1-diphosphonic acid; sodium, potassium, and lithium salts of ethylene diphosphonic acid; and the like; (4) water-soluble polycarboxylates such as the salts of lactic acid, succinic acid, malonic acid, aleic acid, citric acid, carboxymethyloxysuccinic acid, tartrate mono- and disuccinates (ether linked), oxydisuccinate, 2-oxa-l,l,3-propane tricarboxylic acid, 1,1,3,2-ethane, tetracarboxylic acid mellitic acid and pyromellitic acid; (5) water-soluble polyacetals as disclosed in U.S. Patents 4,144,266 and 4,246,495, incorporated herein by reference; and (6) the water-soluble tartrate monosuccinates and disuccinates and mixtures thereof, disclosed in U.S. Patent 4,663,071, Bush et al, issued May 5, 1987, incorporated herein by reference.

Another type of detergency builder material useful in the present compositions comprises a water-soluble material capable of forming a water-soluble reaction product with water hardness cations preferably in combination with a crystallization seed which is capable of providing growth sites for said reaction product. Such "seeded builder" compositions are fully disclosed in British Patent Specification No. 1,424,406.

A further class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates, particularly those described in U.S. Patent 4,605,509, issued August 12, 1986, incorporated herein by reference. The detergent compositions of this invention can contain all of the usual components of detergent compositions including the ingredients set forth in U.S. Patent 3,936,537, Baskerville et al , incorporated herein by reference. Such components include color speckles, suds boosters, suds suppressors, antitarnish and/or anticorrosion agents, soil-suspending agents, soil-release agents, dyes, fillers, optical brighteners, germicides, alkalinity sources, hydrotropes, antioxidants, enzymes, enzyme stabilizing agents, etc. A more complete disclosure of suitable enzymes can be found in U.S. Patent 4,101,457, Place et al, issued July 18, 1978, incorporated herein by reference.

The following nonlinviting examples illustrate the process and compositions of the present invention.

All parts, percentages and ratios herein are by weight unless otherwise specified.

EXAMPLE I A freshly-prepared sample of NAPAA wet cake, which typically consists of about 60% water, about 2% peroxyacid available oxygen (AvO) (corresponding to about 36% NAPAA), and the rest (about 4%) unreacted starting material, is obtained. This wet cake is the crude reaction product of NAAA (monon nyl amide of adipic a_^cid), sulfuric acid, and hydrogen peroxide which is subsequently quenched by addition to water followed by filtration, washing with distilled water, phosphate buffer washing and final suction filtration to recover the wet cake. A portion of the wet cake is air-dried at room temperature to obtain a dry sample which typically consists of about 5% AvO (corresponding about to 90% NAPAA) and about 10% unreacted starting material. When dry, the sample pH is about 4.5. The average amide peroxyacid particle (agglomerate) size is about 90-100 microns and the median particle size is about 40-50 microns, as determined by Malvern particle size analysis. NAPAA granules are prepared by mixing about 51.7 parts of the dried NAPAA wet cake (containing about 10% unreacted), about 11.1 parts of sodium C12.3 linear alkyl benzene sulfonate (LAS) paste (45% active), about 43.3 parts of sodium sulfate, and about 30 parts of water in a Cuisiπart mixer. After drying, the granules (which contain about 47% NAPAA) are sized by passing through a No. 14 Tyler mesh sieve and retaining all particles not passing through a No. 65 Tyler mesh.

The bleach granules are then admixed with a granular detergent to provide a finished bleach-containing detergent composition having the following Composition A. Similar bleach granules made containing about 50% NAPAA and 40% sulfate are admixed with a granular detergent to provide the following Composition B.

Weight %

Components

Sodium C1 .3 linear alkyl benzene sulfonate

Sodium C1 -15 alkyl sulfate

Zeolite A

Sodium carbonate

Sodium silicate (1.6)

Bleach granules

Sodium perborate monohydrate

Protease

Sodium diethylenetriamine pentaacetate

Citric acid

Polyethylene glycol 8000

Sodium polyacrylate (4500 .wt.)

