Note: Descriptions are shown in the official language in which they were submitted.
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FABRIC CARE COMPOSITIONS
Field of the Invention
The present invention relates to fabric care compositions. More
specifically, the invention relates to rinse cycle fabric care
compositions which reduce the wrinkling of fabrics and in
particular the dry or in-wear wrinkling giving fabrics an all-
day-ironed look.
Background of the Invention
Fabric care compositions which reduce the wrinkling of fabrics
being worn are known.
Mechanical wrinkle reduction techniques, such as heat and
pressure, for example, ironing are effective ways of flattening
garments. However the effect is not permanent and wrinkles
reappear due to a range of shear, torsion and compressive
deformation forces applied in wear. The body's heat and
humidity work on the fabric to relax it and hence to enhance the
wrinkling of these deformational forces.
The prior art anti-wrinkle teaching can be rationalised into
three approaches;
(a) using lubricants to improve recovery from crease,
(b) using cross-linkers and film formers to stiffen the
fibres to resist creases in the first place, and
(c) combining (a) and (b).
The lubricants used in the prior art include silicones eg PDMS,
aminosilicones, modified silicones, silicone copolymers,
softeners (e.g. quaternary ammonium compounds) and other
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lubricants such as clays, waxes, polyolefins, synthetic and
natural oils.
Film formers and cross-linkers used in the prior art include:
Natural Polymers - enzymes proteins, cyclodextrins,
polysaccharides e.g. starch, chitin, chitosan, cellulose, 3-
1,4-polysaccharides, SCMC, guar gum, HEC etc.,
Synthetic Polymers - polyamides, polyurethanes, polyamines,
polyolefins, polyols, PEGs, polystyrene, PVA, PVC, vinyl
polymers, acrylics,
Film forming polymers - copolymers, adhesives,
Reactive polymers - epichlorohydrin containing, isocyanate
containing, epoxy containing Curable,
Elastomeric polymers - thermoplastic silicone elastomers,
Small Molecules - Salts, amino acids, sugars, saccharides,
oligosaccharides, alcohols, acids, and
Crosslinkers - methylol urea based, carboxylic acid,
formaldehyde, ammonia, triazine, epoxide.
WO 2004/018762A1 (Philips) discloses on wrinkle benefit using
fusible elastomer film formers with cross-linked particles to
improve recovery from wrinkle in spray or iron cartridge
applications
WO 2004/048677 (Philips) discloses film formers for recovery in
spray or iron cartridge applications including fusible
elastomers + polycation salt for x-linking of elastomer.
~
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WO 2001/25381-5 (Ciba) disclose compositions with (A) a fabric
softener, (B) an additive and (C) selected polyorganosilicones
to endow fabrics in domestic applications with anti-pilling,
elasticity, hydrophilicity, drape, and wrinkle recovery
respectively. These properties are endowed by the
organosilicone. Amongst the additives polysilicic acid is
mentioned.
WO 2002/088293 and US-A1-2002/019236 (Unilever) both disclose
fabric care compositions comprising coated particles comprising
a solid core with a D3,2 average particle size of between 10 to
700 nm in diameter and a coating of silicone polymer covalently
bonded to the solid core. Silica is mentioned in a list of
suitable solid core materials.
EP 1201817 (A1)(Procter & Gamble) discloses aminosilicones with
sterically hindered functional groups for in-wear wrinkle
resistance, which are preferably delivered from a spray during
domestic ironing process.
EP 1096060 (A1) (Procter & Gamble) discloses water-soluble
silicone lubricants in combination with various polymeric
compounds (film formers) which are said to provide fabrics with
a wrinkle recovery angle of at least +15 units over and above
water.
EP 953675 (A2,A3) (Dow Corning) a textile fabric coated with an
elastomeric silicone-based compound with a reinforcing filler
preferably a silica + a second laminar filler preferably talc
and mica. The coated fabrics amongst other benefit have less
friction and are used for car seat belts. No teaching exists on
the wrinkle benefit of the mixed silicone + particulate fillers.
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GB 842027 (Monsanto Chemicals) discloses textile friction
enhancing compositions based on silica nanoparticles dispersed
inside an oil emulsion droplets. The oil can be any of the
known textile oils including mineral or vegetable oils. The oil
to silica ratio exceeds 6 and deposition levels of 3-7% oil and
0.1-0.5% of silica per weight of fabric are preferred.
US 2635056 (Monsanto) discloses treating textiles and fabrics
with an aquasol of silica plus a polyhydic alcohol such as
glycerol. The blends are termed alco-aquasols and provide
exceptional slip resistance to textiles and surprisingly good
handle and fabric feel attributed to the presence of glycerol.
