U.S. patent application number 11/258331 was filed with the patent office on 2006-02-23 for fabric treatment compositions.
This patent application is currently assigned to Unilever Home & Personal Care USA, Division of Conopco., Inc.. Invention is credited to Paul Hugh Findlay, Joseph Edward Hunter, Laxmikant Tiwari, Nicola Whilton.
Application Number | 20060040842 11/258331 |
Document ID | / |
Family ID | 9934282 |
Filed Date | 2006-02-23 |
United States Patent
Application |
20060040842 |
Kind Code |
A1 |
Findlay; Paul Hugh ; et
al. |
February 23, 2006 |
Fabric treatment compositions
Abstract
Fabric treatment compositions comprising a textile compatible
carrier and particles having a layered structure comprising oxygen
atoms and silicon and/or phosphorus atoms and comprising organic
functional groups which are bonded to silicon and/or phosphorus
atoms by direct covalent bonds between the silicon and/or
phosphorus atoms and a carbon atom. The functional groups are
selected to impart lubricating properties to the particles.
Inventors: |
Findlay; Paul Hugh;
(Bebington, GB) ; Hunter; Joseph Edward;
(Liverpool, GB) ; Tiwari; Laxmikant; (Bebington,
GB) ; Whilton; Nicola; (Bebington, GB) |
Correspondence
Address: |
UNILEVER INTELLECTUAL PROPERTY GROUP
700 SYLVAN AVENUE,
BLDG C2 SOUTH
ENGLEWOOD CLIFFS
NJ
07632-3100
US
|
Assignee: |
Unilever Home & Personal Care
USA, Division of Conopco., Inc.
|
Family ID: |
9934282 |
Appl. No.: |
11/258331 |
Filed: |
October 25, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10406952 |
Apr 4, 2003 |
|
|
|
11258331 |
Oct 25, 2005 |
|
|
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Current U.S.
Class: |
510/334 |
Current CPC
Class: |
C11D 3/1253 20130101;
C11D 3/1226 20130101; C01B 33/44 20130101 |
Class at
Publication: |
510/334 |
International
Class: |
C11D 3/12 20060101
C11D003/12 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 4, 2002 |
GB |
0207850.9 |
Claims
1. Fabric treatment composition comprising a textile compatible
carrier and particles having a layered structure comprising oxygen
atoms and silicon and/or phosphorus atoms, and comprising organic
functional groups which are bonded to silicon and/or phosphorus
atoms in the layers by direct covalent bonds between the silicon
and/or phosphorus atoms and a carbon atom, characterised in that
the functional groups are selected from: (i) a group of the
formula: --Y-T (i) in which: Y comprises a chain of at least 6
carbon atoms optionally interrupted by one or more heteroatoms
selected from N, O and S providing there are at least 3, preferably
at least 4 carbon atoms for each heteroatom in the chain, Y being
linked to said silicon or phosphorous atom through a carbon atom,
and T represents H or a terminal group which is not capable of
self-cross-linking and/or forming covalent bonds to cellulosic
and/or proteinaceous fibres during domestic washing and rinsing
cycles; (ii) a group of the formula: --R.sup.1--NR.sup.2R.sup.2
(II) in which: R.sup.1 represents an alkylene group of at least 4
carbon atoms, each R.sup.2 is independently lower alkyl and
--NR.sup.2R.sup.2 is preferably, but need not be, a terminal group;
(iii) a group of the formula: ##STR10## in which: R.sup.3
represents an alkylene group of at least 3 carbon atoms, each
R.sup.4 is independently selected from alkyl groups of from 1 to 25
carbon atoms provided at least one R.sup.4 is lower alkyl of 1 to
16 carbon atoms, (iv) a group of the formula ##STR11## in which
each R.sub.1a group is independently selected from C.sub.1-4 alkyl
or hydroxyalkyl groups or C.sub.2-4 alkenyl groups; each R.sub.2a
group is independently selected from C.sub.8-28 alkyl or alkenyl
groups; R.sub.3a is a linear or branched alkylene group of 1 to 5
carbon atoms, X is ##STR12## and p is 0 or is an integer from 1 to
5, with the proviso that one of R.sub.1a and R.sub.2a is an
alkylene group of at least 3 carbon atoms attached to said silicon
or phosphorus atom; (v) a group of the formula: ##STR13## in which
R.sub.1a, p and R.sub.2a are as defined above; (vi) a group of the
formula: ##STR14## in which: T is as defined above, R.sup.5
represents a group of at least one carbon atom, preferably at least
3 carbon atoms, which may be interrupted by one or more heteroatoms
selected from N, O and S providing there are at least 3 carbon
atoms for each heteroatom, n is an integer of at least 6; and (vii)
a group of the formula: ##STR15## in which: T and R.sup.5 are as
defined above, each R.sup.6 independently represents an alkyl
group, a fluorinated alkyl group, an amino substituted alkyl group,
an alkyl group substituted with a sugar moiety, or a sidechain
comprising an ethoxylated and/or propoxylated chain, and x is an
integer of at least 5.
2. A composition as claimed in claim 1 in which --Y-T is an alkyl
group of from 6 to 20 carbon atoms.
3. A composition as claimed in claim 1 in which each R.sup.2 is
lower alkyl of from 1 to 6 carbon atoms.
4. A composition as claimed in claim 1 in which at least one of
R.sup.2 is an alkyl group of at least 8 carbon atoms.
5. A composition as claimed in claim 4 in which each R.sup.2 is an
alkyl group of at least 8 carbon atoms.
6. A composition as claimed in claim 1 in which T is selected from
hydrogen, alkyl, ether, carboxylic acid, SO.sub.3 and SO.sub.4
groups, phosphate and phosphonate.
7. A composition as claimed in claim 1 in which the particles
comprise two or more different functional groups selected from
formulas (I) to (VII).
8. A composition as claimed in claim 1 wherein the particles
comprise layers which further comprise atoms selected from
magnesium, aluminium, nickel, zirconium and mixtures thereof.
9. A composition as claimed in claim 1 wherein the particles are of
a clay in which the organic functional groups have been introduced
during formation of the clay.
10. A composition as claimed in claim 1 wherein the particles are
of an organophyllosilicate.
11. A composition as claimed in claim 1 which is a main wash
detergent composition and wherein the textile compatible carrier
comprises a detergent active compound.
12. A composition as claimed in claim 1 which is a fabric
conditioner comprising one or more fabric softening or conditioning
agents.
13. A composition as claimed in claim 1 comprising one or more
further components selected from builders and enzymes.
14. A composition as claimed in claim 1 comprising from 0.01% to
50% by weight of the particles.
15. A composition as claimed in claim 14 comprising from 0.1% to
20% by weight of the particles.
16. Use of particles as defined claim 1 in the treatment of a
fabric.
17. Use of particles as defined in claim 1 to treat a fabric to
provide enhanced lubricating properties to the fabric.
18. Use of particles as defined in claim 1 to treat a fabric to
decrease the Kawabata shear of the fabric measured according to the
Kawabata Shear Test defined herein.
19. Use of particles as defined in claim 1 to treat a fabric to
provide improved softness and/or ease of ironing and/or
anti-wrinkle properties and/or anti-abrasion properties.
20. Use of a composition according to claim 1 in the treatment of a
fabric.
21. Use of a composition according to claim 1 to treat a fabric to
provide enhanced lubricating properties to the fabric.
22. Use of a composition according to claim 1 to treat a fabric to
decrease the Kawabata shear of the fabric measured according to the
Kawabata Shear Test defined herein.
23. Use of a composition according to claim 1 to treat a fabric to
provide improved softness and/or ease of ironing and/or
anti-wrinkle properties and/or anti-abrasion properties.
24. Use as claimed in any one of claims 16 to 23 in which the
treatment is part of a domestic laundering process.
25. A method of treating a fabric comprising contacting the fabric
with a fabric treatment composition as defined in claim 1.
