Note: Descriptions are shown in the official language in which they were submitted.
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DETERGENT COMPOSITION
Tp~hnisal Field
The present invention relates to fabric washing detergent
compositions. In particular, the invention relates to fabric
washing detergent compositions containing photofading
inhibitors.
Background and prior art
The fading of coloured articles by sunlight is a major
consumer problem in many parts of the world. Thus
susceptible articles from temperate and low latitude regions
in addition to those from the tropics can be severely faded
during wear or whilst drying. Sun fading of fabrics is of
specific concern to consumers because the contrast between
exposed and unexposed areas makes it particularly noticeable.
e.g on collars, inside versus outside of garments, and on
wrap around garments such as saris.
The use of certain sunscreens has already been discussed in
the literature. US 4 788 054 (Bernhardt) teaches the use of
N-phenylphthalisomides as ultraviolet radiation absorbers for
cotton, wool, polyester and rayon. The compositions require
an aqueous sulphuric acid vehicle for deposition. Fabric care
compositions comprising a water dispersible / water soluble
copolymers which prevent photofading are disclosed in
EP 0 523 956 (Unilever).
US 5 474 691 (Severns) also discloses the use of a tumble
drier sheet to transfer photofading inhibitors to fabrics.
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7
None of these systems is suitable for delivering photofading inhibitors to the
fabric
surface during washing.
However the major problem that needs to be overcome is how to deposit
photofading
inhibitors onto fabric during the wash using a detergent containing washing
system,
which is designed to suspend particulate materials and solubilise oils.
The present invention addresses these problems, and relates to an improved
method of
depositing photofading inhibitors to fabrics during the washing process. In
addition the
present invention also relates to a method of improving the perfume delivery
of
compositions.
Definition of the Invention
Thus according to one aspect of the invention there is provided a detergent
composition
comprising:
i) a nonionic detergent surfactant;
ii) a cationic quaternary ammonium compound material;
iii) a liquid photofading inhibitor having a log P value of at least 1.9 or a
solid
photofading inhibitor dissolved in a liquid the liquid having a log P of at
least 1.9 or
mixtures thereof; and
iv) optionally, an anionic surfactant;
wherein the ratio of (i) nonionic surfactant to (ii) cationic material at
least 1:1 by weight
and in which (if anionic surfactant (iv) is present), the ratio of (ii)
cationic material to
(iv) anionic surfactant is at least 1:1, preferably at least 2:1 by weight.
AA~fNDED SHEET
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The invention further relates to the use of a detergent
composition as described above for the deposition of a
photofading inhibitor onto a fabric.
Detailed Description of the Invention
The Photofadina inhibitor
Without being bound by theory it is thought that the extent
of individual dye fading is dependent on the light
wavelength. Some dyes are photodegraded primarily by the W
component of solar radiation, for other dyes the visible
component of solar radiation is the main cause of colour
loss, whilst others are equally affected by both visible and
W radiation. Thus, in order to minimise photofading across
the mix of dyes encountered in the home, it is essential to
protect articles from the whole solar spectrum.
Protection against solar radiation can be achieved with UVA
and WB absorbing materials with high extinction
coefficients. These compounds are commonly called
sunscreens. However, the use of such materials is preferably
limited for protection against UV radiation with a wavelength
of 400nm or below as compounds with the whole or part of
their spectra above 400nm will be coloured.
Protection from visible radiation with a wavelength of 400nm
or greater is preferably achieved by using singlet oxygen
quenchers, free radical traps and anti-oxidants.
It is therefore advantageous to deliver to the fabric surface
both UV sunscreens and materials that will protect dyes from
visible radiation and thus mixtures of sunscreens and
antioxidants, singlet oxygen quenchers or free radical traps
are used..
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If liquid, the photofading inhibitors must have a log P value of at least 1.9,
more
preferably of at least 2.5, most preferably Greater than 3.5.
If solid the photofading inhibitor must be dispersed in a liquid, the liquid
having a log P
value of at least 1.9, more preferably of at least 2.5, most preferably
greater than 3 5. It
is also beneficial if the liquid in which the solid photofading inhibitor is
to be dissolved
is immiscible in water or only sparingly soluble. By sparingly soluble a
solubility of no
more than 0 04 moles/litre is meant.
Log P is the octanol!water partition coefficient and can be used to measure
the
hydrophobicity of a molecule. Log P can be determined experimentally or by
calculation. Both procedures are described in Chemical Reviews Volume 71,
number 5,
pages ~2-5-616 ( 1971 ).
It is preferred that the photofading inhibitor or photofading inhibitor
mixture is present
?0 at levels from 0.01 wt% to 10 wrt% of the total weight of the composition.
The more
preferred level of sunscreen is from 0.025 wt% to 2.5 wt%, and most preferably
0.0~
w't% to 0. ~ w't%.
The Sunscreen
In the context of this invention a sunscreen is described as any material
which absorbs
UVA or L1VB radiation. It is advantageous if the sunscreens have a molar
extinction
coefficient (E) of greater than ?,000 molt cm's.