The silica to glycerol ratio used in the example is 1.4. It is
stated that polyhydric alcohol level should not exceed twice
that of silica.
WO-2001/083875 (Ajinomoto Co.) discloses the application of
silica and a softener with a cationic acrylic binder followed by
application of a treatment solution containing arginine to nylon
tights so as to provide skin care benefits when the tights are
worn.
EP 1024119 (A2,A3)(Relats) discloses textile articles made of
Si02-containing fibres and procedure for improving their thermal
stability.
JP 04255767 (Nichihan Kenkyusho K.K.) discloses coating
compositions for textiles comprising a synthetic emulsion
(acrylic), colloidal or microparticle metal oxide silica gel and
a zeolite to provide textile coatings with good antibacterial,
deodorising, drying and heat retention properties.
NL 8900473 (Hesco Fashion Netherlands) discloses the manufacture
of viscose rayon-polyester coated with a mixture of a nonionic
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fatty acid condensates fabric softener and a blocking agent
(blocking free movement of warp and weft - friction enhancer)
acidic silica dispersion. The ratio of the softener to silica
is 1:1 and the level applied 1% of silica and 1% of softener.
5
EP 0474207, US 2881146, US 3077460 and US 5102930 all disclose
fabric treatment compositions comprising silica, an
organopolysiloxane and a catalyst/curing agent to cause a
polymer film to form on the fabrics.
There is no product available on the market that meets consumers
need for an effective in-wear wrinkle resistance from the main
wash or from the rinse.
Therefore, there is a need for an effective and efficient means
for preventing wrinkles from reappearing after the ironing
process in wear whilst the fabrics maintains a good handle,
softness and comfort in wear.
It is desirable for consumers to have a composition for use in
the rinse which provides effective elimination or reduction of
wrinkles in dry fabric in wear in addition to the benefits of
good softness and perfume normally expected from rinse added
products.
In addition, it is particularly desirable that the in-wear
wrinkle resistance is provided by the composition after the
first wash cycle in which it is used.
Objects of the Invention
The present invention seeks to address one or more of the above-
mentioned problems.
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Summary of the Invention
According to one aspect of the present invention there is
provided a fabric treatment composition for use in the rinse
cycle of a washing machine for reducing in-wear wrinkle in
fabrics, the composition comprising:
a) a nanoparticle dispersion comprising particles having
an average particle size in the range 5 to 500nm,
b) a lubricant phase selected from a cationic fabric
softener, a silicone oil, sucrose polyester oil and mixtures
thereof, and
c) water
in which the weight ratio of a) : b) is in the range 3 : 1 to 1
3.
The compositions of the invention are used in the rinse cycle of
a laundry process and impart in-wear crease resistance to the
treated fabrics. The compositions comprise a blend of
nanoparticles, which act as a friction element, and a lubricant
phase. The balance of the nanoparticles and lubricant phase
provides the desired properties by virtue of their physical
properties. The compositions of the invention are free from
catalysts and curing agents and do not react to form a film when
deposited on the fabric.
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Detailed Description of the invention
The compositions of the present invention are typically for use
as part of a fabric care composition which is delivered to the
rinse cycle of an automatic washing machine.
Nanoparticles
The compositions of the present invention comprise a
nanoparticle dispersion which act as a frictional element when
deposited on the fabrics. The particles may be inorganic or
organic or a mixture of one or more types of nanoparticles.
Suitable inorganic nano-particles include silicas, Si02, titania,
Ti02, alumina, A1203r zinc oxide, ZnO, and the mixed oxides
class such as ITO (indium-tin oxide, In203-Sn02).
The widely commercial and preferred inorganic nanoparticle are
amorphous silicas available in the sol or colloidal form as
defined on page 330 of The Chemistry of Silica, by R K Iler,
Wiley-Interscience, New York, 1979.
Silica nanoparticles could also be of non-siliceous core as long
as the surface of the nanoparticle is coated with silica as
described on page 330 of Iler's book. The core can be of
organic polymeric nature.
Suitable organic particles include those derived from silicon
including silicone resins. The organic particles are not of the
type which comprise a solid core coated with a polymer, such as
a silicone polymer. The organic particles are non-coated and
comprise solid particles of polymer or resin. In the context of
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the present invention, "nanoparticle" denotes particles having
an average particle size ranging from 5 to 500 nm. Larger
particle size silica also aid crease resistance but apparently
they are not as effective as those between 15-100 nm.
Preferably all of the particles have a particle size below 500
nm, more preferably below 100 nm.
It has been found that a particle size of 500 nm or less
provides excellent crease resistance on poplin fibres and a
particle size of 300 nm or less provides excellent crease
resistance on cotton fibres.