26. A compound having a layered structure comprising oxygen atoms
and silicon and/or phosphorus atoms, and comprising organic
functional groups which are bonded to silicon and/or phosphorus
atoms in the layers by direct covalent bonds between the silicon
and/or phosphorus atoms and a carbon atom, characterised in that
the functional groups are selected from: (i) a group of the
formula: --R.sup.1--NR.sup.2R.sup.2 (II) in which: R.sup.1
represents an alkylene group of at least 4 carbon atoms, each
R.sup.2 is independently lower alkyl and --NR.sup.2R.sup.2 is
preferably, but need not be, a terminal group; (ii) a group of the
formula: ##STR16## in which: R.sup.3 represents an alkylene group
of at least 3 carbon atoms, each R.sup.4 is independently selected
from alkyl groups of from 1 to 25 carbon atoms provided at least
one R.sup.4 is lower alkyl of 1 to 16 carbon atoms, (iii) a group
of the formula ##STR17## in which each R.sub.1a group is
independently selected from C.sub.1-4 alkyl or hydroxyalkyl groups
or C.sub.2-4 alkenyl groups; each R.sub.2a group is independently
selected from C.sub.8-28 alkyl or alkenyl groups; R.sub.3a is a
linear or branched alkylene group of 1 to 5 carbon atoms, X is
##STR18## and p is 0 or is an integer from 1 to 5, with the proviso
that one of R.sub.1a and R.sub.2a is an alkylene group of at least
3 carbon atoms attached to said silicon or phosphorus atom; (iv) a
group of the formula: ##STR19## in which R.sub.1a, p and R.sub.2a
are as defined above; (v) a group of the formula: ##STR20## in
which: T represents H or a terminal groups which is not capable of
self-cross-linking and/or forming covalent bonds to cellulosic
and/or proteinaceous fibres during domestic washing and rinsing
cycles; R.sup.5 represents a group of at least one carbon atom,
preferably at least 3 carbon atoms, which may be interrupted by one
or more heteroatoms selected from N, O and S providing there are at
least 3 carbon atoms for each heteroatom, n is an integer of at
least 6; and (vi) a group of the formula: ##STR21## in which: T and
R.sup.5 are as defined above, each R.sup.6 independently represents
an alkyl group, a fluorinated alkyl group, an amino substituted
alkyl group, an alkyl group substituted with a sugar moiety, or a
sidechain comprising an ethoxylated and/or propoxylated chain, and
x is an integer of at least 5.
27. A compound as claimed in claim 26 in which each R.sup.2 is
lower alkyl of from 1 to 6 carbon atoms.
28. A compound as claimed in claim 26 in which at least one of
R.sup.2 is an alkyl group of at least 8 carbon atoms.
29. A compound as claimed in claim 26 in which each R.sup.2 is an
alkyl group of at least 8 carbon atoms.
30. A compound as claimed in claim 26 in which T is selected from
hydrogen, alkyl, ether, carboxylic acid, SO.sub.3 and SO.sub.4
groups, phosphate and phosphonate.
31. A compound as claimed in claim 26 which comprises two or more
functional groups selected from formulae (II) to (VII).
32. A compound as claimed in claim 26 which additionally comprises
a group of the formula: --Y-T (I) in which Y comprises a chain of
at least 6 carbon atoms optionally interrupted by one or more
heteroatoms selected from N, O and S providing there are at least
3, preferably at least 4 carbon atoms for each heteroatom in the
chain, Y being linked to said silicon or phosphorous atom through a
carbon atom, and T represents H or a terminal group which is not
capable of self-cross-linking and/or forming covalent bonds to
cellulosic and/or proteinaceous fibres during domestic washing and
rinsing cycles.
Description
[0001] This is a continuation of Ser. No. 10/406,952 filed Apr. 4,
2003
TECHNICAL FIELD
[0002] This invention relates to fabric treatment compositions, to
their use in the treatment of fabric and to a method of treating
fabric with the compositions.
BACKGROUND AND PRIOR ART
[0003] It is known that the physical properties of fabrics can be
modified by certain treatments. For example, fabric may be treated
in order to modify its physical properties either in an industrial
pretreatment or during laundering.
[0004] Fabrics in general, and cotton in particular, are prone to
the formation of creases before, during and after laundering and
drying. In order to remove such creases from the fabric, a
considerable amount of time and effort must be spent ironing upon
each occasion of laundering and drying. The terms "crease" and
"wrinkle" and related terms, such as "anti-crease" and
"anti-wrinkle", refer to non-permanent deformations in the fabric
which can be removed by flattening at elevated temperature and
moisture (eg, by ironing) and are used synonymously herein.
[0005] Some of the previous attempts to address the problems of
crease formation with regard to fabrics have been based on the use
of insoluble particulate materials.
[0006] U.S. Pat. No. 3,892,681, for example, discloses the use of
granular, substantially water-insoluble starch particles having a
diameter between 1 to 45 .mu.m in detergent compositions. Such
particles are said to impart anti-wrinkling and ease of ironing
benefits in addition to other fabric conditioning properties.
[0007] A detergent composition featuring a substantially
water-insoluble particulate material with a diameter from about 5
to 30 .mu.m is described in U.S. Pat. No. 4,051,046. The
particulate material may be a glass, ceramic or polymer-based bead,
or a starch that has been treated with a hydrophobic agent to
reduce its water solubility. In order to permit ironing, the
particles must have a melting point above 150.degree. C. These
compositions are said to confer a range of fabric benefits,
including anti-wrinkling and ease of ironing.
[0008] The use of smectite clay as a softening agent is disclosed
in U.S. Pat. No. 3,936,537. In this document, the clay is combined
with a quaternary ammonium salt, which confers anti-static
benefits, and a dispersion inhibitor consisting of a solid organic
material, in a detergent compatible composition.
[0009] Smectite clay is also used in the fabric-softening detergent
compositions disclosed in U.S. Pat. No. 4,062,647. Again the clay
is said to impart improved softening and/or antistatic
characteristics.
[0010] A fabric softening detergent composition comprising a
synthetic non-soap detergent, builder salt and clay is disclosed in
GB 1400898. The clay, added for softening benefits, is a
three-layer smectite-type clay with an ion exchange capacity of at
least 50 meq/100 g. The combination of builder salt and clay is
described as helping prevent agglomeration of the clay, thus
allowing efficient deposition of the clay on fabric. In GB 1428061,
a similar fabric softening composition is disclosed with a
water-insoluble quaternary ammonium salt present as an anti-static
agent. The smectite-type clay, responsible for imparting softness
benefits, has a particle size below 50 microns and an ion-exchange
capacity of at least 50 meq/100 grams.
[0011] In U.S. Pat. No. 5,443,750, clay, which may be smectite
clay, is used in conjunction with an enzyme in a detergent
composition to afford increased softening properties.
[0012] EP-A-0 381 487 describes the use of liquid detergent
compositions in which a clay (an aluminosilicate eg, smectite) is
treated with a barrier material, selected from a siloxane, a
polysiloxane, a polyacrylate, dialkyl citrate, alkoxylated dialkyl
citrate, alkoxylated glycerol mono- and di-stearates, and
alkoxylated N-alkyl alkanolamides, prior to incorporation of the
clay into the formulation.
[0013] The treatment of a range of water insoluble materials,
including clay, with an organosilicon compound bearing a quaternary
ammonium group is taught in U.S. Pat. No. 4,557,854. The
organosilicon groups are grafted onto the surface of the clay
particles and, therefore, will be bound to the silicon atoms in the
layers of the clay by way of Si--O linkages. The effect of the
treatment is described as being to increase the cleaning power of
conventional organic surface-active agents.
[0014] The treatment of cotton fabrics with cross-linking agents,
such as butane-1,2,3,4-tetracarboxylic acid (BTCA), is known to
impart anti-wrinkle properties. However, such treatments tend to
make the fabric stiff and relatively easy to tear.
[0015] U.S. Pat. No. 4,844,821 discloses liquid laundry detergent
and liquid fabric softener compositions containing a smectite-type
clay fabric softener in combination with an antisettling agent and,
optionally, a softness enhancing amount of a polymeric
clay-flocculating agent.
[0016] U.S. Pat. No. 3,948,790 discloses detergent compositions
containing a quaternary ammonium clay. The clay is an impalpable
smectite clay in which from 5 to 100 molar percent of the
exchangeable cations are alkyl-substituted ammonium ions.
[0017] U.S. Pat. No. 4,828,723 discloses non-aqueous heavy duty
laundry detergent composition in the form of a suspension of a
builder salt in liquid nonionic surfactant which is stabilised
against phase separation by the addition of a low density filler
and a small amount of organophilic modified clay such as a
water-swellable smectite clay in which the metal cations are fully
or partially exchanged with mono- or di-long chain quaternary
ammonium compounds.
[0018] U.S. Pat. No. 5,336,647 discloses organophilic clay
complexes which are dispersible in non-aqueous fluids to form a gel
therein. The organophilic clay complex comprises the reaction
product of: [0019] (a) a smectite-type clay; [0020] (b) a first
organic cation an amount of from about 75% to about 150% of the
cation exchange capacity of the smectite-type clay; and [0021] (c)
a second organic cation provided by a polyalkoxylated quaternary
ammonium salt; wherein the second organic cation is present in an
amount of from about 0.01% to about 20% by weight of the total
organic cation content.