A~~I~DED SHEET
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The International Commission on Illumination (CIE)in 1970
defined the UV wavelength subdivisions as:-
UVA 315-400nm
UVB 280-315nm
WC 100-280nm
The sunscreen can be an oily liquid with a loge of at least
1.9 or a solid organic material that can be dissolved in a
water immiscible or sparingly water soluble liquid, the
liquid having a loge of greater than 1.9.
Preferably the sunscreen absorbs light at a wavelength from
about 280-400nm.
Suitable sunscreens are described in:
N.A. Saath, Cosmestics and Toiletries Vol 102 March 1987 page
21-39 Classifications given as table 2 on page 22,;
N.A. Saath, Evolution of modern sunscreen chemicals pages 3-
35; Cosmetics and Toiletries Vol 107 March 1992. Sunscreen
use in cosmetic formulas, pages 45-47; Ultra violet absorbers
by S.B. Miller, G.R. Lappin, and C.E. Tholstrup in 1968-1969
Modern Plastics Encyclopedia, pages 442-447 and; G.R. Lappin,
Encyclopedia of polymer science and technology, vol 14, pages
125-148, Ultra violet radiation absorbers.
Examples of typical sunscreens but not meant to be exclusive
are:
Cinnamates
2-Ethylhexyl-4-methoxy cinnamate (Parsol MCX)
2-Ethoxyethyl-4-methoxy cinnamate
Propyl-4-methoxy cinnamate
i-Amyl-4-methoxy cinnamate
Cyclohexyl-4-methoxy cinnamate
i-Propyl-4-methoxy cinnamate
Octyl cinnamate
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Ethyl-4-iso-propyl cinnamate
Ethyl-di-iso-propyl cinnamate and methyl ester
Ethyl-a-cyano-b-phenyl cinnamate
2-Ethylhexyl-a-cyano-b-phenyl-cinnamate
Salicvlates
2-Ethylhexyl salicylate (Sunarome TnTMO)
3,3,5-Trimethyl cyclohexyl-2-hydroxy benzoate
3,3,5-Trimethyl cyclohexyl-2-acetamido benzoate
2-Ethylhexyl-2-(4-phenylbenzoyl)benzoate
4-Isopropylbenzyl salicylate
Amyl salicylate
Menthyl salicylate
Homomenthyl salicylate
Phenyl salicylate
Benzyl salicyclate
i-Decyl salicylate
Aminobenzoates
Ethyl 4-bis(hydroxypropyl)amino benzoate (Amerscheen P)
2,3-Dihydroxypropyl-4-amino benzoate (Nipa GMPA)
Menthyl-2-aminobenzoate (Sunarome UVA)
2-Ethylhexyl-4-dimethylamino benzoate (Escalol 507)
Amyl-4-dimethylamino benzoate
Ethyl-4-dimethylaminobenzoate
Butyl-4-dimethylaminobenzoate
4-bis(polyethoxy)-4-aminobenzoic acid polyethoxyethyl ester
(Uvinul P-25)
N-propoxylated ethyl-4-amino benzoate
Benzobhenones
2-hydroxy-4-methoxy benzophenone (Uvinul M40)
2,2'-Dihydroxy-4-methoxybenzophenone (Spectra-Sorb UV-24)
2,4-Dihydroxybenzophenone (Uvinul 400)
2,2',4,4'-Tetrahydroxybenzophenone (Uvinul D-50)
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2,2'-Dihydroxy-4,4'-dimethoxybenzophenone (Uvinul D-49)
2-Hydroxy-4-(2-ethylhexyloxy)benzophenone (Uvinu1408)
2-Hydroxy-4-methoxy-4'-methylbenzophenone (Mexenone)
4-Phenyl-benzophenone
2-Ethylhexyl-4'-phenyl-benzophenone-2-carboxylate
2-Hydroxy-4-n-octoxybenzophenone
2-Hydroxy-3-carboxybenzophenone
Acrvlates
2-Ethylhexyl-2-cyano-3,3'-diphenylacrylate (Uvinul N-539)
Ethyl-2-cyano-3,3'-diphenylacrylate (Uvinul N-35)
3-Imidazol-4yl acrylic acid and ethyl ester
2-Cyano-3-(4-methoxyphenyl)acrylate and hexyl ester
Dibenzovlmethanes
1-(4-Isopropyl phenyl)-3-phenyl propan-1,3-dione (Eusolex
8020)
1-(4-t-Butylphenyl)-3-(4-methoxyphenyl)propan-1,3-dione
1,3-bis(4-Methoxyphenyl)propane-1,3-dione
3-(4-Methylbenzylidene)-bornan-2-one (Eusolex 6300)
5-(3,3-Dimethyl-2-norbonylidene)-3-penten-2-one
3-Benzylidene bornan-2-one
Digalloyl trioleate
2-Hydroxy-1,4-naphthalenedione
5-Methyl-2-phenylbenzoxazole
2,4,6-Trianilino-4-(carbo-2'-ethylhexyl-1'-oxy)-1,3,5-
triazine (Uvinul T-150)
2,2'-hydroxy-5-methylphenyl-benzotriazol
2,2'-hydroxy-5-t-octylphenyl-benzotriazol
Dibenzaldehydeamine
Dianisoyl methane
Methyl eugenol
2-Amino-6-hydroxypurin
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N-(4-Ethoxycarbony!phenyl)-N'-methyl-N'-
phenylformamidine (Givosorb W1)
N-(4-Ethoxycarbonylphenyl)-N'-ethyl-N'-phenylformamidine
(Givosorb W2)
2-(2H-benzotriazol-2-yl)-4-methylphenol (Tinuvin P)
2-(6-Chloro-2H-benzotriazol-2-yl)-4-methyl-6-t-butyl phenol
(Tinuvin 326)
2-(6-Chloro-2H-benzotriazol-2-yl)-4,6-di-t-butyl phenol
(Tinuvin 327)
2-(2H-benzotriazol-2-yl)-4,6-di-t-pentyl phenol (Tinuvin 328)
3-(4'-Methylbenzylidene)-Camphor
Preferred sunscreen compounds contain at least one
chromophore selected from the following groups
and mixtures thereof.
