Note: Descriptions are shown in the official language in which they were submitted.
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DETERGENT COMPOSITIONS
COMPRISING PRO-FRAGRANCE COMPOUND
FIELD
The present invention relates to a detergent composition comprising an
acetal or a ketal pro-fragrance compound.
BACKGROUND
Most consumers have come to expect scented laundry products and to
expect that fabrics which have been laundered will also have a pleasing
f,~yra"ce. It is also desired by consumers for launcJer~:~l fabrics to maintain the
pleasing ~, ~9~ a,~ce over time. Perfume additives may make laundry
co,~rositions more aesll,etically pleasi"~ to the consumer, and in some cases
the perfume illlpalb a pleasant ~ds,_nce to fabrics ll~:dled therewith. However,the amount of perfume carry-over from a detergent solution onto a fabric surfaceis often ,,,aryillal and does not last long on the fabric surface. In additio", some
perfume delivery systems are not stable under alkaline condiliol)s, such as in
laundry delergent COIl~pOsitiG"s and deteryent sohltions. Also, f,ayral1ce
"~al~rials are often very costly. Thus, their inefficient use in delt:ryenl~ andi"er~.;ti~e delivery from det~rye~ts to fabric surface usually results in a high cost
to both consumers and detery~nt manufacturers. Industry, ll,er~rort:, continues
to seek more efficient and effective perfume delivery in laundry products.
Acetals and ketals have long been known in perfumery. See Steffen
Af~lal~der, "Perfume and Flavor Cl,c:l"icals," Arctander, N.J., 1969. The majority
of these are methyl and ethyl types, and molecular weight~ may range widely.
See, for exal"~le, Arctander abstract numbers 6, 11, 210, 651, 689, 1697, 1702,
2480, 2478. However, the known ~cet~ls and ketals are generally not desirable
for use in laundry products. For 2478, which is phenylacePIdehyde dicitronellyl
acetal, molecular weight 414.7, Arctander reports " ... and it is not exaggerated to
say that this acetal is practically abandoned and obsolete in today's perfumery."
35 For 2480, which is phenylacetaldehyde digeranyl acetal, Arctander reports "the
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title material does not offer substantial advantages or unique odor type and it
may be considered of little more than academic interest today." This latter
material was still commercially available in 1992 as ROSETAL A (Catalogue,
IFF).
5Carrier mechanisms for perfume delivery, such as by encapsulation, are
also known in the art. See for example, U.S. Patent 5,188,753, issued Feb. 23,
1993.
Early efforts to delay release of perfumes in detergents include the use of
certain organometallic compounds, such as titanate or zirconate esters. See
10U.S. Patent 3,849,326, issued Nov. 19, 1974 and U.S. Patent 3,923,700, issued
Dec. 2, 1975. Limited amounts of titanium or zirconium can be used as catalysts
for synthesizing pro-perfume "~aterials.
Personal care compositions, such as deodorant sticks, comprising "body-
activated" fragrances are also known. The terrn apparently refers to the
15previously known tendency of materials such as ~cet~ls derived from perfume
alcohols to hydrolyze under acidic pH con.litiG"s thereby r~leasil1g fragrance.
See, for example, U.S. Patent 5,378,468, issued Jan. 3, 1995 and U.S. Patent
3,932,520, issued January 13, 1976.
Pote"lial fragrance ",aterials for use in such personal care compositions
20include particular acet~s and ketals, exemplified by propylene glycol vanillinacetal. The materials exemplified apparently are rather hydrophilic short chain
alcohol or diol derivatives of fragrance aldehydes and upon hydrolysis, deliver
one mole of the aldehyde per mole of the potential r,dgrance ",aterial. This
developl),ent is designed to be incorporated with a personal care product vehicle,
25resulting in clear deodorant sticks and the like, and the compositions containing
the potential fragrance ,nateric.ls are al-p~ecl directly to the subsl,ate (i.e. skin);
ther~for~, the deposition pr~l~lems resulting from the dilution, rinsing, etc.,
~ssoci~tcd with the laundry process are not at issue.
Factors affecting subst~rltivity of fragrance materials on fabrics are
30discussed in Estcher et al. JAOCS 71 p. 31-40 (1994).
Laundry detergents are used in dilute aqueous form and contain
numerous detergent adjuncts such as synthetic detergents, builders, enzymes
and the like which are capable of micellizing, or solubilizing the pro-fragrance.
Further, the laundry process includes rinsing, and sometimes drying with
35tumbling machines a~ter washing. The rinsing tends to remove the useful pro-
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fragrance material deposited. The tumble-drying further exacerbates the
problem of delivering adequate residual fragrance to textile fabric surfaces.
Based on the foregoing, there is a need for a detergent composition
having a pro-fragrance compound with improved dispersability in aqueous
5 solutions, particularly detergent solutions, enhanced deposition on fabric
surfaces in the wash solution, and enhanced retention on the washed surface
during rinsing. None of the existing art provides all of the advantages and
benefits of the present invention.
l 0 SUMMARY
The present invention is directed to a deteryent composition comprising a
pro-fragrance co".pound selected from the group consisting of an acetal, a. ketal,
and mixtures thereof, wherein at least one of a parent aldehyde, ketone, or
alcohol of the pro-r.dgrd"ce acetal or ketal is a fragrance compound, the pro-
fragrance compound having a CLogP of less than about 4, wherein the detergent
composition has a pH of at least 7.1 when measured as a 1% solution in distilled-
water at 20 C, and a detersive suRactant.
These and other features, aspe~is, and advantages of the present
invention will becGn.e better uncler:itood from a reading of the following
description, and a"penJed claims.
DETAILED DESCRIPTION
While the specificalion concludes with claims particularly pointing out and
dislinctly claill.i,lg the invention, it is believcd that the present invention will be
better under:jtoGJ from the following desc,iption of preferred embodiments.
All percenlayes and ratios used hereindner are by weight of total
composition, unless other~,vise indicated.