[0022] U.S. Pat. No. 5,527,871 discloses a layered
inorganic-organic polymer which has its inorganic portion in the
form of a layered clay-like structure composed of one or two sheets
of tetrahedrons (whose central atom is Si or a metal) and a sheet
of octahedrons (whose central atom is a metal). The central atoms
of the tetrahedrons are partially or entirely bonded to organic
groups. The organic groups may contain functional groups e.g. the
functional groups may participate in a polymerisation reaction.
[0023] U.S. Pat. No. 4,287,086 discloses organophilic organic-clay
complexes which are dispersible in organic liquids to form a gel.
The gels may be useful as lubricating greases, oil base muds, oil
base packer fluids, paint-varnish-lacquer removers, paints and
foundry moulding sand binders. The organophilic clay is the
reaction product of a smectite clay and a methyl benzyl dialkyl
ammonium salt.
[0024] U.S. Pat. No. 5,429,99 discloses an organophilic clay
gellant useful in a non-aqueous fluid system such as paints, inks
and coatings. The organophilic clay gellant comprises the reaction
product of: [0025] (a) a smectite clay having a cation exchange
capacity of at least 75 milliequivalents per 100 grams of natural
clay without impurities; [0026] (b) a first organic cation in an
amount of from about 75% to about 150% of the cation exchange
capacity of the smectite clay; [0027] (c) a second organic cation
provided by a polyalkoxylated quaternary ammonium salt; and [0028]
(d) one or more organic anions(s) that is capable of reacting with
said first and second organic cations, to form an organic
cation-organic anion complex with said smectite clay.
[0029] Co-pending PCT/EP01/12580 discloses fabric treatment
composition comprising a textile compatible carrier and water
insoluble particles having a layered structure comprising oxygen
atoms and silicon and/or phosphorus atoms, and comprising organic
functional groups which are bonded to silicon and/or phosphorus
atoms in the layers by direct covalent bonds between the silicon
and/or phosphorus atoms and a carbon atom.
[0030] In a preferred embodiment the use of fabric compositions
comprising water-insoluble particles having a layered structure and
comprising one or more organic functional groups which are capable
of self cross-linking and/or reacting with the fibres of the fabric
leads to improved anti-wrinkle, ie, crease reduction, performance
of fabrics, without the disadvantages of conventional cross-linking
agents such as butane-1,2,3,4-tetracarboxylic acid (BTCA) Hence,
fabrics treated with compositions comprising such water-insoluble
particles have good antiwrinkle properties but are less stiffness
prone to discolouring and less susceptible to tearing than fabrics
treated with some conventional cross-linking agents.
[0031] Cellulosic fibres possess hydroxyl groups; proteins possess
a range of functional groups. Preferably, the organic functional
groups comprise electrophilic groups which are capable of reacting
with hydroxyl groups for reaction with, for example, cellulosic
fibres or proteinaceous fibres and/or thiol groups for more
specific reaction, for example, with proteinaceous fibres. Suitable
examples of electrophilic groups include: acid anhydrides,
epoxides, acid chlorides, isocyanates, azetidinium-containing
groups, carboxylic acids, vinyl sulfones, aldehydes, ketones, enol
esters, aziridines, azalactones and mixtures thereof. The epoxide
group is especially preferred.
[0032] It has now been found that a particular range of functional
groups will provide particles capable of delivering enhanced
lubricating properties to a fabric compared to particles without
the functional groups.
[0033] According to one aspect of the present invention there is
provided fabric treatment composition comprising a textile
compatible carrier and particles having a layered structure
comprising oxygen atoms and silicon and/or phosphorus atoms, and
comprising organic functional groups which are bonded to silicon
and/or phosphorus atoms in the layers by direct covalent bonds
between the silicon and/or phosphorus atoms and a carbon atom,
[0034] characterised in that the functional groups are selected
from: [0035] (i) a group of the formula: --Y-T (I) [0036] in which:
[0037] Y comprises a chain of at least 6 carbon atoms optionally
interrupted by one or more heteroatoms selected from N, O and S
providing there are at least 3, preferably at least 4 carbon atoms
for each heteroatom in the chain, Y being linked to said silicon or
phosphorous atom through a carbon atom, and [0038] T represents H
or a terminal groups which is not capable of self-cross-linking
and/or forming covalent bonds to cellulosic and/or proteinaceous
fibres during domestic washing and rinsing cycles; [0039] (ii) a
group of the formula: --R.sup.1--NR.sup.2R.sup.2 (II) [0040] in
which: [0041] R.sup.1 represents an alkylene group of at least 4
carbon atoms, [0042] each R.sup.2 is independently lower alkyl and
--NR.sup.2R.sup.2 is preferably, but need not be, a terminal group;
[0043] (iii) a group of the formula: ##STR1## [0044] in which:
[0045] R.sup.3 represents an alkylene group of at least 3 carbon
atoms, [0046] each R.sup.4 is independently selected from alkyl
groups of from 1 to 25 carbon atoms provided at least one R.sup.4
is lower alkyl of 1 to 16 carbon atoms, [0047] (iv) a group of the
formula ##STR2## [0048] in which each R.sub.1a group is
independently selected from C.sub.1-4 alkyl or hydroxyalkyl groups
or C.sub.2-4 alkenyl groups; [0049] each R.sub.2a group is
independently selected from C.sub.8-28 alkyl or alkenyl groups;
[0050] R.sub.3a is a linear or branched alkylene group of 1 to 5
carbon atoms, [0051] X is ##STR3## [0052] and p is 0 or is an
integer from 1 to 5, with the proviso that one of R.sub.1a and
R.sub.2a is an alkylene group of at least 3 carbon atoms attached
to said silicon or phosphorus atom; [0053] (v) a group of the
formula: ##STR4## in which R.sub.1a, p and R.sub.2a are as defined
above; [0054] (vi) a group of the formula: ##STR5## in which:
[0055] T is as defined above, [0056] R.sup.5 represents a group of
at least one carbon atom, preferably at least 3 carbon atoms, which
may be interrupted by one or more heteroatoms selected from N, O
and S providing there are at least 3 carbon atoms for each
heteroatom, [0057] n is an integer of at least 6; and [0058] (vii)
a group of the formula: ##STR6## in which: [0059] T and R.sup.5 are
as defined above, [0060] each R.sup.6 independently represents an
alkyl group, a fluorinated alkyl group, an amino substituted alkyl
group, an alkyl group substituted with a sugar moiety, or a
sidechain comprising an ethoxylated and/or propoxylated chain, and
[0061] x is an integer of at least 5.
[0062] The organic functional groups are selected to delivery
enhanced lubricating properties compared to corresponding materials
which do not possess the functional groups. When applied to fabrics
the materials provide a lubricating effect reducing the inter-yarn
friction at the yarn/yarn contacts. The effect of the materials can
be assessed by Kawabata shear as discussed hereinafter. The
enhanced lubricating properties may provide improved softness, ease
of ironing, anti-wrinkle, anti-abrasion and related benefits.
[0063] The materials may be used to treat fabric by simply bringing
them in contact with the fabric. The materials are water
dispersible and may be delivered to the fabric in the main wash or
in the rinse conditioner. The lubrication performance delivered by
these materials can exceed the lubrication performance delivered by
conventional rinse conditioner cationic surfactant systems.
[0064] The desired functional groups may be introduced during the
synthesis of the materials, through post-modification of
pre-synthesised functional materials or modification of an existing
clay.
[0065] The present invention involves the use of particles having a
layered structure comprising oxygen atoms and silicon and/or
phosphorus atoms, and comprising organic functional groups which
are bonded to silicon and/or phosphorus atoms in the layers by
direct covalent bonds between the silicon and/or phosphorus atoms
and a carbon atom. The particles tend to be water-insoluble. The
particles are dispersible in water at 20.degree. C. and in some
cases will appear to give solutions as they may break down into
submicron fragments.
[0066] The particles used in the invention are of a size such that
they are not perceived as distinct particles to the touch.
Preferably, the particles used in the invention have an average
size of from 0.01 to 100 .mu.m. More preferably, the particles used
herein have an average size in the range of from about 1 .mu.m to
50 .mu.m. The size of the particles refers to their maximum
dimension, such as their diameter when the particles are
substantially spherical.
