Source: http://www.patentsencyclopedia.com/app/20100234258
Timestamp: 2017-02-28 10:32:35
Document Index: 571829625

Matched Legal Cases: ['§120', '§120', '§120', '§120', '§120', '§120', '§120', '§120', '§120', '§120', '§120', '§371', '§119', 'art 2']

Jean-Luc Philippe Bettiol (Brussels, BE)
Alfred Busch (Londerzeel, BE)
Hugo Denutte (Hofstade (aalst), BE)
Christophe Laudamiel (Brussels, BE)
Peter Marie Kamiel Perneel (Brugge, BE)
Marie Montserrat Sanchez-Pena (Brussels, BE)
Johan Smets (Lubbeek, BE)
Patent application number: 20100234258
USPC Class: Publication date: 09/16/2010
The present invention relates to a product of reaction between a primary
and/or secondary amine and one or more active ingredients. By the present
invention, there is provided a release of the active component over a
longer period of time than by the use of the active itself.Claims:
1. A product of reaction between:a.) an amine containing component
comprising a primary or secondary amine, said component having an Odor
Intensity Index of less than that of a 1% solution of methylanthranilate
in dipropylene glycol, with the proviso that said amine containing
component is not an aminostyrene;b.) an active component selected from a
ketone, an aldehyde, and mixtures thereof;said product of reaction having
a Dry Surface Odor Index of more than 5.
2. A product of reaction according to claim 1, wherein said amine
containing component is selected from the group consisting of amino
substituted polysaccharides, dendrimers, amino acids, amino acid
derivatives, polyalkyleneimines, polyethyleneimines, partially
alkoxylated polyethylenimines, partially alkoxylated polyalkyleneimines,
polyaminoalkylpolysiloxanes, amino functionalized polydialkylsiloxanes,
amino functionalized organo silanes, amino functionalized
organic-organosilicon copolymers, alkyleneamines,
2,2',2''-triaminotriethylamine; polyetheramines, polyoxyalkyleneamines,
2,2'-diamino-diethylamine; 3,3'-diamino-dipropylamine, 1,3 bis
aminoethyl-cyclohexane; piperazines with more then one amine groups; and
3. A product of reaction according to claim 1, wherein said amine
containing component comprises dendrimers of polyethyleneimines,
polypropyleneimines or polyamidoamines, polyalkyleneimines,
polyethyleneimines, and mixtures thereof.
4. A product of reaction according to claim 1, wherein said amine
containing component comprises polyaminoalkylpolysiloxanes,
polyetheramines, alkyleneamines, piperazines with more then one amine
group and mixtures thereof.
5. A product of reaction according to claim 1, wherein said amine
containing component comprises a material having at least 2 amine groups,
said material being selected from the group consisting of
polyethyleneimines, polyaminoalkylpolysiloxanes, polyetheramines,
alkanolamines, ethyleneamines, polysaccharides, alkyleneamines and
7. A softening composition according to claim 6, wherein said product of
reaction is preformed before being incorporated into the fully-formulated
8. A softening composition according to claim 6, wherein said product of
reaction is present in an amount of from 0.001% to 10% by weight of the
9. A softening composition according to claim 8, wherein said product of
reaction is present in an amount of from 0.005% to 5% by weight of the
10. A softening composition according to claim 9, wherein said product of
reaction is present in an amount of from 0.01% to 2% by weight of the
11. A product of reaction according to claim 1, wherein said active
compound is selected from the group consisting of flavour ketone or
aldehyde ingredients, pharmaceutical ketone or aldehyde actives,
biocontrol ketone or aldehyde agents, perfume ketone or aldehyde
components, refreshing cooling ketone or aldehyde agents and mixtures
12. A product of reaction according to claim 11, wherein said active
component comprises an insect and/or moth repellant.
13. A product of reaction according to claim 12 comprising an insect
and/or moth repellant selected from the group consisting of citronellal,
citral, N,N diethyl meta toluamide, Rotundial, 8-acetoxycarvotanacenone
14. A product of reaction according to claim 11, wherein said active
component comprises an anti-microbial.
15. A product of reaction according to claim 14, wherein said active
component comprises an anti-microbial selected from the group consisting
of Glutaraldehyde, Cinnamaldehyde and mixtures thereof.
16. A product of reaction according to claim 11, wherein said active
component comprises a perfume aldehyde.
17. A product of reaction according to claim 16, wherein said active
component comprises a perfume aldehyde, selected from the group
consisting of 1-decanal, benzaldehyde, florhydral,
2,4-dimethyl-3-cyclohexen-1-carboxaldehyde;
cis/trans-3,7-dimethyl-2,6-octadien-1-al; heliotropin;
2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde; 2,6-nonadienal;
alpha-n-amyl cinnamic aldehyde, alpha-n-hexyl cinnamic aldehyde, P.T.
Bucinal, lyral, cymal, methyl nonyl acetaldehyde, hexanal,
trans-2-hexenal, and mixtures thereof.
18. A product of reaction according to claim 11, wherein said active
component comprises a perfume ketone.
19. A product of reaction according to claim 18, wherein said active
component comprises a perfume ketone selected from the group consisting
of Alpha Damascone, Delta Damascone, Iso Damascone, Carvone,
Gamma-Methyl-Ionone, Iso-E-Super, 2,4,4,7-Tetramethyl-oct-6-en-3-one,
Benzyl Acetone, Beta Damascone, Damascenone, methyl dihydrojasmonate,
methyl cedrylone, and mixtures thereof.
20. A product of reaction according to claim 11 wherein said perfume has
an Odor Detection Threshold lower than or equal to 1 ppm.Description:
U.S.C. §120 to U.S. application Ser. No. 12/603,730, filed Oct. 22,
2009, which in turn is a continuation of and claims priority under 35
U.S.C. §120 to U.S. application Ser. No. 12/357,587, filed Jan. 22,
U.S.C. §120 to U.S. application Ser. No. 12/154,109, (now
abandoned), filed May 20, 2008 which in turn is a continuation of and
claims priority under 35 U.S.C. §120 to U.S. application Ser. No.
11/805,738, filed May 24, 2007, (now abandoned), which in turn is a
continuation of and claims priority under 35 U.S.C. §120 to U.S.
application Ser. No. 11/636,052, filed Dec. 8, 2006, (now abandoned),
which in turn is a continuation of and claims priority under 35 U.S.C.
§120 to U.S. application Ser. No. 11/395,716, filed Mar. 31, 2006,
(now abandoned), which in turn is a continuation of and claims priority
under 35 U.S.C. §120 to U.S. application Ser. No. 11/165,644, filed
Jun. 24, 2005, (now abandoned), which in turn claims priority under 35
U.S.C. §120 to U.S. application Ser. No. 10/911,283, filed Aug. 4,
2004, (now abandoned), which in turn claims priority under 35 U.S.C.
§120 to U.S. application Ser. No. 10/403,867, filed Mar. 31, 2003,
(now U.S. Pat. No. 6,790,815), which in turn claims priority under 35
U.S.C. §120 to U.S. application Ser. No. 10/157,790, filed May 29,
2002, (now U.S. Pat. No. 6,566,312 B2), which in turn claims priority
under 35 U.S.C. §120 to U.S. application Ser. No. 09/720,395, filed
Jul. 12, 1999, (now U.S. Pat. No. 6,413,920 B1), which is an entry into
the U.S. National Stage under 35 U.S.C. §371 of PCT International
Application Serial No. PCT/US99/15665, filed Jul. 12, 1999, which claims
priority under 35 U.S.C. §119 to European Application Serial Number
98870156.1, filed Jul. 10, 1998 and European Application Serial Number
98870227.0, filed Oct. 28, 1998.
[0002]The present invention relates to product of reaction between an
amine and an active component, in particular an active aldehyde or
ketone, more preferably an aldehyde or ketone perfume. More particularly,
it relates to such product of reaction for use in softening compositions.
[0003]Perfumed products are well-known in the art. However, consumer
acceptance of such perfumed products like softening products is
determined not only by the performance achieved with these products but
also by the aesthetics associated therewith. The perfume components are
therefore an important aspect of the successful formulation of such
[0004]It is also desired by consumers for treated fabrics to maintain the
pleasing fragrance over time. Indeed, perfume additives make such
compositions more aesthetically pleasing to the consumer, and in some
cases the perfume imparts a pleasant fragrance to fabrics treated
therewith. However, the amount of perfume carried-over from an aqueous
laundry bath onto fabrics is often marginal and does not last long on the
fabric. Furthermore, fragrance materials are often very costly and their
inefficient use in laundry and cleaning compositions and ineffective
delivery to fabrics results in a very high cost to both consumers and
laundry and cleaning manufacturers. Industry, therefore, continues to
seek with urgency for more efficient and effective fragrance delivery in
laundry and cleaning products, especially for improvement in the
provision of long-lasting fragrance to the fabrics.
[0005]One solution is to use carrier mechanisms for perfume delivery, such
as by encapsulation. This is taught in the prior art and described in
U.S. Pat. No. 5,188,753.
[0006]Still another solution is to formulate compounds which provide a
delayed release of the perfume over a longer period of time than by the
use of the perfume itself. Disclosure of such compounds may be found in
WO 95/04809, WO 95/08976 and co-pending application EP 95303762.9.
[0007]However, notwithstanding the advances in the art, there is still a
need for a compound which provides a delayed release of the active
component, in particular a perfume ingredient.
[0008]That need is even more acute for perfume ingredients which are
characteristic of the fresh notes, namely the aldehydes and ketones
perfume ingredients. Indeed, whilst these provide a fresh fragrance,
these perfumes are also very volatile and have a low substantivity on the
surface to be treated like fabrics.
[0009]Accordingly, it is a further object of the invention to provide a
softening composition comprising a perfume component which provides a
fresh fragrance and is substantive to the treated surface.
[0010]The Applicant has now found that specific reaction products of amine
compounds with an active aldehyde or ketone, such as imines compounds,
also provide a delayed release of the active such as a perfume.
[0011]Imine compounds are known in the art under the name of Schiff bases
which is the condensation of an aldehyde perfume ingredient with an
anthranilate. A typical description can be found in U.S. Pat. No.
4,853,369. By means of this compound, the aldehyde perfume is made
substantive to the fabrics. However, a problem encountered with these
Schiff bases is that the methylanthranilate compound also exhibits a
strong scent, which as a result produces a mixture of fragrances, thereby
reducing or even inhibiting the aldehyde and/or ketone fragrance
[0012]To achieve such perfume composition with comparable aldehyde or
ketones fresh notes whilst still having satisfactory fabric
substantivity, perfumers have formulated around the composition. For
example, by having a carrier or encapsulating material for such notes
such as with cyclodextrin, zeolites or starch.
[0013]Still another solution is the use of a glucosamine as described in
JP 09040687. However, this compound has been found to give a very low
stability in the wash process. As a result, insufficient perfume
residuality on the treated fabric has been found with these glucosamine
compounds. Its use in softening composition is not disclosed.
[0014]A further solution is described in Chemical release control,
Kamogawa et Al., J. Poly. Sci. Polym. Chem. Ed. Vol 20, 3121 (1982) which
describe the use of amino styrene compounds condensed with aldehydes
perfumes, whereby the release of the perfume is triggered by means of
copolymerisation or acidification of the compound. Its application is
however not mentioned.
[0015]The Applicant has now found that a reaction product between a
specific primary and/or secondary amine and an active component also
fulfill such a need.
[0016]Another advantage of the compounds of the invention is their ease of
manufacture rendering their use most desirable.
[0017]The present invention relates to product of reaction between a
primary and/or secondary amine compound and an active component selected
from ketone, aldehyde, and mixtures thereof, characterised in that said
amine compound has an Odor Intensity Index of less than that of a 1%
solution of methylanthranilate in dipropylene glycol, Dry Surface Odor
Index of more than 5; and with the proviso that said amine compound is
not an aminostyrene.
[0018]In another aspect of the invention, there is provided a softening
composition comprising a primary and/or secondary amine compound and an
active component selected from ketone, aldehyde, and mixtures thereof,
characterised in that said amine compound has an Odor Intensity Index of
less than that of a 1% solution of methylanthranilate in dipropylene
[0019]In a further aspect of the invention, there is provided a method of
delivering residual fragrance to a surface which comprises the steps of
contacting said surface with a compound or composition of the invention
and thereafter contacting the treated fabric with a material so that the
active is released from the reaction product between the amine and the
[0020]The essential component of the invention is the product of reaction
between a primary and/or secondary amine compound and an active component
selected from ketone, aldehyde, and mixtures thereof, characterised in
that said amine compound has an Odor Intensity Index of less than that of
a 1% solution of methylanthranilate in dipropylene glycol, Dry Surface
Odor Index of more than 5; and with the proviso that said amine compound
is not an aminostyrene.
[0021]When incorporated in softening compositions, the amine reaction
product is a product of reaction between a primary and/or secondary amine
compound and an active component selected from ketone, aldehyde, and
mixtures thereof, characterised in that said amine compound has an Odor
in dipropylene glycol. Preferably, this compound has a Dry Surface Odor
Index of more than 5.
I-Product of Reaction Between a Compound Containing a Primary and/or
Secondary Amine Functional Group and a Perfume Component
[0022]An essential component of the invention is a product of reaction
between a compound containing a primary and/or secondary amine functional
group and a perfume component, so called hereinafter "amine reaction
[0023]By "primary and/or secondary amine", it is meant a compound which
carries at least one primary and/or secondary amine and/or amide
[0024]The primary and/or secondary amine compound is also characterized by
an Odor Intensity Index of less than that of a 1% solution of
methylanthranilate in dipropylene glycol.
[0025]By Odor Intensity Index, it meant that the pure chemicals were
diluted at 1% in Dipropylene Glycol, odor-free solvent used in perfumery.
This percentage is more representative of usage levels. Smelling strips,
or so called "blotters", were dipped and presented to the expert
panellist for evaluation. Expert panellists are assessors trained for at
least six months in odor grading and whose gradings are checked for
accuracy and reproducibility versus a reference on an on-going basis. For
each amine compound, the panellist was presented two blotters: one
reference (Me Anthranilate, unknown from the panellist) and the sample.
The panellist was asked to rank both smelling strips on the 0-5 odor
intensity scale, 0 being no odor detected, 5 being very strong odor
[0026]The following represents the Odor Intensity Index of an amine
compound suitable for use in the present invention and according to the
above procedure. In each case, numbers are arithmetic averages among 5
expert panellists and the results are statistically significantly
different at 95% confidence level:
[0027]A general structure for the primary amine compound of the invention
[0028]Compounds containing a secondary amine group have a structure
similar to the above excepted that the compound comprises one or more
--NH-- groups instead of --NH2. Further, the compound structure may also
have one or more of both --NH2 and --NH-- groups.
[0029]Preferred B carriers are inorganic or organic carriers.
[0030]By "inorganic carrier", it is meant a carrier which is non- or
substantially non carbon based backbones.
[0031]Among the inorganic carriers, preferred inorganic carriers are mono
or polymers or organic-organosilicon copolymers of amino derivatised
organo silane, siloxane, silazane, alumane, aluminum siloxane, or
aluminum silicate compounds. Typical examples of such carriers are:
organosiloxanes with at least one primary amine moiety like the
diaminoalkylsiloxane [H2NCH2(CH3) 2Si]O, or the organoaminosilane (C6H5)
3SiNH2 described in: Chemistry and Technology of Silicone, W. Noll,
Academic Press Inc. 1998, London, pp 209, 106).
[0032]Mono or polymer or organic-organosilicon copolymers containing one
or more organosilylhydrasine moiety are also preferred. A typical example
of such a class of carrier material is the
N,N'-bis(trimethylsilyl)hydrazine (Me3Si) 2NNH2 described in: The
OrganoSilicon Chemistry Second international Symposium, Pure and Applied
Chemistry, Vol, 19 Nos 3-4, (1969).
[0033]The following are also preferred mono or poly silazanes and which
are exemplified by the
1,1,1,3,3,3,-hexamethyl-2-phenyldiaminosilyldisilasane [(CH3) 3Si]
2NSi(C6H5)NH2) 2 described in: OrganoSilicon Compounds, 1965, V.
Bazant and al. Academic Press). Still other preferred examples of polymer
silicone derivatives are the cyclic
1,1,5,5,7,7,711,11-Octamethyl-3-9-bis-[2-(2-aminoethylamino)-ethyl]-1,5,7-
,11-tetrasila-3,9-diaza-6,12-dioxacyclododecane and the Hexaethoxydiamino
cyclotetrasiloxane (C6H5) (NH2) 2Si4O4, id, Vol 2 part 2, p 474, p454).
