Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
W093tO1794 PCT/US92/05686
2113~13
PERFUME ADD~ V~S FOR FABRIC-SO~ NG
COMPOSITIONS
Technical Field
The prese~t in~ention relat~s to perfume
additive~ ~or u~e in combination with ~abric-
softening compositions.
.
Back~u,ld
Fabric~softening cGmpositions to ~e added in
the rinse step of a laundry cycle are well known.
The ov~all:function of such compositions can
be defineid as the improvement of fabrics
aesthetics/feel, a~t~r a wash cycle; this is why,
in addition to softness, perfume delivery on
fabrics from:such compositions i5 an ~specially
important aspect, and continuous efforts ~re made
to improve suah perfume delivery, so as to make it
not only consumer-noticeable, but also long
lasting.
WO 93/01794 2 1 1 3 6 1 3 2 PCr/US92/05686
In EP-A-0 397 245 and EP-A-397 246 have been
described perrume particles wherein perfume is
dispersed within certain water-insoluble pol~meric
carrier materials, and the resulting particles are
used in fabric cleaning or conditioning
compositions. Not all perfume compositions,
however, are compatible with said polymeric
carrier materials.
It has now b~en found a simple and inexpen~ive
carrier system for perfumes, which is ~ully
compatible with any perfume, and is very
convenient to use.
Such a carrier system consists of porous
silica onto which a mixture, at specific ratios,
of perfume and softening active i~ adsorbed.
rhe use of porous spheroidal silica per ~é as
carrier for a wide range of material including
perfumes, has been disclosed~in EP-A-294 206, not
r~l~ting to softening of fabri s nor any
combir.ation with sof~ening active.
.
:~ ~ Summar~ of the Invention
The present~ invention relates to a perfume
additive in granular form for u~e with ~abric-
softening compositions, containing :
from 30~ to~80~:by~weight of a mixture of perfume
:and softening'~active,: in a ratio of perfume to
: softening active of l:lO~to 5~ preferably 1:5 to
from:2Q~ to:70% by~weight oP porous silica on which
said~mixture of perfume and softening active is
: adsorbed, the particle size of~ the porous silica not
exceeding 500 micrometers.
:
: ~
WO93/01794 211~3 613 PCT/US92/0~686
The present invention also encompasses the use of
said additives as single doses during use of f~bric
softening compositions, or the preparation of ready-
to-use fabric softening compositions out of
concentrates.
~etailed Desc~.iption o~ t~e Invention
The por~us silica
The porous silica useful herein i3 a
precipitated spheroidal silica, having a particle
size not exceeding 500 micrometers.
The silica herein typically hss a pore volume
in the range 25 to 75%. This cilica i~ furth~r
characterized by a BET surface area* superior to
50m2/g (DIN 66131) an~ a high abso~ption ~alue.
The absiorption can be expressed a~ Dibutylphtalate
(~BP) number, this DBP nu~ber should be a~ove
lOOg/lOOg, preferably above ~OOg/lOOg (DIN 53601,
AS'rM ~ 2414).
Porousi~silica correipon~ling to the above
specifications is available under the trade name
SipernatR from Degussa. The additives herein -
~ontain fro~ 20% to 70~ of porous silica.
: The ~erfume/so~tenin~ active mixture
: The characterizing ~eature of the present
inv~ntion is that per~ume is mixed with a
softening actiYe be~ore being adsorbed onto the
porous silica.
* measured accord~ing to the method developed by
~: Brunauer, Emmet and Teller (BET), J. Amer. Chem.
Soc. 60, 309~ (l93a).
: ~
:
W093/01794 - PCT/US92/05686
2113~13 4
The ratio of perfume to softening active is
~rom l:lO to 5:l, preferably l:5 to 3:l.
Perfume, in the sense of perfume components or
compositions of perfums components, can be any
odorifirous materials or.any materials which act
as a malodour counteractent. The perfume will
most o~ten be liquid at ambient temperatures~ but
also can be liquified solid such as the various
camphoraceous perfumes known in the art. The
perfume can be relatively simple in composition or
can comprise highly sophisticated, compact
miXtures of natural or synthetic ch~mical
components, all chosen to provide any desired
odour.