Dispersions having an average particle size in the range 10 to
50 nm are particularly useful. The amount to deposit between
0.25 to 2% and preferably between 0.25 to 0.5 wt% owf
(0.0025 to 0.005 g/g of fabric).
Nanoparticles depending on their structure can provide
additional benefits - aid odour absorption during the wear,
increase longer lasting freshness, reduced glare and shine on
ironing items, resistance to staining, and ease of stain removal
in following washes can be achieved.
Preferred nanoparticles for use in the invention are colloidal
silica. The term 'colloidal silica' here refers to dispersions
or sols of discrete particles of amorphous silica, which are
preferably stable. Reacted silica is the hydrophobic fumed
silica as used in anti-foaming emulsions mentioned above.
Commercial colloidal silica is available containing up to 50%
silica with particle diameter between 10-21 nm under the trade
name Ludox (ex Grace Davison) and Snowtex (ex Nissan).
Particular examples include Ludox Cl (a cationic silica) and
Ludox HS50 (an anionic silica), both having a particle size of
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20 nm. The quoted size represents the linear diameter of the
particle.
It is well known in the art that the surface of silica particles
can be easily modified to endow them with additional benefits.
For example modification with aluminates allows surface charge
modification (positive charge). Silicas can be modified
organically (organosols as described on page 412 of the above
reference). The preferred silicas have suitable modification
for surface charge and/or other textile functional benefits
including antimicrobial, dermal and transdermal, controlled
release of fragrance and repellent agents, improved abrasion
stability, water and oil, dirt repellency, and UV protection as
described in Journal of Sol-Gel Science and Technology 27, 43-
52, 2003 by B Mahltig and H Bottcher; Modified Silica Sol
coatings for Water-Repellent Textiles.
Lubricant phase
The compositions of the present invention comprise a fibre
lubricant selected from silicone oils, sucrose polyester oils or
oily sugar derivatives and quaternary ammonium fabric softening
materials.
The lubricant phase of interest include silicone oils and oily
sugar derivatives.
The silicone lubricants of interest include the classical three
classes of non-reactive silicone polymers (PDMS), reactive
silicone polymers (silanol terminated PDMS) and modified
silicone polymers (amino/amide functional siloxanes, non-ionic
modified siloxanes or polyether modified siloxanes). Preferred
silicones are PDMS types in emulsion or microemulsion format,
which are commercially available, for example, Dow Corning 1716
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(cationic) microemulsion, etc. Also DC amino silicones 2-8669
nonionic microemulsion, 2-8203 nonionic microemulsion, 28197
nonionic macroemulsion.
5 Another class of preferred silicones are those ex Wacker
including Wetsoft CTA (amino glycol PDMS), Finish CT 34E (amino
PDMS emulsion), Finish CT 208E (amino OH PDMS emulsion), Finish
CT 96 E (amino PDMS emulsion), and their Fluid L range, Fluid L
652 for example (amino PDMS).
Although silicone oils are preferred to improve the fabric
handle and softness non-silicone lubricants such as sucrose
polyester oils can provide the lubrication needed for fabric
recovery from wrinkle. W02002/019236A1 (Unilever) provides a
fuller list of silicone polymers of interest and EP1205538
(Unilever) the class of drying oils.
A preferred class of commercial materials in which the
particulate phase and a lubricant phase are combined include but
not limited to Dow Corning's silicone + reacted silica blends
marketed as anti-foaming agents including DOW CORNING Antifoam
B, DOW CORNING 544, DOW CORNING@ Q2-3302 ANTIFOAM COMPOUND,
DOW CORNING 1581 WATER REPELLENT, DOW CORNING 2-1912 FLUID.
Another preferred class of materials in which the particulate
phase and the lubricant phase are combined include but not
limited to Dow Corning MQ silicone resin range which contains a
PDMS silicone oil and a silicone resin nano-particulate phase.
Suitable sucrose polyester oils are the reaction products of
fatty acid methyl ester (FAME) of natural oils and sucrose.
Suitable oils and their preparation are described in EP323670B1,
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EP 383404B1, WO 2001/46210, WO 98/16538, WO 01/46359A1 and
British Patent Application No. 0501006.1.
Preferred oils are derived from natural oils predominantly
comprising C16 and C18 hydrocarbon chains e.g. palm kernel oil,
soy bean oil.
The quaternary ammonium fabric softening material is generally
one that is able to form a lamellar phase dispersion in water,
in particular a dispersion of liposomes.
The quaternary ammonium compound "QAC" is preferably one having
two C12_28 groups, that may independently be alkyl or alkenyl
groups, connected to the nitrogen head group, preferably being
connected to the nitrogen head group by at least one ester link,
and more preferably by two ester links.