All measulen,ents referred to herein are made at 25~C unless otherwise
specified.
All percentages, ratios, and levels of ingredients referred to herein are
based on the actual amount of the ingredient, and do not include solvents, fillers,
or other ",d~erials with which the ingredient may be combined as a commercially
available product, unless otherwise indicated.
All publications, patent applications, and issued patents mentioned herein
are hereby incorporated in their entirety by reference. Citation of any reference
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is not an admission regarding any determination as to its availability as prior art
to the claimed invention.
As used herein, "Comprising" means that other steps and other
components which do not affect the end result can be added. This terrn
encompasses the terms ''consisting o~' and "consisting essentially of."
PRO-FRAGRANCES
A detergent composition of the present invention comprises a pro-
fragrance compound including acetals, ketals, or mixtures thereof, provided thatcompounds from which they are formed comprise at least one fragrance
10 compound.
As used herein, "pro-fragrance" compound means a compound which may
or may not be odoriferous in itself but which, upon hydrolysis, produces a
desi,dl~le odor which is characteristic of one or more of its hydrolysis products.
This term includes mixtures of pro-fragrance compounds and further
15 encompasses the term "pro-per~ume." Acetals and ketals can be coi,sider~d as
derivable from aldehydes or ketones in combination with alcohols. These
aldehydes, ketones and alcohols are herein terrned "parents" or "parent
compounds" of the acetal or ketal. At least one parent of any of the instant
acetals or ketals is a r,dg,ance compound.
The pro-fragrance compound of this invention has a CLogP of less than
about 4, wherein the CLogP is the logarill,n, to base 10 of the OctanolN~ater
Partition Coefficient of the pro-~,agl~nce compound. The pro-fragrances having
the CLogP of less than about 4 give good dispersibility in the aqueous solution.Without being bound by theory, it is believed that the CLogP, as described
25 herein, can be lower when the number of alkoxy moiety included in the pro-
fragrance co"".ound is increased.
These pro-fragrances can further be characteri~ed as having a molecular
weight of at least about 170 and a half-life of less than 60 minutes when
measured at pH 0 by the Hydrolysis Half-life (t-112) Test as described herein.
The pro-fragrance compounds of the present invention are stable under
pH conditions encountered in the formulation and storage of detergent products
which have a pH of from about 7.1 to about 13, and during solution-use of such
products. Due to hydrophilicity and high degree of heteroatom incorporation,
these pro-fragrance compounds give reasonably good deposition from a
35 laundering solution onto fabrics. Because the pro-fragrance compounds are
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subject to hydrolysis when the pH is reduced, they hydroiyze to release their
component fragrance compounds when the fabrics (or other surface) upon which
they have been deposited are exposed even to reduced pH such as is present in
rinse water, air and humidity. Such a reduction in pH should be at least about
0.1, preferably at least about 0.5 units. Preferably the pH is reduced by at least
about 0.5 units to a pH of about 7.5 or less, more preferably about 6.9 or less.Preferably, the solution in which the fabric (or other surface) is washed is
alkaline.
The pr~:rer,t:d pro-fragrance compounds of this invention can be cyclic or
10 acyclic (including mixtures of both cyclic and acyclic) having at least 3 oxygens
more preferably, the cyclic pro-fragrance compound having at least two
alkoxylate moiety and the acyclic pro-fragrance compound having at least 4
alkoxylate moiety.
Preferred ~cet~ls and ketals herein are those derived from a fragrance or
15 non-fragrance alcohol, particularly C6-C20 (preferably C~1-C20, more preferably
C14-C1g alcohols) saturated or unsaturated, linear or branched aliphatic
alcohols, commonly referred to as detergent alcohols and a r,~yra,1t Cg- or
higher unsaturated aldehyde or a fragrance ketones.
Preferably, parent alcol,ols of the present invention have at least one
alkoxy moiety. Due to increasi,)g the ",e",ber of alkoxy moiety as described
above, the pro-fragrances having the CLogP of less than about 4 give good
dispersibility in detergent solution. The preferred parent alcohols can include the
alkoxylates of detergent alcohols, mono-alkyl ethers of short-chain
polyalkoxylates, polyols including those which are alkoxylated with 1 to 30 groups
of ethylene oxide or propylene oxide.
More generally, a wide range of ~cet~ls and ketals are included within the
invention. Many fragrant aldehydes, ketones, and alcohols which are suitable
parents for the present ~cet~ls and ketals are known to the art. See, for exa")ple,
Arctander's compilation refer~,lced hereinabove for fragrant parents. These will30 be also obtainable commercially from perfume houses such as IFF, Firmenich,
Takasago, H&R, Givaudan-Roure, Dragoco, Aldrich, Quest, and others.
Acetals
The pro-fragrances of the present invention include an acetal. The acetal
can be used to deliver fragrance aldehydes, fragrance alcohols, or both,
35 preferably to deliver fragrance aldehydes derived from parent aldehydes.
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Acetals suitable in the present invention include the following structure:
R1~1--X
X and Y are derived from a starting alcohol and R1 and the H is derived from a
starting aldehyde.
X and Y in the above general structure which can be either fragrant
alcohols or non-fragrant alcohols includes variable alkoxy moieties. X and Y canbe the same or different allowing the delivery of more than one type of fragrantalcohol. When the alcohols are non-fragrant alcohols, it is preferred that they are
C6-C20 alcohols, e.specially fatty alcohols, which may optionally be modified byethoxylation or propoxylation. X and Y can be simple alcohols containing a
single OH group, or can be polyols containing 2 or more OH groups, more
preferabty, diols.
In general, alcohols can be saturated, unsaturated, linear or branched,
alkyl, alkenyl, alkylaryl, alkylalkoxylate derivatives with one or more alcohol
groups. The alcohols may conta;., additional functionality such as amines,
amides, ethers, or esters as a part of their structure.
