CA2096254C - Granular detergent or bleaching compositions containing amidoperoxyacid bleach and perfume - Google Patents

Abstract

Granular detergent or bleaching compositions, preferably for laundry use, containing amidoperoxyacid bleach and selected perfume ingredients having improved stability when in direct contact with the bleach.

Description

WO 92t08780 PCl /US91 /08206 2~9~2~
GRANULAR DETERGENT OR BLEACHING COMPOSITIONS
CONTAINING AMIDOPEROXYACID BLEACH AND PERFUME

TErHNICAL FIELD
This invention relates to granular detergent or bleaching compositions containing amidoporo(yacid bl3ach and selected perfume ingredients which have improved stability when in direct contact ~ith the bleach. Prererably, a complete perfume containing the stabl2 perfume ingredients is sprayed directly onto the granular detergent or bleaching composition containing the amidoperoxyacid bleaçn. The compositions are preferably used for cleaning laundry, bur can also oe used for cleaning or bleaching hard sur~aces.
BAC~G20UND OF ~E I~IYENTION
PerTumes are a desiraole part or the iaundry 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. EYen this does not avoid oxidation of ; 25 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 incomDatibility problem is encapsulation ' of the perfume. This increases the expense and complexity of formulation and does not always provide sufficient protection.
European Patent Application i32,259, published September 13, 1989, discloses granular detergent or bleaching compositions containing peroxyacid bleach, including amidoperoxyacids, and perfumed silica particles which seDarate and protect the perfume from oxidation by the bleach.
~ U.S. Patents 4,634,5il, Burns et al, issued January 6, 1987, ;, - ~ ' , . ;- . :
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~5~6~053, ~urns, issued August 11, 1987, and 4,909,953, Sadlowski et al, issued ,~arch 20, 1990, disclose amidoperoxyacid bleaches useful in thP prPsQnt in~/Pntion. These compositions can include olher ingredients such as perfumes, but no specific perfume .g~,~q~,~n~ 2,~q -r.~n~io~d.
S. Patent ~,023,531, Sims et al, issued May 8~ 1g90, discloses bl2ach and/or dec2rgent compositions containing peracid aleach an~ per,-u",e ingredien,s ~hich do not contain alkeliyl or a1kynyl qroups and h~ve peracid stability values of at least 6~%.
Despite the above disclosures in the art, there is a continuina need for the development or identification of perfumes -uitlble ~or us2 in granula, dete-rgent or bleaching compositions concaining 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-OOH or R1-C-NH-R2-C-OOH
, 11 11 11 11 .
' : . O O O O
~; wherein Rl is an alkyl group containing from about 6 to about 12 carbon atoms and R2 js 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 - leist 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, -tricyclodecenyl acetate, geraniol, Herbavert, '~ ionone beta, ionone gamma methyl, keone, methyl cedrylone. Methyl cyclogerania~2. rose oxide DL.
patchouli, phen~l ethyl alcohol, terpineol, Tonalid~
Undecavertol, vanillin. '~lang Oliffac 765, Ambretone.
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Linacsol, Methanyl acetate T, ~ethyl sandeflor, Trepanol, Dihydroterpineol T, Grisalva, Mayol, Ambrox coeur, ParmanthemP, coumarin, LRG 201, paramethoxy acetophenone, musk ketone, Gala~olide 50, tricyclo decenyl proprionate, Traseolide 70, Sinocitryl, dimethyl octanol, musk xylol, Cashmeran, Clonal, Camekol DH, Sandalore, Rhubafuran '/-90~2, Ceromel 3, Mar2nil (N), - Corps rhubarb, clove oil, ph2nyl eLhyl acetate, tonkalacton~, Exaltoliae. iso ~asmone, amore~tolide, Dihydrofloralol, cedar englis~ lardorosol, ;enchjl alcohol, B napthyl methyl e'cher, and - tridecene-2-nitril D;
wherein said perfume is in direct contact ~.lith said ~1 15 amidoperoxyacid bleach.
DETAILED DESCRIPTION OF THE INYENTION
The granular detergent or bleaching compositions of the present invention comprise amidoperoxyacid bleach and selected perfume ingredients which have improved stability when in direct 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 lmproved perfu,l,e stabil itj', the present compositions have improved amidoperoxyacid bleach 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 R1 - NH - C - R2 - C - OOH or R1-C-NH-R2-C-OOH
': 11 il ' 11 11 -:~ O ~O O O
.; , wherein Rl is an alkyl group containing from about 6 to about 12 ;~ : carbon atoms, and R2 is an alkylene containing from 1 to about 6 carbon atoms. Preferably, Rl i5 an alkyl group containing from .
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about 8 to about 10 carbon atoms. and R2 is an alkylene group containing from about 2 to about d. Bleach granules for use by themselves o. as an additiYe for granular detergPnt compositions S prereraoly contain ;rom about 20Jo to about 70%, more preferably From about 30% to about 60Y" by w~ight of the amidoparox~acid b1each. Fully ,~ormulated granular detergents preferably contain from about ~~,' to about 10~'~, more oreferably from about 3% to about ~ o.~ m~ ro,~:ic,d bl~ac~.
lO A p,e,-erred al,lidopeio,xyacid herein is the monononylamide of peroxysuccinlc acid (",~IAI'S~"). ,~ost ~re,~errA-d is the mononony-lamide of peroxyadipic acid ("NAP M "). Another name for NAP M is 6-~nonylamino)-6-oxo-caoroic acid. The chemical formula for NAPAA
i s :
H O ~
~ B 11 CH3(CH2)gN C (CH2)4COOH
The molecular weight of NAP M 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 NAPM , 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 strons acid with which the peroxyacid was made), and filtered again.
The amidoperox~acid 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 i. It has been found that if the pH of the amidoperoxyacid wet cake is raised too high, the 3~ 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 ~o 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 des~roylng the weak acid which is the .

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peroxyacid. A buffer accomplishes this puroose. It has been determined that phosphate buFfer, but not 2cetate or wator ~ashing, stabilizes the amidoperoxyacid. ~ince ~arer Jashing to the same pH does not achieve the same e,~fect as the phosphat2 buffer wash, it is theorized that some of ~he ?hosphat3 re!nains in the wet cake after contact wi-th the phospna~e burrer, whicn also helps storage stability. This is furtn2r ~orne out by he fac~
that phosphate buffer ~ashing follo~2d b~ ,wate,~ was,~ g r3sIJl s in the peroxyacid having less stability than pno.3nat2 ouf,~~r ~ashi,lg alone.
The phosphate buffer is preferably orthophosphate or pyrophosphate in a concentration range of From abollt 0 01 ?~
(moles/liter) to about 1 M. Most preferred i5 a 0.10 M solution of orthophosphates. These can be selected from the group consisting of H3P04 (phosphoric acid), NaH2P04 (monobasic sodium phosphate), Na2HP04 (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 S.
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 i & Hall, 197~).
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 9 of wet cake ir 400 ml o, 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 th2n bP air dried overnight. Conceivably, less phosphate buffer solution of a stronger concentration could be used. A 0.1 ~ phosphate buffer solution is preferred since it provides more volume and. when :'; ' , ~ ~ , . . . . .

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Anothor preFerred ~lay of concaccing the ~Yet cake ~ith the burfer is ~o pour 1~2 bu,re,~ over t~e wet cake and chen apply vacuum filtration. In a plant the fllt~red ~Yet cake could be placed dn a ,luid be~ ,-or i-inal drying oefore it is incorporated into the final detergent cc~pc~ltion or bl~achins ag?nt.
T~e ~hosphate ~u~ ei ias;l s,loul(i be done be;ore the ;~ 10 amidop~,oi~yacid llaS dec~mpose~. lilP product ilas decomposed when th re is so iittl2 ainidope,Aoxy2rid r maining thac it is no longer an effective bleach. The activity or the amidoperoxyacid can be measured by the a~/ailable oxy~lPn Gsnerally, the higher the AvO
is, the better the pero~acid ~ill 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 4,686,0~53, 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 ; diplcolinic arid and tetr3so~ium py,op~osphate, a chelating stabilization system.
It is preferred that the phosphate buffer washed amidoperoxyacid be rormed in,o granules, dried~ and used either ; separately or as part of a granular delersent composition. The granules can be comprised of rrom about 1% to about 75% of the phosphate bufier i~ashed amidoperoxyacid, preferably from about 20%
to about 70%, more preferably from about 30% to about 60% of NAPSA
or NAPM ; from 0% to about 25% of an exotherm control agent, preferably from about 5~' ~o absut 15% oi~ boric acid if present;
from 0 to about 10% of C11 13 linear alkylbenzene sulfonate or Cl~ l5 al~yl sulfat_. preferably from about 2% to about 7',' of Cll l3 linear alkylbenzene sulfonate; from about 20% to about 70%, , .

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preferably from about 30% to about 60%, sulfate; and from ~ to about 20% of a chelating agent, prQferably from about 0.02% co about 0.10% tetrasodium pyrophosphate and From about C.~% 'c~
about 0.20% of dipicolinic acid if present.
Chelants can optionally be included in the phos,hqta bll~,~er before contact with the ~et cake. Without wishing ro oe oound by theory, it is believed that adding the chelantc in ~hls ~ay improves their effecti~/Dness by more e~/Qnly dis;~ribucing l'-1J
chelants throughout the wet ca~e.
Examples of suitable chelants for use h~rein are:
carboxylates, such as ethylene diamine tetraacetate (EDTA) and diethylene triamine pentaacetate (OTPA~: polyphospha~~~~ surh ?.5 ' sodium acid pyrophosphate (SAPP), tetr2sodium pyro~ho,ph~ve '~ 15 (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 granulardetergent composition or in a separate granular bleaching i' composition. It' is more preferred that 'he amldope,ox~acid Le incorporated into a granular laundry detergént 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 d2~2rsent composition.
Particulary preferred herein are bleach granules comprising three ingredients: NAPAA, bleach-stable surfactant, and a hydratable, NAPAA~compatible material.
~'~ NAPM can be prepared by, '~or example, first reacting ,~A
(monononyl amide of adipic acid), sulfuric acid, and hydrogen peroxide. The reaction product is quenched by addition to ice ~ater followed by filtration, washing with distilled water, and ~,. : . . .
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W O 92/08780 PC~/~S91/Og206 2 0 9 ~ 2 ~ 4 final suction filtration to rero~/er the wet ca!~2. 'las,1ing can be continued until the p~ of the filtrate is neutr21.
Small particle size NAPAA anglomerates arq d?sirqd herein to increase the amount of erTecti~/e bleacn which is in the wash solution and thereby impro~/e bl~'e~ nJ/Cle-'.'li;''.~ 0~ '-b';'i~. i~l ~hq wash. This is partic~larlv use,~ul in a hard watsr wash7 i.e. wash ~: water with more than about S grains o,' hai-dnqsat bec~usa Itardness, specificall~Y calcium ions, h.ls h.qen ,een .o in,;-r;qrq wi h aYailable oxygen (A~/O) rrom NA~IA with larger particlq sizq.
While not meaning to be bound by theor~, it is oelie~/ed ~hac che calcium ions in the hard water surround large NAPAA particles.
i.e. greater than about 30~ m -.~on,. aild lt~ Jit.1 t,l dissolution of the NAPAA, and cnat the smaller (about 0.1-260 microns) NAPAA particles dissolve rapidly in the wash water with minimal interference from the hardness ions. Small NAP M
particles are preferably recovered by quenching in water with high shear applied, e.g. rapid stirring, during addition of the NAPAA
-solution to wat~r. Other known means of achieving small particle size may be used as appropriate. The NAP M 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 o~ shear applied. EYen better solusility ~in harder water can be achieved, though, with a NAP M average .~25 particle size of between about 1 and 160 microns. The aYerage particle size is preferably from about S to 100 microns, and most preferably from about S 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.

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WO 92/08781) PCI /US91 /08206 209~2~
g NAPM filter cake herein is preferably washed twice in phosphate buffer. It has been found that two successive phosphate buffer washes lend optimal stability to NAPM. It is also highly preferred that the NAPAA pH (10% solids in water) be between abaut 4.2 and 4.7~. Surprisingly, this pH results in more therma11y 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 ~/O
bleach-stable detergent surfactant is preferred and about 2 to 7 weight ~,' is most preferred. Anionic surfactant is preferrPd and salts of Cl1 I3 linear alkyl benzene sulfonate and~or C12 16 alkyl sulfate are more preferred. Sodium C12 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 . .

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:; , ~ ' ' : ' WO 92/08780 PCI/US~1/08206 salts, of organic sulfuric reaction products ha~/ing in their mo1ecular structure an alkyl group containing from abou-c 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid es,er group. (Included in the term "alkyl" is the alkyl portion OT acyl groups.) Examples of this group of synthetic ~UPlc~,7'-~ -~r~ t~
sodium and potassium alkyl sul;ates, especia71~/ tnose obcained by sulfating the higher alcohols (CR C1,q carbon atoms) âUC.l as t hose produced by reducing the glycerid2s of tallow or COCOnlJ; )il; and the sodium and potassium alkylbenzene sul,ona-ces in Inich the alkyl group contains from about 9 to abouc 1~ carbon a'o,ms, in straight chain or branched chain configuration, e.g , those o; the type described in U.S. Patents 2.220.09a and 2 177 3q3.
Especially valuable are linear straight chain alkylben7ene sulfonates in which the average number of carbon atoms in the alkyl group is from about 1I to 13, abbreviated as C11 13LAS.
Other anionic surfactants herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher i 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 I0 units of ethylene oxide per molecule and wherein tha alkyl s.oups contain f rum about i3 ~o 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 inclu~e the witer-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-1-sulfonic acids containiilg from about 2 to 9 carbon atoms in the acyl group and from about 9 , . , to about 23 carbon atoms in the alkane moiety; ~ater-soluble salts 35 of olefin and paraffin sulfonates containing from about 12 to 20 ' .

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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.
'~ater-soluble nonionic surfactants are also useful in the composi~ions of the invention. Such nonionic materials includP
compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compoundi whicn 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 ~nd hyd,o~hobic 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 1.5 carbon atoms, in either a straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alkyl 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 lO 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 phosphine 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 .

