Note: Descriptions are shown in the official language in which they were submitted.
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USE OF COMPOSITION TO REDUCE WEEPING AND MIGRATION THROUGH A WATER
SOLUBLE FILM
TECHNICAL FIELD
The present invention relates to the use of a composition comprising anionic
surfactant and solvent,
when encapsulated within a water-soluble film, for reducing migration and
weeping of the
composition through the film.
BACKGROUND OF THE INVENTION
Water-soluble unitized dose products have become popular in recent years. The
compositions held
within the water-soluble film must have a controlled amount of water so as not
to preemptively
dissolve the film. Instead of water, unitized dose compositions comprise
solvents to solubilise
ingredients and act as a carrier. In addition to these effects, solvents in
the composition within the
product or within the film, plasticise the film, making it more elastic and
supple. However
depending on the choice of solvent or amount thereof, the Applicants have
found that the solvent
can also negatively affect the film structure and integrity. The Applicants
have found that solvents
can affect whether or not, or the speed of which components of the composition
migrate or weep
through the film. This is particularly a problem where the weeping is
excessive and the pouch takes
on a slimy, unpleasant feeling. Moreover if weeping is too great, the external
surface of the pouch
becomes moist, and premature dissolution of points in the film results in
adjacent pouches sticking
to one another. Furthermore, if the pouch is a multi-compartment pouch
comprising different,
potentially incompatible, compositions in each compartment, then migration of
the composition
from one compartment to another can have other undesirable consequences. For
example, a
migrating component of the composition may deactivate andenzyme or perfume, or
a dye may
colour the other composition, or cause an unwanted reaction. Hence the object
of the present
invention has been to reduce the above problems, by reducing and controlling
the level of weeping
and migration of a composition or components of the composition through the
film.
SUMMARY OF THE INVENTION
According to the present invention there is provided the use of a composition
comprising
a) anionic surfactant; and
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b) solvent system comprising at least one primary solvent having Hansen
solubility (8) of
less than 29, said composition being encapsulated in a water soluble film
pouch, for reducing
migration and weeping of said composition through said film.
DETAILED DESCRIPTION OF THE INVENTION
The present application relates to the use of a composition for controlling
migration and weeping of
a composition through a water soluble film. By the term weeping it is meant
the travel of a
composition, or components of the composition, encapsulated within a water-
soluble film pouch,
from within a pouch to outside the pouch. By the term migration it is meant
weeping from one
compartment of a multi-compartment pouch, to another compartment of the same
pouch.
Plasticization is a term used to describe the elasticity, flexibility and
brittleness of film. A film that
is completely elastic, will recover its original shape once having been
stretched. A film that is
overplasticized tends to gain elasticity, eventually losing rigidity and
becoming floppy.
Eventually, if plasticization continues, the film can become so weak, that it
fails, rips and/or
developing holes. By contrast if a plasticizer is not used, is lost or too
little is used then the film
becomes increasingly brittle over time, which again results in failure.
Plasticizing solvents can be
incorporated into the film on production, indeed this is most often the case,
for ease of processing.
However in addition plasticizing solvent can also be present in the
composition which the film
encapsulates. It is the Applicants belief that incorporating the specific
plasticizing solvents of the
present invention provides a beneficial plasticization of the film, that
encourages the reduction of
migration and weeping.
Detergent Composition
The detergent composition comprises an anionic surfactant and a solvent
system. The solvent
system comprises at least one primary solvent having Hansen solubility (8) of
less than 29.
Anionic Surfactant
The composition of the present invention comprises an anionic surfactant.
Preferably the
composition comprises from 1% to 80% by weight of an anionic surfactant. More
preferably the
composition comprises from 2 to 60%, more preferably from 7 to 50% and most
preferably 10 to
40% anionic surfactant by weight of the composition.
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Useful anionic surfactants can themselves be of several different types. For
example, water-soluble
salts of the higher fatty acids, i.e., "soaps", are useful anionic surfactants
in the compositions herein.
This includes alkali metal soaps such as the sodium, potassium, ammonium, and
alkyl ammonium
salts of higher fatty acids containing from about 8 to about 24 carbon atoms,
and preferably from
about 12 to about 18 carbon atoms. Soaps can be made by direct saponification
of fats and oils or
by the neutralization of free fatty acids. Particularly useful are the sodium
and potassium salts of the
mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or
potassium tallow and
coconut soap.
Additional non-soap anionic surfactants which are suitable for use herein
include the water-soluble
salts, preferably the alkali metal, and ammonium salts, of organic sulfuric
reaction products having
in their molecular structure an alkyl group containing from about 10 to about
20 carbon atoms and a
sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is
the alkyl portion of acyl
groups.) Examples of this group of synthetic surfactants are a) the sodium,
potassium and
ammonium alkyl sulfates, especially those obtained by sulfating the higher
alcohols (C8-C18 carbon
atoms) such as those produced by reducing the glycerides of tallow or coconut
oil; b) the sodium,
potassium and ammonium alkyl polyethoxylate sulfates, particularly those in
which the alkyl group
contains from 10 to 22, preferably from 12 to 18 carbon atoms, and wherein the
polyethoxylate
chain contains from 1 to 15, preferably 1 to 6 ethoxylate moieties; and c) the
sodium and potassium
alkylbenzene sulfonates in which the alkyl group contains from about 9 to
about 15 carbon atoms, in
straight chain or branched chain configuration, e.g., those of the type
described in U.S. Patents
2,220,099 and 2,477,383. Especially preferred are linear straight chain
alkylbenzene sulfonates in
which the average number of carbon atoms in the alkyl group is from about 11
to 13, abbreviated as
C11-C13 LAS, sodium, potassium and ammonium alkyl polyethoxylate sulfates
having from 12 to 18
carbon atoms and mixtures thereof.