[0067] The layered nature of the particles preferably involves an
ordered array comprising oxygen atoms and silicon and/or phosphorus
atoms. The layers may also comprise other metallic and/or
non-metallic atoms. Other atoms which may be present in the layers
include, for example, di- and/or tri-valent metal atoms, such as of
alkaline earth metals (eg, magnesium or calcium), of transition
metals (eg, copper, nickel and/or zirconium), of Group IIIB of the
periodic table (eg, aluminum) or of mixtures thereof. Suitable
particles may comprise discrete, repeating units of layers or
sheets. Layers or sheets are substantially two-dimensional arrays
of atoms. Preferably, the repeating unit consists of a plurality of
(eg, two or three) layers, or sheets, of atoms with a metallic atom
or a mixture of metallic atoms forming the central layer and a
range of non-metallic atoms bridging and/or forming the surrounding
layers. Also present within the repeating unit may be a variety of
atomic, ionic or molecular species, including for example,
polyvalent metal ions such as sodium and/or calcium and/or
hydroxonium ions.
[0068] Suitable examples of layered structures include those
comprising divalent or trivalent metal ions, or a mixture thereof,
in the central layer. Preferably, the central layer comprises
magnesium, nickel or aluminium ions, or mixtures thereof, which are
connected via oxygen atoms and/or hydroxyl groups to the
surrounding layer. Preferably, the surrounding layers comprise a
mixture of silicon atoms and oxygen atoms as well as other cationic
and/or molecular species.
[0069] The interlayer spacing in the particles which are used in
the invention is preferably greater than 10.sup.8.sub.3, more
preferably greater than 12.sup.8.sub.3, as determined by X-ray
crystallography. The interlayer spacing preferably does not exceed
about 100.sup.8.sub.3 and, more preferably, it does not exceed
about 50.sup.8.sub.3.
[0070] When the central layer comprises divalent ions and the outer
layer comprises silicon atoms, with bridging oxygen atoms and
hydroxyl groups, the layered structure is analogous to that of
talc-like smectite, or phyllosilicate clays.
[0071] Smectite clays can broadly be differentiated on the basis of
the number of octahedral metal-oxygen arrangements in the central
layer for a given number of silicon-oxygen atoms in the outer
layer. Those clays featuring primarily divalent metal ions comprise
the prototype talc and the members hectorite, saponite, sauconite
and vermiculite. When the clays feature primarily trivalent metal
ions the structures change and now comprise the prototype
pyrophillite, montmorillonite, nontronite and volchonskoite.
[0072] The particles comprise one or more organic functional
groups. The functional groups in each particle may be a single type
of functional group or a mixture of different types of functional
groups. These organic functional groups can be at least partly
responsible for conferring the desired properties on the fabric,
after treatment with the particles or compositions comprising the
particles.
[0073] The functional groups of formula (I) are preferably long
chain alkyl or alkylene groups preferably having at least 6, or
preferably from 8 to 20 carbon atoms. Alkyl groups are
preferred.
[0074] The terminal group T may be hydrogen or any group which is
not capable of self-cross-linking and/or forming covalent bonds to
cellulose and/or proteinaceous fibres during domestic washing and
rinsing cycles. For enhanced lubrication, there should be no
stiffening of the fabric by the materials crosslinking or bonding
to the fibres. In general, if a terminal group is present, it is
selected to improve the dispersibility of the material. Suitable
groups include alkyl, ether, carboxylic acid, sulphonate, sulphate,
phosphate and phosphinate groups.
[0075] In the groups of formula (II), the amine group is linked via
R.sup.1 which is an alkylene group of at least 4 carbon atoms. At
least 1, preferably both, of the R.sup.2 groups is an alkyl group
of at least 8 carbon atoms.
[0076] The quaternary group of formula (III) is linked via R.sup.3
which represents an alkylene group of at least 3 carbon atoms.
R.sup.3 may have a long chain e.g. up to 20 carbon atoms.
Generally, 1 or 2 of the R.sup.4 groups is lower alkyl e.g. methyl
and the other has a longer chain length e.g. up to 20 carbon atoms.
In one embodiment, two of the R.sup.4 groups are long chain alkyl
groups.
[0077] The groups of formula (IV) and (V) are based upon the
structure of known cationic fabric softening compounds. It is
possible to introduce these groups into the material of the
particles either during synthesis of the material or through
post-modification of a pre-synthesised functional clay.
[0078] Similarly, it is possible to introduce a polyethylene glycol
chain as a functional group as represented by formula (VI) and a
silicone chain as represented by formula (VII). The silicone
backbone may have side chains in a similar manner to known silicone
polymers. Suitable side chains include alkyl groups, perfluro side
chains, side chains having amino functionality, side chains having
sugar moieties and epoxylated and/or propoxylated side chains.
[0079] The materials may comprise a mixture of two or more
functional groups.
[0080] Materials having octyl and dodecyl groups are disclosed in
Ukrainczyk, R. A. Bellman, A. B. Anderson, J. Phys. Chem. B., 1997,
101, 531-539.
[0081] Compounds having the functional groups of formula (II) to
(VII) are believed to be new and form a further aspect of the
invention.
[0082] The particles are preferably of a clay functionalised by the
introduction of organic functional groups during its synthesis. The
organic functional groups may be converted to different organic
functional groups by reaction of the clay, after it has been
synthesised, with an appropriate reagent, to form another clay
which is suitable for use in the present invention. Appropriate
reagents and reaction conditions for the interconversion of
functional groups are well-known to those skilled in the art.
Alternatively, the clay may need no conversion of functional groups
prior to use in the compositions of the invention.
[0083] More preferably, the functionalised particles are of the
general class of inorganic-organic hybrid clays known as an
organo(phyllosilicates). Examples of synthetic methods for forming
organo(phyllosilicates), or organoclays, are described in J. Mater.
Chem., vol. 8, 1998, p 1927-1932, J. Phys. Chem. B. 1997, 101,
531-539, J. Chem. Soc., Chem. Commun., 1995, 241-242 and J. Mater.
Chem. 2000, 10, 1457-1463. In these examples, the organic
functionality is introduced into the clay by assembling a metal
oxide/hydroxide framework in the presence of an
organotrialkoxysilane. The particles of the present invention are
preferably produced according to this method. Therefore, the
particles are preferably obtainable by the hydrolysis of an
organotrialkoxysilane in the presence of at least one di- or
tri-valent metal ion in an alcoholic solution at a suitable pH
appropriate to the metal ion used.
[0084] The skilled person is readily able to determine a suitable
pH for the hydrolysis on the basis of the teaching of the prior
art. For example, for magnesium, the pH is typically greater than 7
and for aluminium it will typically be in the range of from pH 5-12
(preferably from 5.5 to 6.5).
[0085] Other functionalised particles are also suitable for use in
the present invention. For example, metal organophosphates
(including zirconium (which is preferred), titanium, hafnium,
vanadium (V), magnesium (II), manganese (II), calcium (II), cadmium
(II), lanthanum (III), samarium (III), cerium (III) and iron (III))
can be prepared by a precipitation reaction involving mixing a
solution of the metal ion and a solution of an organic phosphoric
or phosphinic acid. Crystallisation of the layered structure
results. Synthetic routes of this type are described, for example,
in Acc. Chem. Res., 1992, 25, 420-427, Chem. Mater. 1994, 6, 2227,
Acc. Chem. Res., 1978, 11, 163 and Chem. Rev., 1988, 88, 55.
Zirconium organophosphates, and other metal organophosphates,
typically comprise, in each layer, a plane of metal atoms linked
together by phosphonate groups. The metal atoms are preferably
octahedrally coordinated by oxygen atoms, with the three oxygen
atoms of each phosphonate tetrahedron bound to three different
metal atoms.
[0086] The preferred particles used in the invention are
organoclays and more preferably three-layer clays consisting of a
central metal-containing layer, as in the analogous talc-like
structures, together with bridging oxygen and hydroxyl groups and
silicon atoms in the outer two layers. Unlike talc, however, the
outer silicon atoms are attached to organic groups as well as
oxygen atoms. Preferably, a high proportion (for example greater
than 50% by number, more preferably greater than 75% by number) of
the Si atoms in any given organoclay particle are covalently bonded
to at least one carbon atom. However, the layered structure may
contain varying amounts of Si atoms that are not covalently bonded
to a carbon atom, and these particles will also operate effectively
within the scope of the invention.