The average chain length of the alkyl and/or alkenyl groups is
preferably at least C14 and more preferably at least C16. It is
particularly preferred that at least half of the groups have a
chain length of C18. In general, the alkyl and/or alkenyl
groups are predominantly linear.
A first group of QACs suitable for use in the composition is
represented by formula (I) :
~ (CH2)n(TR) ] m
I
R1-N+-L(CH2)n(OH)13-m X (I)
wherein each R is independently selected from a C5-35 alkyl or
alkenyl group; R1 represents a C1-4 alkyl, C2_4 alkenyl or a C1-4
hydroxyalkyl group; T is generally O-CO. (i.e. an ester group
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bound to R via its carbon atom), but may alternatively be C0.0
(i.e. an ester group bound to R via its oxygen atom); n is a
number selected from 1 to 4; m is a number selected from 1, 2,
or 3; and X- is an anionic counter-ion, such as a halide or
alkyl sulphate, e.g. chloride or methylsulphate. Di-esters
variants of formula I (i.e. m = 2) are preferred and typically
have mono- and tri-ester analogues associated with them. Such
materials are particularly suitable for use in the present
invention.
Especially preferred agents are di-esters of triethanolammonium
methylsulphate, otherwise referred to as "TEA ester quats".
Commercial examples include Prapagen TQL, ex Clariant, and
Tetranyl AHT-1, ex Kao, (both di-[hardened tallow ester] of
triethanolammonium methylsulphate), AT-1 (di-[tallow ester] of
triethanolammonium methylsulphate), and L5/90 (di-[palm ester]
of triethanolammonium methylsulphate), both ex Kao, and Rewoquat
WE15 (a di-ester of triethanolammonium methylsulphate having
fatty acyl residues deriving from C10-C20 and C16-C18 unsaturated
fatty acids), ex Witco Corporation.
The second group of QACs suitable for use in the composition is
represented by formula (II):
(R1)3N+-(CH2)n-CH-TR3 X (II)
I
CH2TR3
wherein each R1 group is independently selected from C1_4 alkyl,
hydroxyalkyl or C2-4 alkenyl groups; and wherein each R2 group is
independently selected from C8-28 alkyl or alkenyl groups; and
wherein n, T, and X- are as defined above.
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Preferred materials of this second group include 1,2
bis[tallowoyloxy]-3-trimethylammonium propane chloride, 1,2
bis[hardened tallowoyloxy]-3-trimethylammonium propane chloride,
1,2-bis[oleoyloxy]-3-trimethylammonium propane chloride, and 1,2
bis[stearoyloxy]-3-trimethylammonium propane chloride. Such
materials are described in US 4,137,180 (Lever Brothers).
Preferably, these materials also comprise an amount of the
corresponding mono-ester.
A third group of QACs suitable for use in the composition is
represented by formula (III):
(R1)2-N+-[(CH2)n-T-R2]2 X (III)
wherein each R1 group is independently selected from C1_4 alkyl,
or C2_4 alkenyl groups; and wherein each R2 group is
independently selected from C8_28 alkyl or alkenyl groups; and
n, T, and X- are as defined above. Preferred materials of this
third group include bis(2-tallowoyloxyethyl)dimethyl ammonium
chloride and hardened versions thereof.
A fourth group of QACs suitable for use in the composition is
represented by formula (IV):
(R1)2-N+-(R2)2 X (IV)
wherein each R1 group is independently selected from C1_4 alkyl,
or C2_4 alkenyl groups; and wherein each R2 group is
independently selected from C8_28 alkyl or alkenyl groups; and
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X is as defined above. Preferred materials of this fourth
group include di(hardened tallow)dimethylammonium chloride.
The iodine value of the softening agent is preferably from 0 to
20, more preferably from 0 to 4, and most preferably from 0 to
2. Essentially saturated material, i.e. having an iodine value
of from 0 to 1, is used in especially high performing
compositions. At low iodine values, the softening performance
is excellent and the composition has improved resistance to
oxidation and associated odour problems upon storage.
Iodine value is defined as the number of grams of iodine
absorbed per 100 g of test material. NMR spectroscopy is a
suitable technique for determining the iodine value of the
softening agents of the present invention, using the method
described in Anal. Che.m., 34, 1136 (1962) by Johnson and
Shoolery and in EP 593,542 (Unilever, 1993).
The softening agent is usually present in the compositions of
the invention at a level of 5% or greater by weight of the total
composition.
References to levels of cationic softening agent in this
specification are to the total level of cationic softening
agent, including all cationic components of a complex raw
material that could enter aqueous lamellar phase together. With
a di-ester softening agent, it includes any associated mono-
ester or tri-ester that may be present.