Useful perfumes are those odorous materials
that ~.eposit~on fabrics during the laundry process
and are detectable:by people~with normal olfac~ory
sensitivity. Many of the perfume ingredients
along with their~odor haracter and their physical
and chemical:properties are given in "Perfume and
Flavor chemicals (aroma chemicals) I~ ! Stephen
Arctender, Vo~ls:.::I:and~ Aurthor, Montclair,
H.J. and the~Merck Index, 8th Edition, Merck &
Co~, Inc~ RahWay, N.J.~ ; Per~ume components and .-
compositions~can~ also be found in the art, e.g~ US
Patent Nos. 4,145,184, 4:,152,~72,~ 4,2:09,4l7 or
4,515,705.
A wide variety~of:chemicals~a~re known for
perfume use in~cluding materials~such as~aldéhydes,
ketones, esters~ and the:~like. :More aommonly,
naturally occurring~plant~and animal oils and
exudates compris~ing complex mixtures~of various
chemical components:are known:for use as perfume,
and~such~materials~can be~used~herein. :Typical
:perfumes can:~comprise~e.g. woody~earthy bases
containing e:xotic materia~s such:as sandalwood
W093/01794 2 1 1 3 6 1 3 P~T/US92/0~686
5 .:
oil, civ~t and patchouli oil. The perfume also
can b~ of a light floral fragrance e.g. rose or
violet extract. Further the perfume can be
formulated to provide desirable fruity odours e.g.
lime, limon or orange.
Particular exampl~s of useful perfume
components and compositions are anetvle,
benzaldehyde, benzyl acetate, benzyl alcohol,
benzyl formate, i.so-bornyl acetate, camphene, cis
citral (neral~, citronellal, c~tronellol,
citronellyl acetate, paracymene, decanal,
dihydrolinalool, dihydromyrcenol, dime~hyl phenyl
carbinol, eucalyptol, geranial, geraniol, geranyl
acetate, geranyl nitrile, cis-3-hexenyl acetate,
hydroxycitrone}lal, d-limonene, linalool, linalool
oxide, linalyl acetate, linalyl propionate, methyl
anthranilate, alpha-methyl ionone, methyl nonyl
acetaldehyde, methyl~phenyl carbinyl acetate,
laevo-menthyl acetate, menthone, iso-menthone,
myrcene, myrcenyl acetate, myrcenol, nerol, neryl
acetate, nonyl~acetate, phenyl:ethyl alcohol,
alpha-pinene, beta-pinene, gamma-terpinene, alpha-
terpineol,~beta-terpineol, terpinyl acetate,
vertenex (para-tertia~ry-butyl~ cyclohexyl ace~ate),
amyl cinnamic a1dehyde, iso-amyl salicylate, beta-
caryophyllene, aldehyde,;i~so-amyl ~alicylate,
beta-carophyllene, cedrene~,~ cinnamic alcohol,
couramin,~dimeth~1 benzyl~carbinyl acetate, ethyl
vanillin, éu~enol,:iso-eu~enol~, flor acetate,
he1iotrophine,~3-cis-hexenyl~salicylate, hexyl
silicylate,~:~lilial (para-t-rtiarybutyl-alpha-
methyl hydrccinnamic:aldehyde)~:, ga~ma-methyl
ionone, n~ro1idol,:~patchouli:~a~lcohol, phenyl
hexanol, beta-selinene~,;;trichloromethyl phenyl
car~inyl acatate:,~ triethyl citrate, vanillin,
:veratraldehyde, alpha-aedrsne, beta-cedrene,
5~24sesquiterpenas;,;;benzophenonet benzyl
salicylate,: ethylene~brassylate, galaxolide
(1,3,4,6,7,8-hexahydro-4,6,7,8,8,-hexamethyl-
W093/01794 ~ 1 1 3 ~ 1 3 PCT/U~92/~5686
cyclo-pe~ta-gamma-2-benzopyran), hexyl cinnamic
aldehyde, lyral (4 (4-hydroxy-4-methyl phenyl)-3-
cyclohexene-lo-carboxaldehyde), methyl cedrylone,
methyl dihydro jasmonate, methyl-beta-naphthyl
ketone, musk ambrette, musk idanone, musk ketone,
musk tibetine, musk xylol, aurantiol and
phenylethyl phenyl acetate.