P~eferdbly, the acetal of the present invention can be cyclic or acyclic, and
may contain one or more acetal groups through derivatizing one or more
aldehydes. The terrns cyclic and acyclic in this context refers to the presence or
absence of a covalent bond connecting moieties X and Y of the acetal. X and Y
of the cyclic acetals form a ring structure and have at least two alkoxylate
",oi~lies. The l~r~r,t:d acyclic acetals having at least four alkoxylate moieties
incG"~orate linear alcohols.
The cyclic acetals are derived from polyols. Plefer,t:d polyols include
those which are alkoxylated with 1 to 30 units of ethylene oxide or propylene
oxide. Nonl;."iti"g examples of the polyols include sorbitol, glucose, sucrose,
and other saccharides.
The acyclic acetals are derived from mono-alcohols. Preferred mono-
alcohols containing a single OH group can include the alkoxylates of detergent
alcohols and mono-alkyl ethers of short-chain polyalkoxylates. Preferably, the
mono-alkyl ethers of short-chain polyalkoxylates include C1-Cs alkyl moiety.
Nonli",ilins~ exa",ples of the parents alcohols include ethyl alcohol, propyl
alcohol, butyl alcohol, lauryl alcohol, and myristyl alcohol.
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R1 and the H of the above general structure are derived from a starting
aldehyde. In general, both fragrant and non-fragrant aldehydes incorporated intothe instant acetals can be aliphatic, allylic or benzylic. The aldehydes can be
saturated, unsaturated, linear, branched, or cyclic. The structures can include
5 alkyl, alkenyl, or aryl moieties, as well as additional functional groups such as
alcohols, amines, amides, esters, or ethers.
Preferably, acetals herein, will be derived from parent aldehydes having
molecular weight above about 80.
Many fragrant aldehydes and alcohols which are suitable parents for the
10 present acetals and ketals are known to the art. See, for example, Arctander's
compilation referenced hereinabove for fragrant parents. Nonlimiting examples
of the fragrant parent aldehydes include but are not limited by the following
examples: hydrat,-,~ualdehyde, p-t-bucinal, FloralozoneT~, phenylpropanal,
anisaldehyde, cymal, cyclamal, triplal, helional, hexylcinnamic aldehyde, vanillin,
15 ethyl vanillin, citral, ethyl citral, citronellal, methyl octyl acetaldehyde, methyl
nonyl ~cet~ldehyde, octanal, decanal, dodecanal, lauric aldehyde, chrysanthal,
isosyslocit,dl, melonal, t~ns4-decenal, adoxal, hydroxycitronellal, and is~
hexenyl cyclohexenyl carboxaldehyde.
Specific preferred pro-fragrance acetal compounds are nonlimitingly
20 illustrated by the following:
~~ <
~ J
~o~
~<
which is derived from P.T. Bucinal and tripropylene glycol.
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Also preferred is:
\
,IJ~_~/
which is derived from cyclal c and tripropylene glycol.
S Some specific examples of acyclic acetals useful herein include:
~ o(CH2CH20)6C 1 2H25
T o(CH2CH20)6C 12H25
which is derived from P.T. Bucinal and Neodol 6-25 and
/=\ O(CH2CH20)70CH3
(CH2CH2O)~ CH3
which is derived from P.T. Bucinal and PEG-300 methyl ether.
Additionally, s~~iPhle aceta's herein are cyclic acet~ls derived from the
reaction of fragrance aldehydes with polyhydroxyglucosidss, including the
polyhydroxyamides. Typical exa",ples of suitable polyhydroxy amides include
the C12-C1g N-methylglucamides. See WO 9,206,154. Other sugar-derived
acetal or ketal parent compounds herein include the N-alkoxy polyhydroxy fatty
20 acid amides, such as C10-C1g N-(3-methoxypropyl) glucamide.
Ketals
The pro-fragrance compound of the present invention includes a ketal.
The ketal can be used to deliver a fragrance ketone. The discussion for the
ketals herein can be constructed using structural principles analogous to those
25 used in discussing acetals supra.
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Ketals suitable in the present invention include the following structure:
R3
R2~,-X
y
- X and Y are derived from alcohols or polyols and R2 and R3 are derived from the
parent ketone, and can be the same or different.
As noted in defining the acetals supra, X and Y for ketals in the above
general structure can be either fragrant alcohols or non-fragrant alcohols
including variable alkoxy moieties. The parent alcohols for the ketals can
include, but are not limited to, those described as the parent alcohols of the
acetals in the section of acetals.
In general, alcohols can be saturated, unsaturated, linear or branched,
alkyl, alkenyl, alkylaryl, alkylalkoxylate derivatives with one or more alcohol
groups. The parent alcohols may contain additional functionality such as amines,amides, ethers, or esters as a part of their structure.
R2 and R3 of the above general structure are derived from the parent
ketone. In general, both fragrant and non-fragrant ketones can be aliphatic,
allylic or benzylic. The ketones can be saturated, unsaturated, linear, branched,
or cyclic, preferably including alkyl, alkenyl, or aryl moieties as well as other
functional groups including amides, amines, ethers, or esters.
Nonlimiting examples of the parent ketones include, for example, irone
alpha, alpha-ionone, beta-ionone, gamma-methyl ionone, methyl beta-naphthyl
ketone, cisjas~"o,le, darl,asce"one, a/pha-damascenone, benzylacetone, methyl
dihyd,ujasl"onate, methyl amyl ketone, methyl heptyl ketone, methyl hexyl
ketone, methyl nonyl ketone, carvone, cassione, menthone, and geranylacetone.
Other suitable ketones include diketones, e.g. 2,4-pentadione.
The non-fragrant ketone can contain one or more ketone functional groups
and such groups can be further derivatized so that the ketal is polymeric. Whilepolyketals are included herein, they are less preferred than mono- and di-ketals.
Nlonoketals are most preferred.
Specific preferred pro-r,~yrdi,ce ketal compounds are nonlimitingly
illu~l~alecl by the following:
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0~0
~~
which is derived from alpha-ionone and tripropylene glycol.
Some specific examples of acyclic ketals useful herein include:
\~O(CH2CH20)6C 12H25
~\O(CH2CH20)6C 12H25
S which is derived from 2-octane and Neodol 6-25 and
O(CH2CH2O)7OCH3
~ O(CH2CH2O~7OCH3
which is derived from 2-octanone and PEG-300 methyl ether.
Variations of the present invention include laundry detergents which
10 incorporate acetals or ketals wherein the parent alcohol is a polymer such aspolyvinyl alcohol, starch or synthetic copolymers incorporating tri- or polyhydric
alcohols as monomers.
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The pro-fragrance compound herein can be used at widely ranging levels.
Thus, a pro-fragrance acetal, ketat or mixture thereof is formulated in the present
detergent compositions at levels in the general range about 0.0001% to about
10%, more preferably from about 0.001% to 5%, more preferably still, from about
5 0.01% to about 1%.
A pro-fragrance compound can be used as the sole fragrance compound
of the present detergenl compositions, or in combination with other pro-
fragrances andlor in combination with other fragrance materi~'s, extenders,
fixatives, diluents and the like. For exai"ple, incorporation of the pro-fragrance
10 material into a waxy substance, such as a fatty triglyceride, may further improve
storage stability of the present pro-fragrance compounds in granular laundry
detergents, especially those comprising bleaches. In liquid or gel forms of
detergent compositions, hydrophobic liquid extenders, diluents or fixatives can be
used to form an emulsion wherein the pro-fragrance compound is further
15 stabilized by separating it from the aqueous phase. Nonlimiting examples of
such stabilizing materials include dipropylene glycol, diethyl phthalate and acetyl
triethyl citrate. Just as there exist hydrophobic perfumery i"gred;en~s which can
be used to stabilize the pro-r,~grance rnaterial~ there also exist detergency
ingredients which also have a perfume stabilizing effect and can be formulated
20 with the pro-fragrance material. Such ingredients include fatty acid amines, low
foaming waxy nonionic ",aterials co-llnlonly used in auloi"dt,c dishwashing
detergents, and the like. In ge"eral, where pro-fragrances are used along with
other fragrance materials in detergent compositions herein, it is preferred that the
pro-f,dyrance be added separately from the other r,dgrance materials.
25 Svnthesis of pro-r,a~r~nces
Acetals and ketals can be p,epared by the acid-catalyzed reaction of an
aldehyde or ketone with an alcohol (or diol), using conventional acid catalysis
such as HCI or p-toluenesulfonic acid, or supported sulfonic acid catalysts e.g.,
AMBERLYST 15TM. See Meskens, F., Synthesis, (7) 501 (1981) and Meskens,
30 F., Jannsen Chim Acta (1) 10 (1983). Many aldehyde, ketone and alcohols
useful in the synthesis of acetal and ketal pro-rla9rallces of the present invention
are sensitive to strong acid conditions and can undergo undesirable side
reactions. See Bunton, C.A. et al, J. Org. Chem. (44), 3238, (1978), and Cort,
O., et al, J. Org. Chem. (51), 1310 (1986). It is also known that acetals of alpha,
35 beta-unsaturated aldehydes can undergo migration of the double bond under the
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12
inappropriate selection of the acid catalyst. See Meskens, F., Synthesis, (7),
501, (1981) and Lu, T.-J, et al. J. Org. Chem. ~60), 2931, (1995). For acid
sensitive materials, acid catalysts with pKa's among 3 and 4 are the most
desirable to minimize double bond migration while maintaining the reactivity
5 necess~ry to produce the acetal (or ketal). For example, in the synthesis of
digeranyl decanal, p-toluenesulfonic acid (pKa =1 ) c~uses undesirable side
reactions with geraniol. Citric acid (pKa1=3 1~ pKa2=4.8~ pKa3=6.4) can be used
to form the acetal without side reactions.
Another technique of avoiding side reactions in preparing acetals and
10 ketals of acid sensitive ",aterial, such as geraniol, is by transacet~ ,.lion of a
dimethyl acetal or ketal with a higher molecular weight alcohol, using a mild
Lewis acid such as titanium isopropoxide or boron trifluoride etherate as the
catalyst.
Detersive Surfactants
The detergent composition of the present invention includes a detersive
surfactant in addition to the pro-fragrance compound(s).
Non-limiting examples of sy"tllt:lic detersive sulrd~;tdllts useful herein
typically at levels from about 0.5% to about 90%, by weight, include the
conventional C11-C1g alkyl benzene sulfonates ("LAS") and primary, branched-
20 chain and random C10-C20 alkyl sulf~t.es ("AS"), the C10-C18 secondary (2,3)
alkyl sulfates of the formula CH3(CH2)X(CH(CH3)OSO3-M+) and CH3
(CH2)y(CH(CH2CH3)0S03 M ) wherein x and y are i"tegers and wherein each
of x and (y ~ 1) is least about 7, preferably at least about 9, and M is a water-
solubilizing cation, especi~"y sodium, unsaturated sulfates such as oleyl sulfate,
25 the C10-C18 alkyl alkoxy sulf~tes ("AEXS"; especially EO 1-7 ethoxy sulfates),
C10-C18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates),
the C10-C1g glycerol ethers, the C10-c18 alkyl polyglycosi~es and their
cor,espol,Jing sulfated polyglycosides, and C12-C1g alpha-sulronated fatty acid
esters. If desired, the conventional nonionic and amphoteric surfactants such as30 the C12-C1g alkyl ethoxylates ("AE") including the so-called narrow ~,eak3d alkyl
ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and
mixed ethoxy/propoxylates), C12-C1g betaines and sulfobetaines ("sultaines"),
C1 0-C18 amine oxides, and the like, can also be included in the overall
compositions. The C10-c18 N-alkyl polyhydroxy fatty acid amides can also be
35 used. Typical examples include the C12-C1g N-methylgluca",ides. See WO
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9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy
fatty acid amides, such as C10-C1g N-(3-methoxypropyl) glucamide. The N-
propyl through N-hexyl C12-C1g glucamides can be used for low sudsing. C10-
C20 conventional soaps may also be used; however, synthetic detetgents are
5 preferred. If high sudsing is desired, the branched-chain C10-C16 soaps may beused. Mixtures of anionic and nonionic surfactants are especially useful. Other
conventional useful surfactants are listed in standard texts. See also U.S. Patent
3,664,961, issued May 23, 1 g72.
Preferred compositions incorporating only synthetic detergents have a
10 detergent level of from about 0.5% to about 50%. CG"~posilions con~ail-ing soap
prefera~,ly comprise from about 10% to about 90% soap.
The detergent compositions herein, prt:ferably, have a pH of from about
7.1 to about 13, more typically from about 7.5 to about 9.5 for liquid detergents
and from about ~ to about 12 for granular detergents when measured at 1%
15 concentration of the distilled water at 20~C.
Test Methods
Calcul~tion of CLogP
The pro-fragral~ces of the invention are characterized by their
octanol/water ,uallilio,) coefficient P. The octanol/water partition coerr,c.~nl of a
20 pro-fragrance is the ratio between its equilibrium conce~,t,dliGri in octanol and in
water. Since the p...lilion coerr,cients of the pro-r,ay~ ce compounds are large,
they are more conveniently given in the form of their logarithm to the base 10,
logP.
The logP of many compounds has been repG,Ied. For example, the
25 Por"ona92 d~t~h~se, available from Daylight Ch~ um~alion Systems, Inc.
(Daylight CIS), contains many such vaJues, along with cildlions to the original
literature.
Howevcr, the logP values are most conveniently c~lcu'ated by the
"CLOGP" program, also available from Daylight CIS. This program also lists
30 experimental logP values when they are available in the Pomona92 database.
The "calcu~ated logP" (CLogP) is determined by the fragment approach of
Hansch and Leo (cf., A. Leo, in Comprehensive Medicinal Chel"i~l,y, Vol. 4, C.
Hansch, P.G. Sammens, J.B. Taylor and C.A. Ramsden, Eds., p. 295, Pergamon
Press, 1990). The fragment approach is based on the chemical structure of a
35 compound and takes into account the numbers and type of atoms, the atom
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14
connectivity, and chemical bonding. The CLogP values, which are the most
reliable and widely used eslirllates for this physicochemical property, are
preferably instead of the experimental logP values in the selection of pro-
fragrances.
Determination of Hydrolysis Half-life (t-1/2)
Hydrolysis half-life is the measurement used to determine the ease with
which the pro-fragrance compound undergoes acid hydrolysis and thereby
rele~ses its fragr~nce component(s) upon exposure to acid conditions. The pro-
fragrance compounds of the invention have a half-life of less than 60 minutes,
10 under the described hydrolysis conditions at pH 0. Preferably, pro-fragrances of
the invention have a half-life at pH 2 of less than 60 minutes. For granular
detergents, the more reactive pro-fragrances, that is, those with half-life at pH 2
of less than one minute, are most suitable, although those having a half-life ofless than 60 minutes at pH 0 are also useful. For liquid detergent applicalions,15 pro-fragrances having a half-life of less than 60 minutes at pH 0, and half-life
greater than one minute at pH 2 should preferably be used.
Hydrolysis half-life is cleter-"ined by UVN spectroscopy in a 90/10
dioxane/water system at 30~C by following the appeard"ce of the carbonyl
absorbance. Rec~use of the hydrophobicity of the pro-fragrance compounds of
20 the invention, a high dioxane/water ratio is needed to ensure solubility of the pro-
fragrance. The pH of the water used is achieved by using aqueous HCI. The
conce"l,dlion of the pro-fragrance in the dioxanc/waler system can be adjusted
to achieve convenient, measurable absorbance changes.
All measu-eme"ts are carried out using a I Icv~ Packard 8452 A Diode
25 Array Specl,ophotometer using quartz 1 cm path length cuvette cells. Materials
used include 1,4-dioxane HPLC Grade 99.9% (Sigma-Aldrich), ~N HCI volumetric
solution (J.T. Baker), deionized water fiitered with MilliQPlus (Millipore) at
resistivity of 18.2 M Ohm cm. The pH's are measured using an Orion 230 A
standardized with pH 4 and pH 7 buffers. The 1N HCI standard is used directly
30 for pH 0 conditions. For pH 2 condilions, 1 N HCI is diluted with deionized water.
Pro-fragrance is weighed out in a 10ml volumetric flask using an analytical
balance (Mettler AE 200) Precision is 1/10 mg. The weighed material is
dissolved in about 8ml dioxane. Both the dioxane solution of pro-fragrance and
aqueous acid solution prepared as described supra are pre-heated in their
35 separate containers to a temperature of 30 + 0.25~C by means of a water-bath.
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1.000ml of aqueous acid solution is added to the pro-fragrance solution by
means of an Eppendorf pipetter. This is followed by diluting to the 10ml mark
with dioxane. Hydrolysis time is measured starting upon addition of the acid.
The pro-fragrance solution is mixed for 30 seconds by shaking and the solution
5 is transferred to a quartz cuvette. The absorbance of the pro-fragrance solution
(At) is followed at a regular series of time intervals and the cuvette is kept in the
water-bath at the above-indicaled ten,peralure between measurements. Initial
absorbance (Ao) measurei"e"ts are carried out using an equal concentration of
pro-r,ayra,lce in a 90/10 v/v dioxane - deionized water solution and final
10 absorbance (Af) measurer"ents are taken using the hydrolyzed pro-r,agrance
solution after the hydrolysis is cGmp'_te. The wavelength at which the hydrolysis
is followed is chosen at the wavelength of the absorbance maximum of the
parent aldehyde or ketone.
Re~ction h-~f lifes are determined using conventional procedures. The
15 observed first-order rate cGnsla"t (kobs) is determined by slope of the line
provided by plotting the foll~J;.,y function vs time (min):
Ln l(Ao - Af)/ (At - Af)]
wherein said function is the natural log of the ratio between the absorbance
difference at initial time (Ao) and final time (Af) over the absorbance difference at
20 time t (At) and final time (Af).