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~N\
N ~ ~ Phenylbenzotriazoles
~ ~..N/
O O
c
H2 ~ Dibenzoylmethsne
Rt O
v
N Esters of p-eminobenzoic acid (PABA)
OH
O
Eaters of ainnamic acid
OH
2 ~ Esters of 2-oyano 3- Biphenyl 2-propanoic acid
H O
Esters of salicylic acid
O OH
2-Hydroxybenzophenones
~N
Phenylbenzimidazole
~N
c
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J
Wherein R1 and R2 is a hydrogen, methyl, ethyl, Cl-C,2 branched or straight
chain
alkyl group; and mixtures thereof, preferably a methyl group.
Preferably the sunscreen compound containing at least one chromophore is
selected
10 from the group consisting of phenylbenzotriazoles, esters of cinnamic acid,
benzophenones, esters of para aminobenzoic acid, esters of salicylic acid,
dibenzoyl
methane and mixtures thereof.
Most preferably the sunscreen is selected from the following groups and
mixtures
thereof.
AMENDED SHEEF
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WO 97/44422 PCT/EP97/02000
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10
Rf
~o
R, ~~
O
\Ri3
R,5 \
0
i~'here R9 is a hydrogen, a hydroxy group, a C1-CZZ alkyl group,
preferably a hydrogen or a hydroxy group and most preferably
a hydroxy group.
4~~here R5 is is a hydrogen, a hydroxy group, a C1-Cz~ alkyl
group, more preferably a C,-CH alkyl group and most preferably
a tertiary amyl group or tertiary butyl group.
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H~C.C
H~oIa.CH3
Nr.
Diazobicyclo[2,2,2Joctanc
N
Acetyl-a-tocopherol
2,6-di-tert.-butyl-4-methoayphenol
2,6-di-tert.-butyl-4-methylphenol
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Where R6 is is a hydrogen, a hydroxy group, a C1-C22 alkyl
group, more preferably a C1-C8 alkyl group and most preferably
a tertiary amyl group or tertiary butyl group.
An example where R9 is hydroxyl and RS and R6 are tertiary
amyl groups is the commercial sunscreen Tinuvin 328, and
where R4 is hydroxyl and RS and R6 are tertiary butyl groups
is Tinuvin 327. Both these sunscreens are manufactured by
Ciba.
Where R~ is a hydrogen, a hydroxy group, a methoxy group,Cl-
C22 alkyl group, and mixtures thereof.
Where R8 is a hydrogen, a hydroxy group,Cl-C22 alkyl group, and
mixtures thereof.
Where R9 is a hydrogen, a hydroxy group, C1-C22 alkyl group,
and mixtures thereof.
Where R1o is a hydrogen, or a C1-Cz2 alkyl group.
Where R11 is a hydrogen, or a C1-Czz alkyl group.
Where R13 is a C1-Czz alkyl group.
Where R14 is a C1-Czz alkyl group
Where R15 is a hydrogen, methoxy or a C1-C2~ alkyl group.
The antioxidants, singlet oxygen quenchers or free
radical trap
In the context of this invention the term antioxidant refers
to a non-fabric staining, light stable antioxidant compound,
that is either an oily liquid with a loge of at least 1.9 or
a solid organic material that can be dissolved in a water
immiscible or sparingly water soluble liquid with a loge of
greater than 1.9.
Examples of anti-oxidants meeting these requirements can be
found in Kirk-Othmer Encyclopaedia of Chemical Technology,
fourth edition, volume 3, pages 424-447.
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Examples of typical antioxidant compounds and/or singlet
oxygen quenchers include .
