WO1996031590A1

WO1996031590A1 - Bleaching compositions with selected perfumes for masking bleach odor

Info

Publication number: WO1996031590A1
Application number: PCT/US1996/004023
Authority: WO
Inventors: Jill Bonham Costa; Miguel Orlando Martinez-Baco; John Michael Jolicoeur
Original assignee: The Procter & Gamble Company
Priority date: 1995-04-03
Filing date: 1996-03-25
Publication date: 1996-10-10
Also published as: BR9604793A; MX9707588A; CZ308797A3; CA2216778A1; JPH11503192A; HUP9801774A2; CN1185804A; ZA962667B; EP0821723A1; HUP9801774A3

Abstract

A bleaching composition is provided which comprises: (a) a peroxygen bleaching agent; (b) a bleach activator; and (c) a perfume. The perfume contains, by weight of the perfume, (i) at least about 25 % of a fragance material selected from the group consisting of aldehydes with a molecular weight greater than 200 AMU, esters with a molecular weight above 200 AMU, alcohols with a molecular weight between 120 and 160 AMU and mixtures thereof, wherein at least about 10 % by weight of the fragance material has an Odor Detection Threshold (ODT) value of less than about 100 parts per trillion; and (ii) at least about 1.0 % of an adjunct material with an Odor Detection Threshold (ODT) value of less than about 100 parts per trillion. The perfume is substantially free of halogenated fragance materials and nitromusks.

Description

BLEACHING COMPOSITIONS WITH SELECTED PERFUMES FOR MASKING BLEACH ODOR

FIELD OF THE INVENTION

The present invention generally relates to bleaching compositions having selected perfumes especially suitable for masking the "bleach" odor associated with such compositions More particularly, the invention relates to bleaching compositions containing a bleaching agent, a bleach activator and a perfume which effectively masks the odor of the composition before and during use

BACKGROUND OF THE INVENTION

It has long been common practice for consumers to use bleaching compositions to provide effective and efficient surface bleaching of textiles before and/or during typical fabric laundering processes There are numerous categories of bleaches which are well known in the art Of the wide variety currently available, chlorine releasing bleaches, inorganic peroxygen bleaches, and organic peroxygen or peroxyacid bleaches are the most common The chlorine releasing bleaches have certain disadvantages associated with their use such as, for example, their tendency to weaken or degrade fabrics, a tendency to react with other components in the composition in which they are present and their general propensity for fading colors in many dyed fabrics Additionally, under several bleaching conditions chlorine bleaches cause yellowing of certain synthetic fabrics

While inorganic peroxygen bleaches overcome many of the disadvantages found with chlorine bleaches, they have limitations on use in that they must be used at relatively high temperatures, such as 85°C or higher This drawback becomes significant in light of the washing practices in countries where lower wash temperatures are used which are generally less than about 60°C in order to reduce energy costs and prolong the life of the fabric This problem also renders the product ineffective when used to "pre-soak" especially soiled fabrics As a consequence, it is generally necessary to improve the low temperature performances of inorganic peroxygen bleaches through the addition of peroxygen bleach activators also known as peroxyacid precursors

Many have also used peroxygen or peroxyacid bleaches, either alone or in combination with a bleach activator, as an alternative to the chlorine and inorganic peroxygen bleaches described above. Various products including peroxygen bleaches and activators therefor have been used, for example, detergent compositions containing a bleach/bleach activator system and bleach additive products which are added separately from the detergent composition. Other bleaching compositions include those which are used as a "pre-soak" product for extensively soiled fabrics. The previously mentioned detergent compositions and bleaching compositions can be used in this manner, as well. In use, the pre-soak products or other bleach-containing products require the user to immerse the soiled fabrics and bleach-containing product into a washing solution that is typically contained in a bucket, sink or similar open container for 20 to 30 minutes (or longer) during which a strong "bleach" odor is emitted from the washing solution. Consumers are offended by such readily detectable bleach odor, a problem which is exacerbated when the product contains high levels of bleach. This problem has been very noticeable in products which contain peroxygen bleach and activators therefor.

Accordingly, despite the aforementioned disclosures in the art, there is still a need for a bleaching composition which includes a bleaching agent, a bleach activator and a perfume that effectively masks the odor of such components. There is also a need for such a composition which contains a perfume that effectively masks the odor of the bleaching agent and bleach activator, even when the composition is used as a pre-soak product and contains high levels of bleach.

BACKGROUND ART

The following references disclose bleaching compositions: Hardy et al, U.S. Patent No. 4,536,314 (Procter & Gamble); Thompson et al, U.S. Patent No. 4,539,130 (Procter & Gamble); and Burns, U.S. Patent No. 4,606,838 (Procter & Gamble). The following reference discloses a bleaching composition with perfumes: Nicholson, U.S. Patent No. 5,248,434 (Procter & Gamble).