[0034]Preferred amino functionalized inorganic polymeric carriers for use
herein are polyaminoalkyl polysiloxanes. Typical disclosure can be found
in JP 79,131,096, and EP 058 493. Still other inorganic polymeric
carriers suitable for use herein are the amino functionalized
polydi-alkylsiloxanes, as described in EP 150 867 and having the general
[0035]Wherein R═C1-16 preferentially C1-4 alkyl; n is an
integer from 0 to 16 preferentially from 1 to 6, R'=nil, O, C═O, COO,
NC═O, C═O--NR, NR, SOm, m=2,3.
[0036]By organic carriers, it meant carriers having essentially carbon
bond backbones. Typical amines having organic carrier include aminoaryl
derivatives, polyamines, aminoacids and derivatives, substituted amines
and amides, glucamines, dendrimers and amino-substituted mono-, di-,
oligo-, poly-saccharides.
[0037]Of course, the amine compound can be interrupted or substituted by
linkers or cellulose substantive group. A general formula for this amine
compound may be represented as follows:
wherein each m is an index of value 0 or at least 1, and n is an index of
value of at least 1 as defined herein before. As can be seen above, the
amine group is linked to a carrier molecule as defined by classes
hereinafter described. The primary and/or secondary amine group is either
directly linked to the carrier group or via a linker group L. The carrier
can also be substituted by a R* substituent, and R* can be linked to the
carrier either directly or via a linker group L. Of course, R* can also
contain branching groups like e.g. tertiary amine and amide groups.
[0038]It is important for the purpose of the invention that the amine
compound comprises at least one primary and/or secondary amine group to
react with the perfume aldehyde and/or ketone to form the reaction
products. Of course, the amine compound is not limited to having only one
amine function. Indeed, more preferably, the amine compound comprises
more than one amine function, thereby enabling the amine compound to
react with several aldehydes and/or ketones. Accordingly, reaction
products carrying mixed aldehyde(s) and/or ketone(s) can be achieved,
thereby resulting in a mixed release of such fragrances.
[0039]Typical linker group include:
[0040]L can also be a combination [0041]e.g.
[0042]L can also contain --O-- if this group is not directly linked to N
[0043]Most of the compounds described in the classes of amine compounds
hereinafter will contain at least one substituent group classified as R*.
[0044]R* contains 1 to 22 carbon atoms in the main chain and optionally
can be an alkyl, alkenyl, or alkylbenzene chain. It can also contain
alicyclic, aromatic, heteroaromatic or heterocyclic systems, either
inserted into the main chain or by substitution of an H atom of the main
chain. Further, R* can either be linked to the carrier B material or via
a linker L, as defined herein before. In this instance, L can also be
[0045]The main chain can contain from 1 to up to 15 R* groups.
[0046]Typical R* insertion groups include:
[0047]the arrow indicates upto 3 substitutions in position 2,3,4
[0048]R* can also contain several insertion groups linked together: e.g.
[0049]e.g.:
[0050]Furthermore, R* can carry a functional end group E that provides
additional surface substantivity. Typical organic groups of this end
group E include
[0051]E can also be an aromatic, alicyclic, heteroaromatic, or
heterocyclic group including mono-, di-, oligo-, polysaccharides
[0052]In addition, the R* group can also be modified via substitution of
one or more H atoms in the main chain. The substitution group can either
be E or the insertion groups as defined above where the insertion group
is terminated by any of H, E, or R*.
[0053]R* can also be a group made of ethoxy or epoxy groups with n ranging
from 1 to 15, including groups like:
[0054]As defined herein before, preferred amine having organic carrier
material B may be selected from aminoaryl derivatives, polyamines,
aminoacids and derivatives, substituted amines and amides, glucamines,
amino-substituted mono-, di-, oligo-, poly-saccharides, dendrimers and/or
[0055]In this class of compounds, the amino group is preferably attached
to a benzene ring. The benzene ring is further substituted in the para-
and/or meta-position with R* as defined herein before. R* can be attached
to the benzene ring via a linker L. The benzene ring can be substituted
by other aromatic ring systems including naphtalene, indole,
benzimidazole, pyrimidine, purine, and mixtures thereof.
[0056]Preferably, the R* is attached to the benzene ring in its para
[0057]Typical amino-benzene derivatives have the following formula:
[0058]Preferred amino-benzene derivatives have the following formula:
[0059]Preferred amino-benzene derivatives are alkyl esters of 4-amino
benzoate compounds, preferably selected from ethyl-4-amino benzoate,
phenylethyl-4-aminobenzoate, phenyl-4-aminobenzoate,
4-amino-N'-(3-aminopropyl)-benzamide, and mixtures thereof.
[0060]The polyamines of the invention need to have at least one,
preferably more than one free and unmodified primary and/or secondary
amine group, to react with the active aldehyde or ketone. In the
polyamines, H can be substituted by R*, optionally via a linker group L.
Additionally, the primary and/or secondary amine group can be linked to
the polymer end via a linker group L.
[0061]The polyamines compounds suitable for use in the present invention
are water-soluble or dispersible, polyamines. Typically, the polyamines
for use herein have a molecular weight between 150 and 2*106,
preferably between 400 and 106, most preferably between 5000 and
106. These polyamines comprise backbones that can be either linear
or cyclic. The polyamine backbones can also comprise polyamine branching
chains to a greater or lesser degree. Preferably, the polyamine backbones
described herein are modified in such a manner that at least one,
preferably each nitrogen of the polyamine chain is thereafter described
in terms of a unit that is substituted, quaternized, oxidized, or
[0062]For the purposes of the present invention the term "modification" as
it relates to the chemical structure of the polyamines is defined as
replacing a backbone --NH hydrogen atom by an R' unit (substitution),
quaternizing a backbone nitrogen (quaternized) or oxidizing a backbone
nitrogen to the N-oxide (oxidized). The terms "modification" and
"substitution" are used interchangeably when referring to the process of
replacing a hydrogen atom attached to a backbone nitrogen with an R'
unit. Quaternization or oxidation may take place in some circumstances
without substitution, but substitution is preferably accompanied by
oxidation or quaternization of at least one backbone nitrogen.
[0063]The linear or non-cyclic polyamine backbones that comprise the
polyamine have the general formula:
[0064]The cyclic polyamine backbones that comprise the polyamine have the
[0065]The above backbones prior to optional but preferred subsequent
modification, comprise primary, secondary and tertiary amine nitrogens
connected by R "linking" units
[0066]For the purpose of the present invention, primary amine nitrogens
comprising the backbone or branching chain once modified are defined as V
or Z "terminal" units. For example, when a primary amine moiety, located
at the end of the main polyamine backbone or branching chain having the
is modified according to the present invention, it is thereafter defined
as a V "terminal" unit, or simply a V unit. However, for the purposes of
the present invention, some or all of the primary amine moieties can
remain unmodified subject to the restrictions further described herein
below. These unmodified primary amine moieties by virtue of their
position in the backbone chain remain "terminal" units. Likewise, when a
primary amine moiety, located at the end of the main polyamine backbone
as a Z "terminal" unit, or simply a Z unit. This unit can remain
unmodified subject to the restrictions further described herein below.
[0067]In a similar manner, secondary amine nitrogens comprising the
backbone or branching chain once modified are defined as W "backbone"
units. For example, when a secondary amine moiety, the major constituent
of the backbones and branching chains of the present invention, having
as a W "backbone" unit, or simply a W unit. However, for the purposes of
the present invention, some or all of the secondary amine moieties can
remain unmodified. These unmodified secondary amine moieties by virtue of
their position in the backbone chain remain "backbone" units.
[0068]In a further similar manner, tertiary amine nitrogens comprising the
backbone or branching chain once modified are further referred to as Y
"branching" units. For example, when a tertiary amine moiety, which is a
chain branch point of either the polyamine backbone or other branching
chains or rings, having the structure
as a Y "branching" unit, or simply a Y unit. However, for the purposes of
the present invention, some or all or the tertiary amine moieties can
remain unmodified. These unmodified tertiary amine moieties by virtue of
their position in the backbone chain remain "branching" units. The R
units associated with the V, W and Y unit nitrogens which serve to
connect the polyamine nitrogens, are described herein below.
[0069]The final modified structure of the polyamines of the present
invention can be therefore represented by the general formula
for cyclic polyamine. For the case of polyamines comprising rings, a Y'
unit of the formula
serves as a branch point for a backbone or branch ring. For every Y' unit
there is a Y unit having the formula
that will form the connection point of the ring to the main polymer chain
or branch. In the unique case where the backbone is a complete ring, the
polyamine backbone has the formula
wherein k is the number of ring forming branching units. Preferably the
polyamine backbones of the present invention comprise no rings.
[0070]In the case of non-cyclic polyamines, the ratio of the index n to
the index m relates to the relative degree of branching. A fully
non-branched linear modified polyamine according to the present invention
that is, n is equal to 0. The greater the value of n (the lower the ratio
of m to n), the greater the degree of branching in the molecule.
Typically the value for m ranges from a minimum value of 2 to 700,
preferably 4 to 400, however larger values of m, especially when the
value of the index n is very low or nearly 0, are also preferred.
[0071]Each polyamine nitrogen whether primary, secondary or tertiary, once
modified according to the present invention, is further defined as being
a member of one of three general classes; simple substituted, quaternized
or oxidized. Those polyamine nitrogen units not modified are classed into
V, W, Y, Y' or Z units depending on whether they are primary, secondary
or tertiary nitrogens. That is unmodified primary amine nitrogens are V
or Z units, unmodified secondary amine nitrogens are W units or Y' units
and unmodified tertiary amine nitrogens are Y units for the purposes of
[0072]Modified primary amine moieties are defined as V "terminal" units
having one of three forms: [0073]a) simple substituted units having the
[0074]b) quaternized units having the structure:
[0074]wherein X is a suitable counter ion providing charge balance; and
[0075]c) oxidized units having the structure:
[0076]Modified secondary amine moieties are defined as W "backbone" units
having one of three forms: [0077]a) simple substituted units having the
[0078]b) quaternized units having the structure:
[0078]wherein X is a suitable counter ion providing charge balance; and
[0079]c) oxidized units having the structure:
[0080]Other modified secondary amine moieties are defined as Y' units
having one of three forms: [0081]a) simple substituted units having the
[0082]b) quaternized units having the structure:
[0082]wherein X is a suitable counter ion providing charge balance; and
[0083]c) oxidized units having the structure:
[0084]Modified tertiary amine moieties are defined as Y "branching" units
having one of three forms: [0085]a) unmodified units having the
[0086]b) quaternized units having the structure:
[0086]wherein X is a suitable counter ion providing charge balance; and
[0087]c) oxidized units having the structure:
[0088]Certain modified primary amine moieties are defined as Z "terminal"
units having one of three forms: [0089]a) simple substituted units
[0090]b) quaternized units having the structure:
[0090]wherein X is a suitable counter ion providing charge balance; and
[0091]c) oxidized units having the structure:
[0092]When any position on a nitrogen is unsubstituted of unmodified, it
is understood that hydrogen will substitute for R'. For example, a
primary amine unit comprising one R' unit in the form of a hydroxyethyl
moiety is a V terminal unit having the formula (HOCH2CH2)HN--.
[0093]For the purposes of the present invention there are two types of
chain terminating units, the V and Z units. The Z "terminal" unit derives
from a terminal primary amino moiety of the structure--NH2. Non-cyclic
polyamine backbones according to the present invention comprise only one
Z unit whereas cyclic polyamines can comprise no Z units. The Z
"terminal" unit can be substituted with any of the R' units described
further herein below, except when the Z unit is modified to form an
N-oxide. In the case where the Z unit nitrogen is oxidized to an N-oxide,
the nitrogen must be modified and therefore R' cannot be a hydrogen.
[0094]The polyamines of the present invention comprise backbone R
"linking" units that serve to connect the nitrogen atoms of the backbone.
R units comprise units that for the purposes of the present invention are
referred to as "hydrocarbyl R" units and "oxy R" units. The "hydrocarbyl"
R units are C2-C12 alkylene, C4-C12 alkenylene, C3-C12 hydroxyalkylene
wherein the hydroxyl moiety may take any position on the R unit chain
except the carbon atoms directly connected to the polyamine backbone
nitrogens; C4-C12 dihydroxyalkylene wherein the hydroxyl moieties may
occupy any two of the carbon atoms of the R unit chain except those
carbon atoms directly connected to the polyamine backbone nitrogens;
C8-C12 dialkylarylene which for the purpose of the present invention are
arylene moieties having two alkyl substituent groups as part of the
linking chain. For example, a dialkylarylene unit has the formula
although the unit need not be 1,4-substituted, but can also be 1, 2 or 1,3
substituted C2-C12 alkylene, preferably ethylene, 1,2-propylene, and
mixtures thereof, more preferably ethylene. The "oxy" R units comprise
--(R1O)xR5(OR1)x--, --CH2CH(OR2)CH2O)z(R1O)yR1(OCH2CH(OR2)CH2)w--,
--CH2CH(OR2)CH2-, --(R1O)xR1-, and mixtures thereof. Preferred R units
are selected from the group consisting of C2-C12 alkylene, C3-C12
hydroxy-alkylene, C4-C12 dihydroxyalkylene, C8-C12 dialkylarylene,
--(R1O)xR1-, --CH2CH(OR2)CH2-,
--(CH2CH(OH)CH2O)z(R1O)yR1(OCH2CH--(OH)CH2)w--, --(R1O)xR5(OR1)x-, more
preferred R units are C2-C12 alkylene, C3-C12 hydroxy-alkylene, C4-C12
dihydroxyalkylene, --(R1O)xR1-, --(R1O)xR5 (OR1)x--,
--(CH2CH(OH)CH2O)z(R1O)yR1(OCH2CH--(OH)CH2)w--, and mixtures thereof,
even more preferred R units are C2-C12 alkylene, C3 hydroxyalkylene, and
mixtures thereof, most preferred are C2-C6 alkylene. The most preferred
backbones of the present invention comprise at least 50% R units that are
ethylene.R1 units are C2-C6 alkylene, and mixtures thereof,
preferably ethylene.R2 is hydrogen, and --(R1O)xB, preferably hydrogen.R3
is C1-C18 alkyl, C7-C12 arylalkylene, C7-C12 alkyl substituted aryl,
C6-C12 aryl, and mixtures thereof, preferably C1-C12 alkyl, C7-C12
arylalkylene, more preferably C1-C12 alkyl, most preferably methyl. R3
units serve as part of R' units described herein below.R4 is C1-C12
alkylene, C4-C12 alkenylene, C8-C12 arylalkylene, C6-C10 arylene,
preferably C1-C10 alkylene, C8-C12 arylalkylene, more preferably C2-C8
alkylene, most preferably ethylene or butylene.R5 is C1-C12 alkylene,
C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, C8-C12 dialkylarylene,
--C(O)--, --C(O)NHR6NHC(O)--, --C(O)(R4)rC(O)--, --R1 (OR1)-,
--CH2CH(OH)CH2O(R1O)yR1OCH2CH(OH)CH2-, --C(O)(R4)rC(O)--,
--CH2CH(OH)CH2-, R5 is preferably ethylene, --C(O)--, --C(O)NHR6NHC(O)--,
--R1 (OR1)-, --CH2CH(OH)CH2-, --CH2CH(OH)CH2O(R1O)yR1OCH2CH--(OH)CH2-,
more preferably --CH2CH(OH)CH2-. R6 is C2-C12 alkylene or C6-C12 arylene.
[0095]The preferred "oxy" R units are further defined in terms of the R1,
R2, and R5 units. Preferred "oxy" R units comprise the preferred R1, R2,
and R5 units. The preferred polyamines of the present invention comprise
at least 50% R1 units that are ethylene. Preferred R1, R2, and R5 units
are combined with the "oxy" R units to yield the preferred "oxy" R units
in the following manner. [0096]i) Substituting more preferred R5 into
--(CH2CH2O)xR5(OCH2CH2)x-yields --(CH2CH2O)xCH2CHOHCH2(OCH2CH2)x-.
[0097]ii) Substituting preferred R1 and R2 into
--(CH2CH(OR2)CH2O)z-(R1O)yR1O(CH2CH(OR2)CH2)w- yields
--(CH2CH(OH)CH2O)z-(CH2CH2O)yCH2CH2O(CH2CH(OH)CH2)w--. [0098]iii)
Substituting preferred R2 into --CH2CH(OR2)CH2- yields
[0098]--CH2CH(OH)CH2--.