ascorbic palmitate, butylated hydroxy anisole, tertiary butyl
hydroquinone, natural tocopherols and derivatives such as
vitamin E acetate and Irganox antioxidants as supplied by
Ciba Geigy such as Irganox 1010 (tetrakis methylene (3,5-di-
tert-butyl-4hydroxycinnamate)) methane), Irganox 1035
(thiodiethylene bis (3,5-di-tert-butyl-4-
hydroxyhydrocinnamate)), Irganox 1076 (octadecyl propan-(3-
benzene-3',5' di tert butyl-4' hydroxy)-oate, Irganox 1425
(calcium bis (monoethyl(3,5-di-tert-butyl-4-hydroxybenzyl)
phosphonate), Irganox 3052 2-propanoic acid 2-(1,1-di-
tertiary butyl)-6 -[3-(l,ldi-tertiary butyl)-2-hydroxy-5-
methylphenyl]-4-methylphenyl ester, Irganox 3114 (1,3,5-
tris( 3,5-di-tert-butyl-4-hydroxybenzyl)-s-triazine-2,4,6-
(1H, 3H, 5H)trione Irganox 3125 3,5-di-tert-butyl-4-
hydroxyhydrocinnamic triester with 1,3,5,-tris(2-
hydroxyethyl)-s_triazine-2,4,6-(1H, 3H, 5H)-trione), Irganox
1098 (N,N'-hexamethylene bis(3,5-di-tert-butyl-4-
hydroxyhydrocinnamamide), Diazobicyclo[2,2,2]octane (DABCO)
and mixtures thereof.
Preferred materials include
3 ~ Octadccyl-3-(3,5-di-tert.Butyl-4-hydroxy-
phenyl)-proprionate (Irganox 1076)
r
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03725
S
HoC.C
1 ~ CHI
o)o.CHo
N~
Diazobicvclo(=.'_,~]octme
N
1 j
CHI OH CHI
-l~a,-
CHo
..lcetyl-a-tocoplierol
..v-Ji-tert.-bunU-~+-methoNyphenol
.,6-di-tzrt.-butr l-1-metln~lphenol
~!'~I~l~: ~ S~ F r. ~
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The nonionic surfactant
The composition of the invention requires the presence of
a nonionic surfactant.
Nonionic surfactants that may be used include the primary and
secondary alcohol ethoxylates, especially the C8-C20
aliphatic alcohols ethoxylated with an average of from 1 to
20 moles of ethylene oxide per mole of alcohol, and more
especially the C10-C15 primary and secondary aliphatic
alcohols ethoxylated with an average of from 1 to 10 moles of
ethylene oxide per mole of alcohol. Non-ethoxylated nonionic
surfactants include alkylpolyglycosides, glycerol monoethers,
and polyhydroxyamides (glucamide>.
It is preferred if the level of nonionic surfactant is from 2
wt% to 40 wt%, preferably from 10 wto to 30 wto of the total
product.
The choice of detergent-active compound (surfactant), and the
amount present, will depend on the intended use of the
detergent composition. In fabric washing compositions,
different surfactant systems may be chosen, as is well known
to the skilled formulator, for handwashing products and for
products intended for use in different types of washing
machine.
The Anionic Surfactant
Although an anionic surfactant may be present in compositions
of the invention it is preferred if it is absent.
If present it is preferred if the ratio of cationic material
to anionic material is at least 2:1.
If present suitable anionic surfactants are well-known to
those skilled in the art and include alkylbenzene sulphonate
a
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C3726
16
primary and secondary alkyl sulphates, particularly CR-Cis primary alkyl
sulphates;
alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl
sulphosuccinates; ethercarbo~ylates; isothionates; sarcosinates and fatty acid
ester
sulphonates, Sodium salts are generally preferred.
Detergent compositions suitable for use in most automatic fabric washing
machines
Qenerally contain anionic non-soap surfactant, or nonionic surfactant, or
combinations
of the two in any ratio, optionally together with soap.
1 ~ For compositions in solid form, especially powder, the detergent
surfactant is
advantageously solid at room temperature as this provides crisp composition
panicles.
The Cationic Compound
The compositions of the invention must contain a quaternary ammonium compound
cationic compound.
It is advantageous if the quaternary ammonium compound is a quaternary
ammonium
compound having at least one C,~-C2, alkyl chain.
It is preferred if the quaternary ammonium compound has the following formula:
AMENp~p 5~~,.
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C3726
17
in which R~ is a C~2 to C,~ alkyl or alkenyl chain; R2, R3 and R~ are
independently
selected from C,-Ca alkyl chains and K is a compatible anion. A preferred
compound
of this type is the quaternary ammonium compound cetyl trimethyl quaternary
ammonium bromide.
A second class of materials for use with the present invention are the
quaternary
ammonium compound having the following formula:
R=
R1 ' N~ - R' X'
R'
in which R1 and Rz are independently selected from C1z to C22 alkyl or alkenyl
chain;
R3 and R'' are independently selected from Cl-C4 alkyl chains and X- is
compatible
anion.
Other suitable quaternary ammonium compounds are disclosed in EP 0 239 910
(Procter and Gamble).
It is preferred if the ratio of cationic to nonionic surfactant is from 1:100
to X0:50, more
preferably 1:50 to 20:50.
The cationic compound may be present from 0.02 wt% to 20 wt% of the total
weight of
the composition.
Preferably the cationic compound may be present from 0.05 wt% to 15 wrt%, a
more
preferred composition range is from 0.2 wt% to 5 wt%, and most preferably the
composition range is from 0.4 wt% to 2.5 wt% of the total weight of the
composition.
~~~~~ SHEET
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If the product is a liquid it is preferred if the level of
cationic surfactant is from 0.05wt~ to l0wt~ of the total
weight of the composition. Preferably the cationic compound
may be present from 0.2wt~ to 5 wt~, and most preferably from
0.4 wt~ to 2.5 wt~ of the total weight of the composition.