Moisture

Sodium sulfate, misc. & minors Balance

Perfume ingredients are evaluated for stability when in direct contact with the above unperfumed detergent compositions

(ingredients tested with Composition B are noted by *, the other ingredients are tested with Composition A), using the following method.

(1) 25g of the unperfumed detergent composition containing NAPAA is weighed into a 12 oz capacity wax-laminated cardboard cup. (2) 0.075g (+ 0.005g) of perfume ingredient is dropped onto the product from a disposable pipette to give a perfume level of _.0.3% (+ 0.02%). Solid perfume ingredients are first diluted to a 10% solution in diethyl phthalate (an odorless perfume solvent). The solution is then added to the product at a level of 3% (+0.2%) so that the perfume ingredient is present at 0.3% (+.0.02%).

(3) The cup is then capped and shaken vigorously for ten to fifteen seconds.

(4) After storage at room temperature for 3 months and 6 months, the samples are evaluated by an expert perfumer using the following scales for perfume intensity and character. Perfume Intensity Scale

1 = there is no perfume

2,3 = I think there is no perfume

4,5 = I think there is perfume

6 = there is perfume

7,8,9= there is a strong perfume (where 9 = the strongest)

Perfume Character Scale

A - indistinguishable from fresh perfume character as applied to product B = slightly different from fresh perfume chracter C = obviously changed from fresh perfume character, but still usable D - different from fresh perfume character, not usable. The results are as follows.

eugenol 8B tricyclodecenyl acetate 7B

Herbavert (Henkel) 8A ionone beta 8B

Irisantheme 6B keone 8B methyl cedrylone 7B rose oxide (DL) 7B nerol 6C Methyl cyclogeraniate

(Firmenich) 9B terpineol 7B trichloro methyl phenyl carbinyl acetate 6A

Ylang Oliffac 765 (IFF) 9C

Trepanol (Takasago) 9A

Linacsol ethyl ether (") 6C

Methyl sandeflor (") 7B

Li onene methyl ether (") 6B

Dihydroterpineol T (") 8A

Mayol (Firmenich) 8B

Ambrox coeur (") 9A cou arin 7B moskene 6B

^♦musk ketone 8A ^♦tricyclo decenyl

^♦proprionate 7A

^♦Sinocitryl (Quest) 9B

^♦musk xylol 8A

^♦Clonal (IFF) 9A

^♦Camekol DH (IFF) 9A

^♦Jasmolactone (Firmenich) 6B

^♦Ceromel 3 (Givaudan) 7B ^♦Corps rhubarb (Firmenich)7A ^♦phenyl ethyl acetate 7A

^♦Exaltolide (Firmenich) 7B

^♦ambrettolide 7A

^♦cedar english 7A

^♦fenchyl alcohol 9A

^♦Lime oxide (Givaudan) 7C

^♦ele i oil 6C

^♦melisse 6C cis jasmone 5D

Dihydro rose oxide(FD&O) ID methyl benzoate 3D para cresyl methyl ether ID undecylenic aldehyde 4D

1-citronellal (Takasago) ID

1-citronellyl formate (") ID 1-citronellyl N butyrate (Takasago) 4D 1-citronellyl phenyl

1-citronellyl propionate (")4D acetate (Takasago) 3D

1-laurinal (Takasago) 3D verdox (2-tertiary butyl

P.T. butyl cyclohexyl cyclohexanyl acetate 4D acetate 4D Delphone (Firmenich) 4D labdanum clair 4D ^♦orivone 5C ^♦diphenyl oxide 4D ^♦Veloutone (Firmenich) 4D

^♦tetrahydromuguol 4D ^♦cymal 4D

^♦geranyl nitrile 4D ^♦Camek DH (IFF) 4D

^♦Piconia (IFF) 4D ^♦Mefrosal (Quest) 4D

^♦benzoin claire 50% 4D ^♦tetra hydro alloci en- ^♦fenchyl acetate 4D ^♦inol extra 4D