[0087] The organoclays preferably comprise silicon or phosphorus,
oxygen, metal (eg, magnesium, nickel, zirconium or aluminium or
mixtures thereof) and, optionally, hydrogen atoms, in addition to
the organic functional groups and the organic functional groups in
the water insoluble particles.
[0088] Preferred particles of the invention may have the general
formula (without the functional groups)
M.sub.xSi.sub.8-yO.sub.16-3y(OH).sub.4+3y, wherein: [0089] M is Mg,
Ni, Cu or Al [0090] x is 6 when M is Mg, Ni or Cu; and 4 when M is
Al [0091] y is between 0 and 4
[0092] In a particularly preferred example of the invention, the
organoclay may be represented by the formula
Mg.sub.6Si.sub.8R.sub.8O.sub.16(OH).sub.4, with a silicon to
magnesium ratio of 1.33 and where R is any one of the suitable
organic functional groups listed above. Again, the particles are
conveniently functionalised by virtue of a direct Si--C covalent
bond created during the synthesis of the whole material, not by
synthetic post-modification (eg, by grafting onto the surface of a
preformed clay particle); this allows far more organic functional
groups to be incorporated at the surface of, and/or within the
layers of, the particle.
[0093] Treatment of fabric with the fabric treatment compositions
of the invention comprises any step in which the compositions are
applied to fabric.
[0094] Typically, application occurs with the composition in the
form of an aqueous dispersion or suspension. Treatments include
laundering of the fabric.
[0095] The fabric preferably comprises synthetic or non-synthetic
fibres or mixtures thereof. Non-synthetic fibres include, for
example, cellulosic (eg, cotton) or proteinaceous (eg, wool or
silk) fibres. Synthetic fibres include, for example, nylons and
polyesters.
[0096] The invention may also be carried out in non-domestic
environments. For example, the method of the invention may involve
the treatment of fabric (before or after it has been made into
finished articles such as garments) on an industrial scale.
[0097] The particles having a layered structure and comprising one
or more organic functional groups are preferably present in the
fabric treatment composition in an amount of from 0.01% to 50% by
weight of the composition; more preferably they are present in an
amount of from 0.1% to 20% by weight of the composition, most
preferably 0.1-10% by weight of the composition. However, the
particles may be supplied as concentrates e.g. for adding to a
treatment liquor, in which case the particles may be present in
concentrations up to 100%.
[0098] The fabric treatment composition contains one or more
textile compatible carriers.
[0099] The nature of the textile compatible carrier will be
dictated to a large extent by the stage at which the composition of
the invention is used in a laundering process, the compositions
being capable of being used, in principle, at any stage of the
process. For example, where the compositions are for use as main
wash detergent compositions, which is preferred, the one or more
textile compatible carriers comprise a detergent active compound.
Where the compositions are for use in the rinsing step of a
laundering process, the one or more textile compatible carriers may
comprise a fabric softening and/or conditioning compound.
[0100] The compositions of the invention preferably comprise a
perfume, such as of the type which is conventionally used in fabric
care compositions. The compositions may be in the form of packaged
articles which are labelled as being for use in a domestic
laundering process.
[0101] The textile compatible carrier is a component which can
assist in the interaction of the first component with the fabric.
The carrier can also provide benefits in addition to those provided
by the first component e.g. softening, cleaning etc.
[0102] If the composition of the invention is to be used before, or
after, the laundry process it may be in the form of a spray or
foaming product.
[0103] The laundering processes of the present invention include
the large scale and small scale (eg domestic) cleaning of fabrics.
Suitable fabrics include fabrics which are in the form of garments.
Preferably, the processes are domestic.
Detergent Active Compounds
[0104] If the composition of the present invention is in the form
of a detergent composition, the textile-compatible carrier may be
chosen from soap and non-soap anionic, cationic, nonionic,
amphoteric and zwitterionic detergent active compounds, and
mixtures thereof.
[0105] Many suitable detergent active compounds are available and
are fully described in the literature, for example, in
"Surface-Active Agents and Detergents", Volumes I and II, by
Schwartz, Perry and Berch.
[0106] The preferred textile-compatible carriers that can be used
are soaps and synthetic non-soap anionic and nonionic
compounds.
[0107] Anionic surfactants are well-known to those skilled in the
art. Examples include alkylbenzene sulphonates, particularly linear
alkylbenzene sulphonates having an alkyl chain length of
C.sub.8-C.sub.15; primary and secondary alkylsulphates,
particularly C.sub.8-C.sub.15 primary alkyl sulphates; alkyl ether
sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl
sulphosuccinates; and fatty acid ester sulphonates. Sodium salts
are generally preferred.
[0108] Nonionic surfactants that may be used include the primary
and secondary alcohol ethoxylates, especially the C.sub.8-C.sub.20
aliphatic alcohols ethoxylated with an average of from 1 to 20
moles of ethylene oxide per mole of alcohol, and more especially
the C.sub.10-C.sub.15 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).
[0109] Cationic surfactants that may be used include quaternary
ammonium salts of the general formula
R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+ X.sup.- wherein the R groups
are independently hydrocarbyl chains of C.sub.1-C.sub.22 length,
typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is
a solubilising cation (for example, compounds in which R.sub.1 is a
C.sub.8-C.sub.22 alkyl group, preferably a C.sub.8-C.sub.10 or
C.sub.12-C.sub.14 alkyl group, R.sub.2 is a methyl group, and
R.sub.3 and R.sub.4, which may be the same or different, are methyl
or hydroxyethyl groups); and cationic esters (for example, choline
esters) and pyridinium salts.
[0110] The total quantity of detergent surfactant in the
composition is suitably from 0.1 to 60 wt % e.g. 0.5-55 wt %, such
as 5-50 wt %.
[0111] Preferably, the quantity of anionic surfactant (when
present) is in the range of from 1 to 50% by weight of the total
composition. More preferably, the quantity of anionic surfactant is
in the range of from 3 to 35% by weight, e.g. 5 to 30% by
weight.
[0112] Preferably, the quantity of nonionic surfactant when present
is in the range of from 2 to 25% by weight, more preferably from 5
to 20% by weight.
[0113] Amphoteric surfactants may also be used, for example amine
oxides or betaines.
[0114] The compositions may suitably contain from 10 to 70%,
preferably from 15 to 70% by weight, of detergency builder.
Preferably, the quantity of builder is in the range of from 15 to
50% by weight.
[0115] The detergent composition may contain as builder a
crystalline aluminosilicate, preferably an alkali metal
aluminosilicate, more preferably a sodium aluminosilicate.
[0116] The aluminosilicate may generally be incorporated in amounts
of from 10 to 70% by weight (anhydrous basis), preferably from 25
to 50%. Aluminosilicates are materials having the general formula:
0.8-1.5 M.sub.2O. Al.sub.2O.sub.3. 0.8-6 SiO.sub.2 where M is a
monovalent cation, preferably sodium. These materials contain some
bound water and are required to have a calcium ion exchange
capacity of at least 50 mg CaO/g.
[0117] The preferred sodium aluminosilicates contain 1.5-3.5
SiO.sub.2 units in the formula above. They can be prepared readily
by reaction between sodium silicate and sodium aluminate, as amply
described in the literature.
Fabric Softening and/or Conditioner Compounds
[0118] If the composition of the present invention is in the form
of a fabric conditioner composition, the textile-compatible carrier
will be a fabric softening and/or conditioning compound
(hereinafter referred to as "fabric softening compound"), which may
be a cationic or nonionic compound.
[0119] The softening and/or conditioning compounds may be water
insoluble quaternary ammonium compounds. The compounds may be
present in amounts of up to 8% by weight (based on the total amount
of the composition) in which case the compositions are considered
dilute, or at levels from 8% to about 50% by weight, in which case
the compositions are considered concentrates.
[0120] Compositions suitable for delivery during the rinse cycle
may also be delivered to the fabric in the tumble dryer if used in
a suitable form. Thus, another product form is a composition (for
example, a paste) suitable for coating onto, and delivery from, a
substrate e.g. a flexible sheet or sponge or a suitable dispenser
during a tumble dryer cycle.
[0121] Suitable cationic fabric softening compounds are
substantially water-insoluble quaternary ammonium materials
comprising a single alkyl or alkenyl long chain having an average
chain length greater than or equal to C.sub.20 or, more preferably,
compounds comprising a polar head group and two alkyl or alkenyl
chains having an average chain length greater than or equal to
C.sub.14. Preferably the fabric softening compounds have two long
chain alkyl or alkenyl chains each having an average chain length
greater than or equal to C.sub.16. Most preferably at least 50% of
the long chain alkyl or alkenyl groups have a chain length of
C.sub.18 or above. It is preferred if the long chain alkyl or
alkenyl groups of the fabric softening compound are predominantly
linear.