If the product is a solid it is preferred if the level of
cationic surfactant is 0.05 wt~ to 15 wto of the total
weight of the composition. A more preferred composition range
is from 0.2 wt~ to 10 wt~, and the most preferred composition
range is from 0.9 wt~ to 3.0 wt~ of the total weight of the
composition.
~eteraencv Build r
The detergent compositions of the invention will generally
also contain one or more detergency builders. The total
amount of detergency builder in the compositions will
suitably range from 5 to 80 wto, preferably from 10 to
60 wt~.
Inorganic builders that may be present include sodium
carbonate, if desired in combination with a crystallisation
seed for calcium carbonate, as disclosed in GB 1 437 950
(Unilever); crystalline and amorphous aluminosilicates, for
example, zeolites as disclosed in GB 1 473 201 (Henkel),
amorphous aluminosilicates as disclosed in GB 1 473 202
(Henkel) and mixed crystalline/amorphous aluminosilicates as
disclosed in GB 1 470 250 (Procter & Gamble); and layered
silicates as disclosed in EP 164 514B (Hoechst). Inorganic
phosphate builders, for example, sodium orthophosphate,
pyrophosphate and tripolyphosphate are also suitable for use
with this invention.
The detergent compositions of the invention preferably
contain an alkali metal, preferably sodium, aluminosilicate
builder. Sodium aluminosilicates may generally be
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- 19
incorporated in amounts of from 10 to 70% by weight
(anhydrous basis), preferably from 25 to 50 wt%.
The alkali metal aluminosilicate may be either crystalline or
amorphous or mixtures thereof, having the general formula:
0.8-1.5 Na20. A12O3. 0.8-6 Si02
These materials contain some bound water and are required to
20 have a calcium ion exchange capacity of at least 50 mg Ca0/g.
The preferred sodium aluminosilicates contain 1.5-3.5 Si02
units (in the formula above). Both the amorphous and the
crystalline materials can be prepared readily by reaction
between sodium silicate and sodium aluminate, as amply
described in the literature.
Suitable crystalline sodium aluminosilicate ion-exchange
detergency builders are described, for example, in
GB 1 429 143 (Procter & Gamble). The preferred sodium
aluminosilicates of this type are the well-known commercially
available zeolites A and X, and mixtures thereof.
The zeolite may be the commercially available zeolite 4A now
widely used in laundry detergent powders. However, according
to a preferred embodiment of the invention, the zeolite
builder incorporated in the compositions of the invention is
maximum aluminium zeolite P (zeolite MAP) as described and
claimed in EP 384 070A (Unilever). Zeolite MAP is defined as
an alkali metal aluminosilicate of the zeolite P type having
a silicon to aluminium ratio not exceeding 1.33, preferably
within the range of from 0.90 to 1.33, and more preferably
within the range of from 0.90 to 1.20.
Especially preferred is zeolite MAP having a silicon to
aluminium ratio not exceeding 1.07, more preferably about
1.00. The calcium binding capacity of zeolite MAP is
generally at least 150 mg Ca0 per g of anhydrous material.
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Organic builders that may be present include polycarboxylate
polymers such as polyacrylates, acrylic/maleic copolymers,
and acrylic phosphinates; monomeric polycarboxylates such as
citrates, gluconates, oxydisuccinates, glycerol mono-, di-
and trisuccinates, carboxymethyloxysuccinates,
carboxymethyloxymalonates, dipicolinates,
hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and
succinates; and sulphonated fatty acid salts. This list is
not intended to be exhaustive.
Especially preferred organic builders are citrates, suitably
used in amounts of from 5 to 30 wto, preferably from 10 to
25 wt~; and acrylic polymers, more especially acrylic/maleic
copolymers, suitably used in amounts of from 0.5 to 15 wto,
preferably from 1 to 10 wt~.
Builders, both inorganic and organic, are preferably present
in alkali metal salt, especially sodium salt, form.
Bleach Components
Detergent compositions according to the invention may also
suitably contain a bleach system. Fabric washing
compositions may desirably contain peroxy bleach compounds,
for example, inorganic persalts or organic peroxyacids,
capable of yielding hydrogen peroxide in aqueous solution.
Suitable peroxy bleach compounds include organic peroxides
such as urea peroxide, and inorganic persalts such as the
alkali metal perborates, percarbonates, perphosphates,
persilicates and persulphates. Preferred inorganic persalts
are sodium perborate monohydrate and tetrahydrate, and sodium
percarbonate.
Especially preferred is sodium percarbonate having a
protective coating against destabilisation by moisture.
Sodium percarbonate having a protective coating comprising
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sodium metaborate and sodium silicate is disclosed in
GB 2 123 044B (Kao).
The peroxy bleach compound is suitably present in an amount
of from 0.1 to 35 wt~, preferably from 0.5 to 25 wt~.
The peroxy bleach compound may be used in conjunction with a
bleach activator (bleach precursor) to improve bleaching
action at low wash temperatures. The bleach precursor is
suitably present in an amount of from 0.1 to 8 wt~,
preferably from 0.5 to 5 wt~.