^♦αpinene 4D ^♦terpine T 4D

^♦terpinolene 4D EXAMPLE I I

A pefume composition of the present invention i s as fol l ows :

Ingredient Wt. % amyl sal icyl ate 3.00 benzyl sal icyl ate 15.00 cycl ohexyl sal icyl ate (Henkel ) 5.00

Gal axol ide 50% 15.00

LRG 201 (Roure) 0.50

Mayol (Firmenich) 10.00 methyl cedrylone 15.00 methyl cyclogeraniate (Firmenich) 0.50

Nardorosol (Quest) 10.00 paramethoxy acetophenone 0.50 phenyl ethyl alcohol 10.00

Tonalid (PFW) 10.00

Trepanol (Takasago) 0.50

Ylang Oliffac 765 (IFF) 5.00 Total 100.00

The above perfume composition, which contains 100% by weight of perfume ingredients having a stability grade of 7B or higher after three months and 75% by weight of ingredients having a stability grade of 8B or higher after three months, is sprayed directly onto the following granular detergent and bleaching composition of the present invention.

Components Weight %

Spray Dried Base Granules

Sodium C12.3 linear alkyl benzene sulfonate 19.60 Sodium C14-15 alkyl sulfate 5.90

Sodium tallow fatty acid 2.17

Sodium tartrate succinate^ 5.70

Sodium carbonate 10.49

Sodium polyacrylate/ aleate (70,000 .wt.) 3.33 Polyethylene glycol 8000 0.83

Sodium silicate (2.Or) 11.00

Sodium sulfate 14.40 Admix

Bleach granules according to Example I except con¬ taining about 35% NAPAA, 3.5% LAS and 58% sulfate and having an average partice size of about 5-40 microns . 8.80 Protease enzyme 1.25

Coconut alcohol polyethoxylate (6.5) 2.50

Perfume (spray on) 0.12

Zeolite A 5.00 ^'

Moisture + minors Balance * 80% monosuccinate, 20% disuccinate mixture according to U.S. Patent 4,663,071, Bush et al , issued May 5, 1987.

EXAMPLE III

The perfume composition of Example II is sprayed directly onto the following granular detergent and bleaching composition of the present invention.

Components Weight % Spray Dried Base Granules

Sodium C12.3 linear alkyl benzene sulfonate 7.34 Sodium C14-15 alkyl sulfate 7.34

Sodium tripolyphosphate 29.75

Sodium silicate (1.6r) 8.25

Sodium polyacrylate (4500 .wt.) 0.73

Sodium sulfate 8.28 12-I3 alcohol polyethoxylate (6.5T) 0.50

Polyethylene glycol 8000 0.30

Sodium diethylenetriamine pentaacetate 0.44

Sodium carbonate 0.47

Moisture 4.19 Miscel l aneous & minors Bal ance to 68.27 Admix

Sodium carbonate 17.94

Bleach granules from Example IB (50% NAPAA) except having an average particle size of about 5-40 microns 4.26

Sodium perborate monohydrate 0.69

Protease 0.63

Ci2-13 alcohol polyethoxylate (6.5T) (spray on) 0.25

Perfume (spray on) 0.30 Sodium sulfate Balance to 100

Claims (7)

WHAT IS CLAIMED IS:

1. A granular detergent or bleaching composition characterized in that it σcmprises, by weight:

(a) from 1% to 75% of an amidoperoxyacid bleach of the formula: R^NH-C^-C-OCH or R^X-<:-NH-R²-C-O0H

II II II II

O O 0 0 wherein R is an alkyl group containing frcm 6 to 12, preferably frcm 8 to 10, carbon atcms and R 2 i.s an alkylene group containing frcm 1 to