Solvent system
The composition of the present invention comprises a solvent system. The
solvent system
comprises at least one primary solvent having Hansen solubility (8) of less
than 29, more preferably
less than 28.5 and preferably greater than 10, more preferably greater than
15.
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The Hansen solubility parameter is a well known and calculated parameter based
on a three
component measuring system. The Hansen solubility parameter is based on a
dispersion force
component (8d), a hydrogen bonding component (8h) and a polar component (p).
The Hansen
solubility parameter (8) is derived from the fact that the total cohesive
energy, which is the energy
required to break all the cohesive bonds, is the combination of the dispersion
forces (d), the
molecular dipole forces (p) and the hydrogen bonding forces (h) according to
the following
equation:
82 = 8,12+ 81,2 8112
8 is achieved by finding the square root of 82
Dispersion forces are weak attractive forces between non-polar molecules. The
magnitude of these
forces depends on the polarizability of the molecule, and the dispersion
hansen solubility parameter
(8d) typically increases with increasing volume (and size) of the molecule,
all other properties being
roughly equal. Hansen solubility parameters are calculated at 25 C, with
ChemSW's molecular
modeling Pro v6.1.9 software package which uses an unpublished proprietary
algorithm that is
based on values published in the Handbook of solubility Parameters and other
parameters by Allan F
M Barton (CRC Press 1983) for solvents obtained experimentally by Hansen.
The primary solvent preferably has molecular weight of less than 1500, more
preferably less than
1000, even more preferably less than 700. The primary solvent preferably has a
molecular weight of
greater than 10, more preferably greater than 100. The primary solvent
preferably has a cLog P of
greater than -1.0 and more preferably less than +10. The primary solvent
preferably has a Hydrogen
bonding component (8h) of less than 20.5, and preferably greater than 10.
The primary solvent is preferably selected from the group consisting of
polyethylene glycol (PEG)
polymer having molecular weight between 300 and 600, dipropylene glycol (DPG),
nbutoxy
propoxy propanol (nBPP) and mixtures thereof. More preferably the primary
solvent is selected
from the group consisting of polyethylene glycol (PEG) polymer having
molecular weight between
400 and 600, dipropylene glycol (DPG), nbutoxy propoxy propanol (nBPP) and
mixtures thereof.
Table 1 shows the Hansen Solubility components of the preferred primary
solvents and some
comparative solvents falling outside of the scope of the invention.
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Solvent 6 Dispersion 6 Polarity 6 H-bonding 6 cLog P
PEG 200 16.54 11.22 20.91 28.9 -1.47
PEG 300 16.23 10.09 20.17 27.8 -1.22
PEG 400 15.81 8.21 19.12 26.1 -0.7
PEG 600 18.98 11.22 20.91 28.9 -0.74
DPG 16.67 10.86 20.35 28.5 -0.6
Propane diol 16.41 10.82 23.07 30.3 -1.1
Glycerol 17.29 12.22 27.34 34.6 -1.94
Sorbitol 19.24 11.5 23.4 32.4 -2.54
nBPP 15.99 5.42 8.91 19.1 +1.99
Table 1: Hansen solubility component parameters
The primary solvent is preferably present at a level of from 1 to 25%,
preferably from 2.5 to 20%,
more preferably from 4 to 19% by weight of the composition.
5
In a preferred embodiment, the solvent system also comprises a secondary
solvent. The secondary
solvent is preferably selected from the group consisting of glycerol, water
and mixtures thereof.
When the secondary solvent comprises glycerol, glycerol is preferably present
at a level of less than
5%, more preferably less than 4%, more preferably less than 3%, most
preferably less than 2% by
weight of the composition. Preferably the glycerol secondary solvent is
present at a level of greater
than 0.1%, more preferably greater than 0.5%, most preferably greater than 1%
by weight of the
composition. The secondary solvent may also comprise water. When water is
present it is
preferably present at a level of less than 20%, more preferably less than 15%,
most preferably less
than 10% by weight of the composition.
In a further preferred embodiment the ratio of primary solvent to secondary
solvent glycerol is from
7:1 to 1:5, more preferably from 6.5:1 to 1:3, most preferably 3:1 to 1:1.
Negatively Charged Hueing Dye
The compositions of the present invention preferably comprise a negatively
charged hueing dye. By
the term negatively charged hueing dye it is meant that the dye residue
comprises a moiety capable
of being negatively charged in the composition. Preferably the composition
will comprise from
0.00001wt% to 0.5wt% of hueing dye.