Preferred bleach precursors are peroxycarboxylic acid
precursors, more especially peracetic acid precursors and
pernoanoic acid precursors. Especially preferred bleach
precursors suitable for use in the present invention are
N,N,N',N'-tetracetyl ethylenediamine (TAED) and sodium
noanoyloxybenzene sulphonate (SNOBS). The novel quaternary
ammonium and phosphonium bleach precursors disclosed in
US 4 751 015 and US 4 818 426 (Lever Brothers Company) and EP
402 971A(Unilever), and the cationic bleach precursors
disclosed in EP 284 292A and EP 303 520A (Kao) are also of
interest.
The bleach system can be either supplemented with or replaced
by a peroxyacid. Examples of such peracids can be found in
US 4 686 063 and US 5 397 501 (patent on TPCAP - Unilever).
A preferred example is the imido peroxycarboxylic class of
peracids described in EP A 325 288, EP A 349 940, DE 382 3172
and EP 325 289. A particularly preferred example is
phtalimido peroxy caproic acid (PAP). Such peracids are
suitably present at 0.1 - 12°s, preferably 0.5 - 10%.
A bleach stabiliser (heavy metal sequestrant) may also be
present. Suitable bleach stabilisers include ethylenediamine
tetraacetate (EDTA), the polyphosphonates such as bequest
(Trade Mark) and non-phosphate stabilisers such as EDDS
(ethylene diamine di-succinic acid). These Bleach
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stabilisers are also useful for stain removal, especially in
products containing low levels of bleaching species or no
bleaching species.
An especially preferred bleach system comprises a peroxy
bleach compound (preferably sodium percarbonate optionally
together with a bleach activator), and a transition metal
bleach catalyst as described and claimed in EP 458 397A,
EP 458 398A and EP 509 787A (Unilever).
The Enzyme
Suitable enzymes include the proteases, amylases, cellulases,
oxidases, peroxidases and lipases usable for incorporation in
detergent compositions.
Preferred proteolytic enzymes (proteases) are, catalytically
active protein materials which degrade or alter protein types
of stains when present as in fabric stains in a hydrolysis
reaction. They may be of any suitable origin, such as
vegetable, animal, bacterial or yeast origin.
Proteolytic enzymes or proteases of various qualities and
origins and having activity in various pH ranges of from 4-12
are available and can be used in the instant invention.
Examples of suitable proteolytic enzymes are the subtilisins,
which are obtained from particular strains of _B. subtilis and
_B. licheniformis, such as the commercially available
subtilisins Maxatase (Trade Mark), as supplied by Gist-
Brocades N.V., Delft, Holland, and Alcalase (Trade Mark), as
supplied by Novo Industri A/S, Copenhagen, Denmark.
Particularly suitable is a protease obtained from a strain of
Bacillus having maximum activity throughout the pH range of
8-12, being commercially available, e.g. from Novo Industri
A/S under the registered trade-names Esperase (Trade Mark)
and Savinase (Trade-Mark). The preparation of these and
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analogous enzymes is described in GB 1 243 785. Other
commercial proteases are Kazusase (Trade Mark) (obtainable
from Showa-Denko of ,Tapan), Optimase (Trade Mark) (from Miles
Kali-Chemie, Hannover, West Germany), and Superase (Trade
Mark) (obtainable from Pfizer of U.S.A.).
Detergency enzymes are commonly employed in granular form in
amounts of from about 0.1 to about 3.0 wt~.
Any perfume is suitable for use with the present invention.
However we have found that the presence of a photofading
inhibitor aids the deposition of perfume, this affect is
especially pronounced with non-volatile perfume ingredients.
The converse of this is also true, in that the presence of
perfume aids the deposition of the photofading inhibitor.
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Other ingredients
The compositions of the invention may contain alkali metal,
preferably sodium carbonate, in order to increase detergency
and ease processing. Sodium carbonate may suitably be
present in amounts ranging from 1 to 60 wt~, preferably from
2 to 40 wt~. However, compositions containing little or no
sodium carbonate are also within the scope of the invention.
Powder flow may be improved by the incorporation of a small
amount of a powder structurant, for example, a fatty acid (or
fatty acid soap), a sugar, an acrylate or acrylate/maleate
polymer, or sodium silicate.
One preferred powder structurant is fatty acid soap, suitably
present in an amount of from 1 to 5 wt%.
Other materials that may be present in detergent compositions
of the invention include sodium silicate; antiredeposition
agents such as cellulosic polymers; inorganic salts such as
sodium sulphate; lather control agents or lather boosters as
appropriate; proteolytic and lipolytic enzymes; dyes;
coloured speckles; foam controllers; fabric softening
compounds, soil release polymers, fluorescers and decoupling
polymers. This list is not intended to be exhaustive.
The detergent composition when diluted in the wash liquor
(during a typical wash cycle) will give a pH of the wash
liquor from 7 to 10.5.
The detergent components of the present invention may be
incorporated in detergent compositions of all physical types,
for example, powders, liquids, gels and solid bars.
Detergent compositions of the invention may be prepared by
any suitable method.
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Particulate detergent compositions are suitably prepared by
spray-drying a slurry of compatible heat-insensitive
ingredients, and then spraying on or postdosing those
ingredients unsuitable for processing via the slurry. The
skilled detergent formulator will have no difficulty in
deciding which ingredients should be included in the slurry
and which should not.
Particulate detergent compositions of the invention
preferably have a bulk density of at least 400 g/1, more
preferably at least 500 g/1.
Especially preferred compositions have bulk densities of at
least 650 g/litre, more preferably at least 700 g/litre.
Such powders may be prepared either by post-tower
densification of spray-dried powder, or by wholly non-tower
methods such as dry mixing and granulation; in both cases a
high-speed mixer/granulator may advantageously be used.
Processes using high-speed mixer/granulators are disclosed,
for example, in EP 340 013A, EP 367 339A, EP 390 251A and
EP 420 317A (Unilever).
Liquid detergent compositions can be prepared by admixing the
essential and optional ingredients thereof in any desired
order to provide compositions containing components in the
requisite concentrations. Liquid compositions according to
the present invention can also be in compact form which means
it will contain a lower level of water compared to a
conventional liquid detergent.
The invention will now be illustrated with reference to the
following non-limiting Examples.
Comparative examples are illustrated by a letter and examples
of the invention are illustrated by a number.
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Examt~les
Examples A-D and 1-3
Testinar Methods
Five sequential washes were carried out in a Tergotometer
under the following conditions.
Initial wash volume 1200m1
Washes with systems were carried out in distilled water at a
total surfactant concentration of 1 g/1.
Water Demineralised
Load 40 g of knitted cotton
Liquor to Cloth ratio 30:1
Temperature 30°C isothermal
Wash time 30 minutes
Paddle Speed 75 rpm
Rinsing 3 rinses at 40:1 L/C, short (2
minute) agitation times
Drying Fabric pieces were dried in
the dark in an oven set at 60°C
Fabrics were removed at the end of each wash, and the liquor
volume for subsequent washes adjusted to 30:1
Determination of Sunscreen Level on Cotton
The Parsol MCX present on the dry fabric was recovered by
solvent extraction. A 3g piece of knitted cotton was placed
in a 20 ml screw top vial, and 15 ml of high purity isopropyl
alcohol added. The vial was roller mixed for 3 hours on a
Luckham Multimix Major, before sonicating for 30 minutes in a
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small sonic bath. The concentration of Parsol MCX present in
the extract was then determined by GC/MS analysis (Finnigan
Magnum fitted with a 25 metre SGE BPX-5 (non-polar) glass
capillary column of internal diameter 0.22mm with a film
thickness of 0.25um). UV/visible absorbance procedures were
also employed as a check of sunscreen deposition level. A
Perkin Elmer ~,2 spectrometer was used to measure the
absorbance of the isopropyl alcohol extract solutions at the
hmax of the sunscreen. The amount of sunscreen deposited was
determined using a calibration plot obtained from measurement
of the absorbance of standard sunscreen solutions.
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TABLE 1 Composition of test formulations
Component Example Example Example Example Example
A B C 1 2
Coco PAS 0.85% - - - -
Synperonic - - - - -
7E0
1:1 mix of 16.15% 17.0% 15.0% 15.0% 16.15%
Coco 3E0
and 7E0 NRE
CTAB - - 1.5% 1.5% 0.85%
Ethanol 5% 5% 5% 5% 5%
Borax 1.5% 1.5% 1.5% 1.5% 1.5%
EDTA 0.08% 0.08% 0.08% 0.08% 0.08%
Perfume - - 0 . 5 0 . 5 % -
(PWG3345) %
Parsol MCX 0.1% 0.1% - 0.1% 0.1%
Distilled to 100% to 100% to 100% to 100% to 100%
water
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Table 2:Composition of test formulations
Component Example 3 Example D
Arquad 2T 0.85 -
Synperonic A7 16.15 g
PAS - 8.0~
Ethanol 5.0o 5.0o
Borax 1.5~ 1.5%
EDTA 0.08 0.08
Parsol MCX 0.1~ 0.1%
Water to 100 to 100
Coco PAS - Coconut primary alcohol sulphate
Coco 7E0 NRE - Clz_14 alcohol ethoxylate with a mean
ethylene oxide chain length of 7.
Coco 3E0 NRE - Clz-14 alcohol ethoxylate with a mean
ethylene oxide chain length of 3.
NRE - Narrow range ethoxylate
CTAB - Cetyl trimethyl ammonium bromide.
ARQUAD 2T - dimethyl ditallow ammonium chloride
(non-hardened)
Synperonic A7 - C11-13 alcohol ethoxylate with a mean
ethylene oxide chain length of 7
Parsol MCX is 2-Ethylhexyl 4-methoxycinnamate with a log P
value of 5.2.
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TABLE 3: Deposition of Parsol MCX on cotton from duplicate
washes containing Examples 2 and 3, 5, 6 and Example B and D.
Deposition monitored as ppm of Parsol MCX in iso-propyl
alcohol extract. Level determined by GC/MS.