[0099]R' units are selected from the group consisting of hydrogen, C1-C22
alkyl, C3-C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl,
--(CH2)pCO2M, --(CH2)qSO3M, --CH(CH2CO2M)CO2M, --(CH2)pPO3M,
--(R1O)mB, --C(O)R3, preferably hydrogen, C2-C22 hydroxyalkylene, benzyl,
C1-C22 alkylene, --(R1O)mB, --C(O)R3, --(CH2)pCO2M, --(CH2)qSO3M,
--CH(CH2CO2M)CO2M, more preferably C1-C22 alkylene, --(R1O)xB,
--C(O)R3, --(CH2)pCO2M, --(CH2)qSO3M, --CH(CH2CO2M)CO2M, most
preferably C1-C22 alkylene, --(R1O)xB, and --C(O)R3. When no modification
or substitution is made on a nitrogen then hydrogen atom will remain as
the moiety representing R'. A most preferred R' unit is (R1O)xB.
[0100]R' units do not comprise hydrogen atom when the V, W or Z units are
oxidized, that is the nitrogens are N-oxides. For example, the backbone
chain or branching chains do not comprise units of the following
[0101]Additionally, R' units do not comprise carbonyl moieties directly
bonded to a nitrogen atom when the V, W or Z units are oxidized, that is,
the nitrogens are N-oxides. According to the present invention, the R'
unit --C(O)R3 moiety is not bonded to an N-oxide modified nitrogen, that
is, there are no N-oxide amides having the structure
[0102]B is hydrogen, C1-C6 alkyl, --(CH2)qSO3M, --(CH2)pCO2M,
--(CH2)q-(CHSO3M)CH2SO3M, --(CH2)q(2M)CH2SO3M, --(CH2)pPO3M, --PO3M,
preferably hydrogen, --(CH2)qSO3M, --(CH2)q(CHSO3M)CH2SO3M,
--(CH2)q--(CHSO2M)CH2SO3M, more preferably hydrogen or --(CH2)qSO3M.
[0103]M is hydrogen or a water soluble cation in sufficient amount to
satisfy charge balance. For example, a sodium cation equally satisfies
--(CH2)pCO2M, and --(CH2)qSO3M, thereby resulting in --(CH2)pCO2Na, and
--(CH2)qSO3Na moieties. More than one monovalent cation, (sodium,
potassium, etc.) can be combined to satisfy the required chemical charge
balance. However, more than one anionic group may be charge balanced by a
divalent cation, or more than one mono-valent cation may be necessary to
satisfy the charge requirements of a poly-anionic radical. For example, a
--(CH2)pPO3M moiety substituted with sodium atoms has the formula
--(CH2)pPO3Na3. Divalent cations such as calcium (Ca2+) or magnesium
(Mg2+) may be substituted for or combined with other suitable mono-valent
water soluble cations. Preferred cations are sodium and potassium, more
preferred is sodium.
[0104]X is a water soluble anion such as chlorine (Cl--), bromine (Br--)
[0105](I--) or X can be any negatively charged radical such as sulfate
(SO42-) and methosulfate (CH3SO3-).
[0106]The formula indices have the following values: p has the value from
1 to 6, q has the value from 0 to 6; r has the value 0 or 1; w has the
value 0 or 1, x has the value from 1 to 100; y has the value from 0 to
100; z has the value 0 or 1; m has the value from 2 to 700, preferably
from 4 to 400, n has the value from 0 to 350, preferably from 0 to 200;
m+n has the value of at least 5. Preferably x has a value lying in the
range of from 1 to 20, preferably from 1 to 10.
[0107]The preferred polyamines of the present invention comprise polyamine
backbones wherein less than 50% of the R groups comprise "oxy" R units,
preferably less than 20%, more preferably less than 5%, most preferably
the R units comprise no "oxy" R units.
[0108]The most preferred polyamines which comprise no "oxy" R units
comprise polyamine backbones wherein less than 50% of the R groups
comprise more than 3 carbon atoms. For example, ethylene, 1,2-propylene,
and 1,3-propylene comprise 3 or less carbon atoms and are the preferred
"hydrocarbyl" R units. That is when backbone R units are C2-C12 alkylene,
preferred is C2-C3 alkylene, most preferred is ethylene.
[0109]The polyamines of the present invention comprise modified
homogeneous and non-homogeneous polyamine backbones, wherein 100% or less
of the --NH units are modified. For the purpose of the present invention
the term "homogeneous polyamine backbone" is defined as a polyamine
backbone having R units that are the same (i.e., all ethylene). However,
this sameness definition does not exclude polyamines that comprise other
extraneous units comprising the polymer backbone which are present due to
an artifact of the chosen method of chemical synthesis. For example, it
is known to those skilled in the art that ethanolamine may be used as an
"initiator" in the synthesis of polyethyleneimines, therefore a sample of
polyethyleneimine that comprises one hydroxyethyl moiety resulting from
the polymerization "initiator" would be considered to comprise a
homogeneous polyamine backbone for the purposes of the present invention.
A polyamine backbone comprising all ethylene R units wherein no branching
Y units are present is a homogeneous backbone. A polyamine backbone
comprising all ethylene R units is a homogeneous backbone regardless of
the degree of branching or the number of cyclic branches present.
[0110]For the purposes of the present invention the term "non-homogeneous
polymer backbone" refers to polyamine backbones that are a composite of
various R unit lengths and R unit types. For example, a non-homogeneous
backbone comprises R units that are a mixture of ethylene and
1,2-propylene units. For the purposes of the present invention a mixture
of "hydrocarbyl" and "oxy" R units is not necessary to provide a
non-homogeneous backbone.
[0111]Preferred polyamines of the present invention comprise homogeneous
polyamine backbones that are totally or partially substituted by
polyethyleneoxy moieties, totally or partially quaternized amines,
nitrogens totally or partially oxidized to N-oxides, and mixtures
thereof. However, not all backbone amine nitrogens must be modified in
the same manner, the choice of modification being left to the specific
needs of the formulator. The degree of ethoxylation is also determined by
the specific requirements of the formulator.
[0112]The preferred polyamines that comprise the backbone of the compounds
of the present invention are generally polyalkyleneimines (PAI's),
preferably polyethyleneimines (PEI's), or PEI's connected by moieties
having longer R units than the parent PAI's or PEI's.
[0113]Preferred amine polymer backbones comprise R units that are C2
alkylene (ethylene) units, also known as polyethylenimines (PEI's).
Preferred PEI's have at least moderate branching, that is the ratio of m
to n is less than 4:1, however PEI's having a ratio of m to n of 2:1 are
most preferred. Preferred backbones, prior to modification have the
wherein R', m and n are the same as defined herein above. Preferred PEI's
will have a molecular weight greater than 200 daltons.
[0114]The relative proportions of primary, secondary and tertiary amine
units in the polyamine backbone, especially in the case of PEI's, will
vary, depending on the manner of preparation. Each hydrogen atom attached
to each nitrogen atom of the polyamine backbone chain represents a
potential site for subsequent substitution, quaternization or oxidation.
[0115]These polyamines can be prepared, for example, by polymerizing
ethyleneimine in the presence of a catalyst such as carbon dioxide,
sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid,
acetic acid, etc. Specific methods for preparing these polyamine
backbones are disclosed in U.S. Pat. No. 2,182,306, Ulrich et al., issued
Dec. 5, 1939; U.S. Pat. No. 3,033,746, Mayle et al., issued May 8, 1962;
U.S. Pat. No. 2,208,095, Esselmann et al., issued Jul. 16, 1940; U.S.
Pat. No. 2,806,839, Crowther, issued Sep. 17, 1957; and U.S. Pat. No.
2,553,696, Wilson, issued May 21, 1951; all herein incorporated by
[0116]Preferred polyamines are polyethyleneimines commercially available
under the tradename Lupasol like Lupasol FG (MW 800), G20wfv (MW 1300),
PR8515 (MW 2000), WF (MW 25000), FC (MW 800), G20 (MW 1300), G35 (MW
1200), G100 (MW 2000), HF (MW 25000), P (MW 750000), PS (MW 750000), SK
(MW 2000000), SNA (MW 1000000).
[0117]Still other polyamines suitable for use in the present invention are
α-(2-aminomethylethyl)-ω-(2-aminomethyl-ethoxy)- (=C.A.S. No.
9046-10-0); poly[oxy(methyl-1,2-ethanediyl)],
α-hydro-)-ω-(2-aminomethylethoxy)-, ether with
2-ethyl-2-(hydroxymethyl)-1,3-propanediol (═C.A.S. No. 39423-51-3);
commercially available under the tradename Jeffamines T-403, D-230,
D-400, D-2000; 2,2',2''-triaminotriethylamine; 2,2'-diamino-diethylamine;
3,3'-diamino-dipropyl-amine, 1,3 bis aminoethylcyclohexane commercially
available from Mitsibushi and the C12 Sternamines commercially available
from Clariant like the C12 Sternamin(propylenamine)n with n=3/4, and
[0118]Still other suitable compounds for use in the present invention are
aminoacids and their derivatives, especially ester and amide derivatives.
More preferred compounds are those providing enhanced surface
substantivity due to its structural feature. For clarification, the term
amino acids and derivatives does not encompass polymeric compounds.
[0119]Suitable amino acids have the following functionality of formula:
[0120]Wherein R1═H, R* or (L)-R* and R is the amino acid side
group, generally referred to as the "R group" such as in "Principles of
Biochemistry" by Lehninger et al., 1997, Second Edition, Worth,
pp114-116.
[0121]Preferred amino acids for use herein are selected tyrosine,
tryptophane, lysine, glutamic acid, glutamine, aspartic acid, arginine,
asparagine, phenylalanine, proline, glycine, serine, histidine,
threonine, methionine, and mixture thereof, most preferably selected from
tyrosine, tryptophane, and mixture thereof.
[0122]Still other preferred compound are the amino acid derivatives
selected from tyrosine ethylate, glycine methylate, tryptophane ethylate
and mixture thereof,
[0123]For clarification, the term substituted amines and amides does not
encompass polymeric compounds. Substituted amine and amide compounds
suitable for use herein have the following general formula:
[0124]NH2-L-R**, in which L is --CO-- in case of an amide.
[0125]Other optional linker group may be as defined under R*.
[0126]R** is as defined herein before under R* with the proviso that it
contains at least 6 carbon atoms and/or N atoms and/or cyclohexyl-,
piperidine, piperazine, and other heterocyclic groups like:
[0127]Optionally, H in NH can be substituted by R*.
[0128]Preferred substituted amines and amides for use herein are selected
from nipecotamide, N-coco-1,3-propenediamine; N-oleyl-1,3-propenediamine;
N-(tallow alkyl)-1,3-propenediamine; 1,4-diamino cyclohexane;
1,2-diamino-cyclohexane; 1,12-diaminododecane, and mixtures thereof.
[0129]Still a further preferred class of amine compound is the class of
glucamines of general structure: NH2-CH2-(CH(OH))x--CH2OH, wherein
one or several OH-function can be substituted, preferably by --OR*, and
wherein x is an integer of value 3 or 4. R* can be linked to the OH
groups either directly or via linker unit as mentioned herein before
[0130]For clarification, the term glucamine does not encompass polymeric
[0131]Preferred compound of this class are selected from
2,3,4,5,6-pentamethoxy-glucamine; 6-acetylglucamine, glucamine, and
[0132]Another further class of amine compounds is the class of dendrimers.
Suitable dendrimers carry free primary and/or secondary amine groups at
the periphery of the spherical molecules, that can be reacted with
(perfume) aldehydes or ketones to form the desired amine reaction product
(perfume component) of the invention.
[0133]By dendrimers it is understood that the molecule is built up from a
core molecule as described e.g. in WO 96/02588 and in Synthesis, February
1978, p. 155-158 or in Encyclopedia of Polymer Science & Engineering,
2nd ed., Hedstrand et al., in particular pages 46-91. The core is
typically connected to multifunctional components to build up the
"generations". For the purpose of the present invention, the nature of
the inner generations is not critical. They can be based on e.g.
polyamidoamines, polyamidoalcohols, polyethers, polyamides,
polyethylenimines, etc. Important for the purpose of the present
invention is that the outer generation(s) contain accessible primary
and/or secondary amino functions.
[0134]Also suitable are the glyco dendrimers as described in e.g.
Nachrichten aus Chemie 11 (1996), p. 1073-1079 and in WO 97/48711
provided that free primary and/or secondary amine groups are present at
the surface of these molecules.
[0135]Preferred compounds are the polyethylenimine and polypropylenimine
dendrimers, the commercially available Starburst® polyamidoamines
(PAMAM) dendrimers, generation G0-G10 from Dendritech and the dendrimers
Astromols®, generation 1-5 from DSM being DiAminoButane PolyAmine DAB
(PA)x with x=2n×4 and n being generally comprised between 0
[0136]Also suitable for the purpose of the present invention are specific
amino-substituted mono-, di-, oligo-, poly-saccharides.
[0137]For the amino-substituted mono-saccharides of the present invention,
it is necessary that the hemi-acetal and/or hemi-ketal functionality is
blocked via a suitable substituent to provide sufficient stability for
the intended application. As indicated here above, glucoseamine is not a
suitable amine. However, if the hemi-acetal OH function is substituted by
R*, said monosaccharide becomes suitable for the purpose of the present
invention. The amino group can be in position 2 to 5 or 6 depending on
the type of monosaccharide and is preferably in C2, C5 or C6 position.
Suitable amino-substituted mono-saccharides are: [0138]C5
aldosen/ketosen: ribose, arabinose, xylose, lyxose, ribulose, xylulose;
[0139]C6 aldosen/ketosen: allose, altrose, glucose, mannose, gulose,
idose, galactose, talose, fructose, sorbose, tagatose, psicose.
[0140]For amino-substituted di-saccharides with non-substituted aldose or
ketose groups, the free OH-- group needs to be substituted by R*, e.g. in
lactose and maltose, whereas in sucrose there is no free acetal/ketal OH
group. Optionally, more than one OH group can be substituted by R*.
Suitable amino-substituted di-saccharides are amino substituted lactose,
maltose, sucrose, cellobiose and trehalose.
[0141]Suitable amino-substituted oligo-, poly-saccharides are
amino-substituted starch, cyclodextrin, dextran, glycogen, cellulose,
mannan, gueran, levan, alternan glucose, mannose, galactose, fructose,
lactose, maltose, sucrose, cellobiose, cyclodextrin, chitosan, and/or
mixtures thereof. The molecules need to carry at least 1, preferably
several, amino groups. Chitosan does not require additional amino
[0142]Also suitable for coupling carboxyl- or aldehyde-containing
compounds are the following functionalised oligo-, poly-saccharides &
glycans commercially available from the company Carbomer. Please find in
brackets the reference number from Carbomer:
[0143]Amino alginate (5,00002), Diamino alginate (5,00003), Hexanediamine
alginate (5,00004-5,00006-5,00008), dodecanediamine alginate
(5,00005-5,00007-5,00009), 6-amino-6-deoxy cellulose (5,00020),
O-ethylamine cellulose (5,00022), O-methylamine cellulose (5,00023),
3-amino-3-deoxy cellulose (5,00024), 2-amino-2 deoxy cellulose (5,00025),
2,3-diamino-2,3-dideoxy cellulose (5,00026),
6-[N-(1,6-hexanediamine)]-6-deoxy cellulose (5,00027),
6-[N-(1,12-docedanediamine)]-6-deoxy cellulose (5,00028),
0-[methyl-(N-1,6-hexanediamine)] cellulose (5,00029),
0-[methyl-(N-1,12-dodecanediamine)]cellulose (5,00030),
2,3-di-[N-(1,12-dodecanediamine)] cellulose (5,00031),
2,3-diamino-2,3-deoxy alpha-cyclodextrin (5,00050), 2,3-diamino-2,3-deoxy
beta-cyclodextrin (5,00051), 2,3-diamino-2,3-deoxy gamma-cyclodextrin
(5,00052), 6-amino-6-deoxy alpha-cyclodextrin (5,00053), 6-amino-6-deoxy
beta-cyclodextrin (5,00054), O-ethyleamino beta-cyclodextrin (5,00055),
6[N-(1,6-hexanediamino)-6-deoxy alpha cyclodextrin (5,00056),
6[N-(1,6-hexanediamino)-6-deoxy beta cyclodextrin (5,00057), Amino
dextran (5,00060), N-[di-(1,6-hexanediamine)] dextran (5,00061),
N-[di-(1,12-dodecanediamine)] dextran (5,00062),
6-amino-6-deoxy-alpha-D-galactosyl-guaran (5,00070), O-ethylamino guaran
(5,00071), Diamino guaran (5,00072), 6-amino-6-deoxy-starch (5,00080),
O-ethylamino starch (5,00081), 2,3-diamine-2,3-dideoxy starch (5,00082),
N-[6-(1,6-hexanediamine)]-6-deoxy starch (5,00083),
N-[6-(1,12-dodecanediamine)]-6-deoxy starch (5,00084) and
2,3-di-[N(1,6-hexanediamine)]-2,3-dideoxy starch (5,00085)
[0144]Furthermore, with the use of some of the above compound comprising
at least one primary and/or secondary amine group like the polyamine, the
resulting amine reaction product will beneficially provide fabric
appearance benefits, in particular color care and protection against
fabric wear. Indeed, the appearance of fabrics, e.g., clothing, bedding,
household fabrics like table linens is one of the area of concern to
consumers. Indeed, upon typical consumer's uses of the fabrics such as
wearing, washing, rinsing and/or tumble-drying of fabrics, a loss in the
fabric appearance; which can be at least partly due to loss of color
fidelity and color definition, is observed. Such a problem of color loss
is even more acute after multiwash cycles. It has been found that the
compositions of the present invention provide improved fabric appearance
and protection against fabric wear and improved color care to laundered
fabrics, especially after multiwash cycles.