The s~ftening acti~e for use in the perfume
additi~es herein can be selected from the group of
di-long chain quaternary ammonium compound~, di-
long chain imidazoline compaunds, di-long chain
guaternized imidazoline compounds, as well as
cert~in mono long-chain alkyl quaternary am~onium
com~Gu~s and mono long~chain alkyl amines.
Di-long chain quaternary ammonium compounds
are of the for~ula :
2 +
Rl - N ~ - R3 A-
4 ~ ~
wherein Rl and R2 are C1 4 saturated alkyl
ou~ or hydroxyalkyl group~and R3 and R4 are
~: ~ acyclic aliphatic C8_30, pre:ferably C12_23, more
~: prefer3bly ~l5_22 hydrocarbon:~ouy~ which may be
~ ~ intempted by:ester linkages,~and~A is an anion.
'~ ~ :Preferred~are:ev~oul.ds o~ the formula above
wherein R1:~and. R2 are methyl~groups, and ~3 and R~ .
are derived~from :fatty~;mater~ials:such as tallow.
: Pre~erred compounds of:the~formula above ~or
use herein~inc~lude the~;well known dit~llowdimethyl
am~onium chl:oride::(DTDMACj, ditallowdimethyl
ammonium methyl~sulfate,~and di(hydrogetated
; tallow)dim~thyl~:ammonium~chloride.
~: ,
W093/01794 2113 613 PCT/US92/056X6
.. . , ., ~, . ~ ,
Compounds of the formula above wherein R3 and '
are interrupted by ester groups are.disclosed
in EP-A-239 910; such compounds have the advantage
o~ being more rapidly biodegradable than the
above-described compounds; pre~erred is N,N di(2-
tallowyloxy-~-oxo-ethyl)N,N dimethylammonium
chloride.
Di~long chain imid~zoline compounds are o~ ~he
formula
(CH21m
N N - X - R2
I
Rl
wherein m is an integer from 2 to 4,
preferably 2, an~ Rl and R2 are, independently, a
C8-C30 alkyl or alkenyl, preferably C12-C20 alkyl,
more pre~erably Cls-Clg alkyl, or mixtures of such
alkyl radicals. Examples of such mixtures are the
alkyl radicals obtained from coconut oil, "soft"
: (non-hardened) tallow, and hardened tallow;
: X is~- R4 - T - C -
wherein T is O or NRs, Rs being H or Cl-C4
~alkyl, preferably H, and R4 is a divalen~ Cl-C3
alkylene group or (C2H40)m, wherein m is a number
o~ from 1 to;8; or X is R4.
Most preferred imidazol~ine activss of the
~. formula ~above are o~ the following formulae :
:~; :: :
~ '
::
:: :
: ~ :
WOg3/01794 PcT/us92/o5686
~113613
Ia Ib
O O
/~ 11 /~ 11
~, N--( CH2 ) 2 ~H--C--Rl and N~ N ( CH2 ) 2--O--C--Rl
Rl R
whexein Rl is a tallow group.
Compounds of formula Ia are
ditallowimidazolines, while ~ompounds of fo~mula
Ib are ditallowimidazoline esters.
Quaternized di~long chain imidazoline
compounds are of the formula :
(CH2)m
\
~ _ N N - X - Rl A- (I)
~C /
: or : ~ ~
_
(CHz)m R2 ~ +
; I / \ / ~
~: ~ . N N ~ A- (II)
C X -
:; :
; ~ R :
:: :
~ :
': or mixtures thereof, wherein R and Rl are,
independently,~Cll-C2l hydrocar~yl groups, preferably
tallow, R2 is~a Cl-C4 hydrocarbyl group, preferably
:: :
W093/017g4 2 1 1 3 6 1 3 PCT/US~2/056X6
methyl, A is an anion, m is an integer from 2 to 4,
preferably 2 and X is R4 ~ T ~
O
wherein T i5 O or ~R5, ~5 being H or Cl-C4 alkyl,
preferably H, and R4 is a divalent Cl-C3 alkylene group
or (C2H4O)m, wherein m is a number o~ from 1 to 8; or X
is R4. Preferably, T is O and R4 is (CH2)~ (quaternized
ditallow imidazoline ester).