SUMMARY OF THE INVENTION

The invention meets the needs identified above by providing bleaching compositions and detergent compositions containing a bleaching agent and a bleach activator which include a selected perfume particularly suitable for masking the bleach odor emitted by such compositions before and during use. The compositions herein can optionally contain relatively high levels of bleaching agents and activators without significant detection of undesirable odors typically associated with such compositions. As a result, the compositions of the invention can be used in a wide variety of applications including presoak operations wherein soiled fabrics are soaked in open containers, i.e. bucket or sink, prior to conventional laundering operations. The consumer does not notice the bleach odors of the compositions when used in the aforementioned presoaking operations because of the perfume. The selected perfumes used in the compositions herein unexpectedly provide masking of the harsh odors normally associated with the bleach-containing compositions described herein.

As used herein, the phrase "Odor Detection Threshold (ODT)" refers to the value (typically reported as an average value with units of "parts per trillion") commonly used in the perfumery arts which is the lowest concentration at which significant detection takes place that some odorous material is present. See, for example, Calkin et al, Perfumery, Practice and Principles, John Wiley & Sons, Inc., page 243 et seq (1994) which refers to such a value as being well know in the art and defines various means of measurement, the disclosure of which is incorporated herein in its entirety. As used herein, the designation "AMU" refers to atomic weight and may also be expressed as g/mole. All percentages, ratios and proportions used herein are by weight, unless otherwise specified. All documents including patents and publications cited herein are incorporated herein by reference.

In accordance with one aspect of the invention, a bleaching composition is provided. The bleaching composition comprises: (a) a peroxygen bleaching agent; (b) a bleach activator; and (c) a perfume. The perfume contains, by weight of the perfume, (i) at least about 25% of a fragrance material selected from the group consisting of aldehydes with a molecular weight greater than 200 AMU, esters with a molecular weight above 200 AMU, alcohols with a molecular weight between 120 and 160 AMU and mixtures thereof, wherein at least about 10% by weight of the fragrance material has an Odor Detection Threshold (ODT) value of less than about 100 parts per trillion; and (ii) at least about 1.0% of an adjunct material with an Odor Detection Threshold (ODT) value of less than about 100 parts per trillion. The perfume is substantially free of halogenated fragrance materials and nitromusks.

In another aspect of the invention, a granular detergent composition is provided. The granular detergent composition comprises: (a) from about 0.1% to about 40% by weight of a peroxygen bleaching agent selected from the group consisting of percarbonates, perborates, peroxides and mixtures thereof; (b) from about 0 1 % to about 20% by weight a bleach activator having the formula o

II

R— C — LG wherein R is an alkyl group containing from about 5 to about 18 carbon atoms and LG is a leaving group, the conjugate acid of which has a pK_a of from about 4 to about 13, wherein the LG has the formula

wherein Y is selected from the group consisting of SOβ- M⁺ , COO" M⁺, SO4- M⁺, PO4- M⁺ PO3- M+, (N+R2₃)X- and 0<-N(R² ₂ ), M is a cation, X is an anion, and R² is an alkyl chain containing from about 1 to about 4 carbon atoms or H, and (c) from about 0 01 % to about 2% of a perfume containing, by weight of the perfume, (i) at least 25% of a fragrance material selected from the group consisting of aldehydes with a molecular weight greater than 200 AMU, esters with a molecular weight above 200 AMU, alcohols with a molecular weight between 120 and 160 AMU and mixtures thereof, wherein at least 10% by weight of the fragrance material has an Odor Detection Threshold (ODT) value of less than about 100 parts per trillion, and (u) at least 1 0% of an adjunct material with an Odor Detection Threshold (ODT) value of less than about 100 parts per trillion This perfume is also substantially free of halogenated fragrance materials and nitromusks.

In yet another aspect of the invention, a bleaching composition as described herein is provided which is in the form of a liquid. Also a method of laundering soiled clothes is provided, wherein the method comprises the step of contacting the soiled clothes with an aqueous washing solution containing a bleaching composition as described herein A presoaking method is also provided which comprises the steps of soaking the soiled clothes in an aqueous soaking solution of a bleaching composition as described herein and thereafter, contacting the clothes with an aqueous washing solution containing a detergent composition