[0122] Quaternary ammonium compounds having two long-chain
aliphatic groups, for example, distearyldimethyl ammonium chloride
and di(hardened tallow alkyl) dimethyl ammonium chloride, are
widely used in commercially available rinse conditioner
compositions. Other examples of these cationic compounds are to be
found in "Surface-Active Agents and Detergents", Volumes I and II,
by Schwartz, Perry and Berch. Any of the conventional types of such
compounds may be used in the compositions of the present
invention.
[0123] The fabric softening compounds are preferably compounds that
provide excellent softening, and are characterised by a chain
melting L.beta. to L.alpha. transition temperature greater than
25.degree. C., preferably greater than 35.degree. C., most
preferably greater than 45.degree. C. This L.beta. to L.alpha.
transition can be measured by DSC as defined in "Handbook of Lipid
Bilayers", D Marsh, CRC Press, Boca Raton, Fla., 1990 (pages 137
and 337).
[0124] Substantially water-insoluble fabric softening compounds are
defined as fabric softening compounds having a solubility of less
than 1.times.10.sup.-3 wt % in demineralised water at 20.degree. C.
Preferably the fabric softening compounds have a solubility of less
than 1.times.10.sup.-4 wt %, more preferably less than
1.times.10.sup.-8 to 1.times.10.sup.-6 wt %.
[0125] Especially preferred are cationic fabric softening compounds
that are water-insoluble quaternary ammonium materials having two
C.sub.12-22 alkyl or alkenyl groups connected to the molecule via
at least one ester link, preferably two ester links. An especially
preferred ester-linked quaternary ammonium material can be
represented by the formula (VIII): ##STR7## wherein each R.sub.1a
group is independently selected from C.sub.1-4 alkyl or
hydroxyalkyl groups or C.sub.2-4 alkenyl groups; each R.sub.2a
group is independently selected from C.sub.8-28 alkyl or alkenyl
groups; and wherein R.sub.3a is a linear or branched alkylene group
of 1 to 5 carbon atoms, X is ##STR8## and p is 0 or is an integer
from 1 to 5.
[0126] Di(tallowoxyloxyethyl) dimethyl ammonium chloride and/or its
hardened tallow analogue is especially preferred of the compounds
of formula (VIII).
[0127] A second preferred type of quaternary ammonium material can
be represented by the formula (IX): ##STR9## wherein R.sub.1a, p
and R.sub.2a are as defined above.
[0128] It is advantageous if the quaternary ammonium material is
biologically biodegradable.
[0129] Preferred materials of this class such as 1,2-bis(hardened
tallowoyloxy)-3-trimethylammonium propane chloride and their
methods of preparation are, for example, described in U.S. Pat. No.
4,137,180 (Lever Brothers Co). Preferably these materials comprise
small amounts of the corresponding monoester as described in U.S.
Pat. No. 4,137,180, for example, 1-hardened
tallowoyloxy-2-hydroxy-3-trimethylammonium propane chloride.
[0130] Other useful cationic softening agents are alkyl pyridinium
salts and substituted imidazoline species. Also useful are primary,
secondary and tertiary amines and the condensation products of
fatty acids with alkylpolyamines.
[0131] The compositions may alternatively or additionally contain
water-soluble cationic fabric softeners, as described in GB 2 039
556B (Unilever).
[0132] The compositions may alternatively or additionally contain
the polyol polyester (eg, sucrose polyester) compounds described in
WO 98/16538.
[0133] The compositions may comprise a cationic fabric softening
compound and an oil, for example as disclosed in EP-A-0829531.
[0134] The compositions may alternatively or additionally contain
nonionic fabric softening agents such as lanolin and derivatives
thereof.
[0135] Lecithins are also suitable softening compounds.
[0136] Nonionic softeners include L.beta. phase forming sugar
esters (as described in M Hato et al Langmuir 12, 1659, 1666,
(1996)) and related materials such as glycerol monostearate or
sorbitan esters. Often these materials are used in conjunction with
cationic materials to assist deposition (see, for example, GB 2 202
244). Silicones are used in a similar way as a co-softener with a
cationic softener in rinse treatments (see, for example, GB 1 549
180).
[0137] The compositions may also suitably contain a nonionic
stabilising agent. Suitable nonionic stabilising agents are linear
C.sub.8 to C.sub.22 alcohols alkoxylated with 10 to 20 moles of
alkylene oxide, C.sub.10 to C.sub.20 alcohols, or mixtures
thereof.
[0138] Advantageously the nonionic stabilising agent is a linear
C.sub.8 to C.sub.22 alcohol alkoxylated with 10 to 20 moles of
alkylene oxide. Preferably, the level of nonionic stabiliser is
within the range from 0.1 to 10% by weight, more preferably from
0.5 to 5% by weight, most preferably from 1 to 4% by weight. The
mole ratio of the quaternary ammonium compound and/or other
cationic softening agent to the nonionic stabilising agent is
suitably within the range from 40:1 to about 1:1, preferably within
the range from 18:1 to about 3:1.
[0139] The composition can also contain fatty acids, for example
C.sub.8 to C.sub.24 alkyl or alkenyl monocarboxylic acids or
polymers thereof. Preferably saturated fatty acids are used, in
particular, hardened tallow C.sub.16 to C.sub.18 fatty acids.
Preferably the fatty acid is non-saponified, more preferably the
fatty acid is free, for example oleic acid, lauric acid or tallow
fatty acid. The level of fatty acid material is preferably more
than 0.1% by weight, more preferably more than 0.2% by weight.
Concentrated compositions may comprise from 0.5 to 20% by weight of
fatty acid, more preferably 1% to 10% by weight. The weight ratio
of quaternary ammonium material or other cationic softening agent
to fatty acid material is preferably from 10:1 to 1:10.
[0140] The fabric conditioning compositions may include silicones,
such as predominately linear polydialkylsiloxanes, e.g.
polydimethylsiloxanes or aminosilicones containing
amine-functionalised side chains; soil release polymers such as
block copolymers of polyethylene oxide and terephthalate;
amphoteric surfactants; smectite type inorganic clays; zwitterionic
quaternary ammonium compounds; and nonionic surfactants.
[0141] The fabric conditioning compositions may be in the form of
emulsions or emulsion precursors thereof.
[0142] Other optional ingredients include emulsifiers, electrolytes
(for example, sodium chloride or calcium chloride) preferably in
the range from 0.01 to 5% by weight, pH buffering agents, and
perfumes (preferably from 0.1 to 5% by weight).
Further Optional Ingredients
[0143] Further optional ingredients in the compositions of the
invention include non-aqueous solvents, perfume carriers,
fluorescers, colourants, hydrotropes, antifoaming agents,
antiredeposition agents, enzymes, optical brightening agents,
opacifiers, dye transfer inhibitors, anti-shrinking agents,
anti-wrinkle agents, anti-spotting agents, germicides, fungicides,
anti-oxidants, UV absorbers (sunscreens), heavy metal sequestrants,
chlorine scavengers, dye fixatives, anti-corrosion agents, drape
imparting agents, antistatic agents, ironing aids, bleach systems,
soil release agents and unmodified smectite clays. This list is not
intended to be exhaustive.
[0144] The compositions of the invention may also include an agent
which produces a pearlescent appearance, e.g. an organic pearlising
compound such as ethylene glycol distearate, or inorganic
pearlising pigments such as microfine mica or titanium dioxide
(TiO.sub.2) coated mica.
[0145] An anti-settling agent may be included in the compositions
of the invention. The anti-settling agent, which reduces the
tendency of solid particles to separate out from the remainder of a
liquid composition, is preferably used in an amount of from 0.5 to
5% by weight of the composition. Organophilic quaternised
ammonium-clay compounds and fumed silicas are examples of suitable
anti-settling agents.
[0146] A further optional ingredient in the compositions of the
invention is a flocculating agent which may act as a delivery aid
to enhance deposition of the active ingredients (such as the water
insoluble particles) onto fabric. Flocculating agents may be
present in the compositions of the invention in amounts of up to
10% by weight, based on the weight of the organoclay. Suitable
flocculating agents include polymers, for example long chain
polymers and copolymers comprising repeating units derived from
monomers such as ethylene oxide, acrylamide, acrylic acid,
dimethylaminoethyl methacrylate, vinyl alcohol, vinyl pyrrolidone,
ethylene imine and mixtures thereof. Gums such as guar gum,
optionally modified, are also suitable for use as flocculating
agents.
[0147] Other possible delivery aids for the particles include, for
example, the water-soluble or water-dispersible rebuild agents (eg,
cellulose monoacetate) described in WO 00/18860.
Fabric Treatment Products
[0148] The composition of the invention may be in the form of a
liquid, solid (e.g. powder or tablet), a gel or paste, spray, stick
or a foam or mousse. Examples including a soaking product, a rinse
treatment (e.g. conditioner or finisher) or a mainwash product. The
composition may also be applied to a substrate e.g. a flexible
sheet or used in a dispenser which can be used in the wash cycle,
rinse cycle or during the dryer cycle.
[0149] The compositions may include adjunct components imparting
other beneficial properties to the products e.g. lubricants, such
as silicones, anti-wrinkling agents, such as lithium salts, and
perfume ingredients, such as cyclodextrins and fragrances.
[0150] The invention will now be described by way of example only
and with reference to the following non-limiting examples. In the
examples and throughout this specification all percentages are
percentages by weight unless indicated otherwise.
[0151] In the following Examples assessment of fabric softeners and
the lubrication effect of the clay additives was assessed by
Kawabata shear as disclosed, for example, in Melliard Testilbericht
67 (1986) pp 509-516. Samples were tested using a Kawabata KES-FBI
machine, Kato Tech Corporation Ltd. Japan. In this machine samples
are laced between two clamps which are movable relative to each
other.
[0152] For each test, six replicas (20 cm square) were used.
[0153] After treatment(s) samples were dried and ironed flat.
[0154] Samples left to condition for 24 hours prior to testing. All
testing was conducted in a test room at 65% r.h. and 20.degree.
C.
[0155] The specimen is subjected to cyclic shear deformation, the
maximum displacement (shear angle) being 8.degree..
[0156] Shear stiffness is highly correlated with the tightness of
fabric construction and the inter-yarn friction at yarn/yarn
contacts. Shear hysteresis is directly related to the size of the
frictional forces operating between yarns and is highly correlated
with perceived softness in some fabric constructions. From the
shear hysteresis loop, the following parameters are obtained.
[0157] G: fabric stiffness in shear. Slope of the hysteresis curve
between 0.5.degree. and 2.5.degree. shear angle-an average of
positive and negative regions of the curve is taken. [0158] 2HG:
width of the hysteresis loop at 0.5.degree. shear angle-average of
values measured at 0.5.degree. and -0.5.degree. is taken. [0159]
2HG5: width of the hysteresis loop at 5.degree. shear angle-average
of values measured at 5.degree. and -5.degree. is taken.
[0160] Comparative softeners/lubrication effect was assessed by
shear hysteresis at 5.degree. shear angle (2HG5). A decrease in
shear hysteresis reflects increased softness/lubrication
performance.
EXAMPLES 1-5
[0161] Standard Synthesis of Magnesium (Organo)Phyllosilicates
[0162] Examples 1 to 5 employed a direct one-step approach, in
which products were precipitated from basic alcoholic solutions.
Typically, magnesium chloride hexahydrate, MgCl.sub.2.6H.sub.2O was
charged to a reaction vessel and ethanol/methanol was added.
Stirring was employed to dissolve the magnesium salt.
Organotrialkoxysilane was added, under rapid stirring, followed
immediately by the addition of sodium hydroxide solution (0.05 M).
The resultant reaction mixture was stirred at room temperature for
a minimum of 1 hour. The product of the reaction was isolated by
filtration or centrifugation and washed with copious water and
ethanol. The products may be retained as a slurry in water, dried
in air or with or without heating, dried under vacuum with or
without heating or freeze-dried.
[0163] The amount of organotrialkoxysilane added in each case was
equal to the stoichiometric amount required to synthesise materials
with Si/Mg=1.33. Molar ratios of approx. Si:Mg:OH=1:0.75:0.90 were
employed in the synthesis.
[0164] The following starting precursors were used in Examples 1 to
5: TABLE-US-00001 Example Organotrialkoxysilane Precursor 1
Octadecyldimethyl(3- trimethoxysilylpropyl)ammonium chloride 2
Hexyltriethoxysilane 3 Octyltriethoxysilane 4
Dodecyltriethoxysilane 5 (3-Glycidoxypropyl)trimethoxysilane
[0165] Example 5 is not a material for use in fabric treatment in
accordance with the invention but is an example of a clay having a
functional group which can be used in a reaction to introduce
functional groups in accordance with the invention.
EXAMPLES 6 TO 8
Alcoholic, Base-Free Synthesis of Magnesium Amino-Containing
(Organo)Phyllosilicates
[0166] Examples 6 to 8 employed an alternative method for
preparation of amino-containing magnesium organoclays employed
base-free, alcoholic conditions. Magnesium chloride hexahydrate,
MgCl.sub.2.6H.sub.2O, was dissolved in ethanol or methanol and
organotrialkoxysilane was added with rapid stirring. Immediate
clouding of the solution followed by copious precipitation ensued
after 5 minutes stirring. The reaction mixture was left stirring at
room temperature for a minimum of 1 hour. The product of reaction
was isolated by filtration and washed thoroughly with ethanol. The
products of the reaction may be redispersed in ethanol or water and
retained as a slurry, dried in air with or without heating, dried
under vacuum with or without heating or freeze-dried.
[0167] The amount of organotrialkoxysilane added in each case was
equal to the stoichiometric amount required to synthesise materials
with Si/Mg=1.33.
[0168] The following starting precursors were used in Examples 6 to
8: TABLE-US-00002 Example Organotrialkoxysilane Precursor 6
3-Aminobutyltriethoxysilane 7 4-Aminobutyltriethoxysilane 8
N-Trimethoxysilylpropyl-N,N,N- trimethylammonium chloride
EXAMPLES 9 TO 16
[0169] The utility of the pendant epoxide group 3-glycidoxypropyl
on the clay of Example 5 (epoxide clay) to post-functionalisation
by nucleophiles was utilised to introduce alternative functional
groups.
EXAMPLE 9
[0170] The epoxide group was initially ring-opened by heating with
an excess of ethylenediamine to give an amine-terminated clay.
After continuous extraction with acetone the dried clay contained
nitrogen by elemental analysis. The prepared amino clay was then
reacted with succinic anhydride to give a clay with an acid
functionality, the FTIR of the clay showed evidence of an amide and
carboxylicacid carbonyl stretch.
EXAMPLES 11 TO 12
[0171] The functionalisation of the epoxide clay with
amino-terminal polyethyleneglycols (Jeffamines) was analogous to
the reaction of the clay with ethylenediamine, whereby the clays
were heated with an excess solution of the oligomeric amines and
exhaustively extracted after functionalisation. The covalent
attachment of the oligomers was shown by the presence of nitrogen
in the elemental analysis. In total three Jeffamine variants were
reacted; two .alpha.,.omega.-diamines with molecular weights of
2,000 (Example 10) and 3,000 (Example 11) and a mono amine with a
molecular weight of 1,000 (Example 12).
EXAMPLES 13 TO 16
[0172] Polydimethylsiloxane (PDMS)-functionalised clays were
prepared via the reaction of the epoxide clays with
.alpha.,.omega.-diamino PDMS (900, 2000 and 3,000 mwts) (Examples
13 to 15) and .alpha.,.omega.-dihydroxy PDMS oligomers. (Example
16). In the case of the diamine simply heating the epoxide clay
with the diamine was sufficient to ring-open the epoxide while the
diol required the use of 1 equivalent of sodium hydride to form the
more nucleophilic alkoxide.
EXAMPLE 17
[0173] Synthesis of clay having the functional group
--C.sub.3(PEG).sub.6-9OCH.sub.3. Magnesium chloride hexahydrate was
charged to a reaction vessel and ethanol or methanol was added.
Stirring was employed to dissolve the magnesium salt. The
organotrialkoxysilane,2-[method(polyethyleneoxy)propyl]trimethoxysilane,
was added under rapid stirring, followed immediately by the
addition of sodium hydroxide solution (0.05M). The reaction mixture
was stirred at room temperature for a minimum of one hour. Ethanol
and methanol were removed from the reaction mixture by rotary
evaporation and the resultant mixture was freeze-dried.
[0174] The amount of organtrialkoxysilane added in the experiment
was equal to the stoichiometric amount required to synthesise
materials with Si/Mg=1.33. Molar ratios of approx.