Product Duplicate Duplicate
experiment 1 experiment 2
Example B 1.28 1.22
Example D 1.6 1.52
Example 3 10.35 11.23
l0 Example 2 18.1 17.8
TABLE 4 . Deposition of Parsol MCX on cotton from duplicate
washes containing Example B and Example 1. Deposition
monitored as ppm of Parsol MCX in iso-propyl alcohol extract.
Level determined by GC/MS.
Example A Example 1
Number Duplicate Duplicate Duplicate Duplicate
of Wash Experiment Experiment Experiment Experiment
Cycles 1 2 1 2
1 5.46 4.64 17.3 27.2
2 6.8 6.6 36.8 40.0
3 7.1 6.7 56.4 55.9
4 6.5 6.8 65.9 66.9
5 4.5 5.0 125.6 118.0
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Table 5: Deposition of Parsol MCX on cotton from duplicate
washes containing Example A and Example 1. Deposition
monitored as ppm of Parsol MCX in iso-propyl alcohol extract.
Level determined by measurement of the optical density at the
Amax of Parsol MCX.
Example A Example 1
Number of Experiment Experiment Experiment Experiment
Wash 3 4 3 4
Cycles
1 2.8 2.7 23.0 21.5
2 3.6 3.3 57.8 50.3
3 4.0 - g8.g -
4 4.15 3.5 97.5 103.6
5 2.3 2.5 115.5 118.0
The results show better deposition when the nonionic/cationic
ratio of the invention is used.
~xamnle C end Example 1
Table 6 shows the comparison of perfume components delivered
to cotton fabric from a CTAB/nonionic (10/90) liquid product
containing 17o total active. The perfume components are
quoted as concentration (ppm) in a solvent extract from the
washed and dried fabric.
Two products were compared, one containing 0.5~ perfume , the
" other containing 0.5o and 0.1~ Parsol MCX. The perfume has
twenty components, each component of the perfume being
'35 present at equal concentration.
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TABLE 6:
Level of perfume fabric
on
Perfume Component Example C (ppm) Example 2(ppm)
Limonene 0.0074 0.0088
Tetrahydrolinalol 0.022 0.026
Linalol nd nd
Benzyl Acetate nd nd
Inonyl Acetate 0.00 0.019
Dimethylbenzyl 0.027 0.056
cyclohexyl acetate
Anther 0.117 0.279
Cyclamen aldehyde 0.782 1.339
Bourgeonal 0.921 1.696
Florocyclene 0.456 1.704
Lilial 1.081 2.019
Amyl cinnamic 1.800 3.513
aldehyde
Celestolide 1.799 3.122
Hexyl cinnamic 2.232 4.681
aldehyde
Tonalid 1.963 3.611
Phenylethylphenyl 1.111 1.921
acetate
Musk Ketone 1.778 3.308
Ethylene 1.255 1.931
Brassylate
Table 6 shows the level of perfume deposited onto fabric.
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Two non-ionic cationic liquids were prepared containing the
solid sunscreen Tinuvin 328 (2-(2-hydroxy-3,5-di-tertiary-
amyl-phenyl)-2H-benzotriazole ex Ciba Geigy). Examples 4
and E are listed in Table 7. The only difference between the
two formulations is the solvent used to dissolve the Tinuvin
328 sunscreen. Example 4 contains diethylphthalate which has
a loge of 2.15, and Example E contains 2-butoxyethanol which
is water soluble and has a loge of 0.84.
fable 7:
Component Example 4 (wt'y) Example E (wto)
Coconut 5E0 narrow 15.3 15.3
range ethoxylate
CTAB 1.7 1.7
Ethyl alcohol 10 10
Tinuvin 328 0.1 0.1
Diethylphthalate 1.0 -
2-Butoxy ethanol -
1.0
Water to 100 to 100
Washes were carried out in a Tergotometer at 20°C using 6g/1
of each product over a period of 20 minutes in the presence
of 1.14g/1 of borax buffer. An initial liquor volume of
1200m1 was selected for the first wash. Fabrics were removed
after each wash to determine the level of sunscreen deposited
'30 on the fabric. The wash liquor volume was reduced in the
second and third washes to maintain the liquor to cloth ratio
at 30:1. At the end of each wash the fabrics were squeezed to
remove excess liquor and rinsed three times at a liquor to
cloth ratio of 40:1, before air drying in the dark.
CA 02255854 1998-11-17
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34
Dry white cotton pieces measuring 5.08 cm x 11.43 cm (2" x 4.5") taken from
each
wash were each placed in a glass sample vial and 15m1 of ethylacetate added.
The vials
were rolled on a roller mixer (Luckham Multimix Major) for a minimum period of
2
hours. The optical density of the extracts were then measured at 303nm, the
7~",a~ of
Tinuvin 328. The results in table 8 show that delivery of Tinuvin 328 to
cotton was
achieved in the presence of diethyl phthalate. Whereas in the presence of 2-
butoxyethanol readings were close to those obtained with a sunscreen free
control.
Table 8: Deposition of Tinuvin 328 on cotton from washes containing Example E
and Example 4. Deposition monitored as optical density at 7v;"a~ of Tinuvin
328.
Wash cycle Example 4 Example E
1 0.48 0.025
2 0.63 0.05
3 0.78 0.08
~A~EN~iED ~E
ET