Accordingly, it is an object of the invention to provide a bleaching composition which includes a bleaching agent, a bleach activator and a perfume that effectively masks the odor of such components before and during use. It is also an object of the invention to provide a bleaching composition which contains such a perfume that effectively masks the odor of the bleaching agent and bleach activator, even when the composition is used as a pre-soak product and contains high levels of bleaching agents and activators. These and other objects, features and attendant advantages of the present invention will become apparent to those skilled in the art from a reading of the following detailed description of the preferred embodiments, examples and the appended claims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In its broadest aspect, the compositions of the invention comprise a bleaching agent, a bleach activator and a selected perfume for masking the odor of the bleach components. The compositions herein can be in the form of granules, agglomerates, liquid, gel or a bar. Additionally, the. compositions can be used as a bleaching composition, fully formulated detergent composition, or as a bleach or detergent presoak product. Bleaching System

As stated previously, the compositions of the invention must include a bleaching system comprising a bleaching agent and a bleach activator. With regard to the relative proportions, the compositions preferably comprise from about 0.1% to about 40%, more preferably from about 20% to about 35%, and most preferably from about 30% to about 35%, by weight of the peroxygen bleaching agent. Also, the detergent composition comprises from about 0.1 % to about 40%, more preferably from about 5% to about 15%, and most preferably from about 10% to about 15%, by weight of the bleach activator. Optionally, one or more adjunct bleach activators may be used in the same amounts.

The peroxygen bleaching agents can be any of those peroxygen bleaching agents useful for detergent compositions in textile cleaning that are known or become known. Preferably, the bleaching agent is selected from the group consisting of percarbonates, perborates, peroxides and mixtures thereof. While intending not to be limiting, included within this group are sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium perborate (e.g. mono- or tetra-hydrate) and sodium peroxide. It should be understood that other peroxygen bleaches other than those described herein may be used in the detergent composition without departing from the scope of the invention The most preferred bleaching agent is sodium percarbonate

Preferably, the peroxygen bleaching agent used herein is combined with a bleach activator which leads to the in situ production in aqueous solution (i e during the laundering process) of the peroxy acid corresponding to the activator The bleaching mechanism generally, and the surface bleaching mechanism in particular, in the washing solution are not completely understood While not intending to be limited by theory, however, it is believed that the bleach activator undergoes nucleophilic attack by a perhydroxide anion, for example from aqueous hydrogen peroxide, to form a percarboxylic acid This reaction is commonly referenced in the art as perhydrolysis

A second species present in the washing solution is the. diacylperoxide (also referred to herein as "DAP") It is imperative that some DAP production is present in order to improve bleaching of specific stains such as, for example, those stains caused by spaghetti sauce or barbecue sauce The peroxyacid acids are particularly useful for removing dingy soils from textiles As used herein, "dingy soils" are those which have built up on textiles after numerous cycles of usage and washing and thus, cause the white textile to have a gray or yellow tint Accordingly, the bleaching mechanism herein preferably produces an effective amount of peroxyacid and DAP to bleach both dingy stains as well as stains resulting from spaghetti and the like

Further, it is believed that bleach activators within the scope of the invention render the peroxygen bleaches more efficient even at bleach solution temperatures wherein the bleach activators are not necessary to activate the bleach, for example at temperatures above 60°C As a consequence, less peroxygen bleach is required to obtain the same level of surface bleaching performance as compared with peroxygen bleach alone

In a preferred embodiment, the bleach activator used in the granular detergent composition has the general formula o

II

R— C — LG wherein R is an alkyl group, linear or branched, containing from about 1 to 11 carbon atoms and LG is a suitable leaving group As used herein, a "leaving group" is any group that is displaced from the bleach activator as consequence of nucleophilic attack on the bleach activator by the perhydroxide anion, i.e. perhydrolysis reaction.

Generally, a suitable leaving group is electrophilic and is stable such that the rate of the reverse reaction is negligible. This facilitates the nucleophilic attack by the perhydroxide anion. The leaving group must also be sufficiently reactive for the reaction to occur within the optimum time frame, for example during the wash cycle. However, if the leaving group is too reactive, the bleach activator will be difficult to stabilize. In the past, it has been difficult to formulate granular detergent compositions having the desired stability for a practical shelf-life.

These characteristics are generally paralleled by the pK_a of the conjugate acid of the leaving group, although exceptions to this convention are known. The conjugate acid of the leaving group in accordance with the present invention preferably has a pK_a in a range from about 4 to about 13, more preferably from about 6 to about 11 , and most preferably from about 8 to about 11.

Preferably, the leaving group has the formula

wherein Y is selected from the group consisting of SO3" M⁺ , COO" M⁺, SO4- M⁺, P0₄" M⁺, PO3- M⁺, (N⁺R2₃)X- and 0<-N(R² ₂), M is a cation and X is an anion, both of which provide solubility to the bleach activator, and R² is an alkyl chain containing from about 1 to about 4 carbon atoms or H. In accordance with the present invention, M is preferably an alkali metal, with sodium being most preferred. Preferably, X is a hydroxide, methylsulfate or acetate anion.