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Typically the hueing dye provides a blue or violet shade to fabric. Hueing
dyes can be used
either alone or in combination to create a specific shade of hueing and/or to
shade different fabric
types. This may be provided for example by mixing a red and green-blue dye to
yield a blue or
violet shade. Hueing dyes may be selected from any known chemical class of dye
chromophore
including, but not limited to, acridine, anthraquinone (including polycyclic
quinones), azine, azo
(e.g., monoazo, disazo, trisazo, tetrakisazo, polyazo), including
premetallized azo, benzodifurane
and benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine,
diphenylmethane,
formazan, hemicyanine, indigoids, methine, naphthalimides, naphthoquinone,
nitro and nitroso,
oxazine, phthalocyanine, pyrazoles, stilbene, styryl, triarylmethane,
triphenylmethane, xanthenes,
tripehnooxazine and mixtures thereof.
Preferred negatively charged hueing dyes comprise those selected from the
group having
Formula I below.
[D]-[A] n
Formula I
wherein D represents the residue of a dye comprising a chromophore group, and
A is a
moiety selected from the group consisting of OSO3M, SO3M, CO2M, OCO2M, 0P03M2,
OPO3HM
and OPO2M . More preferably A is selected from the group consisting of OSO3M,
503M, CO2M,
and OCO2M. Even more preferably A is selected from the group consisting of
503M and CO2M. M
is any suitable charge balancing counterion. M is preferably selected from the
group consisting of
Hydrogen, an alkali or alkali earth metal ion. More preferably M is selected
from the group
consisting of hydrogen, sodium or potassium ion. The index n is preferably an
integer from 1 to 6,
more preferably from 1 to 4, even more preferably n = 1 or 2.
Typically the dye or mixture of dyes of Formula I will be present in the
composition in an
amount from 0.00001 to 5 wt% of the composition, more usually in an amount
from 0.0001 or from
0.001 to 1 wt% or to 0.5 wt% or to 0.25wt% of the composition.
The dye residue, D, may comprise one or more of any suitable class of
chromophore group.
Suitable chromophore groups include, but are not limited, to any suitable
chromophore, preferably
selected from the group listed above. More preferably the chromophore group is
selected from the
group consisting of benzodifurane, methine, triphenylmethane, azine,
tripehnoxazine,
naphthalimide, pyrazole, naphthoquinone, anthraquinone, mono-azo and bis-azo
and mixtures
thereof. More preferably the dye residue, D, is selected form the group
consisting of Azine,
anthraquinone and azo chromophores may be preferred in some embodiments.
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Preferably the hueing dye is a blue or violet hueing dye, providing a blue or
violet color to a
white cloth or fabric with a hue angle of 240 to 345, more preferably 260 to
325, even more
preferably 270 to 310.
In one aspect, a hueing dye suitable for use in the present invention has, in
the wavelength
range of about 400 nm to about 750 nm, in methanol solution, a maximum
extinction coefficient
greater than about 1000 liter/mol/cm. In one aspect, a hueing dye suitable for
use in the present
invention has, in the wavelength range of about 540 nm to about 630 nm, a
maximum extinction
coefficient from about 10,000 to about 100,000 liter/mol/cm. In one aspect, a
hueing dye suitable for
use in the present invention has, in the wavelength range of about 560 nm to
about 610 nm, a
maximum extinction coefficient from about 20,000 to about 70,000 liter/mol/cm.
Preferred hueing dyes are selected from the group consisting of thiophene azo
carboxylate
dyes having the generalized structure of Formula II:
H3C
CN R1
H3C, N
T R2
NCS
Formula II
wherein R1 and R2 are independently selected from RCH2CR'HO)õ(CH2CR"HO)yQ1, C1-
12 alkyl, C6-
10 aryl, C7-C22 aryl alkyl, with the requirement that at least one of R1 or R2
is
RCH2CWHO),(CH2CR"HO)yQ1, wherein R' is selected from the group consisting of
H, C 1_4 alkyl,
CH20(CH2CH20)zQ, phenyl and ¨CH2OR5;wherein R" is selected from the group
consisting of H,
C 1_4 alkyl, CH20(CH2CH20)zQ, phenyl and CH2OR5; wherein 1 or 2 < x + y < 50,
preferably x +
y < 25, more preferably x + y < 10 ; wherein y? 1; wherein z = 0 or 1 to 20
preferably 0 to 10 or 5;
and wherein Q is selected from the group consisting of H and Y wherein Y is as
defined below; with
the proviso that the dye comprises at least one Q group that is Y;
each R5 is selected from the group consisting of C1-C16 linear or branched
alkyl, C6-C14 aryl and C7-
C16 arylalkyl; preferably R5 is selected from the group consisting of methyl,
ethyl, propyl, isopropyl,
butyl, sec-butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, octyl, decyl,
dodecyl, tetradecyl, hexadecyl,
phenyl, benzyl, 2-phenylethyl, naphthyl and mixtures thereof; and wherein Y is
an organic radical
represented by Formula III
0 R8 R8
CO2M
m n
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Formula III
wherein independently for each Y group, M is H or a charge balancing cation; m
is 0 to 5,
preferably 0, 1, 2 or 3; n is 0 to 5, preferably 0, 1, 2 or 3; the sum of m +
n is 1 to 10, preferably 1, 2
or 3; each R8 is independently selected from the group consisting of H and C3-
18 or C4-C18 or
even C4-7 and/or C9-18 alkenyl, and wherein at least one R8 group is not H.