Half-life as defined herein is the time required for half of the pro-r,ag,ance
to be hydrolyzed and is determined from the observed rate constant (kobs) by
the following function:
Ln (1/2) = -kobs t 112
25 Additional Deteryent Ir,~"ed.~nt~
In addition to the pro-fragrance co",pounds described herein the
detergent c~rnposition of the present invention may further include one or more
additional deterge,nt ingredients co",r"only used in ~leteryel,t products such as
r"aterials for assisling or enhancing cleaning performance treatment of the
30 subsl,dte to be cleaned or to modify the aesthetics of the detergent composition
(e.g. conventional perfumes colorants dyes etc.). Such additional ingredients
are known to those of skill in the art. The following are illustrative examples of
other detergent ingredients.
Builders - Detergent builders can optionally be included in the
35 compositions herein to assist in controlling mineral hardness. Inorganic as well
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as organic builders can be used. Builders are typically used in fabric laundering
compositions to assist in the removal of particulate soits.
The level of builder can vary widely depending upon the end use of the
composition and its desired physical form. When present, the compositions will
5 typically comprise at least about 1 % builder. Liquid formulations typically
comprise from about 5% to about 50%, more typically about 5% to about 30%, by
weight, of detergent builder. Granular formulations typically comprise from about
10% to about 80%, more typically from about 15% to about 50% by weight, of the
detergent builder. Lower or higher levels of builder, however, are not meant to
l0 be excluded.
Inorganic or detergent builders include, but are not limited to phosphate
builders such as, the alkali metal, an"no,~ium and alkanola,n,~,onium salts of
polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and
glassy polymeric meta-phosphates), phosphonates, and phytic acid, and non-
15 phosphorous builders such as silicates, carbonates (including Licarbonates andsesquicarbonates), sulphates, and aluminosilicates. Non-phosphate builders are
required in some locales.
Organic builders suitable for use herein include polycarboxylate builders
such as disclose~l in U.S. Patent 3,308,067, issued Mar. 7, 1967; 4,144,226,
20 issued Mar. 13, 1979 and 4,246,495, issued Mar. 27, 1979.
Soil Rele~se Agents
Soil Release agents are desirably used in laundry deter~ents of the instant
invention. Suitable soil release agents include those of U.S. Patent 4,968,451,
Nov. 6, 1990, such ester oligo",ers can be prepared by (a) ethoxylating allyl
25 alcohol, (b) reacting the product of (a) with di"~etl~yl ter~plltl,alate ("DMT") and
1,2-propylene glycol ("PG") in a two-stage tra. ~ses~erificdliGn/oligomerizationprocedure and (c) reacting the product of (b) with sodium met~hisulfite in water;
the nonionic end-capped 1,2-propylene/polyoxyethylene terephthalate polyesters
of U.S. Patent 4,711,730, issued Dec. 8, 1987, for example, those produced by
30 transesterification/oligome,i~dtion of poly(ethyleneglycol) methyl ether, DMT, PG
and poly(ethyleneglycol) ("PEG"); the partly- and fully- anionic-end-capped
oligomeric esters of U.S. Patent 4,721,580, issued Jan. 26, 1988, such as
oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-
hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric
35 compounds of U.S. Patent 4,702,857, issued Oct. 27, 1987, for example
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produced from DMT, Me-capped PEG and EG and/or PG, or a combination of
DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and
the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. Patent
4,877,896, issued Oct. 31, 1989, the latter being typical of SRA's useful in both
5 laundry and fabric conditioning products, an example being an ester composition
made from m-sulfobenzoic acid monosodium salt, PG and DMT optionally but
preferably further comprising added PEG, e.g., PEG 3400. Another preferred
soil release agent is a sulfonated end-capped type described in U.S. Patent
5,41 5,807.
10 Other Inqredients
The compositions herein can contain other ingredients such as enzymes,
bleaches, fabric softening agents, dye llansr~r inhibitors, suds suppressors, and
chelating agents, all well known within the art.
Formulation with Deterqe, Ib With or W~thout Conventional Perfumery Materials
While the pro-fragrances of the present invention can be used alone and
simply mixed with essential detergent ingredient, most notably surfactant, they
can also be desirably combined into three-part formulations which combine (a) a
non-fragrance detergent base comprising one or more synthetic detergents, (b)
one or more pro-r,dsrd,~ce acetals or ketals in accordance with the invention and
20 (C) a fully-formulated fragrance. The latter provides desirable in-package and in-
use (wash-time) fragrance, while the pro-fragrance provides a long-term
fragrance to the laundered textile fabrics.