Other suitable leaving groups have the following formulas

wherein Y is the same as described above and R^ is an alkyl chain containing from about 1 to about 8 carbon atoms, H or R². While numerous bleach activators as described above are suitable for use in the detergent composition, the preferred bleach activator has the general formula

wherein R is an alkyl chain, linear or branched, containing from about 1 to about 11 carbon atoms Most preferably, the bleach activator has the formula

which is also referred to as sodium n-nonyloxybenzene sulfonate (hereinafter referred to as "NOBS") This bleach activator and those described previously may be readily synthesized by well known reaction schemes or purchased commercially, neither of which is more preferred. Those skilled in the art will appreciate that other bleach activators beyond those described herein which are readily water-soluble can be used in the compositions of the invention without departing from the scope of the invention Another preferred bleach activator is tetra acetyl ethylene diamme ("TAED")

Various additional nonlimitmg examples of bleach activators which may be used herein are disclosed in Mao et al, U S Patent No 4,915,854, the disclosure of which is incorporated herein by reference

Perfume

The compositions of the invention preferably contain from about 0 001 % to about 5%, more preferably from about 0 01% to about 2%, and most preferably from about 0 1% to about 1 0%, by weight of a perfume as described herein The formulator has the luxury of choosing from a wide variety of perfume ingredients in order to arrive at a perfume formulation with the definition stated previously Several exemplary perfume formulations are set forth hereinafter

As stated previously, the perfume preferably includes at least 25%, more preferably from about 40% to about 75%, and most preferably from about 60% to about 70%, by weight of the perfume, of certain aldehydes, esters, alcohols and mixtures thereof Suitable aldehydes with molecular weights greater than 200 AMU, esters with molecular weights greater than 200 AMU and alcohols with molecular weights between 120 - 160 AMU include, but are not limited to hexyl cinnamic aldehyde; amyl cinnamic aldehyde; amyl salicylate; hexyl salicylate; phenyl ethyl alcohol; terpineol; 3,7-dimethyl-cs-2,6-octadien-1 -ol; 2,6-dimethyl-2-octanol; 2,6-dimethyl-7- octen-2-ol, 3,7-dimethyl-3-octanol; 3,7-dimethyl-fraπs-2, 6-octadien-1-ol; 3,7-dimethyl-6-octen-1 -ol; 3,7-dimethyl-1 -octanol.

At least about 10%, more preferably from about 15% to about 30%, and most preferably from about 20% to about 25%, by weight of the perfume, of the aformentioned aldehydes, esters, alcohols and mixtures thereof have an Odor Detection Threshold value of less than about 100 parts per trillion. Suitable aldehydes with molecular weights greater than 200 AMU, esters with molecular weights greater than 200 AMU and alcohols with molecular weights between 120 - 160 AMU having such- measured Odor Detection Threshold (ODT) values include but are not limited to, benzyl salicylate; 2-methyl-3-(para tert butylphenyl)- propionaldehyde; 4-(4-hydroxy-4-methyl pentyl)-3-cyclohexene-1- carboxaldehyde; tricyclodecenyl propionate.

The perfume also comprises at least about 1%, more preferably from about 5% to about 35%, and most preferably from about 20% to about 25%, by weight of the perfume, of an adjunct fragrance material with an Odor Detection Threshold values less than or equal to 100 parts per trillion include, but are not limited to, tricyclodecenyl acetate; anisaldehyde; 2- methyl-2-(para-iso-propylphenyl)-propionaldehyde; ethyl 3-methyl-3-phenyl glycidate; 4-(para-hydroxy phenyl) butan-2-one; 1-(2,6,6-trimethyl-2- cyclohexen-1-yl)-2-buten-1 -one; para methoxy acetophenone; para- methoxy-alpha-phenyl propene; methyl 2-n-hexyl-3-oxo-cyclopentane carboxylate; undecalactone gamma.