6, preferably frcm 2 to 4, carbon atoms, and

(b) frcm 0.1% to 2% of a perfume comprising at least 60%, preferably at least about 70%, by weight of perfume ingredients selected from the group consisting of a yl salicylate, anisaldehyde, benzyl salicylate, butyl cinnamic aldehyde, citronellol, cyclohexyl salicylate, eugenol, Exaltex, tricyclodecenyl acetate, geraniol, Herbavert, ionone beta, ionone gamma methyl, keone, methyl cedrylone, Methyl cyclogeraniate, rose oxide DL, patchouli, phenyl ethyl alcohol, terpineol, Tonalid, Uhdecavertol, vanillin, Ylang Oliffac 765, Ambretone, Linacsol, Methanyl acetate T, Methyl sandeflor, Trepanol, Dihydroterpineol T, Grisalva, Mayol, Ambrox coeur, Parmantheme, coumarin, IRG 201, paramethoxy acetophenone, musk ketone, Galaxolide 50, tricyclo decenyl proprionate, Traseolide 70, Sinocitryl, dimethyl octanol, musk xylol, Cashmeran, Clonal, Camekol CH, Sandalore, Rhubafuran V-9042, Cerσmel 3, Marenil (N) , Corps rhubarb, clove oil, phenyl ethyl acetate, torikalactone, Exaltolide, iso jasmone, ambrettolide, Dihydrofloralol, cedar english, Nardorosol, fenchyl alcohol, B napthyl methyl ether, and tridecene-2-nitrile; wherein said perfume is in direct contact with said amidoperoxyacid bleach.

2. A composition according to Claim 1 wherein the amidoperoxyacid bleach is the nonylamide of peroxyadipic acid ("NAPAA") .

3. A composition according to Claim 2 wherein the NAPAA is present in a bleach granule comprising:

(a) frcm 5 to 70 weight % NAPAA with an average particle size of frcm 0.1 to 260 microns;

(b) from 1 to 40 weight % bleach-stable surfactant selected frcm the group consisting of anionics, nonionics, ampholytics, zwitterionics and ccmbinations thereof; and

(c) frcm 10 to 95 weight % hydratable, NAPAA-compatible material.

4. A composition according to Claim 3 wherein the bleach granule consists essentially of:

(a) from 20 to 60 wei t % NAPAA with a average particle size of from 5 to 40 microns;

(b) from 2 to 7 wei t % sodium C₁₂_₁₃ linear alkyl benzene sulfonate; and

(c) frcm 30 to 50 weight % sodium sulfate.

5. A granular detergent composition comprising frcm 2 to 50 weight % bleach granules according to Claim 4, frcm 5 to 50 weight % detergent surfactant, and frcm 10 to 60 weight % detergency builder.

6. A composition according to any one of the preceding claims wherein the perfume ingredients are selected from the group consisting of amyl salicylate, anisaldehyde, benzyl salicylate, cyclohexyl salicylate, eugenol, Exaltex, Herbavert, ionone beta, keone, Methyl cyclogeraniate, Tonalid, vanillin, Ylang Oliffac 765, Linacsol, Trepanol, Dihydrσterpineol T, Mayol, Ambrox coeur, Parmantheme, IRG 201, paramethoxy acetophenone, musk ketone, Galaxolide 50, Sinocitryl, dimethyl octanol, musk xylol, Cashmeran, Clonal, Camekol DH, Rhubafuran V-9042, Iferenil (N) , torikalaσtcine, iso jasmone, Dihydrofloralol, Nardorosol, fenchyl alcohol, B napthyl methyl ether, and tridecene-2-nitrile.

7. A composition according to any one of the preceding claims wherein the perfume ingredients are selected frcm the group consisting of Exaltex, Methyl cyclogeraniate, vanillin, Ylang Oliffac 765, Trepanol, Ambrox coeur, paramethoxy acetc£4ιenαne, Sinocitryl, Clonal, Camekol EH, iso jasmone, Dihydrofloralol, Nardorosol, fenchyl alcohol, and tridecene-2-nitrile.