In formulating the detergent compositions of the present invention, the
fully-formulated fragrance can be prepared using numerous known odorant
25 ingredients of natural or sy"lhetic origin. The range of the natural raw
sul~st~nces can embrace not only readily-volatile, but also moderatcly-volatile
and slightly-volatile components and that of the sy"l~etics can include
representatives from practically all cl~sses of fragrant sl~bst~nces, as will beevident from the following illustrative compilation: natural products, such as tree
30 moss absolute, basil oil, citrus fruit oils (such as ber~a",ot oil, mandarin oil, etc.),
mastix absolute, myrtle oil, palmarosa oil, patchouli oil, pe~ilyra;i) oil Paraguay,
wormwood oil, alcohols, such as farnesol, geraniol, linalool, nerol, phenylethylalcohol, rhodinol, cinnamic alcohol, aldehydes, such as citral, HelionalTM, alpha-
hexyl-cinnamaldehyde, hydroxycitronellal, LilialTM (p-t-butyl-alpha-methyl
35 dihydrocinnamaldehyde), methyl nonyl acetaldehyde, ketones, such as
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18
allylionone, alpha-ionone, beta-ionone, isoraldein (isomethyl-a/pha-ionone),
methylionone, esters, such as allyl phenoxyacetate, benzyl salicylate, cinnamyl
propionate, citronellyl acetate, citronellyl ethoxolate, decyl acetate,
dimethylbenzylcarbinyl acetate, dimethylbenzylcarbinyl butyrate, ethyl
5 acetoacetate, ethyl acetylacetate, hexenyl isobutyrate, linalyl acetate, methyl
dihydrojasmonate, styrallyl acetate, vetiveryl acetate, etc., lactones, s~ch as
gamma-undecalactone, various components often used in perfumery, such as
musk ketone, indole, p-menthane-8-thiol-3-one, and methyl-eugenol. Likewise,
any conventional fragrant acetal or ketal known in the art can be added to the
10 present composition as an optional component of the conventionally formulatedperfume (c). Such conventional fragrant ~cet~ls and ketals include the well-
known methyl and ethyl ~ceta~s and ketals, as well as acetals or ketals based onbenzaldehyde, those comprising phenylethyl moieties, or more recently
developed specialties such as those described in a U.S. Patent entitled "Acetalsand Ketals of Oxo-Tetralins and Oxo-lndanes, see V.S. Patent 5,084,440, issued
Jan. 28, 1992, assigned to Givaudan Corp. Of course, other recent synthetic
speci~'ties can be included in the perfume co,l,positiol)s for fully-formulated
detergents. These include the enol ethers of alkyl-substituted oxo-tetralins andoxo-indanes as described in U.S. Patent 5,332,725, issued July 26, 1994, and
U.S. Patent 5,264,615, issued Dec. 9, 1991. It is preferred that the pro-fragrance
compound be added separately from the conventional fragrances to the
detergent compositions of the invention.
Formulation with other SPecial-purpose Fragrance Delivering ComPounds
Detergents in accor~ance with the present invention may further,
optionally, if desired, contain other known compounds having the capability to
enhance subst~ntivity of a f,dgr~nce. Such compounds include, but are not
limited to, the aluminum alkoxides such as isobutylaluminium diferanylate as
disclosed in U.S. Patent 4,055,634, issued Oct. 25, 1977; or the known titanate
and zirconate esters or oligoesters of fragrant ,naterials such as those disclosed
in U.S. Patent 3,947,574, issued March 30, 1976 and U.S. Patent 3,779,932,
issued Dec. 18, 1973. When using such organoaluminium, organotitanium or
organozinc derivatives, they may be incorporated into the detergent compositionsof the present invention described herein at their art-known levels.
Methods of Use
In its method aspect, the present invention can be described as:
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19
A method of delivering residual fragrance to a washed surface which
comprises the steps of
(a) washing said surface in an aqueous solution of a detergent composition
comprising a pro-fragrance compound selected from the group consisting
of an acetal, a ketal, and mixtures thereof, wherein the pro-fragrance
compound having a CLogP of less than about 4 and a detersive
surfactant, wherein said detergent cG",position has a pH of at least 7.1
when measured as a 1% solution in distilled-water at 20 C;
(b) subsequently exposing said surface to a reduction in pH.
EXAMPLES
The following examples further describe and demonstrate ~embodiments
within the scope of the present invention. The examples are given solely for thepurpose of illustration and are not to be construed as limitations of the present
15 invention, as many varidlio"s thereof are possiLI~ without depalling from the spirit and scope of the invention.
The detergent compositions shown below can be prepared by any
conventional method well known in the art. A suitable method and formulation
are as follows:
Example 1
[Preparation of Di(Neodol 23-6.5) P.T. Bucinal Acetal by Acid Catalysis]
A 200 ml single necked, round bottom flask is prepared. A 4.099 portion
of P.T. Bucinal (20 mmol), 60ml of benzene, 22.59 of Neodol 23-6.5 (50 mmol),
25 and 0.29 of para-toluene sulfonic acid monohydrate (1 mmol, 5 mol%) is added.The vessel is fitted with a Dean-Stark trap and condenser, and is heated to
reflux. The reaction is continued until an equivalent of water is collected in the
Dean-Stark trap. Upon cooling, the reaction mixture is washed several times
with saturated sodium carbonate and water followed by drying with sodium
30 sulfate. The solvent is removed in vacuo and unreacted parent aldehyde is
removed under bulb-to-bulb distillation at 250~C, 0.2mmHg to yield 19.69 of palebrown oil (80%) identified spectrosco~ lly at the desired ",alerial. The CLogP
of resulting acetal is less than 4.
35 Example 2
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ZO
[Preparation of Tripropylene glycol P.T Bucinal Acetal by Acid Catalysis]
A 200 ml single necked, round bottom flask is prepared. A 4.09g portion
of P.T. Bucinal (20 mmol), 60 ml of benzene, 4.819 of tripropylene glycol (25
mmol), and 0.2g of para-toluene sulfonic acid monohydrate (1 mmol, 5 mol%) is
S added. The vessel is fitted with a Dean-Stark trap and condenser, and is heated
to reflux. The reaction is continued until an equivalent of water is collected in the
Dean-Stark trap. Upon cooling, the reaction mixture is washed several times
with saturated sodium carbonate and water followed by drying with sodium
sulfate. The solvent is removed in vac~lo and unreacted parent aldehyde is
10 removed under bulb-to-bulb dislillalion at 250~C, 0.2~ 119 to yield 6.19 of pale
brown oil (80%) identified spectroscopically at the desired material. The CLogP
of resulting acetal is less than 4.