For ease of formulation, the amount of softening agent is
generally 50% or less, particularly 40% or less, and especially
300 or less by weight -of the total composition. Generally the
softening agent is present in an amount of from 3 to 20% by
weight of the composition.
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Fatty complexing agent
The composition of the present invention may comprise a fatty
5 complexing agent. Especially suitable fatty complexing agents
include fatty alcohols and fatty acids. Of these, fatty
alcohols are most preferred.
Preferred fatty acids include hardened tallow fatty acid
10 (available under the tradename Pristerene, ex Uniqema).
Preferred fatty alcohols include hardened tallow alcohol
(available under the tradenames Stenol and Hydrenol, ex Cognis
and Laurex CS, ex Albright and Wilson) and behenyl alcohol, a
15 C22 chain alcohol, available as Lanette 22 (ex Henkel).
The fatty complexing agent is present in an amount of from 0.1%
to 15% by weight based on the total weight of the composition.
More preferably, the fatty component is present in an amount of
from 0.2 to 10%, most preferably from 0.25 to 5%, e.g. 0.3 to 4%
by weight.
Nonionic surfactant
The compositions further comprise a nonionic surfactant.
Typically these can be included for the purpose of stabilising
the compositions.
Suitable nonionic surfactants include addition products of
ethylene oxide and/or propylene oxide with fatty alcohols, fatty
acids and fatty amines.
Any of the alkoxylated materials of the particular type
described hereinafter can be used as the nonionic surfactant.
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Suitable surfactants are substantially water soluble surfactants
of the general formula:
RY(C2H40) z- C2H40H
where R 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
alkenyl-substituted phenolic hydrocarbyl groups; the hydrocarbyl
groups having a chain length of from 8 to about 25, preferably
10 to 20, e.g. 14 to 18 carbon atoms.
In the general formula for the ethoxylated nonionic surfactant,
Y is typically:
--0-- , --C (0) 0-- , --C (0) N (R) -- or --C (0) N (R) R--
in which R has the meaning given above or can be hydrogen; and Z
is at least about 8, preferably at least about 10 or 11.
Preferably the nonionic surfactant has an HLB of from about 7 to
about 20, more preferably from 10 to 18, e.g. 12 to 16.
Examples of nonionic surfactants follow. In the examples, the
integer defines the number of ethoxy (E0) groups in the
molecule.
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A. Straight-Chain, Primary Alcohol Alkoxylates
The deca-, undeca-, dodeca-, tetradeca-, and pentadeca-
ethoxylates of n-hexadecanol, and n-octadecanol having an HLB
within the range recited herein are useful viscosity/
dispersibility modifiers in the context of this invention.
Exemplary ethoxylated primary alcohols useful herein as the
viscosity/dispersibility modifiers of the compositions are C1g
EO(10); and C18 EO(11). The ethoxylates of mixed natural or
synthetic alcohols in the "tallow" chain length range are also
useful herein. Specific examples of such materials include
tallow alcohol-EO(11), tallow alcohol-EO(18), and tallow
alcohol-EO (25), coco alcohol-EO(10), coco alcohol-EO(15), coco
alcohol-EO(20) and coco alcohol-EO(25).
B. Straight-Chain, Secondary Alcohol Alkoxylates
The deca-, undeca-, dodeca-, tetradeca-, pentadeca-, octadeca-,
and nonadeca-ethoxylates of 3-hexadecanol, 2-octadecanol, 4-
eicosanol, and 5-eicosanol having an HLB within the range
recited herein are useful viscosity and/or dispersibility
modifiers in the context of this invention. Exemplary
ethoxylated secondary alcohols useful herein as the viscosity
and/or dispersibility modifiers of the compositions are: C16
EO(11); C20 EO(11); and C16 EO(14)
C. Branched Chain Alkoxylates
Branched chain primary and secondary alcohols which are
available from the well-known "OXO" process can be
ethoxylated and employed as the viscosity and/or dispersibility
modifiers of compositions herein.
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D. Polyol Based Surfactants
Suitable polyol based surfactants include sucrose esters such
sucrose monooleates, alkyl polyglucosides such as stearyl
monoglucosides and stearyl triglucoside and alkyl polyglycerols.
The nonionic surfactant is preferably present in an amount from
0.01 to 10%, more preferably 0.1 to 5%, most preferably 0.35 to
3.5%, e.g. 0.5 to 2% by weight, based on the total weight of the
composition.
Co-active softeners
In rinse cycle fabric care compositions, co-active softeners may
also be incorporated in an amount from 0.01 to 20% by weight,
more preferably 0.05 to 10%, based on the total weight of the
composition. Preferred co-active softeners include fatty
esters, and fatty N-oxides.