Such dyes are
discussed in the Applicants co-pending currently unpublished patent
application serial number
US61/598014 (Attorney docket CM3724)
Suitable negatively charged dyes may also be selected from the group
consisting of
carboxylate dyes having the structure of Formula IV:
D-L-0O2M
Formula IV
wherein D is as defined above and L is an organic linking group preferably
having a molecular
weight from 14 to 1000 Daltons, or 14 to 600, or 28 to 300, preferably
consisting essentially only of
C, H and optionally additionally 0 and/or N, and in the sequence of bonds
starting from the
carbonyl carbon of the C(0)0M group and ending at the dye moiety, any -(Ca(0)-
0b)- groups are
incorporated such that the oxygen atom Ob is encountered prior to the carbonyl
carbon Ca .
Preferably L is a C1-20 alkylene chain having optionally therein ether (-0-)
and/or ester and/or amide
links, the chain being optionally substituted for example with ¨OH, ¨CN, -NO2,
-502CH3 ,-C1, -Br;
and M is any suitable counterion, typically hydrogen, sodium or potassium ion.
Such dyes are
discussed in the applicants co-pending patent application, serial number
U561/612539 (Attorney
docket CM3732).
Other dyes suitable for use in the present invention include those described
in the applicants
co-pending patent application, serial number US13/478148 (attorney docket
number 12149) and
WO 2012/054058 Al.
Suitable hueing dyes may also include small molecule dyes and polymeric dyes.
Suitable
small molecule dyes may include small molecule dyes selected from the group
consisting of dyes
falling into the Colour Index (C.I.) classifications of Direct, Basic,
Reactive or hydrolysed Reactive,
Solvent or Disperse dyes for example that are classified as Blue, Violet, Red,
Green or Black, and
provide the desired shade either alone or in combination. In another aspect,
suitable small molecule
dyes may include small molecule dyes selected from the group consisting of
Colour Index (Society
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of Dyers and Colourists, Bradford, UK) numbers Direct Violet dyes such as 9,
35, 48, 51, 66, and
99, Direct Blue dyes such as 1, 71, 80 and 279, Acid Red dyes such as 17, 73,
52, 88 and 150, Acid
Violet dyes such as 15, 17, 24, 43, 49 and 50, Acid Blue dyes such as 15, 17,
25, 29, 40, 45, 75, 80,
83, 90 and 113, Acid Black dyes such as 1, Basic Violet dyes such as 1, 3, 4,
10 and 35, Basic Blue
dyes such as 3, 16, 22, 47, 66, 75 and 159, Disperse or Solvent dyes such as
those described in US
2008/034511 Al or US 8,268,016 B2, or dyes as disclosed in US 7,208,459 B2,
and mixtures
thereof. In another aspect, suitable small molecule dyes may include small
molecule dyes selected
from the group consisting of C. I. numbers Acid Violet 17, Direct Blue 71,
Direct Violet 51, Direct
Blue 1, Acid Red 88, Acid Red 150, Acid Blue 29, Acid Blue 113 or mixtures
thereof.
Suitable polymeric dyes may include polymeric dyes selected from the group
consisting of
polymers containing covalently bound (sometimes referred to as conjugated)
chromogens, (dye-
polymer conjugates), for example polymers with chromogens co-polymerized into
the backbone of
the polymer and mixtures thereof. Polymeric dyes may include those described
in W02011/98355,
US 2012/225803 Al, US 2012/090102 Al, US 7,686,892 B2, and W02010/142503.
In another aspect, suitable polymeric dyes may include polymeric dyes selected
from the
group consisting of fabric-substantive colorants sold under the name of
Liquitint (Milliken,
Spartanburg, South Carolina, USA), dye-polymer conjugates formed from at least
one reactive dye
and a polymer selected from the group consisting of polymers comprising a
moiety selected from
the group consisting of a hydroxyl moiety, a primary amine moiety, a secondary
amine moiety, a
thiol moiety and mixtures thereof. In still another aspect, suitable polymeric
dyes may include
polymeric dyes selected from the group consisting of Liquitint Violet CT,
carboxymethyl
cellulose (CMC) covalently bound to a reactive blue, reactive violet or
reactive red dye such as
CMC conjugated with C.I. Reactive Blue 19, sold by Megazyme, Wicklow, Ireland
under the
product name AZO-CM-CELLULOSE, product code S-ACMC, alkoxylated triphenyl-
methane
polymeric colourants, alkoxylated thiophene polymeric colourants, and mixtures
thereof.
Preferred hueing dyes may include the whitening agents found in WO 08/87497
Al,
W02011/011799 and US 2012/129752 Al. Preferred hueing dyes for use in the
present invention
may be the preferred dyes disclosed in these references, including those
selected from Examples 1-
42 in Table 5 of W02011/011799. Other preferred dyes are disclosed in US
8,138,222. Other
preferred dyes are disclosed in US 7,909,890 B2.
The aforementioned fabric hueing agents can be used in combination (any
mixture of fabric
hueing agents can be used).