Additional fragrance materials of synthetic or natural origin may be added to the perfume if desired and include but are not limited to dodecalactone gamma; methyl 2-(2-ρentyl-3-oxo-cyclopentyl) acetate; beta naphthol methyl ether; methyl beta naphthyl ketone; couma n; decyl aldehyde; benzaldehyde; 4-tertiary-butyl cyclohexyl acetate; alpha, alpha- dimethyl phenethyl acetate; methyl phenyl carbinyl acetate; schiff s base of 4-(4-hydroxy-4-methyl pentyl)-3-cyclohexene-1 -carboxaldehyde and methyl anthranilate; cyclic ethylene glycol diester of tridecandioic acid; 3,7- dimethyl-2,6-octadiene-1-nitrile; ionone gamma methyl; ionone alpha; ionone beta; petitgrain; methyl cedrylone; 7-acetyl-1 ,2,3,4,5,6,7,8- octahydro-1 ,1 ,6,7-tetramethyl naphthalene; ionone methyl; methyl 1,6,10- trimethyl-2,5,9-cyclododecatrien-1-yl ketone; 7-acetyl-1 ,1 ,3,4,4,6- hexamethyl tetralin; 4-acetyl-6-tert-butyl-1 ,1 -dimethyl indane, benzophenone; 6-acetyl-1 ,1 ,2,3,3,5-hexamethyl indane; 5-acetyl-3- isopropyl-1 ,1 ,2,6-tetramethyl indane; 1-dodecanal; 7-hydroxy-3,7-dimethyl octanal; 10-undecen-1-al; iso-hexenyl cyclohexyl carboxaldehyde; formyl tricyclodecan; cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acid lactone; 1 , 3,4,6,7, 8-hexahydro-4,6,6, 7, 8,8-hexamethylcyclopenta-gamma- 2-benzopyrane; ambroxane; dodecahydro-3a,6,6,9a- tetramethylnaphtho[2,1 b]furan; cedrol; 5-(2,2,3-trimethylcyclopent-3-enyl)- 3-methylpentan-2-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten- 1 -ol; caryophyllene alcohol; cedryl acetate; para-tert-butyl cyclohexyl acetate; patchouli; olibanum resinoid; labdanum; vetivert; copaiba balsam; fir balsam; and condensation products of: hydroxycitronellal and methyl anthranilate; hydroxycitronellal and indol; phenyl acetaldehyde and indol; 4- (4-hydroxy-4-methyl pentyl)-3-cyclohexene-1 -carboxaldehyde and methyl anthranilate.

Adjunct Ingredients

A variety of optional adjunct ingredients can be included in the compositions disclosed herein. The levels of the ingredients will vary depending upon the context, e.g. liquid or granular, bleaching or detergent composition, etc. The bleaching or granular detergent compositions of the invention can include a wide variety of additional ingredients typically used in the art of detergency. For example, the detergent composition can include from about 1% to about 80%, more preferably from about 5% to about 20%, and most preferably from about 10% to about 30%, by weight of a builder.

Generally, the builder can be selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, crystalline layered and amorphous silicates, borates, polyhydroxy sulfonates, polyacetates, carboxylates, and polycarboxylates. Preferred are the alkali metal, especially sodium, salts of the above. Preferred for use herein are the phosphates, carbonates, silicates, C₁₀_₁g fatty acids, polycarboxylates, and mixtures thereof. More preferred are sodium tripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate mono- and di-succinates, sodium silicate, and mixtures thereof (see below).

Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21 , and orthophosphates. Examples of polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1 , 1 -diphosphonic acid and the sodium and potassium salts of ethane, 1 ,1 ,2-triphosphonic acid. Other phosphorus builder compounds are disclosed in U.S. Patents 3,159,581 ; 3,213,030; 3,422,021 ; 3,422,137; 3,400,176 and 3,400,148, all of which are incorporated herein by reference.

Examples of nonphosphorus, inorganic builders are sodium and. potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a weight ratio of Si0₂ to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4. Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates. Examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.

Polymeric polycarboxylate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, the disclosure of which is incorporated herein by reference. Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid. Some of these materials are useful as the water-soluble anionic polymer as hereinafter described, but only if in intimate admixture with the non-soap anionic surfactant.

Other suitable polycarboxylates for use herein are the polyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al, and U.S. Patent 4,246,495, issued March 27, 1979 to Crutchfield et al, both of which are incorporated herein by reference. These polyacetal carboxylates can be prepared by bringing together under polymerization conditions an ester of glyoxylic acid and a polymerization 96/31590 PC17US96/04023

12 initiator The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymeπzation in alkaline solution, converted to the corresponding salt, and added to a detergent composition. Particularly preferred polycarboxylate builders are the ether carboxylate builder compositions comprising a combination of tartrate monosuccinate and tartrate disuccinate described in U.S. Patent 4,663,071 , Bush et al., issued May 5, 1987, the disclosure of which is incorporated herein by reference.

Water-soluble silicate solids represented by the formula Siθ2»M₂0, M being an alkali metal, and having a SiO^ M^O weight ratio of from about 0.5 to about 4.0, are useful salts in the compositions of the invention at levels of from about 0.1% to about 15%, more preferably from about 0.5% to about 2%, on an anhydrous weight basis. Anhydrous or hydrated paniculate silicate can be utilized, as well.