Preferred fatty esters include fatty monoesters, such as
glycerol monostearate. If GMS is present, then it is preferred
that the level of GMS in the composition, is from 0.01 to 10
wt%, based on the total weight of the composition.
The co-active softener may also comprise an oily sugar
derivative. Suitable oily sugar derivatives, their methods of
manufacture and their preferred amounts are described in WO-Al-
01/46361 on page 5 line 16 to page 11 line 20, the disclosure of
which is incorporated herein.
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Polymeric viscosity control agents
It is useful, though not essential, if the compositions comprise
one or more polymeric viscosity control agents. Suitable
polymeric viscosity control agents include nonionic and cationic
polymers, such as hydrophobically modified cellulose ethers
(e.g. Natrosol Plus, ex Hercules), cationically modified
starches (e.g. Softgel BDA and Softgel BD, both ex Avebe). A
particularly preferred viscosity control agent is a copolymer of
methacrylate and cationic acrylamide available under the
tradename Flosoft 200 (ex SNF Floerger).
Nonionic and/or cationic polymers are preferably present in an
amount of 0.01 to 5wt%, more preferably 0.02 to 4wt%, based on
the total weight of the composition.
Further Optional Ingredients
Other optional nonionic softeners, bactericides, soil-releases
agents may also be incorporated in the rinse cycle fabric care
compositions.
Such compositions may also contain one or more optional
ingredients conventionally included in liquid rinse fabric
conditioning compositions such as pH buffering agents, perfume
carriers, fluorescers, colourants, hydrotropes, antifoaming
agents, antiredeposition agents, polyelectrolytes, enzymes,
optical brightening agents, anti-shrinking agents, anti-spotting
agents, antioxidants, sunscreens, anti-corrosion agents, drape
imparting agents, anti-static agents, ironing aids and dyes.
The lubricant and the particulate phases in the compositions of
the invention can be in a fully dispersed state, partially
flocculated or associated in the form of a Pickering emulsion
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where the particles stud the surface of the emulsion or liposome
droplets to form a nanoparticle-droplet composite - studded
particles.
5 Preparation
The composition may be prepared according to any suitable
method. In one method the nanoparticle dispersion plus the
lubricant emulsion or microemulsion if needed can be post dosed
10 into the fabric softening base after it is manufactured with
minimum agitation to prevent flocculation.
In another method of addition the nanoparticle phase at the
required level can be post-dosed into an off-the-shelf ready
15 fabric conditioner.
Product Form
The product preferably comprises a liquid, preferably an aqueous
20 liquid.
Product Use
The composition can be a rinse cycle fabric care composition for
use in a conventional automatic washing machine.
Sumnnary of Drawings
Figures la and lb represent a standard Wrinkle Recovery Tester
Instrument Model 155 commercially available from James H Heal &
Co. Ltd.,
Figure 2 represents images of the existing AATCC 128 Scale,
Figure 3 represents images of the new U Scale and
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Figure 4 is a plot showing the comparison of the AATCC scale
with the new U Scale.
Evaluation of in-wear wrinkling
It has been discovered that the traditional Crease or Wrinkle
Recovery Angle (CRA) approach for characterising anti-wrinkle
compositions of inventions, that is AATCC66-1990 (see EP-A-
1096060) is largely irrelevant to in-wear wrinkle assessment.
In in-wear wrinkling the sharpness of the fold and deformation
matters and this is not measured by CRA.
There are many textile industry standard methods (Association of
American Textile Chemists and Colourists - AATCC) described for
generating and measuring wrinkling on fabric.
The AATCC 128 Wrinkle Recovery Test is that most widely used to
determine the wrinkle recovery of garments and is referenced
widely in the external literature. A test fabric is wrinkled
under standard conditions of load, time and environmental
conditions using a standard Wrinkle Recovery Tester model 155
device supplied by James H Heal & Co Ltd (Figure 1). The level
of wrinkled state is ranked visually with reference to a
standard 3D (cast)replica scale, WR1-WR5, where WR1 = no
recovery from creasing and WR5 = full recovery using a defined
illumination set-up. Figure 2 shows this 3D AATCC 128 wrinkle
scale.
However, the existing 3D AATCC 128 scale is not ideal when
testing fabrics for in-wear wrinkling for the following reasons.
The existing AATCC 128 3D standards cannot allow a panellist to
distinguish fine differences in intensity of wrinkling. For
example in in-wear wrinkling the range of wrinkle falls around
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2.5 to 3.5 but the 128 scale covers the broad brush scale of 1
to 5 missing details in the 2.5-3.5 range of interest.
Hence there is a need for a more relevant scale to assess the
intensity of wrinkling with good discrimination.