ExamPle 3
15 [Granular Laundry Composition delivering from Di(Neodol 23-6.5) P.T. Bucinal
Acetal]
Pro-fragrance of Example 1 1.0%
C1 1-C13 Dodecyl Benzene Sulro"ate 21.0%
C12-C13 Alkyl Ethoxylate EO 1-8 1.2%
Sodium Tripolyphosphate 35.0%
Zeolite Na 4A 14.0%
Sodium Silicate 2.0 ratio 2.0%
Sodium Carbonate 23.4%
Enzyme (SavinaseTMand/or LipolaseTMfrom Novo) 1.4%
CarboxymethylCellulose 0.3%
Anionic Soil Rele~e Agent *1 0.3%
Brightener 0.2%
Silicone Suds Supp~ssor (Dow Corning Corp) 0.2%
Perfume*2
Sodium Sulfate 0.5%
Moisture balance up to 100%
*1 See U.S. 4,968,451
*2 Perfume composition of the following formula:
Benzyl salicylate 20%
Ethylene brassylate 20%
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Galaxolide (50% soln. in benzyl benzoate) 20%
Hexyl cinnamic aldehyde 20%
Tetrahydro linalool 20%
100%
ExamPle 4
[Granular Laundry Detergent Delivering from Di(Neodol 23-6.5) P.T. Bucinal
Acetal]
Pro-fragrance of Example 1 1.0%
Linear Dodecyl Benzene Sulronate 21.0%
Neodol 23-6.5- Nonionic Surfactant 1.2%
Sodium Tripolyphosphate 35.0%
Zeolite 4A 14.0%
Sodium Silicate 2.0 ratio 2.0%
Sodium Carbonate 23.4%
Enzyme (SavinaseTM andlor LipolaseTM from Novo) 1.5%
Carboxymethyl Cellulose 0.3%
Anionic Soil Rele~se Agent~1 0.3%
Bl ightener 0.2%
Silicone Suds Suppressor (Dow Corning Corp) 0.2%
Perfume~2 0 3%
Sodium Sulfate 0.5%
Moisturebalance upto100%
~1 See U.S. 4,968,451
~2 See~2 in Example 3
Exar"~le 5
[Laundry Detergent Comprising Pro-Fragrance and Fully-Formulated Perfume
30 Composition having a Conventional Ketal fragrance Component]
A laundry detergent composition is prepared by weighing 989 of laundry
detergent according to Exa",,~le 4 with the exception that perfume and pro-
fragrance are not included; admixing to said composition 29 of a perfume of
flowery-woody type made up of a mixture of a first premix and a conventional
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ketal (not in accordance with essential pro-fragrance as defined herein) as
follows:
First Prernix:
Oil of bergarnot 7.5 9
Linalool 4.0 9
Phenyl ethyl alcohol 4.0 9
Benzyl acehte 2.0 9
Citronellol 0.5 9
HedioneTM (a) 10.0 9
Lyral (b) 4.0 9
Hydroxycitronellal 2.5 9
Rose oxide 1 (c) 10% in DPG 2.5 9
Hexyl cinnamic aldehyde, alpha 7.5 9
Patchouly Oil Indonesian 4.0 9
Iso-E~M (b) 2.0 9
Vetiveryl acetate 2.0 g
B,~ na"olTM F (c) 2.0 9
Benzyl Salicylate 2.0 9
cis-3-l l~xenyl Salicylate 1.0
CedramberTM (b) 1.0 9
Musk Xylene 1.0 9
Indole 10% in DPG 0.5 9
Extract of O PGPOIIaX 0.5 g
Extract of Oakmoss 50% in DPG 5.0 9
(a) Fi,lllellich
(b) IFF
(c) DRAGOCO
Total Parts by weight of First Premix: 68.0 9
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The first perfume premix is modified by adding to it 32 parts by weight of
5a/5b (80:20) wherein 5a is 5-ethylenedioxy-3 beta-H-isolongifolane and 5b is 5-ethylenedioxy-3 alpha-H-isolongifolane; these two compounds being
conventional perfume ketals not in accordance with the present invention, and
5 their synthesis is described in "CYCLIC ISOLONGIFOLANONE-KETALS - THEIR
MANUFACTURE AND THEIR APPLICATION", U.S. Patent 5,426,095, issued
June 20, 1995 to Brunke and Schatkowski, assigned to Dragoco.
1.09 of a pro-fragrance according to Example 2 is mixed into the
powdered, perfume-free detergent composition. Finally, about 1.59 of the above
10 perfume composition is sprayed onto the mixture of detergent and pro-fragrance,
to complete the fragranced, pro-fragranced laundry detergent composition. This
co",position has a floral-woody character and leaves an improved, long-lasting
scent on textile fabrics washed therewith.
I 5 Exdl "~ 6
Detergent having the form of a Laundry Bar Comprising Pro-Fragrance]
Pro Fragrance of Example 1 1.0%
Tallow Soap and Coco Soap Mixture (80:20)44.0%
Linear Dodecyl Benzene Sulfonate 12.0%
Sodium Tripolyphosphate 6.0%
Sodium Carbonate 8.0%
Sodium Sulfate 0.5%
Talc 9.0%
Perfume~1 0.2%
Moisture balance up to 100%
~1 See ~2 in Example 3
Exam~le 7
30 [Liquid Detergent Comprising Pro-Fragrance]
Pro Fragrance of Example 1 1.0%
Sodium C12-C15 Alcohol Ethoxylate E 2.5 Sulfate 18.0%
Neodol 23-9 Nonionic surfactant 2.0%
35 C12Alkyl N M~ll,ylglucamide 5.0%
Sodium Cumene Sulfonate 3.0%
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WO 97134989 PCT/US97105372
24
Citric Acid 3.0%
FattyAcid (C12-C14) 2.0%
Boric Acid 3.5%
Sodium Hydroxide 2.8%
Ethoxylated Tetraethylene Pentaimine 1.2%
Soil Release Polymer 0.15%
1,2-Propanediol 8.0%
Ethanol 3.6%
Monoethanolamine 1. 1%
Minors~1 1.8%
Moisturebalance upto100%
*1 Minors include brightner and enzymes
Although the examples and embodiments described herein are illustrative
of the invention, those skilled in the art will be able to recognize that variations or
n,o~lificalions in light thereof are fully within the scope of the invention. In one
such variation, the practioner will minimize the molecular weight while still
seeking the advantages of the invention, for example by sele~.ti,19 pro-fragrances
20 at-1/2 of less than one minute at pH 0.