The detergent composition of the invention optionally can contain various anionic, nonionic, zwitteπonic, etc. surfactants. If used, such surfactants are typically present at levels of from about 1 % to about 50%, more preferably from about 3% to about 35%, and most preferably from about 5% to about 25%, by weight of the composition. Nonlimiting examples of surfactants useful herein include the conventional Cn-Ciβ alkyl benzene sulfonates ("LAS") and primary, branched-cham and random C10-C20 ^alkyl sulfates ("AS"), the C10-C18 secondary (2,3) alkyl sulfates of the formula CH₃(CH2)χ(CHOS0₃ ^"M⁺) CH3 and CH3 (CH₂)y(CHOSθ3^"M⁺) CH2CH3 where x and (y + 1 ) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C10- 18 alkyl alkoxy sulfates ("AE_XS"; especially EO 0.1-7 ethoxy sulfates), C10-C18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C10-I8 glycerol ethers, the C10-C18 ^a'M polyglycosides and their corresponding sulfated polyglycosides, and C12-C18 alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteπc surfactants such as the C12-C18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), Ci2^_c18 betames and sulfobetames ("sultaines"), C10-C18 ^amιne oxides, and the like, can also be included in the overall compositions. The C10-C18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C18 N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl Ci2^_c18 glucamides can be used for low sudsing. C-|o^_c20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C16 ^soaP^{s ma}y ^De used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts. The C10-C18 alkyl alkoxy sulfates ("AE_XS"; especially EO 1-7 ethoxy sulfates) and C-12-C18 alkyl ethoxylates ("AE") are the most preferred for the cellulase- containing detergents described herein

The detergent composition can also include suds boosters or suds, suppresses, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smectite clays, enzymes (e.g. cellulases, proteases, lipases and amylases), and enzyme-stabilizing agents. See U.S. Patent 3,936,537, issued February 3, 1976 to Baskerville, Jr. et al., incorporated herein by reference. A polymeric dispersant such as polyaspartic acid, may also be included in the detergent composition disclosed herein.

Chelating agents are also described in U.S. Patent 4,663,071 , Bush et al., from Column 17, line 54 through Column 18, line 68, incorporated herein by reference. Suds modifiers are also optional ingredients and are described in U.S. Patents 3,933,672, issued January 20, 1976 to Bartoletta et al., and 4,136,045, issued January 23, 1979 to Gault et al., both incorporated herein by reference.

Suitable smectite clays for use herein are described in U.S. Patent 4,762,645, Tucker et al, issued August 9, 1988, Column 6, line 3 through Column 7, line 24, incorporated herein by reference. Suitable additional detergency builders for use herein are enumerated in the Baskerville patent, Column 13, line 54 through Column 16, line 16, and in U.S. Patent 4,663,071 , Bush et al, issued May 5, 1987, both incorporated herein by reference.

Fillers such as sulfates may be included at levels of from about 5% to about 50%, more preferably from about 10% to about 30%, by weight of the composition. A particularly preferred set of adjunct materials in addition to the bleaching system and the perfume described above include, by weight: (a) from about 2% to about 10% of C-J2-13 linear alkylbenzene sulfonate surfactant; (b) from about 2% to about 10% of a mixture of C-14.15 alkyl sulfate/alkyl ethoxylate sulfate (EO = 0.35) surfactants; (c) from about 20% to about 25% of sulfate; (d) from about 10% to about 15% of polyacrylate; (e) from about 0.3% to about 0.6% of polyethylene glycol; (f) from about 0.2% to about 0.5% of sodium silicate; (g) from about 0.1% to about 0.3% of diethylene triamine pentamethylene phosphonic acid; (h) from about 0.1% to about 0.5% of amylase enzyme; (i) from about 0.1 % to about 0.6% of protease enzyme; ( ) from about 10% to about 15% of citric acid; and the balance water and other minors.

In order to make the present invention more readily understood,, reference is made to the following examples, which are intended to be illustrative only and not intended to be limiting in scope.

EXAMPLE I

This Example illustrates three perfume formulations in accordance with the invention. Specifically, Table I sets forth perfume formulations A, B and C which are suitable for use in the compositions of the invention.