The new scale, called U scale hereafter, emerged from images of
woven cotton poplin monitors wrinkled, using the Wrinkle
Recovery Tester model 155, to severity between 0 = not wrinkled
(flat) and 10 = severely wrinkled as shown in Figure 3. This
scale therefore covers a wider spectrum of wrinkles in the
middle range allowing panellists to discriminate fine details in
a systematic manner.
Compared to AATCC128 scale, which manifests a rather flat
insensitive region around a score of 3, the new U scale allows
discrimination between the intensity of wrinkling around this
region. Figure 4 shows the comparison between the two scales
graphically.
Methodology
1. Monitor Preparation
The test solution is prepared with the desired strength or the
desired % owf and stabilised overnight on a roller bank.
The monitor is then weighed (W1), soaked in the test solution and
compressed between the rollers of the Werner Mathis AG padder so
that it weighs double its original weight.
The monitor is left to dry at controlled temperature and RH
(20 C/65oRH) for 24 hours and then re-weighed (W2).
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The weight of additive on the monitor is (W2 - W1) from which
the %owf can be calculated.
The dry monitor is ironed flat using the Philips Azur 4000 iron
on the hottest setting and with highest steam setting and left
to condition for a further 24 hours at controlled T and RH
(20 C/65oRH).
Six such test monitors per treatment are prepared.
In each test there are control monitors for comparison with the
composition treated monitors. These control monitors are
treated with demineralised water instead of the compositions and
prepared in the same way.
2. Wrinkling
To generate wrinkled state the monitors are loaded onto a
Wrinkle Recovery Tester model 155 so that the warp direction is
vertical. The fabric is then compressed (wrinkled) using no
additional weight for 8 minutes.
After wrinkling the monitors are hung up for 24 hours at
20 C/65oRH.
3. Monitor Assessment
A digital photograph image is taken of each monitor using a
Nokia Digital Camera under identical lighting conditions. The
standard lighting conditions are achieved using a Verivide
Crease Imaging Cabinet.
The images are then loaded into a panelling programme and each
image is presented to the panellist to score against images of
the scale being used - either AATCC128 or U Scale.
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Six trained panellists score all monitors for wrinkle intensity
against the scale.
In each test six untreated control monitors are also prepared
and wrinkled in exactly the same way as the treated monitors as
described above to enable comparison with the compositions.
The invention will now be illustrated by the following non-
limiting examples. Further modifications will be apparent to
the person skilled in the art. Samples of the invention are
represented by a number. Comparative samples are represented by
a letter. All values are percentage by weight of the active
ingredient unless stated otherwise.
Examples
The formulations in the following Table 1 were prepared by co-
melting the quaternary ammonium fabric softening material,
tallow alcohol, and nonionic, heating water and adding the co-
melt to the water under stirring to form a homogeneous mixture,
allowing the mixture to cool and then adding the dye/perfume and
preservative at 40 C. The mixture was allowed to cool further
and then the silica dispersion was post-dosed with stirring.
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Table 1
Ingredient Example Example Example A
1 2
Tetranyl AHT-1 14.94 6.035 14.94
(1)
Genapol C200 0.38 0.10 0.38
(2)
Hydronol D(3) 1.00 0.20 1.00
silica(4) 10.96 4.43 -
polymer (5) - 0.030 -
Dye/perfume/pr minor minor minor
eservative
water to 100 to 100 to 100
(1) Tetranyl AHT-1 is a fully hardened tallow triethanolamine
quaternary fabric softener supplied by KAO at 85% active level
5
(2) Genapol C200 is a coco (C9-C11)20E0 nonionic (Clariant)
(3) Hydrenol D(Cognis) is a fully hardened vegetable derived
C16-C18 fatty alcohol.
(4) C820 is a 11% silica dispersion in water (Ciba) with 22 nm
size silica particles. The quantities in the table show the
amount of silica.
(5) Natrasol 331 a hydrophobically modified hydroxy ethyl
cellulose.
The formulation of Examples A and 1 were subject to wrinkle
testing and compared to the application of the silica dispersion
and water. The results are reported in Table 2.
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Table 2. AATCC128 wrinkle score after 24hrs for fabric
conditioner formulation combined with silica sample C820 for
0.3% owf deposition. The HIGHER the score the less the monitors
are wrinkled.
Example A Example I silica (C820) Water
Quat : silica 1:0 1.3:1 0:1 Control
ratio
Score 2.86 3.39 3.53 3.17
As the results in Table 2 show the fabric conditioner
formulation treatment on its own (Example A) provides little or
no in-wear wrinkle benefit as the comparison with water control
demonstrate. However the combination of fabric conditioner with
silica particles in accordance with the invention offers
improved in-wear wrinkle benefit.