Mono long-chain alky~ amines useful herein
include compounds of the formula Rl - N - R2
/
R3
wherein Rl is a C8_30 a~yclic aliphatic ,
preferably C12_23 hydrocarbon group which may be
intempted by ester linkages, R2 and R3 are Cl_4
saturated alkyl y~u~ or hydroxyalkyl groups of
the formula (CH2CH2O)n H where n is an integer
from 1 to 5.
They further include monotallowimidazolines of
the formula :(CH2~m :
N N - X - H
C
R
wherein Rl is a C8_30 alkyl or alkyl group,
preferably C12-20~ more preferà~ly Cls_l8; m is an
inteyer from-2 to 4, preferably 2 and
X is R4 ~ T - C - O
O
wherein T is o or NR5, R5 being H or Cl-C4
alkyl, preferab~ly H, and R4 is a divalent Cl-C3
: alkylene y~ou~ or (C2H4O)m,~wherein m is a number
of fr~m 1 to 8; or X is R4.
Mono alkyl quaternary~:ammonium compounds
useful herein include compounds of the formula
':
WO 93/01794 211 3 61 3 PCr/US92/056X6
R +
Rl-- N -- R4 A-
R3
wherein Rl is an acyclic aliphatic C8_30,
preferably cl2_z3 hydrocarbon group which may be
interupted by ester linkages, R2, R3 and R4 are
Cl_4 saturated alkyl ~ou~s or hydroxy~lkyl
groups; and A is an anion.
A preferred mono-alkyl ammonium compound for
use herein is cetyl trimethylammonium bromide.
The mono long-chain alkyl amines and mono
long-chain alkyl ammonium compounds are preferably
used in combination with the di-long chain alkyl
ammonium or imidazolines described ~ereinabove.
Mo~t preferred softening activ0s for use in
th~ additives herein are ditallowdimethyl
,
ammonium, ditallowimidazoline ester, quaternized
ditallowimidazoline ester, and mixtures thereof.
Ol~tional i~ L~dient
. : The present~additives;may contain additional
ingredients, which can be~:pre-mixed with the
perfume and so~ft~nin~:active:before they are
. : ~ .
adsorbed onto::the porous;silicate, or added, a~ter
thè~ adsorpti~ ;is completed,~to th'e particles.
Ingredients which:can~be:pre-mixed with the
per~ume and softening active are selected ~rom the
group of
sytheti~ and' natural waxes
synthetic and natural~ fats
synthetic and natural~ mono:, di and tri esters
:: : ::
W093/01794 2113 G 13 PCT/US9~tO5686
11
of polyols with C8-C2z carboxylic acids or
mixtures thereof
- Cg_22 alcohols, ethoxylate$ thexeof and esters
thereof with Cl_4 carboxylic acids
- dyes
Ingredients which can be added to the particles
a~ter adsorption is complete include water-so}uble
coatin~ materials/agglomerating materials and dyes
Preferred ingredients ta be pre-mixed are the
ssters of C8~20 alcohols, in particular glyceryl
monostearate.
The water-soluble coating/agglomerating materials
can be selected ~rom the group of polyvinyl alcohol,
polyethylene glycol, sugars, polyacrylamides,
polysaccharides and similar natural and synthetic
polymers.
Dyes are typically used and can be: added to the
mix before adsorption onto silica, or sprayed on the
~ormed particles as a ~ast step.
: Method~of~pre~aration of ~he add~tives herein
: A co-D~lt of the:softQning:active and the per~me
i5 typically made,~ possibly;including an optional
ingredient such as listed above.