TABLE I

(% Weight PERFUME MATERIAL A B C hexyl cinnamic aldehyde 13.25 17.30 11.51 amyl cinnamic aldehyde 10.00 amyl salicylate 7.00 hexyl salicylate 5.00

phenyl ethyl alcohol 22.32 9.23 13.44 terpineol 13.84

3,7-dimethyl-c/s-2,6-octadien-1 -ol 5.00

2,6-dimethyl-2-octanol 2.00

2,6-dimethyl-7-octen-2-ol 8.28 11.53

3,7-dimethyl-3-octanol 6.28

benzyl salicylate 12.30 14.51

2-methyl-3-(para tert butylphenyl)- 7.28 propionaldehyde 4-(4-hydroxy-4-methyl pentyl)-3- 4.97 cyclohexene-1 -carboxaldehyde tricyclodecenyl propionate 9.14

tricyclodecenyl acetate 9.23 9.41 anisaldehyde 6.11

2-methyl-2-(para-iso-propylphenyl)- 1.00 propionaldehyde ethyl 3-methyl-3-phenyl glycidate 0.27

4-(para-hydroxy phenyl) butan-2-one 0.10

1 -(2,6,6-trimethyl-2-cyclohexen-1 -yl)-2- 0.17 0.12 0.44 buten-1 -one para methoxy acetophenone 0.58 para-methoxy-alpha-phenyl propene 0.17 methyl 2-n-hexyl-3-oxo-cyclopentane 13.44 carboxylate undecalactone gamma 1.34

dodecalactone gamma 0.33 methyl 2-(2-pentyl-3-oxo-cyclopentyl) 4.97 acetate beta naphthol methyl ether 0.28 methyl beta naphthyl ketone 0.20 couma n 0.10 decyl aldehyde 0.50 0.12 benzaldehyde 0.33

4-tertiary-butyl cyclohexyl acetate 4.97 alpha, alpha-dimethyl phenethyl acetate 8.28 methyl phenyl carbinyl acetate 9.93 schiffs base of 4-(4-hydroxy-4-methyl 0.23 pentyl)-3-cyclohexene-1 - carboxaldehyde and methyl anthranilate cyclic ethylene glycol diester of 2.31 tridecandioic acid

3,7-dimethyl-2,6-octadiene-1-nitrile 2.31 ionone gamma methyl 4.61 ionone alpha 0.54 ionone beta 0.81 petitgrain 4.61 methyl cedrylone 8.06

Total Percent 100.0 100.0 100.0 EXAMPLES II - IV

These Examples illustrate several compositions within the scope of the invention and which include the perfume formulations of Example I.

TABLE II

(% Weight)

Base Granule ϋ ill ιy.

C 12-13 linear alkylbenzene sulfonate, Na 3.7 3.7 3.7

C 14-15 a'kyl sulfate/alkyl ethoxylate 3.0 3.0 3.0

(EO=0.35) sulfate

Sulfate 3.0 3.0 3.0

Polyacrylate, Na (M.W. = ' 1400) 10.7 10.7 10.7

Polyethylene glycol (M.W. = 4000) 0.5 0.5 0.5

Sodium silicate 0.4 0.4 0.4

DTPA¹ 0.2 0.2 0.2

Brightener 0.2 0.2 0.2

Admix/Sprav-on

TAED² 5.5 5.5 5.5

NOBS³ 6.2 6.2 6.2

Sodium percarbonate 31.9 31.9 31.9

Amylase enzyme 0.3 0.3 0.3

Protease enzyme 0.5 0.5 0.5

Citric acid 10.3 10.3 10.3

Perfume A 0.5 - -

Perfume B - 0.5 -

Perfume C - - 0.5

Water and other minors balance balance balanc e

100.0 100.0 100.0 ¹ diethylene triamine pertamethylene phosphonic acid ²tetra acetyl ethylene diamine ³n-nonyloxybenzene sulfonate

The compositions set forth in Table II are made by conventional detergent processing techniques. In particular, the base granule ingredients are mixed together as a slurry and spray dried in a tower to produce granules. The dry ingredients are then admixed with the granules and the liquid ingredients are spray thereon to provide the finished composition. Alternatively, various liquid and dry ingredients can be agglomerated to provide high density agglomerates to which the remaining ingredients can be sprayed on or admixed as appropriate.

EXAMPLES V - X

These Examples illustrate several compositions within the scope of the invention.

TABLE III

(% Weight)

Base Granule V Y! yji yju ] X

C12-13 linear alkylbenzene 5.8 6.4 5.8 5.8 6.4 6.4 sulfonate, Na

C 14-15 alkyl sulfate/alkyl 4.8 5.2 4.8 4.8 5.2 5.2 ethoxylate (EO=0.35) sulfate

Sulfate 15.1 16.5 15.1 15.1 16.5 16.5

Aluminosilicate 16.4 17.9 16.4 16.4 17.9 17.9

Polyacrylate, Na (M.W. = 1.8 1.9 1.8 1.8 1.9 1.9

1400)

Polyethylene glycol (M.W. 0.8 0.8 0.8 0.8 0.8 0.8

= 4000)