Silica on its own gives the flattest state corresponding to the
least in-wear wrinkle. However the fabric handle is too harsh
and abrasive with silica alone.
Table 3 characterises the fabric handle obtained using the
formulations. A lower 2HG5 score means that there is a more
elastic response when a shearing force is applied to the treated
fabric. A lower G score means that a lower level of stiffness
is experienced when a shearing force is applied.
Table 3 Kawabata shear hysteresis (2HG5)and shear rigidity (G)
data.
% owf Example A Example 1 Silica (C820) water
control
0.3% 10.60 6.30 12.36 10.807
2HG5 -
0.3% 1.98 1.68 2.49 2.00
G
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The results show the combined lubricant/silica (Example 1)
provides the desirable fabric smoothness and softness.
The formulations reported in the following Table 4 were prepared
by mixing a silica dispersion with off-the-shelf fabric
conditioning compositions. The silica dispersions was Ludox
SP532-10519 a 40% silicon dispersion with 50 nm particle size ex
Grace Davison. The fabric conditioning compositions were:
(A) Vernal Blue sky fabric conditioner from Henkel
containing 13.9% by weight of a softener based on a partially
hardened triethanolamine quaternary ammonium compound
(B) Comfort Blue fabric conditioner from Unilever having a
composition as Example A.
Table 4. Formulations and U scale wrinkle scores for fabric
treated (padded) with mixtures of quat:silica (Ludox SP532-
10519) at a 0.5% owf one hour and 24 hours after wrinkling. The
lower the score the less fabric is wrinkled.
Example Example Example Example Example Example Example
3 4 5 6 7 8 A
fabric A A A B B B Control
conditioner
quat:silica 1:1 1:2 2:1 1:1 1:2 2:1 1:0
weight ratio
lhr 3.50 2.72 3.10 2.21 2.32 2.72 4.22
24hr 2.80 2.38 2.50 2.35 2.17 2.48 3.26
Test of the monitors by an expert panel showed their handle and
softness acceptable. Ease of ironing of the quat:silica blends
was comparable with to that of Comfort commercial fabric
conditioner
Another class of lubricant-particle blends belong to the MQ
silicone resin class from Dow Corning shown in Tables 5 and 6.
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The intensity of wrinkling is reduced compared to untreated
after 1 hr and 24hrs at the preferred deposition levels.
Table 5. U scale wrinkle scores after 1 hr and 24hrs for o/w
emulsion of silicone oil/silicone resin blends using cationic
emulsifier.
Ratio PDMS/silicone resin blend (cationic emulsifier)
%owf 40/60 30/70 20/80 Untreated
lhr 24hr lhr 24hr lhr 24hr lhr 24hr
score score score score score score score score
0.1 3.71 2.97 3.17 2.61 3.25 2.49 3.60 2.88
0.25 3.08 2.49 2.78 2.29 2.40 1.93 3.60 2.88
Table 6. U scale wrinkle scores after 1 hr and 24hrs for o/w
emulsion of silicone oil/silicone resin blends using nonionic
emulsifier.
Ratio PDMS/silicone resin blend (non-ionic emulsifier)
% owf 40/60 30/70 20/80 Untreated
lhr 24hr lhr 24hr lhr 24hr lhr 24hr
score score score score score score score score
0.1 2.67 1.67 2.15 2.08 2.75 2.38 3.58 2.89
0.25 1.83 2.14 2.92 2.25 3.58 2.38 4.00 2.89
In Tables 5 and 6 the composition of the internal phase of the
emulsions is the same. They differ in the type of surfactant
used for emulsification.
Table 7 shows the composition of the oil and water phases of the
emulsions. The PDMS/resin blends in D5 (a low molecular weight
silicone oil solvent) are mixed with water and emulsifier (not
shown in Table 7).
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Table 7 : Composition of PDMS/resin blend in emulsions.
In redient % in composition
Water 50
D5 25
PDMS / Resin blend 25
Siloxane resin consisting of monovalent trisiloxy (M) groups
having formula R3Si01/2 and tetravalent siloxy (Q) groups having
formula Si04/2 and the polymer is amino functionalised PDMS with
some degree of OH termination of viscosity 4000 mPa s.
Table 8 provides the droplet sizes of the resin blend emulsions
used in Tables 8 and 9.
Table 8. Emulsion droplet Size of PDMS/silicone resin polymer
blends.
PDMS/MQ blend Surfactant PSD (nm)
ratio Type
40/60 Nonionic 139
30/70 Nonionic 129
20/80 Nonionic 161
40/60 Cationic 116
30/70 Cationic 154
20/80 Cationic 139
The silicon resin blend treated monitors showed better softness
and handle compared to silica at equal add-on level. Their ease
of ironing was also improved compared to the silica.