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Test Methods
I. Method for Determining Deposition for a Dye
a.) Unbrightened Multifiber Fabric Style 41 swatches (MFF41, 5cm x 10cm,
average
5 weight 1.46g) serged with unbrightened thread are purchased from
Testfabrics, Inc. (West Pittston,
PA). MFF41 swatches are stripped prior to use by washing two full cycles in
AATCC heavy duty
liquid laundry detergent (HDL) nil brightener at 49 C and washing 3 additional
full cycles at 49 C
without detergent. Four replicate swatches are placed into each flask.
b.) A sufficient volume of AATCC standard nil brightener HDL detergent
solution is
10 prepared by dissolving the detergent in 0 gpg water at room temperature
at a concentration of 1.55 g
per liter.
c.) A concentrated stock solution of dye is prepared in an appropriate
solvent selected
from dimethyl sulfoxide (DMSO), ethanol or 50:50 ethanol:water. Ethanol is
preferred. The dye
stock is added to a beaker containing 400mL detergent solution (prepared in
step I.b. above) in an
amount sufficient to produce an aqueous solution absorbance at the Xmax of 0.4
AU (+ 0.01AU) in a
cuvette of path length 1.0 cm. Total organic solvent concentration in a wash
solution from the
concentrated stock solution is less than 0.5%. A 125mL aliquot of the wash
solution is placed into 3
separate disposable 250mL Erlenmeyer flasks (Thermo Fisher Scientific,
Rochester, NY).
d.) Four MFF41 swatches are placed into each flask, flasks are capped and
manually
shaken to wet the swatches. Flasks are placed onto a Model 75 wrist action
shaker from Burrell
Scientific, Inc. (Pittsburg, PA) and agitated on the highest setting of 10
(390 oscillations per minute
with an arc of 14.6 ). After 12 minutes, the wash solution is removed by
vacuum aspiration, 125mL
of Ogpg water is added for a rinse, and the flasks agitated for 4 additional
minutes. Rinse solution is
removed by vacuum aspiration and swatches are spun in a Mini Countertop Spin
Dryer (The
Laundry Alternative Inc., Nashua, NH) for 5 minutes, after which they are
allowed to air dry in the
dark.
e.) L*, a*, and b* values for the 3 most consumer relevant fabric types,
cotton, nylon
and polyester, are measured on the dry swatches using a LabScan XE reflectance
spectrophotometer
(HunterLabs, Reston, VA; D65 illumination, 10 observer, UV light excluded).
The L*, a*, and b*
values of the 12 swatches (3 flasks each containing 4 swatches) are averaged
and the hueing
deposition (HD) of the dye is calculated for each fabric type using the
following equation:
HD = DE* = ((L*c - L*)2 (a*c es)2 (b*c b*)2)1/2
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wherein the subscripts c and s respectively refer to the control, i.e., the
fabric washed in
detergent with no dye, and the fabric washed in detergent containing dye
according to the method
described above.
II. Method to Determine if a Dye is a Shading Dye
A dye is considered a shading dye (also known as a hueing dye) for the
purposes of the
present invention if the HDcotton, HDpolyester or Hpnylon is greater than or
equal to 2.0 DE* units
according to the formula above. If the value of HD for each fabric type is
less than 2.0 DE* units,
the dye is not a shading dye for the purposes of the present invention.
Water-Soluble Film
The film of the present invention is soluble or dispersible in water, and
preferably has a water-
solubility of at least 50%, preferably at least 75% or even at least 95%, as
measured by the method
set out here after using a glass-filter with a maximum pore size of 20
microns:
50 grams 0.1 gram of pouch material is added in a pre-weighed 400 ml beaker
and 245m1
lml of distilled water is added. This is stirred vigorously on a magnetic
stirrer set at 600 rpm, for
30 minutes. Then, the mixture is filtered through a folded qualitative
sintered-glass filter with a
pore size as defined above (max. 20 micron). The water is dried off from the
collected filtrate by any
conventional method, and the weight of the remaining material is determined
(which is the dissolved
or dispersed fraction). Then, the percentage solubility or dispersability can
be calculated.
Preferred film materials are preferably polymeric materials. The film material
can, for example, be
obtained by casting, blow-moulding, extrusion or blown extrusion of the
polymeric material, as
known in the art.
Preferred polymers, copolymers or derivatives thereof suitable for use as
pouch material are selected
from polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides,
acrylamide, acrylic acid,
cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl
acetates, polycarboxylic
acids and salts, polyaminoacids or peptides, polyamides, polyacrylamide,
copolymers of
maleic/acrylic acids, polysaccharides including starch and gelatine, natural
gums such as xanthum
and carragum. More preferred polymers are selected from polyacrylates and
water-soluble acrylate
copolymers, methylcellulose, carboxymethylcellulose sodium, dextrin,
ethylcellulose, hydroxyethyl
cellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylates, and
most preferably
selected from polyvinyl alcohols, polyvinyl alcohol copolymers and
hydroxypropyl methyl cellulose
(HPMC), and combinations thereof. Preferably, the level of polymer in the
pouch material, for
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example a PVA polymer, is at least 60%. The polymer can have any weight
average molecular
weight, preferably from about 1000 to 1,000,000, more preferably from about
10,000 to 300,000 yet
more preferably from about 20,000 to 150,000.
Mixtures of polymers can also be used as the pouch material. This can be
beneficial to control the
mechanical and/or dissolution properties of the compartments or pouch,
depending on the
application thereof and the required needs. Suitable mixtures include for
example mixtures wherein
one polymer has a higher water-solubility than another polymer, and/or one
polymer has a higher
mechanical strength than another polymer. Also suitable are mixtures of
polymers having different
weight average molecular weights, for example a mixture of PVA or a copolymer
thereof of a
weight average molecular weight of about 10,000- 40,000, preferably around
20,000, and of PVA or
copolymer thereof, with a weight average molecular weight of about 100,000 to
300,000, preferably
around 150,000. Also suitable herein are polymer blend compositions, for
example comprising
hydrolytically degradable and water-soluble polymer blends such as polylactide
and polyvinyl
alcohol, obtained by mixing polylactide and polyvinyl alcohol, typically
comprising about 1-35% by
weight polylactide and about 65% to 99% by weight polyvinyl alcohol. Preferred
for use herein are
polymers which are from about 60% to about 98% hydrolysed, preferably about
80% to about 90%
hydrolysed, to improve the dissolution characteristics of the material.
Preferred film materials are polymeric materials. The film material can be
obtained, for
example, by casting, blow-moulding, extrusion or blown extrusion of the
polymeric material, as
known in the art. Preferred polymers, copolymers or derivatives thereof
suitable for use as pouch
material are selected from polyvinyl alcohols, polyvinyl pyrrolidone,
polyalkylene oxides,
acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters,
cellulose amides, polyvinyl
acetates, polycarboxylic acids and salts, polyaminoacids or peptides,
polyamides, polyacrylamide,
copolymers of maleic/acrylic acids, polysaccharides including starch and
gelatine, natural gums
such as xanthum and carragum. More preferred polymers are selected from
polyacrylates and
water-soluble acrylate copolymers, methylcellulose, carboxymethylcellulose
sodium, dextrin,
ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose,
maltodextrin,
polymethacrylates, and most preferably selected from polyvinyl alcohols,
polyvinyl alcohol
copolymers and hydroxypropyl methyl cellulose (HPMC), and combinations
thereof. Preferably, the
level of polymer in the pouch material, for example a PVA polymer, is at least
60%. The polymer
can have any weight average molecular weight, preferably from about 1000 to
1,000,000, more
preferably from about 10,000 to 300,000 yet more preferably from about 20,000
to 150,000.
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Mixtures of polymers can also be used as the pouch material. This can be
beneficial to control the
mechanical and/or dissolution properties of the compartments or pouch,
depending on the
application thereof and the required needs. Suitable mixtures include for
example mixtures wherein
one polymer has a higher water-solubility than another polymer, and/or one
polymer has a higher
mechanical strength than another polymer. Also suitable are mixtures of
polymers having different
weight average molecular weights, for example a mixture of PVA or a copolymer
thereof of a
weight average molecular weight of about 10,000- 40,000, preferably around
20,000, and of PVA or
copolymer thereof, with a weight average molecular weight of about 100,000 to
300,000, preferably
around 150,000. Also suitable herein are polymer blend compositions, for
example comprising
hydrolytically degradable and water-soluble polymer blends such as polylactide
and polyvinyl
alcohol, obtained by mixing polylactide and polyvinyl alcohol, typically
comprising about 1-35% by
weight polylactide and about 65% to 99% by weight polyvinyl alcohol. Preferred
for use herein are
polymers which are from about 60% to about 98% hydrolysed, preferably about
80% to about 90%
hydrolysed, to improve the dissolution characteristics of the material.
Preferred films exhibit good dissolution in cold water, meaning unheated water
straight from the tap.
Preferably such films exhibit good dissolution at temperatures below 25 C,
more preferably below
21 C, more preferably below 15 C. By good dissolution it is meant that the
film exhibits water-
solubility of at least 50%, preferably at least 75% or even at least 95%, as
measured by the method
set out here after using a glass-filter with a maximum pore size of 20
microns, described above.
Preferred films are those supplied by Monosol under the trade references
M8630, M8900, M8779,
M9467, M8310, films described in US 6 166 117 and US 6 787 512 and PVA films
of
corresponding solubility and deformability characteristics. Further preferred
films are those
describes in U52006/0213801, WO 2010/119022 and U56787512.
Preferred water soluble films are those resins comprising one or more PVA
polymers, preferably
said water soluble film resin comprises a blend of PVA polymers. For example,
the PVA resin can
include at least two PVA polymers, wherein as used herein the first PVA
polymer has a viscosity
less than the second PVA polymer. A first PVA polymer can have a viscosity of
at least 8 cP (cP
means Centipoise), 10 cP, 12 cP, or 13 cP and at most 40 cP, 20 cP, 15 cP, or
13 cP, for example in
a range of about 8 cP to about 40 cP, or 10 cP to about 20 cP, or about 10 cP
to about 15 cP, or
about 12 cP to about 14 cP, or 13 cP. Furthermore, a second PVA polymer can
have a viscosity of at
least about 10 cP, 20 cP, or 22 cP and at most about 40 cP, 30 cP, 25 cP, or
24 cP, for example in a
range of about 10 cP to about 40 cP, or 20 to about 30 cP, or about 20 to
about 25 cP, or about 22 to
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about 24, or about 23 cP. The viscosity of a PVA polymer is determined by
measuring a freshly
made solution using a Brookfield LV type viscometer with UL adapter as
described in British
Standard EN ISO 15023-2:2006 Annex E Brookfield Test method. It is
international practice to state
the viscosity of 4% aqueous polyvinyl alcohol solutions at 20 .deg.C. All
viscosities specified herein
in cP should be understood to refer to the viscosity of 4% aqueous polyvinyl
alcohol solution at 20
.deg.C, unless specified otherwise. Similarly, when a resin is described as
having (or not having) a
particular viscosity, unless specified otherwise, it is intended that the
specified viscosity is the
average viscosity for the resin, which inherently has a corresponding
molecular weight distribution.
The individual PVA polymers can have any suitable degree of hydrolysis, as
long as the degree of
hydrolysis of the PVA resin is within the ranges described herein. Optionally,
the PVA resin can, in
addition or in the alternative, include a first PVA polymer that has a Mw in a
range of about 50,000
to about 300,000 Daltons, or about 60,000 to about 150,000 Daltons; and a
second PVA polymer
that has a Mw in a range of about 60,000 to about 300,000 Daltons, or about
80,000 to about
250,000 Daltons.
The PVA resin can still further include one or more additional PVA polymers
that have a viscosity
in a range of about 10 to about 40 cP and a degree of hydrolysis in a range of
about 84% to about
92%.
When the PVA resin includes a first PVA polymer having an average viscosity
less than about 11 cP
and a polydispersity index in a range of about 1.8 to about 2.3, then in one
type of embodiment the
PVA resin contains less than about 30 wt.% of the first PVA polymer.
Similarly, when the PVA
resin includes a first PVA polymer having an average viscosity less than about
11 cP and a
polydispersity index in a range of about 1.8 to about 2.3, then in another,
non-exclusive type of
embodiment the PVA resin contains less than about 30 wt.% of a PVA polymer
having a Mw less
than about 70,000 Daltons.
Of the total PVA resin content in the film described herein, the PVA resin can
comprise about 30 to
about 85 wt.% of the first PVA polymer, or about 45 to about 55 wt.% of the
first PVA polymer. For
example, the PVA resin can contain about 50 wt.% of each PVA polymer, wherein
the viscosity of
the first PVA polymer is about 13 cP and the viscosity of the second PVA
polymer is about 23 cP.
One type of embodiment is characterized by the PVA resin including about 40 to
about 85 wt.% of a
first PVA polymer that has a viscosity in a range of about 10 to about 15 cP
and a degree of
hydrolysis in a range of about 84% to about 92%. Another type of embodiment is
characterized by
the PVA resin including about 45 to about 55 wt.% of the first PVA polymer
that has a viscosity in a
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range of about 10 to about 15 cP and a degree of hydrolysis in a range of
about 84% to about 92%.
The PVA resin can include about 15 to about 60 wt.% of the second PVA polymer
that has a
viscosity in a range of about 20 to about 25 cP and a degree of hydrolysis in
a range of about 84% to
about 92%. One contemplated class of embodiments is characterized by the PVA
resin including
5 about 45 to about 55 wt.% of the second PVA polymer.
When the PVA resin includes a plurality of PVA polymers the PDI value of the
PVA resin is greater
than the PDI value of any individual, included PVA polymer. Optionally, the
PDI value of the PVA
resin is greater than 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2,
3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9,
4.0, 4.5, or 5Ø
Preferably the PVA resin that has a weighted, average degree of hydrolysis ( H
.deg. ) between
about 80 and about 92 %, or between about 83 and about 90 %, or about 85 and
89%. For example,
H .deg. for a PVA resin that comprises two or more PVA polymers is calculated
by the formula
H.deg. = (Wi - H, ) where 1/2 is the weight percentage of the respective PVA
polymer and and H, is
the respective degrees of hydrolysis. Still further it is desirable to choose
a PVA resin that has a
weighted log average viscosity between about 10 and about 25, or between about
12 and 22, or
between about 13.5 and about 20. The .micro. for a PVA resin that comprises
two or more PVA
polymers is calculated - YW - In / by the formula .micro. = e (1 1) where
.micro.11 is the viscosity
for the respective PVA polymers.
Yet further, it is desirable to choose a PVA resin that has a Resin Selection
Index (RSI) in a range of
0.255 to 0.315, or 0.260 to 0.310, or 0.265 to 0.305, or 0.270 to 0.300, or
0.275 to 0.295, preferably
0.270 to 0.300. The RSI is calculated by the formula (w1t1 \.micro.111 - A
I)/.Sigma. ((W)iMi ) >
wherein .micro.1(1 is seventeen, /, is the average viscosity each of the
respective PVA polymers, and
Wi is the weight percentage of the respective PVA polymers.
Even more preferred films are water soluble copolymer films comprising a least
one
anionically modified monomer with formula:
Drl- [Gln
wherein Y represents a vinyl alcohol monomer, G represents a monomer
comprising an anionic
group and index n is an integer of from 1 to 3. G can be any suitable
comonomer capable of
carrying of carrying the anionic group, more preferably G is a carboxylic
acid. G is preferably
selected from the group consisting of maleic acid, itaconic acid, coAMPS,
acrylic acid, vinyl acetic
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acid, vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonic acid, 2
acrylamido 1 methyl propane
sulfonic acid, 2 acrylamido 2 methyl propane sulfonic acid, 2 methyl
acrylamido 2 methyl propane
sulfonic acid and mixtures thereof.
The anionic group of G is preferably selected from the group consisting of
OSO3M, SO3M, CO2M,
OCO2M, 0P03M2, OPO3HM and OPO2M. More preferably anionic group of G is
selected from the
group consisting of OSO3M, 503M, CO2M, and OCO2M. Most preferably the anionic
group of G is
selected from the group consisting of 503M and CO2M.