Si:Mg:OH=1:0.75:0.90 were employed in the synthesis.
EXAMPLE 18
Synthesis of a Mixed Functional Group Clay.
[0175] Magnesium chloride hexahydrate was charged to a reaction
vessel and stirred to dissolution. Two organotrialkoxysilanes were
added under rapid stirring, followed immediately by the addition of
sodium hydroxide solution (0.05M). The resultant reaction mixture
was stirred at room temperature for a minimum of one hour. The
product of the reaction was isolated by filtration and washing with
ethanol. The solid product was dried at room temperature.
[0176] A 50:50 stoichiometric mix of
2-[methoxy(polyethyleneoxy)propyl]trimethoxysilane and
octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride was
used in amounts equal to an overall Si/Mg=1.33 Molar ratios of
approx. Si:Mg:OH=1:0.75:0.90 were employed in the synthesis.
EXAMPLE 19
Delivery of Functionalised Clay from a Liquid Detergent
Composition
[0177] The following detergent composition was used: TABLE-US-00003
Anionic surfactants 20% (Sodium benzylsulfonate + sodium alcohol EO
sulfate) Nonionic surfactant (Alkyl ethoxylate) 5% Sodium citrate
4%
[0178] Minor ingredients: enzymes, enzyme stabilizing systems,
fluorescer, perfumes, water etc to make up to 100%
Washing Procedure
[0179] The following wash conditions were employed:--
TABLE-US-00004 Product Fabric washing liquid formulation (A) 1.69
g/litre Functionalised 0, 2.5, 5 and 10% by weight of clay
formulation (A) Fabric Two swatches of Oxford cotton measuring 40
.times. 40 cm cut into 20 .times. 20 cm squares, total fabric
weight 40 g, the warp direction was marked on each piece with an
indelible pen. Liquor 950 ml of demineralised water and 50 ml of
demineralised water containing the required level of functionalised
clay, overall liquor to cloth ratio 25:1 Apparatus Tergotometer set
at 75 rpm Wash time 15 minutes Wash temperature 35.degree. C. After
wash Fabrics removed, squeezed to remove excess water, and allowed
to drain Rinse 1 litre of demineralised water, liquor to cloth
ratio 25:1, 5 minute rinse Rinse temperature 25.degree. C. Spin
cycle Each set of fabric swatches was spun individually (to avoid
cross contamination) in a spin dryer for 30 seconds. Tumble dry
Each set of fabric swatches was dried individually on normal
setting
Evaluation
[0180] The Oxford cotton pieces were conditioned for 24 hours at
20.degree. C. and 65% RH. The shear hysteresis (2HG5) of 6 fabric
pieces was measured in the centre of each piece in the warp
direction. The average 2HG5 and the standard deviation were
calculated for each treatment. Treatments can only be compared
within the experiment. TABLE-US-00005 Test 1 2 3 4 5 Additives Clay
of Clay of Clay of Clay of Clay of Example 1 Example 8 Example 4
Example 3 Example 6 2HG5 2HG5 2HG5 2HG5 2HG5 Fabric 5.64 6.4 5.78
6.49 6.39 washing liquid formulation (A) Formulation 5.43 5.81 5.75
6.01 6.4 (A) + additive 2.5% Formulation 5.16 5.89 5.76 6.16 5.9
(A) + additive 5% Formulation 5.27 6.16 5.05 6.02 5.87 (A) +
additive 10%
[0181] The results clearly demonstrate a reduction in 2HG5 when
additives of the invention are included in the detergent
composition.
EXAMPLE 20
[0182] Performance of functionalised clays in main wash and rinse
application.
[0183] A simulated wash experiment was carried out. 200 ml local
town's supply water heated to 40.degree. C. Four (20.times.20 cm)
unresinated cotton poplin squares (20 g) added to the Linitest pot.
Washing (with agitation) ensued for 30 minutes. Fabrics were
subjected to two cold water rinses for 5 minutes each rinse.
Fabrics were tumble dried, trimmed to 17.times.17 cm and
conditioned for several hours in a humidity-controlled room.
[0184] The following detergent and fabric conditioning compositions
were used:
[0185] Formulation B: Test Wash Detergent Composition (Granular
Detergent) TABLE-US-00006 Weight % Na-LAS 10 Nonionics 7EO + 3EO 6
Zeolite A4 35 Soda ash 7 Made up to 100% with water
[0186] Formulation C: Fabric Conditioning Formulation: Test
Conditioning Formulation TABLE-US-00007 Weight % HEQ* 11 Coco 20EO
1 Tallow fatty acid 1 Minor ingredients: perfume, stabilisers <5
Deionized water to make up to 100% *(hardened tallowoyloxy)
trimethylammonium propane chloride The following tests were
conducted: 6. 1.0 g Formulation B + 7% smectite clay (QPC 200 g) in
formulation applied in main wash 7. 1.0 g Formulation B added along
with 7% functionalised clay of Example 1 in formulation. 8. 1.0 g
Formulation B added at start of wash. 0.5 mL Formulation C applied
in final rinse to give theoretical maximum active levels of 0.3% on
weight of fabric. 9. 1.0 g Formulation B added at start of wash.
0.06 g functionalised clay of Example 1 added in final rinse.
[0187] Experimental Summary TABLE-US-00008 Main Test wash Final
rinse Granulated Additive (% in Ingredient Shear powder
formulation) (% max on hysteresis, composition weight of 2HG5
fabric) 6 Formulation QPC200G (7%) -- 7.6 (B) 7 Formulation Clay of
-- 7.1 (B) Example 1 (7%) 8 Formulation -- Formulation 6.4 (B) (C)
(0.3%) 9 Formulation B -- Clay of 6.0 Example 1 (0.3%)
[0188] Tests 6 and 7 compare the performance between unmodified
smectite clay against the clay of Example 1 in main wash.
[0189] Tests 8 and 9 compare the performance between a standard
fabric conditioner and the clay of Example 1 in the rinse at
approximately equivalent active levels.
[0190] In each case the presence of the clay in accordance with the
invention provides a significant improvement.
EXAMPLE 21
Performance of Functionalised Clay Delivered from a Fabric Washing
Liquid Formulation
Washing Procedure
Wash Loads:
[0191] 20 Oxford pinpoint cotton 40.times.40 cm monitors (ex.
Textile Innovators-TIC 410) and 20 poplin unresinated cotton
40.times.40 cm monitors (ex. Phoenix Calico) [0192] ballast used to
make the load weight to 2.7 kg (100.times.100 cm woven cotton
pieces) Wash Conditions: [0193] 32.degree. C. wash (12 mins),
6.degree. FH `US` water, 65 litres per wash (US Whirlpool machine)
[0194] 4 loads per treatment; fresh monitors and ballast used for
each wash. [0195] each load tumble dried after every wash for 60
mins (US Whirlpool electric dryer, permanent press/heavy setting)
[0196] loads were removed immediately after the tumble dryer
stopped Treatments: [0197] Formulation A of Example 19 (110 g)
[0198] Formulation A (100 g)+Clay of Example 1 (10 g) [0199]
Formulation A (100 g)+smectite clay (Gelwhite GP) (109)
Evaluation:
[0200] Wrinkle assessments were made after single washes for each
formulation on both poplin and Oxford cotton fabric
constructions.
[0201] Monitors were panelled against an in-house wrinkle scale
ranging from 0-10; where 0 is zero wrinkling and 10 is heavy
wrinkling.
[0202] A selection of washed Oxford and poplin monitors were also
measured using Kawabata shear (a measure of lubrication).
[0203] Results TABLE-US-00009 Average Wrinkle scores (0-10 Average
Kawabata wrinkle scale) scores (2HG5) Oxford Poplin Oxford Poplin
Formulation A 6.0 4.1 6.9 5.8 Formulation 5.9 3.9 6.6 5.7 A +
Gelwhite clay Formulation 5.3 2.6 5.4 5.3 A + Clay of Example 1
Wrinkle Scores:
[0204] The difference between the results for Formulation A and
Formulation A+functionalised clay of the invention when averaged
over all single wash tests was approximately 0.7 units on the 0-10
scale on Oxford cotton monitors and 1.5 scale units on poplin
cotton monitors. Thus, these results clearly demonstrate a
reduction in wrinkling when a functionalised clay of the invention
is included in the detergent composition.
Kawabata Scores:
[0205] Results from Kawabata measurements carried out on monitors
following a single wash illustrate the increased level of
lubrication delivered to fabrics when a fuctionalised clay of the
invention is included in the detergent composition.
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