[0145]Therefore, the compositions of the present invention can provide
simultaneously fabric care and long lasting perfume benefits.
[0146]Preferably, for the above mentioned compounds, by active ketone or
active aldehyde, it is meant any chain containing at least 1 carbon atom,
preferably at least 5 carbon atoms.
[0147]Preferably, the active ketone or active aldehyde is respectively
selected from a flavour ketone or aldehyde ingredient, a pharmaceutical
ketone or aldehyde active, a biocontrol ketone or aldehyde agent, a
perfume ketone or aldehyde component, a refreshing cooling ketone or
aldehyde agent and mixtures thereof.
[0148]Flavour ingredients include spices, flavor enhancers that contribute
to the overall flavour perception.
[0149]Pharmaceutical actives include drugs.
[0150]Biocontrol agents include biocides, antimicrobials, bactericides,
fungicides, algaecides, mildewcides, disinfectants, antiseptics,
insecticides, vermicides, plant growth hormones.
[0151]Biocontrol agents include biocides, antimicrobials, bactericides,
fungicides, algaecides, mildewcides, disinfectants, sanitiser like
bleach, antiseptics, insecticides, insect and/or moth repellant,
vermicides, plant growth hormones.
[0152]Typical antimicrobials include Glutaraldehyde, Cinnamaldehyde, and
mixtures thereof. Typical insect and/or moth repellants are perfume
ingredients, such as citronellal, citral, N,N diethyl meta toluamide,
Rotundial, 8-acetoxycarvotanacenone, and mixtures thereof. Other examples
of insect and/or moth repellant for use herein are disclosed in U.S. Pat.
Nos. 4,449,987, 4,693,890, 4,696,676, 4,933,371, 5,030,660, 5,196,200,
and "Semio Activity of Flavor and Fragrance molecules on various Insect
Species", B. D. Mookherjee et al., published in Bioactive Volatile
Compounds from Plants, ASC Symposium Series 525, R. Teranishi, R. G.
Buttery, and H. Sugisawa, 1993, pp. 35-48.
[0153]A typical disclosure of suitable ketone and/or aldehydes,
traditionally used in perfumery, can be found in "perfume and Flavor
Chemicals", Vol. I and II, S. Arctander, Allured Publishing, 1994, ISBN
0-931710-35-5.
[0154]Perfume ketones components include components having odoriferous
[0155]Preferably, for the above mentioned compounds, the perfume ketone is
selected for its odor character from buccoxime; iso jasmone; methyl beta
naphthyl ketone; musk indanone; tonalid/musk plus; Alpha-Damascone,
Beta-Damascone, Delta-Damascone, Iso-Damascone, Damascenone, Damarose,
Methyl-Dihydrojasmonate, Menthone, Carvone, Camphor, Fenchone,
Alpha-Ionone, Beta-Ionone, Gamma-Methyl so-called Ionone, Fleuramone,
Dihydrojasmone, Cis-Jasmone, Iso-E-Super, Methyl-Cedrenyl-ketone or
Methyl-Cedrylone, Acetophenone, Methyl-Acetophenone,
Para-Methoxy-Acetophenone, Methyl-Beta-Naphtyl-Ketone, Benzyl-Acetone,
Benzophenone, Para-Hydroxy-Phenyl-Butanone, Celery Ketone or Livescone,
6-Isopropyldecahydro-2-naphtone, Dimethyl-Octenone, Freskomenthe,
4-(1-Ethoxyvinyl)-3,3,5,5,-tetramethyl-Cyclohexanone, Methyl-Heptenone,
2-(2-(4-Methyl-3-cyclohexen-1-yl)propyl)-cyclopentanone, 1-(p-Menthen-6
(2)-yl)-1-propanone, 4-(4-Hydroxy-3-methoxyphenyl)-2-butanone,
2-Acetyl-3,3-Dimethyl-Norbornane,
6,7-Dihydro-1,1,2,3,3-Pentamethyl-4(5H)-Indanone, 4-Damascol, Dulcinyl or
Cassione, Gelsone, Hexylon, Isocyclemone E, Methyl Cyclocitrone,
Methyl-Lavender-Ketone, Orivon, Para-tertiary-Butyl-Cyclohexanone,
Verdone, Delphone, Muscone, Neobutenone, Plicatone, Veloutone,
2,4,4,7-Tetramethyl-oct-6-en-3-one, Tetrameran.
[0156]Preferably, for the above mentioned compounds, the preferred ketones
are selected from Alpha Damascone, Delta Damascone, Iso Damascone,
Carvone, Gamma-Methyl-Ionone, Iso-E-Super,
2,4,4,7-Tetramethyl-oct-6-en-3-one, Benzyl Acetone, Beta Damascone,
Damascenone, methyl dihydrojasmonate, methyl cedrylone, and mixtures
[0157]Perfume aldehyde components include components having odoriferous
[0158]Preferably, for the above mentioned compounds, the perfume aldehyde
is selected for its odor character from adoxal; anisic aldehyde; cymal;
ethyl vanillin; florhydral; helional; heliotropin; hydroxycitronellal;
koavone; lauric aldehyde; lyral; methyl nonyl acetaldehyde; P. T.
bucinal; phenyl acetaldehyde; undecylenic aldehyde; vanillin;
2,6,10-trimethyl-9-undecenal, 3-dodecen-1-al, alpha-n-amyl cinnamic
aldehyde, 4-methoxybenzaldehyde, benzaldehyde, 3-(4-tert
butylphenyl)-propanal, 2-methyl-3-(para-methoxyphenyl propanal,
2-methyl-4-(2,6,6-trimethyl-2(1)-cyclohexen-1-yl) butanal,
3-phenyl-2-propenal, cis-/trans-3,7-dimethyl-2,6-octadien-1-al,
3,7-dimethyl-6-octen-1-al, [(3,7-dimethyl-6-octenyl)oxy]acetaldehyde,
4-isopropylbenzyaldehyde,
1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde,
2,4-dimethyl-3-cyclohexen-1-carboxaldehyde,
2-methyl-3-(isopropylphenyl)propanal, 1-decanal; decyl aldehyde,
2,6-dimethyl-5-heptenal, 4-(tricyclo[5.2.1.0(2,6)]-decylidene-8)-butanal,
octahydro-4,7-methano-1H-indenecarboxaldehyde, 3-ethoxy-4-hydroxy
benzaldehyde, para-ethyl-alpha, alpha-dimethyl hydrocinnamaldehyde,
alpha-methyl-3,4-(methylenedioxy)-hydrocinnamaldehyde,
3,4-methylenedioxybenzaldehyde, alpha-n-hexyl cinnamic aldehyde,
m-cymene-7-carboxaldehyde, alpha-methyl phenyl acetaldehyde,
7-hydroxy-3,7-dimethyl octanal, Undecenal,
2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde,
4-(3)(4-methyl-3-pentenyl)-3-cyclohexen-carboxaldehyde, 1-dodecanal,
2,4-dimethyl cyclohexene-3-carbox-aldehyde, 4-(4-hydroxy-4-methyl
pentyl)-3-cylohexene-1-carboxaldehyde, 7-methoxy-3,7-dimethyloctan-1-al,
2-methyl undecanal, 2-methyl decanal, 1-nonanal, 1-octanal,
2,6,10-trimethyl-5,9-undecadienal, 2-methyl-3-(4-tertbutyl) propanal,
dihydrocinnamic aldehyde,
1-methyl-4-(4-methyl-3-pentenyl)-3-cyclo-hexene-1-carboxaldehyde, 5 or 6
methoxy0hexahydro-4,7-methanoindan-1 or 2-carboxaldehyde,
3,7-dimethyloctan-1-al, 1-undecanal, 10-undecen-1-al, 4-hydroxy-3-methoxy
benzaldehyde, 1-methyl-3-(4-methylpentyl)-3-cyclhexene-carboxaldehyde,
7-hydroxy-3,7-dimethyl-octanal, trans-4-decenal, 2,6-nonadienal,
para-tolylacetaldehyde; 4-methylphenylacetaldehyde,
2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal,
ortho-methoxycinnamic aldehyde, 3,5,6-trimethyl-3-cyclohexene
carboxaldehyde, 3,7-dimethyl-2-methylene-6-octenal, phenoxyacetaldehyde,
5,9-dimethyl-4,8-decadienal, peony aldehyde
(6,10-dimethyl-3-oxa-5,9-undecadien-1-al),
hexahydro-4,7-methanoindan-1-carboxaldehyde, 2-methyl octanal,
alpha-methyl-4-(1-methyl ethyl)benzene acetaldehyde,
6,6-dimethyl-2-norpinene-2-propionaldehyde, para methyl phenoxy
acetaldehyde, 2-methyl-3-phenyl-2-propen-1-al, 3,5,5-trimethyl hexanal,
Hexahydro-8,8-dimethyl-2-naphthaldehyde,
3-propyl-bicyclo[2.2.1]-hept-5-ene-2-carbaldehyde, 9-decenal,
3-methyl-5-phenyl-1-pentanal, methylnonyl acetaldehyde, hexanal,
trans-2-hexenal, 1-p-menthene-q-carboxaldehyde and mixtures thereof.
[0159]Most preferred aldehydes are selected from 1-decanal, benzaldehyde,
florhydral, 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde;
trans-2-hexenal, and mixture thereof.
[0160]In the above list of perfume ingredients, some are commercial names
conventionally known to one skilled in the art, and also includes
isomers. Such isomers are also suitable for use in the present invention.
[0161]In another embodiment, especially suitable for the purpose of the
present invention are the perfume compounds, preferably the perfume
ketones or active aldehydes, characterised by having a low Odor Detection
Threshold. Such Odor Detection Threshold (ODT) should be lower than or
equal to 1 ppm, preferably lower than or equal to 10 ppb--measured at
controlled Gas Chromatography (GC) conditions such as described here
below. This parameter refers to the value commonly used in the perfumery
arts and which is the lowest concentration at which significant detection
takes place that some odorous material is present. Please refer for
example in "Compilation of Odor and Taste Threshold Value Data (ASTM DS
48 A)", edited by F. A. Fazzalari, International Business Machines,
Hopwell Junction, N.Y. and in Calkin et al., Perfumery, Practice and
Principles, John Willey & Sons, Inc., page 243 et seq (1994). For the
purpose of the present invention, the Odor Detection Threshold is
measured according to the following method:
[0162]The gas chromatograph is characterized to determine the exact volume
of material injected by the syringe, the precise split ratio, and the
hydrocarbon response using a hydrocarbon standard of known concentration
and chain-length distribution. The air flow rate is accurately measured
and, assuming the duration of a human inhalation to last 0.02 minutes,
the sampled volume is calculated. Since the precise concentration at the
detector at any point in time is known, the mass per volume inhaled is
known and hence the concentration of material. To determine the ODT of a
perfume material, solutions are delivered to the sniff port at the
back-calculated concentration. A panelist sniffs the GC effluent and
identifies the retention time when odor is noticed. The average over all
panelists determines the threshold of noticeability. The necessary amount
of analyte is injected onto the column to achieve a certain
concentration, such as 10 ppb, at the detector. Typical gas chromatograph
parameters for determining odor detection thresholds are listed below.
[0163]GC: 5890 Series II with FID detector [0164]7673 Auto sampler
[0165]Column: J&W Scientific DB-1 [0166]Length 30 meters ID 0.25 mm film
thickness 1 micron
[0167]Method: [0168]Split Injection: 17/1 split ratio [0169]Autosampler:
1.13 microliters per injection [0170]Column Flow: 1.10 mL/minute
[0171]Air Flow: 345 mL/minute [0172]Inlet Temp. 245 C [0173]Detector
Temp. 285 C [0174]Temperature Information [0175]Initial Temperature: 50 C
[0176]Rate: 5 C/minute [0177]Final Temperature: 280 C [0178]Final Time: 6
minutes [0179]Leading assumptions: 0.02 minutes per sniff [0180]GC air
adds to sample dilution
[0181]Examples of such preferred perfume components are those selected
from: 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde,
1-(2,6,6-trimethyl-2-cyclohexan-1-yl)-2-buten-1-one and/or
para-methoxy-acetophenone. Even more preferred are the following
compounds having an ODT ≦10 ppb measured with the method described
above: undecylenic aldehyde, undecalactone gamma, heliotropin,
dodecalactone gamma, p-anisic aldehyde, para hydroxy-phenyl-butanone,
cymal, benzyl acetone, ionone alpha, p.t.bucinal, damascenone, ionone
beta and methyl-nonyl ketone.
[0182]Typically the level of active is of from 10 to 90%, preferably from
30 to 85%, more preferably from 45 to 80% by weight of the amine reaction
[0183]Preferred amine reaction products are those resulting from the
reaction of polethyleneimine polymer like Lupasol polymers, with one or
more of the following Alpha Damascone, Delta Damascone, Carvone, Hedione,
Florhydral, Lilial, Heliotropine, Gamma-Methyl-Ionone and
2,4-dimethyl-3-cyclohexen-1-carboxaldehyde. Still other preferred amine
reaction products are those resulting from the reaction of Astramol
Dendrimers with Carvone as well as those resulting from the reaction of
[0184]Most preferred amine reaction products are those from the reaction
of Lupasol HF with Delta Damascone; LupasolG35 with Alpha Damascone;
LupasolG100 with 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde,
[0185]Preparation of the Component is Made as Follows in the Synthesis
Examples. In General, the nitrogen analogs of ketones and aldehydes are
called azomethines, Schiff bases or the more preferred name imines. These
imines can easily be prepared by condensation of primary amines and
carbonyl compounds by elimination of water.
[0186]A typical reaction profile is as follows:
[0187]α,β-Unsaturated ketones do not only condense with amines
to form imines, but can also undergo a competitive 1,4-addition to form
β-aminoketones.
[0188]By means of this simple method, compound and composition containing
said compounds are made which achieve a delayed release of the active
[0189]As can be observed, the perfume ingredient is typically present in
equimolar amount to the amine function so as to enable the reaction to
take place and provide the resulting amine reaction product. Of course,
higher amount are not excluded and even preferred when the amine compound
comprises more than one amine function. When the amine compound has more
than one free primary and/or secondary amine function, several different
perfume raw materials can be linked to the amine compound.
[0190]By the present invention, a delayed release of a perfume ingredient,
i.e. ketone or aldehyde is obtained. Not to be bound by theory, the
release is believed to occur by the following mechanisms:
[0191]For imine compounds, the perfume components are released upon
breaking down of the imine bond, leading to the release of the perfume
component and of the primary amine compound. This can be achieved by
either hydrolysis, photochemical cleavage, oxidative cleavage, or
enzymatic cleavage.
[0192]For β-aminoketone compounds, treatment with air moisture and/or
water successfully releases the perfume component and the amine compound.
However, other means of release are not excluded like hydrolysis,
photochemical cleavage, oxidative cleavage, or enzymatic cleavage.
[0193]Still other means of release for imine as well as β-aminoketone
compounds can be considered such as by the steaming step of ironing the
treated fabric, tumble-drying, and/or wearing.
[0194]The present invention application compositions include compositions
where there is a need of a delayed release of an active ketone or
aldehyde. This includes compositions for use in the rinse such as
softening compositions, personal cleansing such as shower gels,
deodorants, bars, shampoos; stand alone compositions such deodorising
compositions, insecticides, etc. . . . Preferred are those compositions
which result in contacting the compound of the invention with fabric. The
composition of the invention are suitable for use in any step of the
domestic treatment, that is a pre- and/or post-treatment composition, as
a wash additive, as a composition suitable for use in the rinse process.
Obviously, multiple applications can be made such as treating the fabric
with a pre-treatment composition of the invention and thereafter with the
composition suitable for use in the rinse process and/or drying process.
[0195]By compositions suitable for use in the rinse process, these are to
be understood to include compositions such as rinse added fabric softener
compositions and dryer added compositions (e.g. sheets) which provide
softening and/or antistatic benefits, as well as rinse additives.
[0196]Preferred are those compositions which result in contacting the
compound of the invention with fabric. These are to be understood to
include compositions such as rinse added fabric softener compositions and
dryer added compositions (e.g. sheets) which provide softening and/or
antistatic benefits.
[0197]Preferably, the amine reaction product(s) which is incorporated into
such compositions provides a dry surface Odor Index of more than 5
preferably at least 10.
[0198]By Dry Surface Odor Index, it is meant that the amine reaction
product(s) provides a Delta of more than 5, wherein Delta is the
difference between the Odor Index of the dry surface treated with amine
reaction product(s) and of the Odor Index of the dry surface treated with
only the perfume raw material.
[0199]The amine reaction product is added to the unperfumed product base.
[0200]The unperfumed product base, wherein the abbreviations are as
defined herein after for the examples, is as follows:
[0201]Levels of amine reaction product are selected so as to obtain an
odor grade on the dry fabric of at least 20. After careful mixing, by
shaking the container in case of a liquid, with a spatula in case of a
powder, the product is allowed to sit for 24 hrs.
[0202]The resulting product is added into the washing machine in the
dosage and in the dispenser appropriate for its category. The quantity
corresponds to recommended dosages made for the corresponding market
products: typically between 70 and 150 g for a detergent powder or liquid
via current dosing device like granulette, or ariellette, and 25 and 40
ml for a liquid fabric softener. The load is composed of four bath towels
(170 g) using a Miele W830 washing machine at 40° C. short cycle,
water input: 15° Hardness at a temperature of 10-18° C.,
and full spin of 1200 rpm.
[0203]The same process is applied for the corresponding free perfume
ingredient in consideration and is used as the reference. Dosages, fabric
loads and washing cycles for the reference and the sample are identical.
[0204]Within two hours after the end of the washing cycle, the spinned but
still wet fabrics are assessed for their odors using the scale mentioned
below. Afterwards, half of the fabric pieces are hung on a line for 24 hr
drying, away from any possible contaminations. Unless specified, this
drying takes place indoor. Ambient conditions are at temperature between
18-25 C and air moisture between 50-80%. The other half is placed in a
tumble drier and undergoes a full "very dry" cycle, i.e. in a Miele,
Novotronic T430 set on program white-extra dry (full cycle). Tumble dry
fabrics are also assessed on the next day. Fabrics are then stored in
opened aluminum bags in an odor free room, and assessed again after 7
[0205]Odor is assessed by expert panellists smelling carefully the
fabrics. A 0-100 scale is used for all fabric odor gradings. The grading
scale is as follows: [0206]100=extremely strong perfume odor
[0207]75=very strong perfume odor [0208]50=strong odor [0209]40=moderate
perfume odor [0210]30=slight perfume odor [0211]20=weak perfume odor
[0212]10=very weak perfume odor [0213]0=no odor
[0214]A difference of more than 5 grades after 1 day and/or 7 days between
the amine reaction product and the perfume raw material is statistically
significant. A difference of 10 grades or more after one day and/or 7
days represents a step-change. In other words, when a difference of grade
of more than 5, preferably at least 10 is observed between the amine
reaction product and the perfume raw material, after either 1 day or 7
day or both 1 day and 7 days, it can be concluded that the amine reaction
product is suitable for use in the present invention, provided that the
amine compound fulfill the Odor Intensity Index.
[0215]The amine reaction product as defined herein before typically is
comprised at from 0.0001% to 10%, preferably from 0.001% to 5%, and more
preferably from 0.01% to 2%, by weight of the composition. Mixtures of
the compounds may also be used herein.
[0216]Incorporation of the amine reaction product in the invention
compositions can conveniently, if necessary, be carried out by
conventional incorporation means, such as by spray-on, encapsulation like
starch encapsulation, e.g. such as described in GB1464616, dry addition,
or by encapsulation in cyclodextrin. Preferably, the amine reaction
product is preformed before incorporation into the invention
compositions. In other words, the perfume component and the amine
compound are first reacted together to obtain the resulting amine
reaction product as defined in the present invention and only once formed
incorporated into the invention compositions. By being preformed before
the incorporation in fully formulated composition, a better control of
the compound being made is obtained. Hence, the interaction with perfume
composition which may be present in fully formulated composition is
avoided as well as side reaction that could occur. Further, by such means
of incorporation, efficient control of the yield and purity of the
compound is obtained.
[0217]Most preferably, when the invention composition comprises a perfume,
the amine reaction product is incorporated in the composition separately
from the perfume. By this means, the amine reaction product and its
subsequent perfume release is more controlled.
[0218]Typically the invention composition comprises surfactancy
ingredients such as a fabric softening agent, or a surfactant as
described hereinafter as optional ingredients.
[0219]When the compositions comprises a softening agent, the resulting
composition is a softening composition.
[0220]A fabric softener component provides softness and antistastic
properties to the treated fabrics. When used, the fabric softener
component will typically be present at a level sufficient to provide
softening and antistatic properties.
[0221]Said fabric softening component may be selected from cationic,
nonionic, amphoteric or anionic fabric softening component.
[0222]Typical of the cationic softening components are the quaternary
ammonium compounds or amine precursors thereof as defined hereinafter.
[0223](1) Preferred quaternary ammonium fabric softening active compound
each R unit is independently hydrogen, C1-C6 alkyl,
C1-C6 hydroxyalkyl, and mixtures thereof, preferably methyl or
hydroxy alkyl; each R1 unit is independently linear or branched
C11-C22 alkyl, linear or branched C11-C22 alkenyl,
and mixtures thereof, R2 is hydrogen, C1-C4 alkyl,
C1-C4 hydroxyalkyl, and mixtures thereof; X is an anion which
is compatible with fabric softener actives and adjunct ingredients; the
index m is from 1 to 4, preferably 2; the index n is from 1 to 4,
[0224]An example of a preferred fabric softener active is a mixture of
quaternized amines having the formula:
wherein R is preferably methyl; R1 is a linear or branched alkyl or
alkenyl chain comprising at least 11 atoms, preferably at least 15 atoms.
In the above fabric softener example, the unit --O2CR1
represents a fatty acyl unit which is typically derived from a
triglyceride source. The triglyceride source is preferably derived from
tallow, partially hydrogenated tallow, lard, partially hydrogenated lard,
vegetable oils and/or partially hydrogenated vegetable oils, such as,
canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean
oil, tall oil, rice bran oil, etc. and mixtures of these oils.
[0225]The preferred fabric softening actives of the present invention are
the Diester and/or Diamide Quaternary Ammonium (DEQA) compounds, the
diesters and diamides having the formula:
wherein R, R1, X, and n are the same as defined herein above for
formulae (1) and (2), and Q has the formula:
[0226]These preferred fabric softening actives are formed from the
reaction of an amine with a fatty acyl unit to form an amine intermediate
wherein R is preferably methyl, Q and R1 are as defined herein
before; followed by quaternization to the final softener active.
[0227]Non-limiting examples of preferred amines which are used to form the
DEQA fabric softening actives according to the present invention include
methyl bis(2-hydroxyethyl)amine having the formula:
[0228]The counterion, X.sup.(-) above, can be any softener-compatible
anion, preferably the anion of a strong acid, for example, chloride,
bromide, methylsulfate, ethylsulfate, sulfate, nitrate and the like, more
preferably chloride or methyl sulfate. The anion can also, but less
preferably, carry a double charge in which case X.sup.(-) represents half
[0229]Tallow and canola oil are convenient and inexpensive sources of
fatty acyl units which are suitable for use in the present invention as
R1 units. The following are non-limiting examples of quaternary
ammonium compounds suitable for use in the compositions of the present
invention. The term "tallowyl" as used herein below indicates the R1
unit is derived from a tallow triglyceride source and is a mixture of
fatty acyl units. Likewise, the use of the term canolyl refers to a
mixture of fatty acyl units derived from canola oil.
[0230]Other examples of quaternay ammoniun softening compounds are
methylbis(tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate and
methylbis(hydrogenated tallowamidoethyl)(2-hydroxyethyl)ammonium
methyl-sulfate; these materials are available from Witco Chemical Company
under the trade names Varisoft® 222 and Varisoft® 110,
[0231]Particularly preferred is N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl
ammonium chloride, where the tallow chains are at least partially
[0232]The level of unsaturation contained within the tallow, canola, or
other fatty acyl unit chain can be measured by the Iodine Value (IV) of
the corresponding fatty acid, which in the present case should preferably
be in the range of from 5 to 100 with two categories of compounds being
distinguished, having a IV below or above 25.
[0233]Indeed, for compounds having the formula:
derived from tallow fatty acids, when the Iodine Value is from 5 to 25,
preferably 15 to 20, it has been found that a cis/trans isomer weight
ratio greater than 30/70, preferably greater than 50/50 and more
preferably greater than 70/30 provides optimal concentrability.
[0234]For compounds of this type made from tallow fatty acids having a
Iodine Value of above 25, the ratio of cis to trans isomers has been
found to be less critical unless very high concentrations are needed.
[0235]Other suitable examples of fabric softener actives are derived from
fatty acyl groups wherein the terms "tallowyl" and canolyl" in the above
examples are replaced by the terms "cocoyl, palmyl, lauryl, oleyl,
ricinoleyl, stearyl, palmityl," which correspond to the triglyceride
source from which the fatty acyl units are derived. These alternative
fatty acyl sources can comprise either fully saturated, or preferably at
least partly unsaturated chains.
[0236]As described herein before, R units are preferably methyl, however,
suitable fabric softener actives are described by replacing the term
"methyl" in the above examples in Table II with the units "ethyl, ethoxy,
propyl, propoxy, isopropyl, butyl, isobutyl and t-butyl.
[0237]The counter ion, X, in the examples of Table II can be suitably
replaced by bromide, methylsulfate, formate, sulfate, nitrate, and
mixtures thereof. In fact, the anion, X, is merely present as a
counterion of the positively charged quaternary ammonium compounds. The
scope of this invention is not considered limited to any particular
[0238]For the preceding ester fabric softening agents, the pH of the
compositions herein is an important parameter of the present invention.
Indeed, it influences the stability of the quaternary ammonium or amine
precursors compounds, especially in prolonged storage conditions.
[0239]The pH, as defined in the present context, is measured in the neat
compositions at 20° C. While these compositions are operable at pH
of less than 6.0, for optimum hydrolytic stability of these compositions,
the neat pH, measured in the above-mentioned conditions, must preferably
be in the range of from 2.0 to 5, preferably in the range of 2.5 to 4.5,
preferably 2.5 to 3.5. The pH of these compositions herein can be
regulated by the addition of a Bronsted acid.
[0240]Examples of suitable acids include the inorganic mineral acids,
carboxylic acids, in particular the low molecular weight
(C1-C5) carboxylic acids, and alkylsulfonic acids. Suitable
inorganic acids include HCl, H2SO4, HNO3 and
H3PO4. Suitable organic acids include formic, acetic, citric,
methylsulfonic and ethylsulfonic acid. Preferred acids are citric,
hydrochloric, phosphoric, formic, methylsulfonic acid, and benzoic acids.
[0241]As used herein, when the diester is specified, it will include the
monoester that is normally present in manufacture. For softening, under
no/low detergent carry-over laundry conditions the percentage of
monoester should be as low as possible, preferably no more than 2.5%.
However, under high detergent carry-over conditions, some monoester is
preferred. The overall ratios of diester to monoester are from 100:1 to
2:1, preferably from 50:1 to 5:1, more preferably from 13:1 to 8:1. Under
high detergent carry-over conditions, the di/monoester ratio is
preferably 11:1. The level of monoester present can be controlled in the
manufacturing of the softener compound.
[0242]Mixtures of actives of formula (1) and (2) may also be prepared.
2)-Still other suitable quaternary ammonium fabric softening compounds for
use herein are cationic nitrogenous salts having two or more long chain
acyclic aliphatic C8-C22 hydrocarbon groups or one said group
and an arylalkyl group which can be used either alone or as part of a
mixture are selected from the group consisting of: [0243](i) acyclic
quaternary ammonium salts having the formula:
[0244]wherein R4 is an acyclic aliphatic C8-C22 hydrocarbon
group, R5 is a C1-C4 saturated alkyl or hydroxyalkyl
group, R8 is selected from the group consisting of R4 and
R5 groups, and A- is an anion defined as above; [0245](ii) diamino
alkoxylated quaternary ammonium salts having the formula:
[0246]wherein n is equal to 1 to 5, and R1, R2, R5 and
A.sup.- are as defined above; [0247](iii) mixtures thereof.
[0248]Examples of the above class cationic nitrogenous salts are the
well-known dialkyldimethylammonium salts such as
ditallowedimethylammonium chloride, ditallowedimethylammonium
methylsulfate, di(hydrogenatedtallow)dimethyl-ammonium chloride,
distearyldimethylammonium chloride, dibehenyldimethyl-ammonium chloride.
Di(hydrogenatedtallow)di methylammonium chloride and
ditallowedimethylammonium chloride are preferred. Examples of
commercially available dialkyldimethyl ammonium salts usable in the
present invention are di(hydrogenatedtallow)dimethylammonium chloride
(trade name Adogen® 442), ditallowedimethylammonium chloride (trade
name Adogen® 470, Praepagen® 3445), distearyl dimethylammonium
chloride (trade name Arosurf® TA-100), all available from Witco
Chemical Company. Dibehenyldimethylammonium chloride is sold under the
trade name Kemamine Q-2802C by Humko Chemical Division of Witco Chemical
Corporation. Dimethylstearylbenzyl ammonium chloride is sold under the
trade names Varisoft® SDC by Witco Chemical Company and Ammonyx®
490 by Onyx Chemical Company.
[0249]Suitable amine fabric softening compounds for use herein, which may
be in amine form or cationic form are selected from:
(i)-Reaction products of higher fatty acids with a polyamine selected from
the group consisting of hydroxyalkylalkylenediamines and
dialkylenetriamines and mixtures thereof. These reaction products are
mixtures of several compounds in view of the multi-functional structure
of the polyamines.
[0250]The preferred Component (i) is a nitrogenous compound selected from
the group consisting of the reaction product mixtures or some selected
components of the mixtures.
[0251]One preferred component (i) is a compound selected from the group
consisting of substituted imidazoline compounds having the formula:
wherein R7 is an acyclic aliphatic C15-C21 hydrocarbon
group and R8 is a divalent C1-C3 alkylene group.
[0252]Component (i) materials are commercially available as: Mazamide®
6, sold by Mazer Chemicals, or Ceranine® HC, sold by Sandoz Colors &
Chemicals; stearic hydroxyethyl imidazoline sold under the trade names of
Alkazine® ST by Alkaril Chemicals, Inc., or Schercozoline® S by
Scher Chemicals, Inc.; N,N''-ditallowalkoyldiethylenetriamine;
1-tallowamidoethyl-2-tallowimidazoline (wherein in the preceding
structure R1 is an aliphatic C15-C17 hydrocarbon group and
R8 is a divalent ethylene group).
[0253]Certain of the Components (i) can also be first dispersed in a
Bronsted acid dispersing aid having a pKa value of not greater than 4;
provided that the pH of the final composition is not greater than 6. Some
preferred dispersing aids are hydrochloric acid, phosphoric acid, or
methylsulfonic acid.
[0254]Both N,N''-ditallowalkoyldiethylenetriamine and
1-tallow(amidoethyl)-2-tallowimidazoline are reaction products of tallow
fatty acids and diethylenetriamine, and are precursors of the cationic
fabric softening agent methyl-1-tallowamidoethyl-2-tallowimidazolinium
methylsulfate (see "Cationic Surface Active Agents as Fabric Softeners,"
R. R. Egan, Journal of the American Oil Chemicals' Society, January 1978,
pages 118-121). N,N''-ditallow alkoyldiethylenetriamine and
1-tallowamidoethyl-2-tallowimidazoline can be obtained from Witco
Chemical Company as experimental chemicals.
Methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate is sold by
Witco Chemical Company under the tradename Varisoft® 475.
(ii)-softener having the formula:
wherein each R2 is a C1-6 alkylene group, preferably an ethylene
group; and G is an oxygen atom or an --NR-- group; and each R, R1,
R2 and R5 have the definitions given above and A.sup.- has the
definitions given above for X.sup.-.
[0255]An example of Compound (II) is
1-oleylamidoethyl-2-oleylimidazolinium chloride wherein R1 is an
acyclic aliphatic C15-C17 hydrocarbon group, R2 is an
ethylene group, G is a NH group, R5 is a methyl group and A.sup.- is
a chloride anion.
(iii)-softener having the formula:
[0256]An example of Compound (iii) is the compound having the formula:
[0257]Additional fabric softening materials may be used in addition or
alternatively to the cationic fabric softener. These may be selected from
nonionic, amphoteric or anionic fabric softening material. Disclosure of
such materials may be found in U.S. Pat. No. 4,327,133; U.S. Pat. No.
4,421,792; U.S. Pat. No. 4,426,299; U.S. Pat. No. 4,460,485; U.S. Pat.
No. 3,644,203; U.S. Pat. No. 4,661,269; U.S. Pat. No. 4,439,335; U.S.
Pat. No. 3,861,870; U.S. Pat. No. 4,308,151; U.S. Pat. No. 3,886,075;
U.S. Pat. No. 4,233,164; U.S. Pat. No. 4,401,578; U.S. Pat. No.
3,974,076; U.S. Pat. No. 4,237,016 and EP 472,178.
[0258]Typically, such nonionic fabric softener materials have an HLB of
from 2 to 9, more typically from 3 to 7. Such nonionic fabric softener
materials tend to be readily dispersed either by themselves, or when
combined with other materials such as single-long-chain alkyl cationic
surfactant described in detail hereinafter. Dispersibility can be
improved by using more single-long-chain alkyl cationic surfactant,
mixture with other materials as set forth hereinafter, use of hotter
water, and/or more agitation. In general, the materials selected should
be relatively crystalline, higher melting, (e.g. >40° C.) and
relatively water-insoluble.
[0259]Preferred nonionic softeners are fatty acid partial esters of
polyhydric alcohols, or anhydrides thereof, wherein the alcohol, or
anhydride, contains from 2 to 18, preferably from 2 to 8, carbon atoms,
and each fatty acid moiety contains from 12 to 30, preferably from 16 to
20, carbon atoms. Typically, such softeners contain from one to 3,
preferably 2 fatty acid groups per molecule.
[0260]The polyhydric alcohol portion of the ester can be ethylene glycol,
glycerol, poly (e.g., di-, tri-, tetra, penta-, and/or hexa-) glycerol,
xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan.
Sorbitan esters and polyglycerol monostearate are particularly preferred.
[0261]The fatty acid portion of the ester is normally derived from fatty
acids having from 12 to 30, preferably from 16 to 20, carbon atoms,
typical examples of said fatty acids being lauric acid, myristic acid,
palmitic acid, stearic acid and behenic acid.
[0262]Highly preferred optional nonionic softening agents for use in the
present invention are the sorbitan esters, which are esterified
dehydration products of sorbitol, and the glycerol esters.
[0263]Commercial sorbitan monostearate is a suitable material. Mixtures of
sorbitan stearate and sorbitan palmitate having stearate/palmitate weight
ratios varying between 10:1 and 1:10, and 1,5-sorbitan esters are also
[0264]Glycerol and polyglycerol esters, especially glycerol, diglycerol,
triglycerol, and polyglycerol mono- and/or di-esters, preferably mono-,
are preferred herein (e.g. polyglycerol monostearate with a trade name of
Radiasurf 7248).
[0265]Useful glycerol and polyglycerol esters include mono-esters with
stearic, oleic, palmitic, lauric, isostearic, myristic, and/or behenic
acids and the diesters of stearic, oleic, palmitic, lauric, isostearic,
behenic, and/or myristic acids. It is understood that the typical
mono-ester contains some di- and tri-ester, etc.
[0266]The "glycerol esters" also include the polyglycerol, e.g.,
diglycerol through octaglycerol esters. The polyglycerol polyols are
formed by condensing glycerin or epichlorohydrin together to link the
glycerol moieties via ether linkages. The mono- and/or diesters of the
polyglycerol polyols are preferred, the fatty acyl groups typically being
those described herein before for the sorbitan and glycerol esters.
[0267]Further fabric softening components suitable for use herein are the
softening clays, such as the low ion-exchange-capacity ones described in
EP-A-0,150,531.
[0268]Of course, the term "softening active" can also encompass mixed
softening active agents.
[0269]Preferred among the classes of softener compounds disclosed herein
before are the diester or diamido quaternary ammonium fabric softening
active compound (DEQA).
[0270]The fabric softener compounds herein are present at levels of from
1% to 80% of compositions herein, depending on the composition execution
which can be dilute with a preferred level of active from 5% to 15%, or
concentrated, with a preferred level of active from 15% to 50%, most
preferably 15% to 35% by weight of the composition.
[0271]Fully formulated softening compositions preferably contain, in
addition to the herein before described components, one or more of the
[0272]The compositions herein can also optionally contain from 0.005% to
5% by weight of certain types of hydrophilic optical brighteners which
also provide a dye transfer inhibition action. If used, the compositions
herein will preferably comprise from 0.001% to 1% by weight of such
[0273]The hydrophilic optical brighteners useful in the present invention
are those having the structural formula:
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and
NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl,
N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a
salt-forming cation such as sodium or potassium.
[0274]When in the above formula, R1 is anilino, R2 is
species is commercially marketed under the tradename Tinopal-UNPA-GX®
by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic
optical brightener useful in the rinse added compositions herein.
[0275]When in the above formula, R1 is anilino, R2 is
species is commercially marketed under the tradename Tinopal 5BM-GX®
by Ciba-Geigy Corporation.
[0276]When in the above formula, R1 is anilino, R2 is morphilino
and M is a cation such as sodium, the brightener is
commercially marketed under the tradename Tinopal AMS-GX® by Ciba
Geigy Corporation.
[0277]Relatively concentrated compositions containing both saturated and
unsaturated diester quaternary ammonium compounds can be prepared that
are stable without the addition of concentration aids. However, the
compositions of the present invention may require organic and/or
inorganic concentration aids to go to even higher concentrations and/or
to meet higher stability standards depending on the other ingredients.
These concentration aids which typically can be viscosity modifiers may
be needed, or preferred, for ensuring stability under extreme conditions
when particular softener active levels are used. The surfactant
concentration aids are typically selected from the group consisting of
(1) single long chain alkyl cationic surfactants; (2) nonionic
surfactants; (3) amine oxides; (4) fatty acids; and (5) mixtures thereof.
These aids are described in WO 94/20597, specifically on page 14, line 12
[0278]When said dispersibility aids are present, the total level is from
2% to 25%, preferably from 3% to 17%, more preferably from 4% to 15%, and
even more preferably from 5% to 13% by weight of the composition. These
materials can either be added as part of the active softener raw
material, (I), e.g., the mono-long chain alkyl cationic surfactant and/or
the fatty acid which are reactants used to form the biodegradable fabric
softener active as discussed herein before, or added as a separate
component. The total level of dispersibility aid includes any amount that
may be present as part of component (I).
[0279]When the mono-alkyl cationic quaternary ammonium compound is
present, it is typically present at a level of from 2% to 25%, preferably
from 3% to 17%, more preferably from 4% to 15%, and even more preferably
from 5% to 13% by weight of the composition, the total mono-alkyl
cationic quaternary ammonium compound being at least at an effective
level. Such mono-alkyl cationic quaternary ammonium compounds useful in
the present invention are, preferably, quaternary ammonium salts of the
[R4N+E(R5)3]X.sup.wherein
[0280]R4 is C8-C22 alkyl or alkenyl group, preferably
C10-C18 alkyl or alkenyl group; more preferably
C10-C14 or C16-C18 alkyl or alkenyl group;
each R5 is a C1-C6 alkyl or substituted alkyl group (e.g.,
hydroxy alkyl), preferably C1-C3 alkyl group, e.g., methyl
(most preferred), ethyl, propyl, and the like, a benzyl group, hydrogen,
a polyethoxylated chain with from 2 to 20 oxyethylene units, preferably
from 2.5 to 13 oxyethylene units, more preferably from 3 to 10
oxyethylene units, and mixtures thereof; and
[0281]X.sup.- is as defined herein before for (Formula (I)).
[0282]Especially preferred dispersibility aids are monolauryl trimethyl
ammonium chloride and monotallow trimethyl ammonium chloride available
from Witco under the trade names Adogen® 412 and Adogen® 471,
monooleyl or monocanola trimethyl ammonium chloride available from Witco
under the tradename Adogen® 417, monococonut trimethyl ammonium
chloride available from Witco under the trade name Adogen® 461, and
mono soya trimethyl ammonium chloride available from Witco under the
trade name Adogen® 415.
[0283]The R4 group can also be attached to the cationic nitrogen atom
through a group containing one, or more, ester, amide, ether, amine,
etc., linking groups which can be desirable for increased
concentratability of component (I), etc. Such linking groups are
preferably within from one to three carbon atoms of the nitrogen atom.
[0284]Mono-alkyl cationic quaternary ammonium compounds also include
C8-C22 alkyl choline esters. The preferred dispersibility aids
of this type have the formula:
R1C(O)--O--CH2CH2N±(R)3X.sup.wherein R1, R and X.sup.- are as defined previously.
[0285]Highly preferred dispersibility aids include C12-C14 coco
choline ester and C16-C18 tallow choline ester.
[0286]Suitable biodegradable single-long-chain alkyl dispersibility aids
containing an ester linkage in the long chains are described in U.S. Pat.
No. 4,840,738, said patent being incorporated herein by reference.
[0287]When the dispersibility aid comprises alkyl choline esters,
preferably the compositions also contain a small amount, preferably from
2% to 5% by weight of the composition, of organic acid. Organic acids are
described in EP.404,471, which is herein incorporated by reference.
Preferably the organic acid is selected from the group consisting of
glycolic acid, acetic acid, citric acid, and mixtures thereof.
[0288]Ethoxylated quaternary ammonium compounds which can serve as the
dispersibility aid include ethylbis(polyethoxy ethanol)alkylammonium
ethyl-sulfate with 17 moles of ethylene oxide, available under the trade
name Variquat® 66 from Witco Corporation; polyethylene glycol (15)
oleammonium chloride, available under the trade name Ethoquad® 0/25
from Akzo; and polyethylene glycol (15) cocomonium chloride, available
under the trade name Ethoquad® C/25 from Akzo.
[0289]Quaternary compounds having only a single long alkyl chain, can
protect the cationic softener from interacting with anionic surfactants
and/or detergent builders that are carried over into the rinse from the
[0290]Suitable nonionic surfactants to serve as the
viscosity/dispersibility modifier include addition products of ethylene
oxide and, optionally, propylene oxide, with fatty alcohols, fatty acids,
fatty amines, etc. They are referred to herein as ethoxylated fatty
alcohols, ethoxylated fatty acids, and ethoxylated fatty amines.
[0291]Any of the alkoxylated materials of the particular type described
hereinafter can be used as the nonionic surfactant. In general terms, the
nonionics herein, when used alone, in liquid compositions are at a level
of from 0% to 5%, preferably from 0.1% to 5%, more preferably from 0.2%
to 3%. Suitable compounds are substantially water-soluble surfactants of
R2--Y--(C2H4O)z--C2H4OH
wherein R2 for both solid and liquid compositions is selected from
the group consisting of primary, secondary and branched chain alkyl
and/or acyl hydrocarbyl groups; primary, secondary and branched chain
alkenyl hydrocarbyl groups; and primary, secondary and branched chain
alkyl- and alkenyl-substituted phenolic hydrocarbyl groups; said
hydrocarbyl groups having a hydrocarbyl chain length of from 8 to 20,
preferably from 10 to 18 carbon atoms. More preferably the hydrocarbyl
chain length for liquid compositions is from 16 to 18 carbon atoms and
for solid compositions from 10 to 14 carbon atoms. In the general formula
for the ethoxylated nonionic surfactants herein, Y is typically --O--,
--C(O)O--, --C(O)N(R)--, or --C(O)N(R)R--, preferably --O--, and in which
R2, and R, when present, have the meanings given herein before,
and/or R can be hydrogen, and z is at least 8, preferably at least 10-11.
Performance and, usually, stability of the softener composition decrease
when fewer ethoxylate groups are present.
[0292]The nonionic surfactants herein are characterized by an HLB
(hydrophilic-lipophilic balance) of from 7 to 20, preferably from 8 to
15. Of course, by defining R2 and the number of ethoxylate groups,
the HLB of the surfactant is, in general, determined. However, it is to
be noted that the nonionic ethoxylated surfactants useful herein, for
concentrated liquid compositions, contain relatively long chain R2
groups and are relatively highly ethoxylated. While shorter alkyl chain
surfactants having short ethoxylated groups can possess the requisite
HLB, they are not as effective herein.
[0293]Nonionic surfactants as the viscosity/dispersibility modifiers are
preferred over the other modifiers disclosed herein for compositions with
higher levels of perfume.
[0294]Examples of nonionic surfactants follow. The nonionic surfactants of
this invention are not limited to these examples. In the examples, the
integer defines the number of ethoxy (EO) groups in the molecule.
[0295]Suitable amine oxides include those with one alkyl or hydroxyalkyl
moiety of 8 to 22 carbon atoms, preferably from 10 to 18 carbon atoms,
more preferably from 8 to 14 carbon atoms, and two alkyl moieties
selected from the group consisting of alkyl groups and hydroxyalkyl
groups with 1 to 3 carbon atoms.
[0296]Examples include dimethyloctylamine oxide, diethyldecylamine oxide,
bis-(2-hydroxyethyl)dodecyl-amine oxide, dimethyldodecylamine oxide,
dipropyl-tetradecylamine oxide, methylethylhexadecylamine oxide,
dimethyl-2-hydroxyoctadecylamine oxide, and coconut fatty alkyl
dimethylamine oxide.
[0297]Stabilizers can be present in the compositions of the present
invention. The term "stabilizer," as used herein, includes antioxidants
and reductive agents. These agents are present at a level of from 0% to
2%, preferably from 0.01% to 0.2%, more preferably from 0.035% to 0.1%
for antioxidants, and more preferably from 0.01% to 0.2% for reductive
agents. These assure good odor stability under long term storage
conditions. Antioxidants and reductive agent stabilizers are especially
critical for unscented or low scent products (no or low perfume).
[0298]Examples of antioxidants that can be added to the compositions of
this invention include a mixture of ascorbic acid, ascorbic palmitate,
propyl gallate, available from Eastman Chemical Products, Inc., under the
trade names Tenox® PG and Tenox® S-1; a mixture of BHT (butylated
hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, and
citric acid, available from Eastman Chemical Products, Inc., under the
trade name Tenox®-6; butylated hydroxytoluene, available from UOP
Process Division under the trade name Sustane® BHT; tertiary
butylhydroquinone, Eastman Chemical Products, Inc., as Tenox® TBHQ;
natural tocopherols, Eastman Chemical Products, Inc., as Tenox®
GT-1/GT-2; and butylated hydroxyanisole, Eastman Chemical Products, Inc.,
as BHA; long chain esters (C8-C22) of gallic acid, e.g.,
dodecyl gallate; Irganox® 1010; Irganox® 1035; Irganox® B
1171; Irganox® 1425; Irganox® 3114; Irganox® 3125; and
mixtures thereof; preferably Irganox® 3125, Irganox® 1425,
Irganox® 3114, and mixtures thereof; more preferably Irganox®
3125 alone or mixed with citric acid and/or other chelators such as
isopropyl citrate, Dequest® 2010, available from Monsanto with a
chemical name of 1-hydroxyethylidene-1,1-diphosphonic acid (etidronic
acid), and Tiron®, available from Kodak with a chemical name of
4,5-dihydroxy-m-benzene-sulfonic acid/sodium salt, and DTPA®,
available from Aldrich with a chemical name of
[0299]In the present invention, an optional soil release agent can be
added. Typical levels of incorporation in the composition are from 0% to
10%, preferably from 0.2% to 5%, of a soil release agent. Preferably,
such a soil release agent is a polymer.
[0300]Soil Release agents are desirably used in fabric softening
compositions of the instant invention. Any polymeric soil release agent
known to those skilled in the art can optionally be employed in the
compositions of this invention. Polymeric soil release agents are
characterized by having both hydrophilic segments, to hydrophilize the
surface of hydrophobic fibers, such as polyester and nylon, and
hydrophobic segments, to deposit upon hydrophobic fibers and remain
adhered thereto through completion of washing and rinsing cycles and,
thus, serve as an anchor for the hydrophilic segments. This can enable
stains occurring subsequent to treatment with the soil release agent to
be more easily cleaned in later washing procedures.
[0301]If utilized, soil release agents will generally comprise from about
0.01% to about 10.0%, by weight, of the detergent compositions herein,
typically from about 0.1% to about 5%, preferably from about 0.2% to
about 3.0%.
[0302]The following, all included herein by reference, describe soil
release polymers suitable for use in the present invention. U.S. Pat. No.
3,959,230 Hays, issued May 25, 1976; U.S. Pat. No. 3,893,929 Basadur,
issued Jul. 8, 1975; U.S. Pat. No. 4,000,093, Nicol, et al., issued Dec.
28, 1976; U.S. Pat. No. 4,702,857 Gosselink, issued Oct. 27, 1987; U.S.
Pat. No. 4,968,451, Scheibel et al., issued November 6; U.S. Pat. No.
4,702,857, Gosselink, issued Oct. 27, 1987; U.S. Pat. No. 4,711,730,
Gosselink et al., issued Dec. 8, 1987; U.S. Pat. No. 4,721,580,
Gosselink, issued Jan. 26, 1988; U.S. Pat. No. 4,877,896, Maldonado et
al., issued Oct. 31, 1989; U.S. Pat. No. 4,956,447, Gosselink et al.,
issued Sep. 11, 1990; U.S. Pat. No. 5,415,807 Gosselink et al., issued
May 16, 1995; European Patent Application 0 219 048, published Apr. 22,
1987 by Kud, et al.
[0303]Further suitable soil release agents are described in U.S. Pat. No.
4,201,824, Violland et al.; U.S. Pat. No. 4,240,918 Lagasse et al.; U.S.
Pat. No. 4,525,524 Tung et al.; U.S. Pat. No. 4,579,681, Ruppert et al.;
U.S. Pat. No. 4,240,918; U.S. Pat. No. 4,787,989; U.S. Pat. No.
4,525,524; EP 279,134 A, 1988, to Rhone-Poulenc Chemie; EP 457,205 A to
BASF (1991); and DE 2,335,044 to Unilever N. V., 1974 all incorporated
[0304]Commercially available soil release agents include the METOLOSE
SM100, METOLOSE SM200 manufactured by Shin-etsu Kagaku Kogyo K.K.,
SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF
(Germany), ZELCON 5126 (from Dupont) and MILEASE T (from ICI).
[0305]In the present invention, the premix can be combined with an
optional scum dispersant, other than the soil release agent, and heated
to a temperature at or above the melting point(s) of the components.
[0306]The preferred scum dispersants herein are formed by highly
ethoxylating hydrophobic materials. The hydrophobic material can be a
fatty alcohol, fatty acid, fatty amine, fatty acid amide, amine oxide,
quaternary ammonium compound, or the hydrophobic moieties used to form
soil release polymers. The preferred scum dispersants are highly
ethoxylated, e.g., more than 17, preferably more than 25, more preferably
more than 40, moles of ethylene oxide per molecule on the average, with
the polyethylene oxide portion being from 76% to 97%, preferably from 81%
to 94%, of the total molecular weight.
[0307]The level of scum dispersant is sufficient to keep the scum at an
acceptable, preferably unnoticeable to the consumer, level under the
conditions of use, but not enough to adversely affect softening. For some
purposes it is desirable that the scum is nonexistent. Depending on the
amount of anionic or nonionic detergent, etc., used in the wash cycle of
a typical laundering process, the efficiency of the rinsing steps prior
to the introduction of the compositions herein, and the water hardness,
the amount of anionic or nonionic detergent surfactant and detergency
builder (especially phosphates and zeolites) entrapped in the fabric
(laundry) will vary. Normally, the minimum amount of scum dispersant
should be used to avoid adversely affecting softening properties.
Typically scum dispersion requires at least 2%, preferably at least 4%
(at least 6% and preferably at least 10% for maximum scum avoidance)
based upon the level of softener active. However, at levels of 10%
(relative to the softener material) or more, one risks loss of softening
efficacy of the product especially when the fabrics contain high
proportions of nonionic surfactant which has been absorbed during the
washing operation.
[0308]Preferred scum dispersants are: Brij 700®; Varonic U-250®;
Genapol T-500®, Genapol T-800®; Plurafac A-79®; and Neodol
25-50®.
[0309]Examples of bactericides used in the compositions of this invention
include glutaraldehyde, formaldehyde, 2-bromo-2-nitro-propane-1,3-diol
sold by Molex Chemicals, located in Philadelphia, Pa., under the trade
name Bronopol®, and a mixture of
5-chloro-2-methyl-4-isothiazoline-3-one and
2-methyl-4-isothiazoline-3-one sold by Rohm and Haas Company under the
trade name Kathon 1 to 1,000 ppm by weight of the agent.
[0310]The present invention can contain any softener compatible perfume.
Suitable perfumes are disclosed in U.S. Pat. No. 5,500,138, said patent
[0311]As used herein, perfume includes fragrant substance or mixture of
substances including natural (i.e., obtained by extraction of flowers,
herbs, leaves, roots, barks, wood, blossoms or plants), artificial (i.e.,
a mixture of different nature oils or oil constituents) and synthetic
(i.e., synthetically produced) odoriferous substances. Such materials are
often accompanied by auxiliary materials, such as fixatives, extenders,
stabilizers and solvents. These auxiliaries are also included within the
meaning of "perfume", as used herein. Typically, perfumes are complex
mixtures of a plurality of organic compounds.
[0312]Examples of perfume ingredients useful in the perfumes of the
present invention compositions include, but are not limited to, hexyl
cinnamic aldehyde; amyl cinnamic aldehyde; amyl salicylate; hexyl
salicylate; terpineol; 3,7-dimethyl-cis-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-trans-2,6-octadien-1-ol;
3,7-dimethyl-6-octen-1-ol; 3,7-dimethyl-1-octanol;
2-methyl-3-(para-tert-butylphenyl)-propion-aldehyde;
4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbox-aldehyde;
tri-cyclodecenyl propionate; tricyclodecenyl acetate; anisaldehyde;
ethyl-3-methyl-3-phenyl glycidate; 4-(para-hydroxyphenyl)-butan-2-one;
1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one;
para-methoxyacetophenone; para-methoxy-alpha-phenylpropene;
methyl-2-n-hexyl-3-oxo-cyclopentane carboxylate; undecalactone gamma.
Additional examples of fragrance materials include, but are not limited
to, orange oil; lemon oil; grapefruit oil; bergamot oil; clove oil;
dodecalactone gamma; methyl-2-(2-pentyl-3-oxo-cyclopentyl)acetate;
beta-naphthol methylether; methyl-beta-naphthylketone; coumarin;
decylaldehyde; benzaldehyde; 4-tert-butylcyclohexyl acetate;
alpha,alpha-dimethylphenethyl acetate; methylphenylcarbinyl acetate;
Schiff's base of
4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde and methyl
anthranilate; cyclic ethyleneglycol diester of tridecandioic acid;
3,7-dimethyl-2,6-octadiene-1-nitrile; ionone gamma methyl; ionone alpha;
ionone beta; petitgrain; methyl cedrylone;
ionone methyl; methyl-1,6,10-trimethyl-2,5,9-cyclododecatrien-1-yl
4-acetyl-6-tert-butyl-1,1-dimethyl indane; benzophenone;
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;
e; ambroxane; dodecahydro-3a,6,6,9a-tetramethylnaphtho-[2,1b]furan;
cedrol; 5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol;
caryophyllene alcohol; cedryl acetate; para-tert-butylcyclohexyl 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
[0313]More examples of perfume components are geraniol; geranyl acetate;
linalool; linalyl acetate; tetrahydrolinalool; citronellol; citronellol
acetate; dihydromyrcenol; dihydromyrcenyl acetate; tetrahydromyrcenol;
terpinyl acetate; nopol; nopyl acetate; 2-phenylethanol; 2-phenylethyl
acetate; benzyl alcohol; benzyl acetate; benzyl salicylate; benzyl
benzoate; styrallyl acetate; dimethylbenzylcarbinol;
trichloromethylphenylcarbinyl methylphenylcarbinyl acetate; isononyl
acetate; vetiverol acetate; vetiverol;
2-methyl-3-(p-tert-butylphenyl)-propanal;
2-methyl-3-(p-isopropylphenyl)-propanal; 3-(p-tert-butylphenyl)-propanal;
4-(4-methyl-3-pentenyl)-3-cyclohexenecarbaldehyde;
4-acetoxy-3-pentyltetrahydropyran; methyl dihydrojasmonate;
2-n-heptylcyclopentanone; 3-methyl-2-pentyl-cyclopentanone; n-decanal;
n-dodecanal; 9-decenol-1; phenoxyethyl isobutyrate; phenylacetaldehyde
dimethylacetal; phenylacetaldehyde diethylacetal; geranonitrile;
citronellonitrile; cedryl acetal; 3-isocamphylcyclohexanol; cedryl
methylether; isolongifolanone; aubepine nitrile; aubepine; heliotropine;
eugenol; vanillin; diphenyl oxide; hydroxycitronellal ionones; methyl
ionones; isomethyl ionomes; irones; cis-3-hexenol and esters thereof;
indane musk fragrances; tetralin musk fragrances; isochroman musk
fragrances; macrocyclic ketones; macrolactone musk fragrances; ethylene
brassylate.
[0314]The perfumes useful in the present invention compositions are
substantially free of halogenated materials and nitromusks.
[0315]Suitable solvents, diluents or carriers for perfumes ingredients
mentioned above are for examples, ethanol, isopropanol, diethylene
glycol, monoethyl ether, dipropylene glycol, diethyl phthalate, triethyl
citrate, etc. The amount of such solvents, diluents or carriers
incorporated in the perfumes is preferably kept to the minimum needed to
provide a homogeneous perfume solution. Perfume can be present at a level
of from 0% to 10%, preferably from 0.1% to 5%, and more preferably from
0.2% to 3%, by weight of the finished composition. Fabric softener
compositions of the present invention provide improved fabric perfume
[0316]The compositions and processes herein can optionally employ one or
more copper and/or nickel chelating agents ("chelators"). Such
water-soluble chelating agents can be selected from the group consisting
of amino carboxylates, amino phosphonates, polyfunctionally-substituted
aromatic chelating agents and mixtures thereof, all as hereinafter
defined. The whiteness and/or brightness of fabrics are substantially
improved or restored by such chelating agents and the stability of the
materials in the compositions are improved. Without intending to be bound
by theory, it is believed that the benefit of these materials is due in
part to their exceptional ability to remove iron and manganese ions from
washing solutions by formation of soluble chelates.
[0317]Amino carboxylates useful as optional chelating agents include
ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,
nitrilo-triacetates, ethylenediamine tetraproprionates,
triethylenetetra-aminehexacetates, diethylenetriaminepentaacetates, and
ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts
therein and mixtures therein.
[0318]Amino phosphonates are also suitable for use as chelating agents in
phosphorus are permitted in detergent compositions, and include
ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred,
these amino phosphonates do not contain alkyl or alkenyl groups with more
than about 6 carbon atoms.
[0319]Polyfunctionally-substituted aromatic chelating agents are also
May 21, 1974, to Connor et al. Preferred compounds of this type in acid
form are dihydroxy-disulfobenzenes such as
[0320]A preferred biodegradable chelator for use herein is ethylenediamine
disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S.
Pat. No. 4,704,233, Nov. 3, 1987, to Hartman and Perkins.
[0321]The compositions herein may also contain water-soluble methyl
glycine diacetic acid (MGDA) salts (or acid form) as a chelant or
co-builder useful with, for example, insoluble builders such as zeolites,
layered silicates and the like.
[0322]Preferred chelating agents include DETMP, DETPA, NTA, EDDS and
[0323]If utilized, these chelating agents will generally comprise from
about 0.1% to about 15% by weight of the fabric care compositions herein.
More preferably, if utilized, the chelating agents will comprise from
about 0.1% to about 3.0% by weight of such compositions.
[0324]The compositions of the present invention can further contain a
crystal growth inhibitor component, preferably an organodiphosphonic acid
component, incorporated preferably at a level of from 0.01% to 5%, more
preferably from 0.1% to 2% by weight of the compositions.
[0325]By organo diphosphonic acid it is meant herein an organo
diphosphonic acid which does not contain nitrogen as part of its chemical
structure. This definition therefore excludes the organo
aminophosphonates, which however may be included in compositions of the
invention as heavy metal ion sequestrant components.
[0326]The organo diphosphonic acid is preferably a C1-C4
diphosphonic acid, more preferably a C2 diphosphonic acid, such as
ethylene diphosphonic acid, or most preferably ethane
1-hydroxy-1,1-diphosphonic acid (HEDP) and may be present in partially or
fully ionized form, particularly as a salt or complex.
[0327]Still useful herein as crystal growth inhibitor is the organic
monophosphonic acid. Organo monophosphonic acid or one of its salts or
complexes is also suitable for use herein as a CGI.
[0328]By organo monophosphonic acid it is meant herein an organo
monophosphonic acid which does not contain nitrogen as part of its
chemical structure. This definition therefore excludes the organo
invention as heavy metal ion sequestrants.
[0329]The organo monophosphonic acid component may be present in its acid
form or in the form of one of its salts or complexes with a suitable
counter cation. Preferably any salts/complexes are water soluble, with
the alkali metal and alkaline earth metal salts/complexes being
[0330]A preferred organo monophosphonic acid is
2-phosphonobutane-1,2,4-tricarboxylic acid commercially available from
Bayer under the tradename of Bayhibit.
[0331]The compositions and processes herein can optionally employ one or
more enzymes such as lipases, proteases, cellulase, amylases and
peroxidases. A preferred enzyme for use herein is a cellulase enzyme.
Indeed, this type of enzyme will further provide a color care benefit to
the treated fabric. Cellulases usable herein include both bacterial and
fungal types, preferably having a pH optimum between 5 and 9.5. U.S. Pat.
No. 4,435,307 discloses suitable fungal cellulases from Humicola insolens
or Humicola strain DSM1800 or a cellulase 212-producing fungus belonging
to the genus Aeromonas, and cellulase extracted from the hepatopancreas
of a marine mollusk, Dolabella Auricula Solander. Suitable cellulases are
also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
CAREZYME® and CELLUZYME® (Novo) are especially useful. Other
suitable cellulases are also disclosed in WO 91/17243 to Novo, WO
96/34092, WO 96/34945 and EP-A-0,739,982. In practical terms for current
commercial preparations, typical amounts are up to 5 mg by weight, more
typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent
composition. Stated otherwise, the compositions herein will typically
comprise from 0.001% to 5%, preferably 0.01%-1% by weight of a commercial
enzyme preparation. In the particular cases where activity of the enzyme
preparation can be defined otherwise such as with cellulases,
corresponding activity units are preferred (e.g. CEVU or cellulase
Equivalent Viscosity Units). For instance, the compositions of the
present invention can contain cellulase enzymes at a level equivalent to
an activity from 0.5 to 1000 CEVU/gram of composition. Cellulase enzyme
preparations used for the purpose of formulating the compositions of this
invention typically have an activity comprised between 1,000 and 10,000
CEVU/gram in liquid form, around 1,000 CEVU/gram in solid form.
[0332]Another optional, but preferred, ingredient is a liquid carrier. The
liquid carrier employed in the instant compositions is preferably at
least primarily water due to its low cost, relative availability, safety,
and environmental compatibility. The level of water in the liquid carrier
is preferably at least 50%, most preferably at least 60%, by weight of
the carrier. Mixtures of water and low molecular weight, e.g., <200,
organic solvent, e.g., lower alcohols such as ethanol, propanol,
isopropanol or butanol are useful as the carrier liquid. Low molecular
weight alcohols include monohydric, dihydric (glycol, etc.) trihydric
(glycerol, etc.), and higher polyhydric (polyols) alcohols.
[0333]The present invention can include optional components conventionally
used in textile treatment compositions, for example: colorants;
preservatives; surfactants; anti-shrinkage agents; fabric crisping
agents; spotting agents; germicides; fungicides; anti-oxidants such as
butylated hydroxy toluene, anti-corrosion agents, enzyme stabilisers,
materials effective for inhibiting the transfer of dyes from one fabric
to another during the cleaning process (i.e., dye transfer inhibiting
agents), hydrotropes, processing aids, dyes or pigments, and the like.
[0334]The present invention can also include other compatible ingredients,
including those as disclosed in WO96/02625, WO96/21714, and WO96/21715.
[0335]The composition of the invention may take a variety of physical form
including liquid, gel, foam in either aqueous or non-aqueous form,
granular and tablet forms.
[0336]When in a liquid form, the composition may also be dispensed by a
dispensing means such as a spray dispenser, or aerosol dispenser.
[0337]The present invention also relates to such compositions incorporated
into a spray dispenser to create an article of manufacture that can
facilitate treatment of fabric articles and/or surfaces with said
compositions containing the amine reaction product and other ingredients
(examples are cyclodextrins, polysaccharides, polymers, surfactant,
perfume, softener) at a level that is effective, yet is not discernible
when dried on the surfaces. The spray dispenser comprises manually
activated and non-manual powered (operated) spray means and a container
containing the treating composition. Typical disclosure of such spray
dispenser can be found in WO 96/04940 page 19 line 21 to page 22 line 27.
The articles of manufacture preferably are in association with
instructions for use to ensure that the consumer applies sufficient
ingredient of the composition to provide the desired benefit. Typical
compositions to be dispensed from a sprayer contain a level of amine
reaction product of from about 0.01% to about 5%, preferably from about
0.05% to about 2%, more preferably from about 0.1% to about 1%, by weight
of the usage composition.
[0338]Also provided herein is a method for providing a delayed release of
an active ketone or aldehyde which comprises the step of contacting the
surface to be treated with a compound or composition of the invention,
and thereafter subjecting the treated surface with a material, preferably
an aqueous medium like moisture or any other means susceptible of
releasing the active from the amine reaction product.
[0339]By "surface", it is meant any surface onto which the compound can
deposit. Typical examples of such material are fabrics, hard surfaces
such as dishware, floors, bathrooms, toilet, kitchen, skin, and other
surfaces in need of a delayed release of an active ketone or aldehyde
such as that with litter like animal litter. Preferably, the surface is a
[0340]By "delayed release" is meant release of the active component (e.g
perfume) over a longer period of time than by the use of the active
(e.g., perfume) itself.
[0341]Abbreviations used in the following invention composition Examples
In the composition examples, the abbreviated component identifications
have the following meanings: [0342]DEQA: Di-(tallowyl-oxy-ethyl) dimethyl
ammonium chloride [0343]DTDMAC: Ditallow dimethylammonium chloride
[0344]DEQA (2): Di-(soft-tallowyloxyethyl)hydroxyethyl methyl ammonium
methylsulfate. [0345]DTDMAMS: Ditallow dimethyl ammonium methylsulfate.
[0346]SDASA: 1:2 ratio of stearyldimethyl amine:triple-pressed stearic
acid. [0347]Fatty acid: Stearic acid of IV=0 [0348]Electrolyte: Calcium
chloride [0349]PEG: Polyethylene Glycol 4000 [0350]Neodol 45-13: C14-C15
linear primary alcohol ethoxylate, sold by Shell Chemical CO.
[0351]Cellulase: Cellulytic enzyme sold under the tradename Carezyme,
Celluzyme and/or Endolase by Novo Nordisk A/S. [0352]Silicone antifoam:
Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer
as dispersing agent with a ratio of said foam controller to said
dispersing agent of 10:1 to 100:1. [0353]PEI: Polyethyleneimine with an
average molecular weight of 1800 and an average ethoxylation degree of 7
etholeneoxy residues per nitrogen [0354]HEDP: 1,1-hydroxyethane
diphosphonic acid [0355]ARP1: Amine reaction product of ethyl
4-aminobenzoate with 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde as made
from Synthesis example I [0356]ARP2: Amine reaction product of
aminobenzoic acid with 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde made
according to Synthesis example I [0357]ARP3: Amine reaction product of
Lupasol P with α-Damascone as made from Synthesis example III
[0358]ARP4: Amine reaction product of D-glucamine with Citronellal as
made from Synthesis example II [0359]ARP5: Amine reaction product of
LupasolHF with δ-Damascone as made from Synthesis example III
[0360]Polymer: Polyvinylpyrrolidone K90 available from BASF under the
tradename Luviskol K90 [0361]Dye fixative: Dye fixative commercially
available from Clariant under the tradename Cartafix CB [0362]Polyamine:
1,4-Bis-(3-aminopropyl)piperazine [0363]Bayhibit AM:
Bayer [0364]Fabric softener active: Di-(canoloyl-oxy-ethyl)hydroxyethyl
methyl ammonium methylsulfate [0365]HPBDC Hydroxypropyl beta-cyclodextrin
[0366]RAMEB Randomly methylated beta-cyclodextrin [0367]Bardac 2050
Dioctyl dimethyl ammonium chloride, 50% solution [0368]Bardac 22250:
Didecyl dimethyl ammonium chloride, 50% solution [0369]Genamin C100 Coco
fatty amine ethoxylated with 10 moles ethylene oxide and commercially
available from Clariant [0370]Genapol V4463 Coco alcohol ethoxylated with
10 moles ethylene oxide and commercially available from Clariant
[0371]Silwet 7604: Polyalkyleneoxide polysiloxanes of MW 4000 of formula
R--(CH3)2SiO--[(CH3)2SiO]a--[(CH3)(R)SiO].s-
ub.b--Si(CH3)2--R, wherein average a+b is 21, and commercially
available from Osi Specialties, Inc., Danbury, Conn. [0372]Silwet 7600:
Polyalkyleneoxide polysiloxanes of MW 4000, of formula
ub.b--Si(CH3)2--R, wherein average a+b is 11, and commercially
available from Osi Specialties, Inc., Danbury, Conn.
[0373]The following are synthesis examples of compounds according to the
I-Synthesis of ethyl 4-aminobenzoate with
[0374]To an ice cooled stirred solution of 10 g of
2,4-dimethyl-3-cyclohexen-1-carboxaldehyde (0.07 mol) in 35 mL EtOH and
molecular sieves (4 Å, 20 g) 1 eq of the amine was added via an
addition funnel. The reaction mixture was stirred under nitrogen
atmosphere and protected from light. After 6 days the mixture was
filtrated and the solvent was removed. The yield of imine formation is
[0375]Similar results were obtained where the
2,4-dimethyl-3-cyclohexen-1-carboxaldehyde was replaced by bourgeonal, or
trans-2-nonenal. Additionally, similar results were obtained where the
ethyl-4-aminobenzoate was replaced by 4-amino benzoic acid.
II-Synthesis of D-glucamine with
[0376]To an ice cooled solution of 1 mmol D-glucamine in about 30 mL EtOH
and molecular sieves (4 Å, 5 g) 1 eq of the
2,4-dimethyl-3-cyclohexen-1-carboxaldehyde was added. The reaction was
stirred under nitrogen atmosphere and protected from light. After 3 to 4
days, the molecular sieves and the solvent were removed by filtration and
evaporation respectively. The solid imine was obtained in 85 to 90%
[0377]Similar results were obtained where the
2,4-dimethyl-3-cyclohexen-1-carboxaldehyde was replaced by citronellal,
trans-2-nonenal, or decanal.
[0378]The β-amino ketone from Lupasol G100 (commercial available by
BASF content 50% water, 50% Lupasol G100 (Mw. 5000)) and
α-Damascone was prepared using any one of these three different
procedures described as follows: [0379]1. Commercially available Lupasol
G100 was dried using the following procedure: 20 g of the Lupasol
solution was dried at the rotating evaporator during several hours. The
obtained residue, still containing about 4.5 g of H2O, was
azeotropically distilled at the rotating evaporator using toluene. The
residue was then placed in the desiccator dried at 60° C. (using
P2O5 as water absorbing material). On basis of the obtained
weight we concluded that the oil contained less then 10% H2O. On
basis of the NMR-spectra we concluded that this is probably less then 5%.
This dried sample was then used in the preparation of β-amino
[0380]1.38 g of the dried Lupasol G100 was dissolved in 7 ml. ethanol. The
solution was stirred gently with a magnetic stirrer during a few minutes
before 2 g Na2SO4 (anhydrous) was added. After stirring again
for a few minutes 2.21 g α-Damascone was added over a period of 1
minute. After two days reaction, the mixture was filtrated over a Celite
filter (vide supra), and the residue washed thoroughly with ethanol.
About 180 ml. of a light foaming filtrate was obtained. This was
concentrated until dryness using a rotating evaporator and dried over
P2O5 in an desiccator at room temperature. About 3.5 of a
colorless oil was obtained. [0381]2. 4.3 g Lupasol G100 solution was
(without drying) dissolved in 10 ml. ethanol. The solution was stirred
with a magnetic stirrer during a few minutes before 3.47 g
α-Damascone was added over a 1.5 minutes period. After two days
reaction at room temperature the reaction mixture was filtrated over
Celite (vide supra) and the residue washed thoroughly with ethanol. The
filtrate (200 ml., light foaming) was concentrated at the evaporator and
dried in an desiccator (P2O5 as drying agent) at room
temperature. About 6.0 g of a colorless oil was obtained. [0382]3. To
about 3.0 g of Lupasol G100 solution (used as such) was added 2.41 g
α-Damascone. The mixture was stirred without using solvent. After
stirring for 4 days the obtained oil was dissolved in 100 ml. THF, dried
with MgSO4, filtrated and the filtrate concentrated at the rotating
evaporator. After drying in the exsiccator (P2O5) at room
temperature, about 4.1 g of a colorless oil was obtained. This oil still
contained about 13% (w/w) of THF, even after a prolonged drying (3 days).
[0383]The product obtained from the three procedures had identical
NMR-spectra.
[0384]The β-amino ketone from Lupasol P and α-Damascone was
prepared using the procedure described as follows:
[0385]About 1.8 g Lupasol P solution (50% H2O, 50% Lupasol Mw.
750000, as obtained from BASF) was dissolved in 7 ml ethanol, the
solution was stirred for a few minutes with a magnetic stirrer before
1.44 g α-Damascone was added. After three days the reaction mixture
was filtrated over a celite filter (vide supra) and the residue washed
thoroughly with ethanol. After concentrating of the filtrate and drying
of the obtained oil in the desiccator (P2O5) at room
temperature, about 3 g of the reaction product between Lupasol and
α-Damascone was obtained.
[0386]In the following formulation examples all levels are quoted as % by
weight of the composition unless otherwise stated, and incorporation of
the amine reaction product so called herein after "ARP" in the fully
formulated composition is carried out by dry addition (d), encapsulation
in starch (es) as described in GB-1,464,616 or cyclodextrin (ec) or as is
in the composition as defined herein before. The term in bracket for the
ARP in the formulation examples refers to the means of incorporation.
When none is provided, the incorporation is made as it is. The levels
given for the ARP, whether processed or not, refer to the level of ARP as
is and not to the processed ARP.
[0387]The following fabric softening compositions are in accordance with
DTDMAC -- -- -- -- -- 4.5 15.0 15.0
DEQA 2.6 2.9 18.0 18.0 19.0 -- -- --
Fatty acid 0.3 -- 1.0 1.0 -- -- -- --
PEG -- -- 0.6 0.6 0.6 -- 0.6 0.6
ARP 5 0.3 -- 0.2 0.2 -- -- -- 0.2
ARP 3 -- 0.05 -- -- 0.2 -- 0.4 0.4
ARP 4 -- -- -- 0.02 -- 0.05 -- --
Electrolyte -- -- 600 600 1200 -- 1200 1200
[0388]The following rinse added fabric softener composition was prepared
ARP 1 0.5 -- -- -- --
ARP 2 -- 0.3 -- -- 0.04
ARP 3 -- 0.1 0.1 -- --
ARP 4 -- -- -- 0.1 0.1
[0389]The following fabric softener compositions were prepared according
to the present invention:
Fatty acid 0.3 0.3 0.3 0.3 -- -- -- --
ARP 1 0.02 -- -- -- -- 0.1 0.23 0.2
ARP 5 -- 0.2 0.2 -- -- -- -- 0.1
ARP 3 -- -- 0.2 0.05 0.3 0.2 -- 0.2
PEI -- 0.5 0.3 0.3 -- 2.0 1.5 1.5
HEDP -- -- 0.05 0.05 -- -- 0.3 0.3
Electrolyte -- -- -- -- 0.1 0.1 0.1 0.1
[0390]The following dryer added fabric conditioner compositions were
prepared according to the present invention:
DEQA(2) -- -- -- -- 51.8 51.8 51.8
DTMAMS -- -- 26.0 26.0 -- -- --
SDASA 70.0 70.0 42.0 42.0 40.2 40.2 40.2
Neodol 45-13 13.0 13.0 -- -- -- -- --
Ethanol 1.0 1.0 -- -- -- -- --
ARP 1(es) 0.1 -- -- 0.1 0.2 -- --
ARP 2(ec) -- 0.1 -- -- -- -- --
ARP 3(es) -- -- 0.05 -- -- 0.2 --
ARP 5(d) -- -- -- -- -- -- 0.3
Glycoperse S-20 -- -- -- -- 15.4 15.4 15.4
Glycerol -- -- 26.0 26.0 -- -- --
Digeranyl Succinate 0.38 0.38 -- -- -- -- --
Clay -- -- 3.0 3.0 -- -- --
Dye 0.01 0.01 -- -- -- -- --
[0391]The following are non-limiting examples of pre-soak fabric
conditioning and/or fabric enhancement compositions according to the
present invention which can be suitably used in the laundry rinse cycle:
C12-C14 -- 5.0 5.0 -- -- --
Fabric softener -- -- 2.5 2.5 -- --
Genamin C100 0.33 -- 0.33 0.33 0.33 --
Genapol V4463 0.2 -- 0.2 0.2 0.2 --
[0392]The following are non-limiting examples of odor-absorbing
compositions suitable for spray-on applications:
HPBCD 1.0 -- 1.0 -- 1.2
RAMEB -- 1.0 -- 0.8 --
Tetronic 901 -- -- 0.1 -- --
Silwet L-7604 -- -- -- 0.1 --
Silwet L-7600 0.1 -- -- -- 0.1
Bardac 2050 -- -- -- 0.03 --
Bardac 2250 -- 0.2 -- -- 0.1
Diethylene glycol -- 1.0 -- -- 0.2
Triethylene glycol -- -- 0.1 -- --
Ethanol -- -- -- -- 2.5
Perfume 1 0.1 -- -- -- --
Perfume 2 -- 0.05 -- 0.1 --
Perfume 3 -- -- 0.1 -- 0.1
Kathon 3 ppm 3 ppm 3 ppm 3 ppm --
ARP1 5.0 1.0 -- -- --
ARP3 -- -- 0.5 0.1 0.08
[0393]The perfume 1, 2, and 3 have the following compositions:
Anisic aldehyde -- -- 2
Benzophenone 3 5 --
Cedrol 2 -- --
Citronellol 10 -- 5
Coumarin -- -- 5
Cymal -- -- 3
Dihydromyrcenol 10 -- 5
Flor acetate 5 -- 5
Galaxolide 10 -- --
Linalyl acetate 4 -- 5
alpha-Terpineol 5 -- 8
Vanillin -- -- 1
2011-04-07Amine reaction compounds comprising one or more active ingredient
2011-08-25Amine reaction compounds comprising one or more active ingredient
2012-03-15Amine reaction compounds comprising one or more active ingredient
2012-09-20Surfactant composition with a reduction of surface tension, interfacial tension, and critical micelle concentration using a protein-based surfactant synergist
2011-05-26Consumer products comprising algae derived ingredients
2015-11-26Sage odorant
2015-05-21Fabric softener composition
2014-10-30Combination of an amino alcohol, a fragrance and a silicic acid ester, and the use of same as a pro-fragrance
2014-08-214,8-dimethyl-4,9-decadienenitrile
2014-08-07Violet leaves odorants
2016-05-19Benefit agent delivery compositions
2016-05-12Encapsulates
2016-03-31Delivery systems comprising malodor reduction compositions
2016-02-11Perfume systems
2015-12-10Compositions containing benefit agent delivery particles