The~co-~elt is adsorbed on porDus silica~ keeping
the ~emperature, needed to keep the co-melt liquid,
typlca~lly at 50-C; Adsorption:can be achiev~d by
adding the co-Delt in portions to the pre-heat~d
porous~;silica:under:agitation,:or ~y spraying it on
pre-heated poro~s silica in:a "Nauta'~ type mixer~
:
W093/01794 PCT/US92/05686
211361~ 12
The resulting free-flowing powder is cooled to a
temperature ranging from 3-C to ambient, and si2ved
on an appropriate sieve (e.g. Mesh 22); the powder is
th2n agglom~rated in an agglomeration unit, such as a
Plough Shar~ L~dige, po~sibly with the addition of a
coating/agglomeration material; ~he agglomerate is
cooled and sieved over an appropriate sieve (e.g.
Mesh 22).
Use Q~ the ~er~ume additives herein
The perfume additives herein can either be used
as single-dose additives ~or fabric soPtening
compositions, during use, or as additives in the
preparation of fabric-softening compositions out of
concentrates, before use.
Preferably, the pre~ent additives a~ used as
single-dose additives to unperfumed fabric so~tening
compositions during u5e; i.e. a dose o~ additive
suf~icient ~or a typic~l washing machine load is
added to unperfumed ~abric softening composition,
prior to the rinse cycle Q~ the laundry process.
Such an addition can conveniently be mad~ i~ the
dicp~ r of auto~atic wa8hing ~açh~ne~; i.e~ before
startihg the laundry cycle, an:a~ount of fabric
soft~nin~ c~ o~.ition in liquid ~orm is ~irst poured
into the ~ p-n~r o~:~he:w~ n~ machine, and the
specific do8e o~ p~rfume additive in granular form is
added to said fabric ~oftenin~ composition sitting in
the disp,ens~r~f and;is dispersed therein.
The Fesulting mixture is then brought into
.
: contact with ~he:~abrics, during the rinse cycle and
the perfume is released onto the fabrics.
:
: ~ :
The use of the perfume additives herein is not
limited:to liquid fabric softening compositions since
their granular form would render them quite suitable
W093/01794 2 1 1 3 6 1 3 PCT/U~92/05686
13
for use in combination with fabric-so~tening
compos~tions in particulat~ form; such fabric-
softening compositions can be used as is, or diluted
with water before use.
When used as such single-wash doses, the present
additives can conveniently be packaged into ~ingle-
dose sachets containing the powdered additive, such
sachets being made available to the consumer in the
form of boxes containing several of them, said
sachets containing either the same per~ume, or
differe~t perfumes so as to allow the consumer to
choose the perfume to be l~ft on the laundered
: fabrics, for ea~h laundry cycle.
The following examples illustrate the in~ention
and facilitate the understanding.
The following granulates are prepared, according
: to the ~ethod described above (with co~ling
temperature of 4-C).
Pe~ aaç bY weiaht
u,~i~n~ ~ Ex.l ~ Ex.ll Ex 111 Ex.lV Ex.V ExVI Ex.VII Ex.YIII Ex. IX
: :
Perfume ~ 13% 47% 2096 20% 20% 3096 20~ ~9~ ~5
Dlttalc~w Dimeth~ ~.. ",.,on~ -n 5496 2096 15% 24% - -
chk~ride ~: ~
~; ~ Dn~v ImWazoline ~er ~ 4796 30% 2796
CT~8 (C~ Tnm~th~
~ium Brom~l a)~ ~ ~ 149~ 1o%
Glyc~ryl.l~nG~,1ealate~ to% 23~~
rbitan ~ ~rdle~ - - - - 25%
: SiiicaSi~"~lR50 33% ~ 33% 40% 33% 33% . . 34%
: Silica S4~.. ~R22 ~ ~ 40% 33%
Polyell.,~M:s~ycd4000~ - 15% - - - 20%
TC~ohd 8~tirnes
ètnomat~ - - - 32%
added in the pr~mK ~ :
'a sp~aye~ ont~ormed ~ 3
SUB~TITU7~:E SHEET
WO ~3/OJ794 P~/US~X/05686
2 1 1 3 ~ 1 3 14
Dye is sprayed onto the above granulates; the formed
granulates are used as per~ume additives for fabric
so~tening cc3mpositions.
!
' ~ :
:
