Note: Descriptions are shown in the official language in which they were submitted.
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FABRIC SOFTENING COMPOSITIONS COMPRISING ANTIOXIDANTS
FOR MALODOUR REDUCTION
Technical Field
The present invention relates to fabric softening
compositions, in particular to those that soften without
affecting the absorbency of the fabric and which suffer
from a reduced tendency to develop malodour during
manufacture, storage or use.
Background and Prior Art
Rinse added fabric softener compositions are well
known. However, a disadvantage associated with
conventional rinse conditioners is that although
they increase the softness of a fabric they often
simultaneously decrease its absorbency. This means
that its ability to take up water decreases. This
is particularly disadvantageous with towels where
the consumer requires the towel to be soft, and yet,
have a high absorbency.
W098/16538 (Unilever) discloses fabric conditioning
compositions comprising liquid or soft solid
derivatives of a cyclic polyol or a reduced
saccharide which give good softening and retain
absorbency of the fabric.
EP 0 380 406 (Colgate-Palmolive) discloses detergent
compositions comprising a saccharide or reduced saccharide
ester containing at least one fatty acid chain.
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WO 95/00614 (Kao Corporaticn) discloses softenina
compositions comprising polyhyciric alcohol esters and
cationised cellulose.
US 5 447 643 (:-iiils) discloses aqueous fabric softeners
comprising nonionic surfactant and mono, di or tri fatty
acid esters of certain polyols.
WO 96/15213 (Henkel) discloses textile softeninq acrents
containing alkyl, alkenyl and/or acyl group containing sugar
derivatives, which are solid after esterification, in
combination with nonionic and cationic emulsifiers.
Frequently a liquid or soft solid fabric softening agent,
e.g. a CPE or RSE as herein-defined which addresses the
above absorbency problem, is obtained by using unsaturated,
usually predominantly unsaturated , fatty acid chains on the
ester or ether functions. However such compositions may
suffer from the development of product malodour upon
manufacture, storage or use. This is obviously highly
undesirable.
WO 97/13828 (P&G) discloses fabric conditioning compositions
comprising a heavy metal sequestrant.
WO 96/21714 and WO 96/21715 (P&G) disclose fabric
conditioning compositions comprising chelating agents.
WO 96/03481 (P&G) discloses fabric conditioning compositions
comprising ~ to 20 wt% antioxidant.
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The present invention is directed towards alleviating the
above-mentioned tiroblems.
The principal advantaqes of the compositions of the present
invention are that thev soften fabrics without detriment to
the absorbency of the fabric, they are easily manufactured
and do not suffer from unacceptable levels of malodour
development upon manufacture, storage or use.
Definition of the Invention
Thus according to one aspect of the invention there is
provided a fabric softening composition comprising:
i) a liquid or soft solid derivative of a cyclic polyol
(CPE) or of a reduced saccharide (RSE) resulting from 35 to
100% of the hydroxyl groups in the polyol or saccharide
beina esterified or etherified, the CPE or RSE having 2 or
more ester or ether groups independently a--tached to a Cg-C22
alkyl or alkenyl chain , wherein at least one of the chains
attached to the ester or ether groups has at least one
unsaturated bond, and;
ii) a deposition aid; and
iii) one or more antioxidant(s)
wherein the weight ratio of i) to iii) is 20:1 or greater.
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It has been found, surprisingly, that the above compositions
provide an unexpected combination of simultaneous fabric
softening and retention of absorbency and exhibit improved
malodour resistance, even, at elevated temperatures.
According to a further aspect of the invention, there is
provided a method of reducing malodour upon manufacture,
storage or use in a composition comprisinq a CPE or RSE as
herein described b_v the addition of a least one antioxidant.
Detailed Description of the Invention
In the context of the present invention the initials CPE or
RSE stand for a derivative of a cyclic polyol or of a
reduced saccharide respectively which results from 35 to
100% of the hydroxyl groups of the cyclic polyol or reduced
saccharide being esterified or etherified, the CPE or RSE
having two or more ester or ether groups independently of
one another attached to a Cg to C22 alkyl or alkenyl chain,
and in which at least one of the chains attached to the
ester or ether groups has at least one unsaturated bond.
The CPE or RSE
The CPE or RSE used according to the invention does not have
any substantial crystalline character at 200C. Instead it
is preferably in a liquid or soft solid state as herein
defined at 2~
OC.
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The liquid or soft solid (as hereinafter defined) CPEs or
RSEs of the present invention result from 35 to 100% of the
hydroxyl groups of the starting cyclic polyol or reduced
saccharide being esterified or etherified with groups such
5 that the CPEs or RSEs are in the required liquid or soft
solid state. These groups typically contain unsaturation,
branching or mixed chain lengths.
Typically the CPEs or RSEs have 3 or more ester or ether
groups or mixtures thereof, for example 3 to 8, especially 3
to 5. It is preferred if two or more of the ester or ether
groups of the CPE or RSE are independently of one another
attached to a C8 to C22 alkyl or alkenyl chain. The C8 to
C22 alkyl or alkenyl groups may be branched or linear carbon
chains.
Preferably 35 to 85% of the hydroxyl groups, most preferably
40-80%, even more preferably 45-75%, such as 45-70% are
esterified or et~herified.
Preferably the CPE or RSE contains at least 35% tri or
higher esters, eg at least 40%.
The CPE or RSE has at least one of the chains independently
attached to the ester or ether groups having at least one
unsaturated bond. `I'his provides a cost effective way of
making the CPE or RSE a liquid or a soft solid. It is
preferred if predominantly unsaturated fatty chains, derived
from, for example, rape oil, cotton seed oil, soybean oil,
oleic, tallow, palmitoleic, linoleic, erucic or other
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sources of unsaturated vegetable fatty acids, are attached
to the ester/ether groups.
These chains are referred to below as the ester or ether
chains (of the CPE or RSE).
The ester or ether chains of the CPE or RSE are preferably
predominantly unsaturated. Preferred CPEs or RSEs include
sucrose tetratallowate, sucrose tetrarapeate, sucrose
tetraoleate, sucrose tetraesters of soybean oil or cotton
seed oil, cellobiose tetraoleate, sucrose trioleate, sucrose
triapeate, sucrose pentaoleate, sucrose pentarapeate,
sucrose hexaoleate, sucrose hexarapeate, sucrose triesters,
pentaesters and hexaesters of soybean oil or cotton seed
oil, glucose tiroleate, glucose tetraoleate, xylose
trioleate, or sucrose tetra-,tri-, penta- or hexa- esters
with any mixture of predominantly unsaturated fatty acid
chains. The most preferred CPEs or RSEs are those with
monosaturated fatty acid chains, i.e. where any
polyunsaturation has been removed by partial hydrogenation.
However some CPEs or RSEs based on polyunsaturated fatty
acid chains, eg sucrose tetralinoleate, may be used provided
most of the polyunsaturation has been removed by partial
hydrogenation.
The most highly preferred liquid CPEs or RSEs are any of the
above but where the polyunsaturation has been removed
through partial hydrogenation.
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Preferably 40% or more of the fatty acid chains contain an
unsaturated bond, more preferably 50% or more, most
preferably 60% or more. In most cases 65% to 100%, e.g. 65%
to 95% contain an unsaturated bond.
CPEs are preferred for use with the present invention.
Inositol is a preferred example of a cyclic polyol.
Inositol derivatives are especially preferred.
In the context of the present invention, --he term cyclic
polvol encompasses all forms of saccharides. Indeed
saccharides are especially preferred for use with this
invention. Examples of preferred saccharides for the CPEs
or RSEs to be derived from are monosaccharides and
disaccharides.
Examples of monosaccharides include xylose, arabinose,
galactose, fructose, sorbose and glucose. Glucose is
especially preferred. Examples of disaccharides include
maltose, lactose, cellobiose and sucrose. Sucrose is
especially preferred. An example of a reduced saccharide is
sorbitan.
The liquid or soft solid CPEs can be prepared by methods
well known to those skilled in the art. These include
acylation of the cyclic polyol or reduced saccharide with an
acid chloride; trans-esterification of the cyclic polyol or
reduced saccharide fatty acid esters using a variety of
catalysts; acvlation of the cyclic polyol cr reduced
saccharide with an acid anhydride and acylation of the
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cyclic polyol or reduced saccharide with a fatty acid. See
for instance US 4 386 213 and AU 14416/88 (both P&G).
It is preferred if the CPE or RSE has 3 or more, preferably
4 or more ester or ether groups. If the CPE is a
disaccharide it is preferred if the disaccharide has 3 or
more ester or ether groups. Particularly preferred CPEs are
esters with a degree of esterification of 3 to 5, for
example, sucrose tri, tetra and penta esters.
Where the cyclic polyol is a reducing sugar it is
advantageous if each ring of the CPE has one ether or ester
group, preferably at the C1 position. Suitable examples of
such compounds include methyl glucose derivatives.
Examples of suitable CPEs include esters of
alkyl(poly)glucosides, in particular alkyl glucoside esters
having a degree of polymerisation from 1 to 2.
The length cr the unsaturated (and saturated if present)
chains in the CPE or RSE is C8-C22, preferably C12-C22. It is
possible to include one or more chains of Ci-C8, however
these are less preferred.
The liquid or soft solid CPEs or RSEs of the present
invention are characterised as materials having a
solid:liauid ratio of between 50:50 and 0:100 at 20 C as
determined by T? relaxation time NMR, preferably between
43:57 and 0:100, most preferably between 40:60 and 0:100,
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such as, 20:80 and 0:100. The T2 NMR relaxation time is
commonlv used for characterising solid:liquid ratios in soft
solid products such as fats and margarines. For the purpose
of the present invention, any component of the signal with a
T2 of less than 100 s is considered to be a solid
component and any component with T2 _ 100 s is considered
to be a liquid component.
For the CPEs and RSEs, the prefixes (e.g. tetra and penta)
only indicate the average degrees of esterification. The
compounds exist as a mixture of materials ranging from the
monoester to the fully esterified ester. It is the average
degree of esterification which is used herein to define the
CPEs and RSEs.
The HLB of the CPE or RSE is typically between 1 and 3.
The CPE or RSE is preferably present in the composition in
an amount of 0.5-50% by weight, based upon the total weight
of the composition, more preferably 1-30% by weight, such as
2-25%, eg 2-20%.
The CPEs and RSEs for use in the compositions include those
recited in the following examples, including, sucrose
tetraoleate, sucrose pentaerucate, sucrose tetraerucate and
sucrose pentaoleate.
The Deposition Aid
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In the context of the present invention a deposition aid is
defined as any material that aids deposition of the selected
CPE or RSE onto a fabric during the laundering process.
The deposition aid may be selected from cationic compounds,
such as cationic surfactants, nonionic surfactants, anionic
surfactants, polymeric deposition aids or mixtures thereof.
Quaternary ammonium compounds have been found to be
particularly advantageous. A class of preferred deposition
aids is fabric softeninQ compounds.
It is preferred if the deposition aid is cationic in nature.
If a cationic surfactant or cationic softening aid is not
present in the formulation it is preferred if a cationic
polymeric deposition aid is present. Most preferably the
deposition aid is both cationic in nature and is a fabric
softening compound.
Mixtures of deposition aids may be used, for example, a
mixture of a cationic surfactant and a nonionic surfactant,
or a fabric softening compound and a polymeric deposition
aid.
Suitable cationic deposition aids include water soluble
single chain auaternary ammonium compounds. Examples
include cetyl trimethyl ammonium chloride, cetyl trimethyl
ammonium bromide, or any of those listed in European Patent
No. 258 923 (Akzo Nobel).
However, it is preferred if the deposition aid is a
substantially water insoluble fabric softening compound. In
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particular substantially water insoluble quaternary ammonium
materials ccmprising a single alkyl or alkenyl chain having
an average length equal to or greater than C20 are
preferred. 7-ven more preferable are compounds comprising a
polar head group and two alkyl or alkenyl chains each having
an average chain length equal to or greater than C14.
Preferred fabric softening deposition aids have two long
alkyl or alkenvl chains with an average chain length equal
to or greater than C14. More preferably each chain has an
average chain length greater than C16. Most preferably at
least 50% of each long chain alkyl or alkenyl group has a
chain length of C18.
It is preferred if the long chain alkyl or alkenyl groups of
the fabric softening deposition aid are predominantly
linear.
The fabric softening deposition aids used in the
compositions of the invention are molecules which provide
excellent softening.
"Substantially water insoluble" fabric compounds in the
context of th.is invention are defined as fabric compounds
having a solubility less than 1 x 10 3 wt% in demineralised
water at 200C. Preferably the fabric softening deposition
aids have a solubility less than 1 x 10 4 wt% Most
preferably the fabric softening deposition aids have a
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solubility at 200 C in demineralised water from 1 x 10 8 to 1
x l0 6wt o .
Preferred fabric softening deposition aids are quaternary
ammonium compounds, preferably those with at least one ester
link.
It is especially preferred if the fabric softening
deposition aid is a water insoluble quaternary ammonium
material which comprises a compound having two C12-18 alkyl
or alkenyl groups connected to the molecule via at least one
ester link. It is more preferred if the quaternary ammonium
material has two ester links present. An especially
preferred ester-linked quaternary ammonium material for use
in the invention can be represented by the formula (I):
1
R
1 + 2
R N (CH2)n _ ., X Formula
(I)
(CH2)n-T-R2
wherein each R1 group is independently selected from C1-4
alkyl, hydroxyalkyl or C2-4 alkenyl groups; and wherein
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each R 2 group is independently selected from Cg-28 alkyl or
alkenyl groups;
0 0
1~
T is -0-C- or -C-0-;
X is any suitable anion and n is 0 or an integer from 1-5.
Preferred materials of this class include
Di(tallowoyloxyethyl) dimethyl ammonium chloride and Methyl
bis-[ethyl(tallowyl)]-2-hydroxyethyl ammonium methyl
sulphate.
A second preferred type of quaternary ammonium material can
be represented by the formula (II):
OOCR2
(R1) 3N+- (CH2)n CH X Formula (II)
I
CH200CR2
wherein R1, n, X and R2 are as defined above.
It is advantageous for environmental reasons if the
quaternary ammonium material is biologically degradable.
Preferred materials cf this class such as 1,2 bis[hardened
tallowoyloxy]-----trimethylammonium propane chloride and their
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method of preparation are, for example, described ir.
US 4 137 180 (Lever Brothers) Preferably these materials
comprise small amounts of the corresponding monoester as
described in US 4 137 1-80 for example 1-hardened
tallowoyloxy -2-hydroxv 3-trimethylammonium propane
chloride.
The fabric softening cieposition aid of the composition may
also be compounds having the formula (III):
0 0 R4
II II I
(R3-C-O-)mA(-O-C-B-N+-R5)n X Formula (III)
I
6
R
wherein X is an anion, A is an (m+n) valent radical
remaining after the removal of (m+n) hydroxy groups from an
aliphatic nolyol having p hydroxy groups and an atomic ratio
of carbon to oxygen in the range of 1.0 to 3.0 and up to 2
groups per hydroxy group selected from ethylene oxide and
propylene oxide,
m is 0 or an integer from 1 to p-n, n is an integer from 1
to p-m, and p is an integer of at least 2,
B is an alkylene or alkvlidene group containing 1 to 4
carbon atoms,
R3, R4, R5 and R6 are, independently from each other,
straight or branched chain Cl-C48 alkyl or alkenvl groups,
optionally with substitution by one or more functional
groups and/or interruption by at most 10 ethvlene oxide
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and/or propylene oxide groups, or by at most two functional
groups selected from
0 0 0 0 0
ll il J! 1 1 11 11
-C-O-, -0-C-, -C-N-, -N-C-, and -O-C-O-
or R11 and R12 mav form a ring system containing 5 or 6 atoms
in the ring, with the nroviso that the average compound
either has at least one R group having 22-48 carbon atoms,
or at least two R groups having 16-20 carbon atoms, or at
least three R groups having 10-14 carbon atoms. Preferred
compounds of this type are described in EP 638 639 (Akzo).
The deposition aid may also comprise a mixture of different
fabric softening compounds, for example a mixture of
compounds of Formula (I) and Formula (II).
The deposition aid may also be a nonionic surfactant, such
as a nonionic ethoxylated surfactant having an HLB of from
about 10 to about 20. It is advantageous if the surfactant
alkvl group contains at least 12 carbon atoms.
Suitable polymeric deposition aids for use with the
invention include cationic and nonionic polymeric deposition
aids.
Suitable cationic polymeric deposition aids include cationic
guar polymers such as; the JaguarTM series of polymers (ex
Rhodia), cationic cellulose derivatives such as Celquats'n',
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(ex National Starch), UcareTM polymers (ex Amerchol),
cationic starches e.g. potato starch such as SoftGelsTM and
SolvitoseTM such as BDAT"' (ex Avebe), C* bond polymers series
from Cerestar, cationic polyacrylamides such as PCGT"' (ex
Allied Colloids), FlocaidT' series of polymers (ex National
Starch) and cationic chitosan and derivatives. Cationic
polymeric aids are particularly preferred in the absence of
any other cationic material in the composition.
~0 Suitable nonionic deposition aids include PluronicsTM (ex
BASF), dialkyl PEGs, --elluiose derivatives as described in
GB 213 730 (Unilever), hydroxy ethyl cellulose, starch, and
hydrophobically modified nonionic polyols such as AcusolT"
880/882 (ex Rohm & Haas).
Mixtures of any of the aforementioned deposition aids may be
used.
In the fabric softening compositions the weight ratio of CPE
or RSE to deposition aid is preferably within the range of
from 15:1 to 1:10, more preferably within the range from
10:1 to 1:5, most preTerably 8:1 to 1:3.
If a composition is required to give particularly high
absorbency to fabrics it is advantageous if the weight ratio
of CPE or RSE to deposition aid is at least 1:1 (especially
if the deposition aid is a fabric softening compound).
If a highl_v softening composition is required it is
advantageous if the weight ratio of a softening deposition
aid to CPE or RSE is a= least 2:3, preferabl_y at least 1:1.
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To give excellent softening and hydrophobicity to fabrics it
is preferred if the weight ratio of softening deposition aid
to CPE or RSE is from 3:2 to 1:10, more preferably from 2:3
to 1:10.
The fabric softening compositions comprise one or more
antioxidants in a weight ratio to the CPE or RSE of 20:1 or
more.
The deposition aid is preferably present in the compositions
in an amount of 0.05-15% by weight, based upon the total
weight of the composition, more preferably 0.1-10%, such as
0.5-7.5%.
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Antioxidant
Any suitable antioxidant may be used according to the
invention. Preferably the antioxidant comprises at least
one initiation inhibitor antioxidant or at least one
propagation inhibitor. Mixtures of these two types of
antioxidants have been found to be particularly beneficial,
especially in reducing medium to long term malodour. Any
antioxidant referred to in the following examples may be
used.
The compositions preferably comprise 0.0001% to 1% by weight
(in total), based on the total weight of the composition, of
antioxidants, more preferably 0.00015% to 0.75%, even more
preferably 0.002 to 0.5%, e.g. 0.002 to 0.45%.
It has been found that initiation inhibitors antioxidants
can give good short and long term malodour suppression but a
mixture of propagation inhibitor and initiation inhibitor
antioxidants can give a surprisingiy good short and long
term malodour suppression.
Suitable initiation inhibitor antioxidants include peroxide
decomposers (e.g. sulphides, aryl and alkyl phosphites,
metal salts of some thiodipropionates, xanthates and
dithiophosphates).
Suitable peroxide decomposers include (RO2CCH2CH-))2S where
R=C12H25, C,4H29 or C18H37 i.e. TNPP (tris-
nonylphenylphosphite) available as IrgafosTM 186; SandostabT" P-
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EPQ; and IrgafosTM P-EPQ respectively. Where used, peroxide
decomposers are preferablv present at a level of between
0.001% to 0.5% by weight, most preferably 0.005% to 0.1%.
Another type of suitable initiation inhibitor antioxidant
are metal ion sequestrants or deactivators. Suitable such
types include N, N'-disalicylidene-l,2-propanediamine;
oxalyl bis- (benzylidenehydrazide) ;
ethylenediaminetetraacetic acid (EDTA); ethylenediamine-
N,N'-disuccinic acid (EDDS); N-hydroxyethyiene-diamine
triacetic acid; nitrilotriacetic acid (NTA); ethylene
diamine tetrapropionic acid; ethylenediamine-N,N'-diglutamic
acid; 2-hydorxypropylenediamine-N,N'-disuccinic acid;
triethylenetriamine hexacetic acid; diethylenetriamine
pentacetic acid (DETPA); trans 1,2-diaminocyclohexane-
N,N,N',N'-tetraacetic acid; ethanol diglycine;
ethylenediamine tetrakis(methylene phosphonic acid) (EDTMP);
1-hydroxyethane 1,1 diphosphonic acid (HEDP); hydroxyethane
dimethylenephosphonic acid; glucoic acid; citric acid;
tartaric acid; isopropyl citric acid; oxydisuccinic acid;
dipicolinic acid; 4,5 dihydroxy-m-benzenesulphonic acid; 8-
hydroxyquinoline; sodium dithiocarbamate; sodium
tetraphenylboron; ammonium nitrosophenvl hydroxylamine;
ethylene diamine mono succinic acid (EDMS); iminodisuccinic
acid sodium salt (IDS Na salt); Tetrakis[methylene(3,5-di-
tert-butyl--?-hydroxyhydrocinnamate)]methane (Irganox'r" 1010);
Tetrakis[methylene(3,5-di-tert-butyl-4-
hydroxvhydrocinnamate)]methane; 1,3,5-trimethyl-2,4,6-tris-
(3',5' di-tert-butyl-4'-hydroxybenzyl)benzene (IrganoxTM 1330)
and diethylene triaminepenta(methylene phosphonate) (DequestT"
2066)
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Metal ion sequestrants are preferably present at a level of
between 0.0001% to 0.5% by weight, based on the total weight
of the composition, most preferably 0.005% to 0.1%.
Propagation inhibitor antioxidants consist primarily of
hindered phenols/polyphenols. These can include those which
are commonly used in the foods or plastics industries, such
as butylated hydroxvanisole (BHA); butylated hydroxytoluene
(BHT); tert-butvl hydroquinone (TBHQ); tocopherols;
tocotrienols; ascorbic acid; ascobyl palmitate; octyl
gallate; propyl gallate; lauryl gallate; N,N-bis(ethyl
31,51-di-tert-butyl-4-hydroxybenzoate; 2-(N,N-dimethyl-
amino)ethyl 31,51-di-tert-butyl-4'hydroxybenzoate-N-
cocoamine; 2- (N-methyl-N-cocamino) ethyl 31,51-di-tert-butyl-
4'-hydroxybenzoate; 2,2'-methylenebis(4-methyl-6-t-
butylphenol), 4,4'-butylidenebis (2-tert-butyl-5-
methylphenol), n-octadecyl 3,5-di-tert-butyl-4-
hydroxvhydrocinnamate, 1,1,3-tris(3-tert-butyl-4-hydroxy-6-
methylphenvl) butane.
Inhibitor antioxidants are preferably present at a level of
0.0001% to 0.5% by weight, based on the total weight of the
composition, more preferably 0.0002% to 0.05%, most
preferably 0.0002% to 0.02%.
The weight ratio of the initiation inhibitor (i) to the
propagation inhibitor (ii) is preferably within the range
10:1 to 1:10, more preferablv 10:1 to 1:5, even more
preferably 8:1 to 1:1, e.g. 6:1 to 1:1.
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The weight ratio of CPE or RSE to total antioxidant is 20:1
or greater, preferably 50:1 or qreater, more preferably 75:1
or greater. The weight ratio may be as high as 1500:1 or
greater. It is preferred that the weight ratio has an upper
limit of 3000:1, e.g. 2500:1.
Composition pH
The compositions of the invention preferablv have a pH from
1.5 to 7, more preferably from 1.5 to 5.
Other Ingredients
The compositions can also contain fatty acids, for example
C8 - C24 alkyl or alkenyl monocarboxylic acids, or, polymeric
carboxylic acids. Preferably saturated fatty acids are
used, in particular, hardened tallow C16-C18 fatty acids.
The composition can also contain one or more optional
ingredients, selected from electrolytes, non-aqueous
solvents, pH buffering agents, perfumes, perfume carriers,
fluorescers, colorants, hydrotropes, antifoaming agents,
antiredeposition agents, polymeric and other thickeners,
enzymes, optical brightening agents, opacifiers, anti-
shrinking agents, anti-wrinkle agents, anti-spotting agents,
germicides, fungicides, anti-corrosion agents, drape
imparting agents, antistatic agents, sunscreens, colour care
agents and ironing aids.
If the product is a liquid it may be advantaqeous if a
viscositv control aqent 4-s present. Anv -,riscositv control
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agent used with rinse conditioners is suitable for use with
the present invention, for example biological polymers such
as Xanthum gum (KelcoT1' ex Kelsan and RhodopolT"' ex Rhone-
Poulenc), Guar gum (JaguarTM ex Rhone-Poulenc), starches and
cellulose ethers. Synthetic polymers are useful viscosity
control agents such as polyacrylic acid, poly vinyl
pyrrolidone, polyethylene, carbomers, cross linked
polyacrylamides such as AcosolT"' 880/882 polyethylene and
polyethylene glycols.
It is preferred that the compositions are substantially free
of bleaches. Preferably the compositions are entirely free
of bleaches.
Also suitable as viscosity modifiers are decoupling polymers
and deflocculating polymers.
Product Form
The compositions may be in any form conventionally used for
fabric softening compositions e.g., powder, paste, gel or
liquid. Liquids, especially emulsions are preferred.
The compositions may be prepared by any suitable method.
Where the antioxidant is oil soluble, e.g. the propagation
inhibitor, the antioxidant is suitabi-y pre-added with the
CPE or RSE. Where the antioxidant is water soluble, e.g.
the initiation inhibitor, especially metal sequestrants, the
inhibitor is typically post-dosed to a pre-formed emulsion
containing the CPE or RSE.
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Examples
The invention is illustrated by the following non-limiting
examples. Further examples within the scope of the present
invention will be obvious to the man skilled in the art.
Examoles 1-13 and 14-24
The effect of the anti-oxidant in reducing malodour
development on storage in fabric softening compositions
comprising a CPE of the and a deposition aid is demonstrated
below.
All %'s are by weight based on the total weight of the
composition and represent the amount of active compound.
Examples 1 and 14 are controls which do not contain
antioxidant. In Ryoto- 0-170, 85% or greater of the fatty
acid chains contain an unsaturated bond.
Examples 2 to 13 were prepared by dissolving the propagation
inhibitor antioxidant (Irganox 1330 or Irganox 1010) in the
CPE (Ryoto 0-170) and adding this to a separate mixture of a
cationic and water (in an amount to make the composition up
to 100 weight %). The resultant composition was mixed using
a low shear HeidolphT"' mixer to produce an emulsion.
In examples 6 to 13, the initiation inhibitor antioxidant
(Dequest 2066) was post-dosed to this emulsion.
Examples 14 to 24 were prepared by mixing the cationic
surfactant (CTAC) with water and then addina to this mixture
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the CPE (Ryoto 0-170) at room temperature under conditions
of high shear to produce an emulsion.
In examples 15 and 22 to 24, the propagation inhibitor
antioxidant (Irganox 1010) was dissolved in the CPE prior to
emulsification.
In example 16 to 24, the initiation inhibitor antioxidant
(Dequest 2066, DTPA or Na IDS) was post-dosed into the final
emulsion.
The formulations of Examples 1-13 and 14-24 are shown in
Tables 1 and 2 respectively.
SUBSTITUTE SHEET (RULE 26)
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Table 1
Example
Ryoto CTAC initiation propagation propagation
0- b inhibitor inhibitor inhibitor
170a DEQUEST A B
2066c
1 4.5 1.0 - - -
(control)
2 4.5 1.0 - 0.00225 -
3 4.5 1.0 - 0.0045 -
4 4.5 1.0 - - 0.00225
4.5 1.0 - - 0.0045
6 4.5 1.0 0.01 0.00225 -
7 4.5 1.0 0.01 0.0045 -
8 4.5 1.0 0.01 - 0.00225
9 4.5 1.0 0.01 - 0.0045
4.5 1.0 0.05 0.00225 -
11 4.5 1.0 0.05 0.0045 -
12 4.5 1.0 0.05 - 0.00225
73-
4.5 1.0 0.05 - 0.0045
asucrose pentaoleate (from Mitsubishi-Kagaku Food
5 Corporation)
bcetyl trimethyl ammonium chloride; from Aldrich (as a 25%
solution).
c diethylene triaminepenta(methylene phosphonate); available
from solutia.
SUBSTITUTE SHEET (RULE 26)
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"A" is Irganox 1330; 1,3,5-trimethyl-2,4,6-tris-(31,5' di-
tert-butyl-41-hydroxybenzyl)benzene.
"B" is Irganox 1010; Tetrakis[methylene(3,5-di-tert-butyl-
4-hydroxyhydrocinnamate))methane (Both from Ciba Geigy).
Table 2
Example % % % Initiation Water
Ryot CTAC propagation Inhibitor (type
0 0- Inhibitor and %)
170 Irganox
1010
14 4.5 0.5 - None To 100
(control)
4.5 0.5 0.0045 None To 100
16 4.5 0.5 - 0.01 - Dequest To 100
2066a
17 4.5 0.5 - 0.01 - DTPA ITo 100
18 4.5 0.5 - 0.01 - Na IDSc To 100
19 4.5 0.5 - 0.05 - Dequest To 100
2066a
4.5 0.5 - 0.05 - DTPA b To 100
21 4.5 0.5 - 0.05 - Na IDSc To 100
22 4.5 0.5 0.0045 0.01 - Dequest To 100
2066a
23 4.5 0.5 0.0045 0.01 - DTPAb To 100
24 4.5 0.5 0.0045 0.01 - Na IDSc To 100
SUBSTITUTE SHEET (RULE 26)
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adiethylene triamine-N,N,N',N ",N "-pentakis methylene
phosphoric acid (from Solutia)
bdiethvlene triamine pentaacetate (from Akzo Nobel)
c iminodisuccinic acid sodium salt (from Bayer)
The samples were stored in screw-top glass bottles at 37 C
to 45 C. At the intervals aiven in Tables 3 and 4 the
bottles were removed from storage and the samples assessed
for the development of malodour (which was determined by
assessing the level of a rancid 'fatty' smell present).
Before each assessment the samples allowed to equilibrate at
room temperature. The malodour was assessed at room
temperature by sniffing the odours from the equilibrated
sample and assigning a value between 0 and 5 to indicated
the level of malodour. Zero was given if the sample had no
perceivable rancid smell and five was given for a very
strong rancid smell. At least ten people assessed each
sample and the average value was calcu'Lated from their
response.
As a marker of a value of S for a rancid fat an emulsion
containing 1% CTAC and 4.5% by weight PriolubeTM 1446
(neopentyl glycol dioleate ex Unichemai was stored at 45 C
for 4 weeks.
The malodour values of Examples 1-13 and 14-24 are shown in
Tables 3 and 4 resoectively.
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Table 3 below shows the malodour values determined for
examples 1-13 over a 27 week testing period with storage
between 370C-45 C.
SUBSTITUTE SHEET (RULE 26)
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~
N
~! r 1 Ol CO CO Ql m 11 lD Q1 6l Ol
QJ ( l lD r'1 l`'1 lD r-i Ql O r-1 -i r I
Q)
3 d V d' "T N r-I N N c''1 M r'1 C1
Lll
r-i
N 0 ~O L(1 1-1 N r-i N Ql [~ Ol CO l0
Q) (N r-i 1-1 O ri [- k0 -,zv l0 l0 r') N lfl
~ .
N N N N
N
r-i
,S4 c''1 (N N 01 lD N \D Lfl
Q) Lfl r') CO N L(1 N Lfl LCl CO C- CO Ql
v
C''1 N C''1 r-I r-1 r-I rl N N N N
co
~C lD ~ N C c- [- [- r-1 l0 C'')
Q) O 9) CO Ol lD l0 lD d' Lll C'yl
~
3 d 1 N N N r- r-1 r-I r-I N N N N
`1 l 1 r i r!1 Ql (- O rll rl r'1
Q) lll [- tll '3' [- N N V 14' 0 [- C- I-
~ . . .
M N N N N ~ r-I r-I r-1 M N N N
f`'1 f''1 c''1 (`'1 > O
4) N CO Lfl CO r-I r-i N c''1 N O O lD
~ .
N r~ r-1 rI rI ri ~ rI r1 N N N r-I
N
IzT lD r-1 [- Lll LCl lD r-I ~ r-I
~ lD 00 C- 0 CO r-I C (''1 LCl rl N O
Q)
N r-I rl r-I N O .-1 r-1 r-I N N N N
r-I
-s~
C) CO Cn l'') rl 0 0
~
,.~ rl ri ri r-I r-i O O N N N N
r-1
0
~4
lJ
m
a~ a ~ 0
r-i E p U
A RS c
b O r-I N c'll
E'i W .. ri N l''1 f lIl lD t- CO Ol r-I rl ri r
SUBSTITUTE SHEET (RULE 26)
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The above results demonstrate the suppression of malodour in
a sample containing a predominantly unsaturated CPE and a
deposition aid by the addition of an antioxidant. Where
the antioxidant is a mixture of a propagating inhibitor and
S an initiation inhibitor then longer term malodour
suppression was achieved.
Furthermore advantageous synergistic results were obtained
by using 0.01% by weight initiation inhibitor with 0.00225-
0.0045% by weight propagaticn inhibitor (see examples 6-9).
Table 4 below shows the malodour values determined for
examples 14-24 over a 4 week testing period with storage at
45 C.
Table 4
Example Week 1 Week 2 Week 3 Week 4
14 2.50 2.71 2.76 3.00
(control)
15 - 2.43 2.75 2.83
16 1.83 1.86 1.17 1.75
17 1.67 1.79 1.33 1.83
18 1.58 1.93 2.17 1.50
19 2.17 1.86 1.58 1.83
2.25 2.00 1.50 1.67
21 1.75 1.93 1.42 1.83
22 1.60 1.07 1.00 1.42
23 1.17 1.57 1.25 0.83
24 1.00 1.21 1.75 1.25
SUBSTITUTE SHEET (RULE 26)
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The results in table 4 demonstrate that when the only
antioxidant present is an initiation inhibitor, odour
suppression was achieved. Where the antioxidant comprised
both a propagation and an initiation inhibitor,
significantly improved odour suppression was obtained. This
is surprising given that little or no odour suppression was
observed when the only antioxidant present was the
propagation inhibitor.
Therefore, there is a clear synergistic effect between the
propagation and the initiation inhibitor.
Further compositions which have improved malodour
suppression in the presence of propagation and the
initiation inhibitor are given in the following examples.
Examples 25 to 34
Examples 25 to 28 in Table 5 below were prepared by mixing
the listed components together in water.
SUBSTITUTE SHEET (RULE 26)
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Table 5 (Mixtures with CTAC)
Example 25 j 26 27 28
Cetyl trimethyl ammonium 1 1 1 1
chloride (CTAC)
Sucrose pentaoleate (Ryoto 4
0-170)
Sucrose tetraoleate (oily 4
liquid)
Sucrose pentaerucate (RyotoTm 4
ER-190) (soft liquid)
Sucrose tetraeureate (RyotoT' 4
ER-290) (soft liquid)
Irganox 1010 0.002 0.002 0.002 0.002
Dequest 2066 0.01 0.01 0.01 0.01
Water 95 95 95 95
CTAC:oil ratio 1:4 1:4 1:4 1:4
Irganox 1010, Dequest 2066 and CTAC are described above.
The Ryoto products are available from Mitsubishi-Kagaku Food
Corporation.
The Examples in Tables 6 to 9 below were prepared by heating
the ingredients together at 80 C, and mixing at high shear.
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Table 6: Mixtures with HEQ (fabric softening compound)
Example 29 30 31
HEQ1 0.86 2.57 1.71
Fatty Acid 0.14 0.43 0.39
Sucrose pentaoleate (Ryoto 0- 4 2 3
170) (oily liquid)
Irganox 1010 0.004 0.002 0.003
Dequest 2066 0.01 0.01 0.01
Water 95 95 95
HEQ:oil ratio 1:4 3:2 2:3
HEQ1 is 1,2 bis[hardened tallowoyloxy]-3- trimethylammonium
propane chloride available from Hoechst.
Table 7; mixtures with Arquad 2-HT
Example 32 33 134
ArquadTM 2-HTa 1 1 1
Sucrose tetraoleate (oily 4
liquid)
Sucrose pentaeureate (Ryoto 4
ER-190) (oily liquid)
Sucrose tetraeureate (Ryoto 4
ER-290) (oily liquid)
Irganox 1010 0.004 0.004 0.004
Dequest 2066 0.01 0.01 0.01
Water 95 95 95
Arquad 2-HT:oil 1:4 1:4 1:4
aArquad 2-HT is dital?ow dimethyl ammonium chloride
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Examale 35
Example 35 was prepared as a 5% total active
emulsion/dispersion in water comprising 4.5% sucrose
tetraerucate (oily liquid, Ryoto ER 290), 0.5% CTAC, 0.01%
Dequest 2066, 0.0045% Irganox 1010 and 0.2% of a polymer
deposition aid as given below:-
Example 35a FlocAidTM 34 (ex National Starch)
Example 35b SoftgelT`4 BDA (ex Avebe)
Example 36
Example 36 was prepared as a 1:4 emulsion/dispersion (5%
total active) of DEEDMAC:sucrose pentaoleate (Ryoto 0-170)
by mixing at high temperatures. To this is added , 0.01%
Dequest 2066 and 0.004% Irganox 1010.
Exam'Dle 37
A fully formulated fabric softening composition as according
to the present invention was prepared as below:
% by weight
GenapolT" C150a 1.6
ABSb 0.4
Ryoto 0-170 15.4
Cationic potato starchC 2
Perfume 0.96
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Preservative Minor
Dye Minor
Na IDS 0.01
Irganox 1330 0.015
Water Balance
aCoco alcohol 15E0 (ex Clariant)
bdodecyl benzene suiphonic acid sodium salt (ex Aldrich
Chemical Company)
c Softgel EDA (ex Avebe)
Example 38
Table 8 shows the T2 NMR solid:liquid ratio of CPEs and RSEs
used according to the present invention. The ratios were
measured at 20 C. The degree of esterification
/etherirication is stated.
Table 8
Material Solid:Liquid Degree and % of Physical
ratio at 20oc esterification Form
Ryoto 0-170 0:100 5/8 62.50-8 Liquid
Ryoto ER-290 0:100 4/8 50% Liquid
Ryoto ER-190 0:100 5/8 50% soft solid
Sucrose 0:100 4/8 50% Liquid
tetraoleate
Sucrose 0:100 8/8 100% Liquid
octaoleate
The Rvoto materials are described above.
SUBSTITUTE SHEET (RULE 26)
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Examnles 39 to 52
All the compositions in table 9 were prepared as follows:
The propagation inhibitor was dissolved in the sucrose
tetraoleate in a weight ratio of 99.9:0.1. This mixture was
then comelted with the TEA and Coco-15E0 and then added to
water at 60 C with stirring using a low shear Heidolph
mixer. The resulting mixture was stirred for 10 minutes
before being cooled to room temperature. Where an
initiation inhibitor was used, it was post-dosed to the
final mixture as a 5% solution in water with mixing.
SUBSTITUTE SHEET (R ULE 26)
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Table 9
Example % Initiation
TEA sucrose Coco Propagation Inhibitor Water
a tetra 15E0 Inhibitor (% and
oleateb (Irganox type)
1330)
39 10. 3.6 0.1 0.0036 0.01 - To
6 EDDS~ 100
40 10. 3.6 0.1 0.0036 0.01 To
6 Dequest 100
2066
41 10. 3.6 0.1 0.0036 0.01 - Na To
6 IDS 100
42 10. 3.6 0.1 0.0036 0.01 - To
6 DTPA 100
43 10. 3.6 0.1 0.0036 0.01 - To
6 EDTAd 100
44 10. 3.6 0.1 0.0036 0.01 - To
6 DequestTM 100
2047e
45 10. 3.6 0.1 0.0036 None To
6 100
46 7.5 7.5 0.1 0.0075 0.01 - To
EDDS 100
47 7.5 7.5 0.1 0.0075 0.01 - To
Dequest 100
2066
48 7.5 7.5 0.1 0.0075 0.01 - Na To
IDS 100
49 7.5 7.5 0.1 0.0075 0.01 - To
DTPA 100
50 7.5 7.5 0.1 0.0075 0.01 - To
EDTA 100
51 7.5 7.5 0.1 0.0075 0.01 - To
Deauest 100
12047
52 7.5 1 7.5 0.1 10.0075 None To
1 100
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amethyl bis-[ethyl(tallowyl)]-2-hydroxyethyl ammonium methyl
sulphate (available as a 90% paste under the trade name
Rewoquat WE18 from Goldschmidt (ex Witco)).
ba sucrose polyoleate with an approximate degree of
esterification of 4.
c ethylene diamine-N, N' disuccinic acid (from Associated
Octel).
dethylene diamine tetra acetic acid (from Contract
Chemicals).
eethylene diamine tetra(methylene phosphonate) from Solutia.
Table 10 below shows the malodour values determined for
examples 39-52 over a 9 week testing period with storage at
45 C.
All samples were stored in loosely closed glass bottles at
450 C. At weekly intervals, the samples were removed form
the oven and allowed to cool to room temperature prior to
panelling. Malodour scores were ranked on a 0 to 5 basis,
whereby 0 = no malodour smell and 5 = extremely strong
malodour. The results are given in table 10
SUBSTITUTE SHEET (RULE 26)
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Table 10
Example Week 1 Week 2 Week 3 Week 4 Week 6 Week 9
35 0.88 1 1.37 1.28 1.18 1.38 1.30
36 1.59 1.63 1.00 1.27 1.31 1.10
37 1.29 1.47 1.43 1.82 1.23 1.40
38 1.18 1.32 1.07 1.64 1.23 1.65
39 1.12 1.47 1.29 1.36 1.15 1.60
40 1.41 11.32 1.21 1.45 1.08 1.70
41 2.12 1.89 1.71 2.09 1.77 2.50
42 1.65 1.76 1.75 1.73 1.62 1.70
43 1.65 1.47 1.75 1.82 1.62 1.5
44 1.71 1.18 1.92 1.55 1.08 1.10
45 1.82 1.47 1.83 1.18 1.46 1.00
46 1.65 1.53 1.50 1.45 1.38 1.50
47 1.82 1.59 1.75 1.64 1.31 1.40
48 2.12 1.65 2.25 2.27 2.38 2.20
The results demonstrate that when only the propagation
inhibitor was used in the softening compositions, good odour
suppression was observed over the 9 week period. When a
mixture of the propagation and initiation inhibitors was
used in the softening compositions, significantly better
odour suppression was observed over the 9 week period.
SUBSTITUTE SHEET (RULE 26)