Sodium carbonate 6.8 7.4 6.8 6.8 7.4 7.4

Sodium silicate 0.4 0.5 0.4 0.4 0.5 0.5

DTPA¹ 0.3 0.3 0.3 0.3 0.3 0.3

Brightener 0.3 0.3 0.3 0.3 0.3 0.3

Admix/Sprav-on

Sodium perborate 6.8 7.4 6.8 6.8 7.4 7.4

NOBS² 11.5 12.6 11.5 11.5 12.6 12.6 Amylase enzyme 0.1 0.1 0.1 0.1 0.1 0.1

Protease enzyme 04 0.5 0.4 0.4 0.5 0.5

Citric acid 8 4 - 8.4 8.4 - -

DTPA¹ 0.2 0.3 0.2 0.2 0.3 0.3

Bπghtener 0 5 0.5 0.5 0.5 0.5 0.5

Sodium Carbonate 12.2 13.3 12.2 12.2 13.3 13.3

Nonionic³ 0.5 0.5 0.5 0.5 0.5 0.5

Perfume A 0.3 0.3 - - - -

Perfume B - - 0.3 - 0.3 -

Perfume C - - - 0.3 - 0.3

Water and other minors 6 6 7_3 ε 6_6 I L³.

100.0 100.0 100 100. 100 100. 0 0 0 o

1 diethylene triamine pentamethylene phosphonic acid n-nonyloxybenzene sulfonate

³Neodol (23-9) commercially available from Shell Chemical Co.

The compositions set forth in Table III are made in accordance with the processes described with respect to Examples ll-IV hereinabove.

Having thus described the invention in detail, it will be clear to those skilled in the art that various changes may be made without departing from the scope of the invention and the invention is not to be considered limited to what is described in the specification.

What is claimed is:

Claims

CLAIMS:

1 A bleaching composition characterized by:

(a) a peroxygen bleaching agent;

(b) a bleach activator; and

(c) a perfume containing, by weight of said perfume,

(i) at least 25% of a fragrance material selected from the group consisting of aldehydes with a molecular weight greater than 200 AMU, esters with a molecular weight above 200 AMU, alcohols with a molecular weight between 120 and 160 AMU and mixtures thereof; wherein at least 10% by weight of said fragrance material has an Odor Detection Threshold (ODT) value of less than 100 parts per trillion; and

(ii) at least 1.0% of an adjunct fragrance material with an Odor Detection Threshold (ODT) value of less than 100 parts per trillion; wherein said perfume is substantially free of halogenated fragrance materials and nitromusks.

2. A bleaching composition according to claim 1 wherein said adjunct fragrance material is selected from the group consisting of tricyclodecenyl acetate, anisaldehyde, 2-methyl-2-(para-iso-propylphenyl)- propionaldehyde, ethyl 3-methyl-3-phenyl glycidate, 4-(para-hydroxy phenyl) butan-2-one, 1 -(2,6,6-trimethyl-2-cyclohexen-1 -yl)-2-buten-1 -one, para methoxy acetophenone, para-methoxy-alpha-phenyl propene, methyl 2-n-hexyl-3-oxo-cyclopentane carboxylate, undecalactone gamma.

3. A bleaching composition according to claims 1 -2 wherein said perfume is present in an amount from 0.001% to 5% by weight.

4. A bleaching composition according to claims 1 -3 wherein said peroxygen bleaching agent is present in an amount of from 0.1 % to 40% by weight.

5. A bleaching composition according to claims 1-4 wherein said bleach activator has the formula o

II

R— C — LG wherein R is an alkyl group containing from 5 to 18 carbon atoms and LG is a leaving group, the conjugate acid of which has a pK_a of from 4 to 13.

6. A bleaching composition according to claimδ wherein LG has the formula

wherein Y is selected from the group consisting of Sθ3" M⁺ , COO" M⁺, SO4- M⁺, PO4- M⁺, PO3- M⁺, (N⁺R ₃)X- and 0«-N(R ₂ ), M is a cation, X is an anion, and R² is an alkyl chain containing from 1 to 4 carbon atoms or H.

7. A bleaching composition according to claims 1-6 wherein said bleach activator has the formula o

R ^J- - - sfi wherein R is an alkyl chain containing from 1 to 11 carbon atoms.

8. A bleaching composition according to claims 1-7 wherein said bleach activator has the formula

9. A method of laundering soiled clothes characterized by the step of contacting said clothes with an aqueous washing solution containing a bleaching composition according to claims 1-8.

10. A method of laundering soiled clothes characterized by the steps of soaking said clothes in an aqueous soaking solution of a bleaching composition according to claims 1-9 and thereafter, contacting said clothes with an aqueous washing solution containing a detergent composition.