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WO 92/08780 PCr/US91/08206 2~3~;25ll sulfoxides containing one alkyl moiety of from about 10 to 1~
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 or alipnatic or aliphatic derivatives of heterocyclic secondar~ and terti1ry amines in which the aliphatic moiety can be siraighr chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at le st one al i~ ai;lr substituent contains an anionic water-solubilizing group.
Zwitterionic surfactants include derivatives or alipnatic, quaternary, ammonium, phosphonium. and sulfonium compounds in which one of the aliphatic substituents contains fr~m 7b~ut ~ to 18 carbon atoms.
The bleach granules herein also comprise from about 10 to 95 weight % hydratable, NAP M -compatible material. The material preferably has a pH below about 8.0, most preferably below about 7Ø 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 al o 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 halides.
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 go These hydratable materials are useful in processing the bleach granules of this invention and they add int~grity to the .

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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 i allo~ing ~he 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 w2ter the material is heated to a temperature ~uh,ch allows the "ater to be driven off but will not cause the '~ rorms ~Q ~often and stic~ 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.
15An 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 ll, 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 % ~APAA. It is therefore preferred herein not to include boric acid in the NAPM bleach granules.
It has also been found that the present bleach granules are stable in detergent compositions even without the addition of 3Q 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 ~; 35 ' .
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-, ' WO 92/087~0 PCl'/US91/08206 2~2~ 14 , et al, issued March 20, 1990, incorporated herein. Examples of such chelants, which are optionally not included herein, ar~:
carboxylates, such as ethylene diamine te~raacetat2 (EDTA) and diethylene triamine pentaacetate (DTPA); polyphospha'ces, SUC~l as sodium acid pyrophosphate (SAPP), tetrasodium pyrophosphate ; (TSPP), and sodium tripolyphosphate (STPP); phosphonates, such as ethylhydroxydiphosphonate (Dequest~ 2010) and other sequest~ring agents sold under the Dequest~ trade name; dipicolinic acid, picolinic acid, and 8-hydroxyquinoline, and combinations ther?of.
The bleach granules herein are eflective bleaching ag2nt; a,ld ar~ stable in solution and in product, expecially in preferred form, i.e. without boric acid or additional chelants, and where NAPM has been phosphate buffer washed and brought to a pH between about 3.5 and 6 before addition to the bleach granule.
Perfume Inqredients The compositions of the present invention also comprise from about 0.1% to about 2%, preferably from abou~ 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, - 30 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~ tonkalactone, Exaltolide, iso jasmone, ambret-tolide, Dihydrofloralol, cedar english, Nardorosol, fenchyl ,:.
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' 20~2~

alcchol, B napthyl methyl ether, and tridecene-2-nitrile. The above perrume ingredients have a stability grade of 7B or higher arter three months, as described in Example I.
Particularly prererred perfumes herein comprise at least about 60% by ~eight of perfume ingredients selected from the group consisting o,~ amyl salicylate, anisaldehyde, benzyl salicylate, cyclohexyl salicylate, eugenol, Exaltex, Herbavert, ionone beta, k~cne~ Meth~l cyclogeraniate, Tonalid, vanill;n, Ylang Oliffac 7~j, Linacsol~ Trepanol, Dihydrot2rpineol T, Mayol, Ambrox coeur, Parmanthem~, LRG 201, paramerhoxy acetophenone, musk ketone, Galaxolide 50, Sinocitryl, dimethyl octanol, musk xylol, Cashmeran~ Clonal, Camekol DH. Rhubafuran V-9042, Marenil (N~, ' tonkalactone, iso jasmone, Dihydrofloralol, Nardorosol, fenchyl ;~ 15 ~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 thé 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 tridecPne-2-nitrile. These ingredients have a stability grade of 9B or higher after three months.
Preferred perfume ingredients for use herein are those having Z5 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 ~'~ 35 grade of 8B or higher after six months. These include benzyl "

,. ~

; '' .

.. . . .
:
' :: -WO 92/08781~ PCr/US91/08206 20962~

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 ~ost preferred ingredients have a stability grade oF 9aor 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 or perovyacid bleach~s, yet have stability grades of 73 or hisher after three months, as reported in Example I. Th2se include amyl salicylate, benzyl salicylate, citronellol, eugenol, tricyclodecenyl acetate, methyl cedrylone. and tricyclo decenyl propionate.
Particularly perfumes herein comprise at least about 6i%, 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 SO, preferably about 5 to 25, weight ~~O bleach granules according '! to the above description, from about 5 to 50 weight % detergent ; sur~actant, 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 suitzble 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 nd metaphosphates.

:;

WO g2/0878~) PCI/US91/08206 - 17 - 2 ~ ~ 6 2 S ~
Examples of suitable organic alkaline detergency builders include~ ater-solubke amino carboxylates and aminopolyacetates, for e~ample, nitrilotriacetates, glycinates, etilylelled-,ami;lei~e~raacetat~is, N-(2-hydrox~ethyl)nitrilodiacetates and diethylenetriaminepentaacetates; (2) water-soluble salts of phytic acid, for example, sodium and potassium phytates; (3) water-sol UDl2 pol yphosphonates, including sodium, potassium and lithil!m salts of ethane-1-hydroxy-1, 1-diphosphonic acid; sodium, 0 pot?issium~ ~nd 1 ithium salts of ethylene diphosphonic acid; and t'na ,lke; ~ ater-soluble polyca,bo~ylates such as the salts of lactic acid, succinic acid, malonic acid, maleic acid, citric acid~ carDoxymethyloxysuccinic acid, ~artrate mono- and disuccinates (ether linked), oxydisuccinate, 2-oxa-1,1,3-propane ~ trlcarDo~yllc acld, 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 8ritish Patent Specification No. 1,424,406.
' A further class of detergency builder materials useful in the'~ 30 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 compositlons including the ingredients set forth in U.S. Patent 3,936,537, 3askerville et al, incorporated herein by reference. Such components include color speckles, ~uds .
.
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'' ' : - . ' , . ' ' . . . ',, '' . :' .

W o 92/08780 PCT/US9~/08206 '~ ~3 9 ~ 18 -'~ boosters, suds suppressors, antitarnish and/or anticorrosion agents, soil-suspending agents, soil-release agants, dyes, fillers, optical brighteners, germicides, al'~alinity sources, ,:d,-- ropos, antioxid3nts, enzymos~ enzyme stabi l i zi ng agen ~s, etc. A more complete disclosure of suitable enzymes can be found in U.S. Patent 4,101,457, Plac~ et al, issued July 13, 197i3, incorporated herein by reference.
The follo~wing nonlimiting examples illustrate the process and 0 com~ositions of the present invention.
All parts; porcentages and ratios herein are by ~leight unless other.~ise speciried.
EXAMPLE I
A fresnly-prepared sample of NAPM wet cake, which typically consists or 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 cak0 is the crude reactïon product of N M A (monononyl amide of adipic acid), 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~,' AYO (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 or sodium sulfate, and about 30 parts of water in a Cuisinart mixer. After drying, the granules (which contain about 47% NAPAA) are sized by passing through a No.

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W O 92/0878~ PC~r/US91/08206 - 19~ 2~ll 14 Tyler mesh sieve and retaining all particles nat passing through a No. 65 Tyler mesh.
ThQ bleach granules are then admixed with a granular detergenc :o pro~/ide a finished bleach-containing detergent compositicn having the following Composition A. Similar bleach ranules made containing about 50% NAPAA and 40% sulfate are adrnixed ~ith a granular detQrgent to provide the following Composition B.
Weioht %
ClmnonQnts A B
Sodium C12.3 linear al~yl benzene sulfonate11.64 11 98 Sodium C1~ 15 alkyl sul;ace 4.99 5.13 eolice A 23.37 23.96 Sodium carbonate 23.32 24.00 Sodium silicate (1.6) 2.5i 11.38 Bleach granules 8.58 6.74 Sodium perborate monohydrate - ' 0.76 Protease 1.00 0.45 Sodium diethylenetriamine pentaacetate - 0.60 Citric acid 3.00 ;'' Poiyethylene glycol 8000 1.25 Sodium polyacrylate (4500 m.wt.) 3.91 3.68 Mois-cure 6.22 6.84 Sodium sulfate, misc. & minors Balance Perfume ingredients are evaluated for stability ~hen 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) 259 of the unperfumed detergent composition containing NAPAA
is weighed into a 12 oz capacity wax-laminated cardboard cup.
:~

~ ~ ~ 35 :: '' : . , '' :
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W O g2/08780 PCT/~JS91/08206 ~ ~ {3 ~ 20 -(2) 0.075g (+ 0~0059) of perfume ingredient is dropped onto the product from a disposable pipette to give a perfume level of 0.3~,' (~ O.OZ%). Solid perfume ingredients are first di1uted ~o â 10~' solution in diethyl phthalate (an odorless perrume sol~/ent). The solution is then added to the product at a levei oF 3% (+0.~%) so that -the perfume ingr~dient is present ac 0.3% (+0.02%).
(3) Tlle cu~ is then capped and shaken Yigorously for ten to ~ Fi5te~n seconds.
(~) A;-~r storaye at room temperature ;or 3 months and 6 months, tne samples are evaluated by an expert perfumer using the ~; rollo~ing scales for perfume intensity and character.
Perrume Intensitv 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 8 = slightly different from fresh perfume chracter C = obviously changed from fresh perfume character, but still ~ 25 usable : D = different from fresh perfume character, not usable. ~ The results are as follows.
', 3 Month 3 Month Perfume Stability PerfumeStability 30 Inqredient Grade Inaredient Grade amyl sal~cylate 8B anisaldehyde 8B
benzyl propionate 6A benzyl salicylate 8B
butyl cinnamic aldehyd~ 7B citronellol 7A
cyclohexyl salicylate 8Adihydromyrcenol 6B

;:

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...
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.

2~9~cj~
~; - 21 -Dimetol (Gi~Jaudan) 6B eugenol 8B
Exaltex (F;rmenich) 9A tricyclodecenyl acetate 7B
geraniol 7C Herbavert (Henkel) 8A
H~yl cinnamic aldehyd2 6A ionone beta 8B
ionone gamma methyl 7A Irisantheme 6B
Iso c;cloyPraniol (Irr) oZ Iceone 8B
LRG 18~ (.~cure) 6C methyl cedrylone 7B
'' patchoul, 7B rose oxida (DL) 73 10 metn~l pilenyl caroill~l nerol 6C
acecate 63 llethyl cyclogeraniate ::~ phenyl ethyl alcohol 78 (Firmenich) 9B
Pivarose (Quest) 6B terpineol 7B
Tonalid (PF!~) 8A trichloro methyl phenyl ~- ~ 15 Undecavertol (Givaudan) 7A carbinyl acetate 6A
vanillin 9A Ylang Oliffac 765 (IFF) 9C
. Ambretone (Takasago) 7A Trepanol (Takasago) 9A
Linacsol (") 8A Linacsol ethyl ether (") 6C
Methanyl acetate T (") 7A Methyl sandeflor (n) 7B
20 Treflone ~") 6A Limonene methyl ether (") 6B
citronellyl tiglate (") 6A Dihydroterpineol T (") 8A
Grisalva (IFF) 7A Mayol (Firmenich) 8B
; ~ardia (FlrmPnich~ 6C Ambro~ coeur (") 9A
.
Parmantheme (Firmenich) 8B coumarin 7B
LRG 201 (Roure) 8A moskene 6B
'~ paramethoxy acetophenone 9A *musk ketone 8A
' *Galaxolide 50 (IFF) 8A ~tricyclo decenyl . *Cetylia base (Firmenich) 7C *proprionate 7A
*Traseolide 70 (Quest) 7A *Sinocitryl (Quest) 9B
: 30 *dimethyl octanol 8B *musk xylol 8A
*Cashmeran (IFF) 8A *Clonal (IFF) 9A
*Dihydrofloralate (IFF) 6A *Camekol DH (IFF) 9A
*Sandalore (Givaudan) 7B *Jasmolactone (Firmenich) 6B
~: *Rhubafuran V-9042 (Quest) 8A *Ceromel 3 (Givaudan) 7B
35 *Marenil (N) (Quest) 8A *Corps rhubarb (Firmenich)7A

' :

w o 92/08780 PCT/US91/08206 2 ~ ~

*clove oil 7B *phenyl ethyl acetate 7A
*ton~alactone 8B *Exaltolide tFirmenich) 78 *i S3 jasmone 9A -*ambrettolide 7A
~DillJdr'Qi~ oril3l (t.'-~ 98 ~cedar english 7A
- *Nardorosol (Quest) 9B *fenchyl alcohol 9A
~B napthyl methyl etner 8C *Lime oxide (Givaudan) 7C
*trid2cene~ itrilc~ 9A *elemi oil 6C
~phellandrene 7C *melisse 6C
10 b~n~ acetat? lD cis jasmone 5D
c3,iinde, 4D Dihydro rose oxide(FD~0) lD
Intreleven aldehydP (IFF) 4C methyl benzoate 3D
.~ melhyl chavicol lD para cresyl methyl ether lD
P.T. bucinal lD undecylenic aldehyde 4D
'",r~ citronellol (Takasago) lD 1-citronellal (Takasago) lD
~: 1-citronellyl acetate (") lD 1-citronellyl formate (") lD
:' l-citronellyl iso l-citronellyl N
butyrate (Takasago) 4D butyrate (Takasago) 4D
~:~ l-citronellyl nitrile (") 4D l-citronellyl phenyl 20 l-citronellyl propionate (")4D acetate (Takasago) 3D
l-laurinal (Takasago) ~D verdox (2-tertiary butyl ~ P.T. butyl cyclohexyl cyclohexanyl acetate 4D
acetate 4D Delphone (Firmenich) 4D
. labdanum clair 4D *orivone 5C
25 *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 allocimen-30 *fenchyl acetate 4D *inol extra ' 4D
: *~pinene 4D *terpine T 4D
- *terpinolene 4D
' .. ~
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~ ' ' WO 92/08780 PCl/US91/08206 ~$2~

:
~ Month 6 Month Perfum2 Stability PerfumeStability In~redi2nt Grade Tnaredienc Grad~
amyl salicylate 7B anisaldehyde 8C
benzyl salicylate 8B butyl cinnamic aldehyde 6C
citronellol 7A cyclohaxyl salic~late 8A
eugenol 7B E~altax (Firmenich) 7A
10 geraniol 5C Herbavert (Hankel~ 6A
ionone ~eta ~B Iso cyclcgeraniol (IFF) 5C
methyl cedrylone 7B patchouli 7B
phenyl ethyl alconol 6B Pivarose (Questj 6C
: Tonalid (PF~) 7A trichloro methyl phenyl 15 vanillin 9A carbinyl acetate 6A
Ambretone (Takasago) 6A Trepanol (Takasago) 7A
1-citronellyl tiglate (")6B Grisalva (IFF) 7A
Mayol (Firmenich) 6B . Ambrox coeur (Firmenich) 8A
: Parmantheme (") 7B coumarin 7B
.~ : 20 LRG 201 (Roure) 8B moskene 6B
~ paramethoxy acetophenone 9B *musk ketone 8A
: ~Galaxolide S0 (IFF) 7A *Cetylia base (Firmenich) 7C*Traseolide 70 (Quest) 7A *Sinocitryl (Quest) 9B
*dimethyl octanol 6B *musk xylol 7A
25 *Clonal (IFF) 7A *Sandalore (GiYaudan) 7B
: *Rhubafuran V-9042 (Quest)6C *C~romel 3 (") 63 *Marenil (N) (") 8A *Corps rhubarb(Firmenich)6C
*clove oil 7B . *phenyl ethyl acetate 6C
*tonkalactone 7C *Exaltolide (Firmenich) 7B
30 *iso:Jasmone 7B *ambrettolide- 6B
*cedar english 6C *Nardorosol (Quest) 8B
~: ~ *fenchyl alcohol 8A *B napthyl methyl ether 8C
*tridecene-2-nitrile 9A *elemi oil 6C
*phellandrene 7C *melisse 6C
: 35 ' , ~' ' ~: ' , ~ .
::

....

2~2~ll ': EXAMPlE II
A pefume composition of the present invention is as follows:

Inar?dient 'Ylt. %
amyl salicylate 3.00 beil,yl salicylace 15.00 CYC1OheAY1 salicylate (Henkel) S.00 '~ Gala~olide 60~,' 15.00 ," 10 L,~5 201 (~our~) 0'50 ayol (~irm,enich) 10.00 methyl cedrylone 15.00 ~:~ methyl cycloaoraniate (Firmenich) 0.50 ~ ardorosol (Que,~) 10.00 '~. 15 paramethoxy acetopnenone 0.50 '~ phenyl ethyl alcohol 10.00 :, Tonalid (PFW) 10.00 Trepanol (Takasago) O.S0 ' Ylang Oliffac 765 (IFF) 5.00 ., 20 Total100.00 ' 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.
ComDonentS Weiaht %
- SDrav Dried Base Grànules : : Sodium C12,3 linear alkyl,benzene sulfonate 19.60 Sodium C14 15 alkyl sulfate ' 5.90 :~ Sodium tallow fat'ty acid 2.17 : : Sodium tartrate succinate* 5.70 '~ Sodium carbonate 10.49 Sodium polyacrylate/maleate (70,000 m.wt.) 3.33 : 35 ~ ' .

.
.

~; , : 2~2~

Polyethylene glycol 8000 0.83 Sodium silicate (2.0r) 11.00 Sodium sulfate 14.40 5 Admi~
Bleach granules according to Example I except con-Laining about 35% NAPAA, 3.5~~O LAS and 53% sulfate and having an a~Jerage partice size oF about 5-40 microns 8.80 Protease en~yme 1.25 '~ Coconut alcohol poly-e LhO~yl ate ~ ~, 5 ) 2.50 Perfuma (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.
ComDonents Weiaht ~~O
S~raY Dried Base Granules '!iodium 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 m.wt.) 0.73 ~ Sodium sulfate 8.28 ; 30 C12 13 alcohol polyethoxylate (6.5T) 0.50 ~'~ Polyethylene glycol 8000 0.30 Sodium diethylenetriamine pentaacetate 0.44 Sodium carbonate 0.47 Moisture 4.19 Miscellaneous ~ minors8alance to 68.27 :
.. -'........... : - -:. :
' :
' : ~ .

WO 9~/08780 PCI/US91/08206 Admix Sodium carbonate 17.94 3le3ch granules from Example IB (50~~O NA?M) ~;oa~ 'la'Jing an a~/erag~ particle slze or about 5-40 microns 4 26 Sodium perborate monohydrate 0.69 ~rotease 0.63 : C!~ 13 alcohol polyetho~ylate (6.5T) (spray on) 0.25 Per,~ume !spray on) 0.30 :o Sodlum aul Cate Balance to 100 ., .

:
, :

.

:

:

Claims (17)

1. l. A granular detergent or bleaching composition comprising, by weight:
   (a) from about 1% to about 75% of an amidoperoxyacid bleach of the formula:
   or wherein R1 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 50% by weight of perfume ingredients selected from the group consisting or amyl 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, 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, Cashmeran, Clonal, Camekol DH, Sandalore, Rhubafuran V-9042, Ceromel 3, Marenil (N), Corps rhubarb, clove oil, phenyl ethyl acetate, tonkalactone, 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. 2. A composition according to Claim 1 wherein in the amidoperoxyacid bleach R1 is an alkyl group containing from about 8 to about 10 carbon atoms.
3. 3. A composition according to Claim 2 wherein in, the amidoperoxyacid bleach R2 is an alkylene group containing from 2 to 4 carbon atoms.
4. 4. A composition according to Claim 3 wherein the amidoperoxyacid bleach is the nonylamide of peroxyadipic acid ("NAPAA").
5. 5. A composition according to Claim 4 wherein the NAPAA is present in a bleach granule comprising:
   (a) from about 5 to 70 weight % NAPAA with an average particle size of from about 0.1 to 260 microns;
   (b) from about 1 to 40 weight % bleach-stable surfactant selected from the group consisting of anionics, nonionics, ampholytics, zwitterionics and combinations thereof; and (c) from about 10 to 95 weight % hydratable.
   NAPAA-compatible material.
6. 6. A composition according to Claim 5 wherein the bleach granule consists essentially of:
   (a) from 20 to 60 weight % NAPAA with a average particle size of from about 5 to 40 microns;
   (b) from 2 to 7 weight % sodium C12-13 linear alkyl benzene sulfonate; and (c) from 30 to 50 weight % sodium sulfate.
7. 7. A granular detergent composition comprising from about 2 to 50 weight % bleach granules according to Claim 6 from about 5 to 50 weight % detergent surfactant, and from about 10 to 60 weight %
   detergency builder.
8. 8. A composition according to Claim 7 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, Dihydroterpineol T, Mayol, Ambrox coeur, Parmantheme, LRG 201, paramethoxy acetophenone, musk ketone, Galaxolide 50, Sinocitryl, dimethyl octanol, musk xylol, Cashmeran. Clonal.
   Camekol DH, Rhubafuran V-9042. Marenil (N), tonkalactone, iso jasmone, Dihydrofloralol, Nardorosol, fenchyl alcohol, 3 napthyl methyl ether, and tridecene-2-nitrile.
9. 9. A composition according to Claim 8 wherein the perfume ingredients are selected from the group consisting of 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.
10. 10. A composition according to Claim 9 wherein the perfume comprises at least about 70% by weight of the perfume ingredients.
11. 11. A composition according to Claim 1 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, Dihydroterpineol T, Mayol, Ambrox coeur, Parmantheme.
    LRG 201, paramethoxy acetophenone. musk ketone, Galaxolide 50, Sinocitryl, dimethyl octanol, musk xylol, Cashmeran, Clonal, Camekol DH, Rhubafuran V-9042, Marenil (N), tonkalactone. iso jasmone, Dihydrofloralol, Nardorosol, fenchyl alcohol, B napthyl methyl ether, and tridecene-2-nitrile.
12. 12. A composition according to Claim 11 wherein the perfume ingredients are selected from the group consisting of 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.
13. 13. A composition according to Claim 11 wherein the perfume comprises at least about 70% by weight of the perfume ingredients.
14. 14. A composition according to Claim 11 wherein in the amidoperoxyacid bleach R1 is an alkyl group containing from about 8 to about 10 carbon atoms and R2 is an alkylene group containing from 2 to 4 carbon atoms.
15. 15. A composition according to Claim 14 wherein the amidoperoxyacid bleach is the nonylamide of peroxyadipic acid ("NAPAA").
16. 16. A composition according to Claim 15 wherein the NAPAA is present in a bleach granule comprising:
    (a) from apout 5 to 70 weight % NAPAA with an average particle size of from about 0.1 to 260 microns;
    (b) from about 1 to 40 weight % bleach-stable surfactant selecteb from the group consisting of anionics, nonionics, ampholytics, zwitterionics and combinations thereof; and (c) from about 10 to 95 weight % hydratable, NAPAA-compatible material.
17. 17. A composition according to Claim 16 comprising from about 2 to 50 weight % bleach granules according to Claim 16, from about 5 to 50 weight % detergent surfactant, and from about 10 to 60 weight % detergency builder.