Naturally, different film material and/or films of different thickness may be
employed in
making the compartments of the present invention. A benefit in selecting
different films is that the
resulting compartments may exhibit different solubility or release
characteristics.
The film material herein can also comprise one or more additive ingredients.
For example, it
can be beneficial to add plasticisers, for example glycerol, ethylene glycol,
diethyleneglycol,
propylene glycol, sorbitol and mixtures thereof. Other additives include
functional detergent
additives to be delivered to the wash water, for example organic polymeric
dispersants, etc.
Unitised Dose Pouch
The pouches described herein may be single or multi-compartment pouch. Where
the pouch is a
multi-compartment pouch, the compartments preferably have a different
aesthetic appearance. A
difference in aesthetics can be achieved in any suitable way. One compartment
of the pouch may be
made using translucent, transparent, semi-transparent, opaque or semi-opaque
film, and the second
compartment of the pouch may be made using a different film selected from
translucent, transparent,
semi-transparent, opaque or semi-opaque film such that the appearance of the
compartments is
different. The compartments of the pouch may be the same size or volume.
Alternatively the
compartments of the pouch may have different sizes, with different internal
volumes. The
compartments may also be different from one another in terms of texture or
colour. Hence one
compartment may be glossy whilst the other is matt. This can be readily
achieved as one side of a
water-soluble film is often glossy, whilst the other has a matt finish.
Alternatively the film used to
make a compartment may be treated in a way so as to emboss, engrave or print
the film. Embossing
may be achieved by adhering material to the film using any suitable means
described in the art.
Engraving may be achieved by applying pressure into the film using a suitable
technique available
in the art. Printing may be achieved using any suitable printer and process
available in the art.
Alternatively, the film itself may be coloured, allowing the manufacturer to
select different coloured
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films for each compartment. Alternatively the films may be transparent or
translucent and the
composition contained within may be coloured. Thus in a preferred embodiment
of the present
invention a first compartment has a colour selected from the group consisting
of white, green, blue,
orange, red, yellow, pink or purple and a second compartment has a different
colour selected from
the group consisting of white, yellow, orange, blue or green.
The compartments of a multi-compartment pouch can be separate, but are
preferably conjoined in
any suitable manner. Most preferably the second and optionally third or
subsequent compartments
are superimposed on the first compartment. In one embodiment, the third
compartment may be
superimposed on the second compartment, which is in turn superimposed on the
first compartment
in a sandwich configuration. Alternatively the second and third, and
optionally subsequent,
compartments may all be superimposed on the first compartment. However it is
also equally
envisaged that the first, second and optionally third and subsequent
compartments may be attached
to one another in a side by side relationship. In a preferred embodiment the
present pouch
comprises three compartments consisting of a large and two smaller
compartments. The second and
third smaller compartments are superposed on the first larger compartment. The
size and geometry
of the compartments are chosen such that this arrangement is achievable. The
compartments may be
packed in a string, each compartment being individually separable by a
perforation line. Hence each
compartment may be individually torn-off from the remainder of the string by
the end-user, for
example, so as to pre-treat or post treat a fabric with a composition from a
compartment.
The geometry of the compartments may be the same or different. In a preferred
embodiment the
second and optionally third or subsequent compartment has a different geometry
and shape to the
first compartment. In this embodiment the second and optionally third
compartments are arranged
in a design on the first compartment. Said design may be decorative,
educative, illustrative for
example to illustrate a concept or instruction, or used to indicate origin of
the product. In a
preferred embodiment the first compartment is the largest compartment having
two large faces
sealed around the perimeter. The second compartment is smaller covering less
than 75%, more
preferably less than 50% of the surface area of one face of the first
compartment. In the
embodiment wherein there is a third compartment, the above structure is the
same but the second
and third compartments cover less than 60%, more preferably less than 50%,
even more preferably
less than 45% of the surface area of one face of the first compartment.
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Process for Making the Pouch Unitized Dose Product
The pouch of the present invention may be made using any suitable equipment
and method. Single
compartment pouches are made using vertical, but preferably horizontal form
filling techniques
commonly known in the art. The film is preferably dampened, more preferably
heated to increase
the malleability thereof. Even more preferably, the method also involves the
use of a vacuum to
draw the film into a suitable mould. The vacuum drawing the film into the
mould can be applied
for 0.2 to 5 seconds, preferably 0.3 to 3 or even more preferably 0.5 to 1.5
seconds, once the film is
on the horizontal portion of the surface. This vacuum may preferably be such
that it provides an
under-pressure of between +10mbar to +1000mbar, more preferably from +100mbar
to +600mbar.
The moulds, in which the pouches are made, can have any shape, length, width
and depth,
depending on the required dimensions of the pouches. The moulds can also vary
in size and shape
from one to another, if desirable. For example, it may be preferred that the
volume of the final
pouches is between 5 and 300m1, or even 10 and 150m1 or even 20 and 100m1 and
that the mould
sizes are adjusted accordingly.
Heat can be applied to the film, in the process commonly known as
thermoforming, by any means.
For example the film may be heated directly by passing it under a heating
element or through hot
air, prior to feeding it onto the surface or once on the surface.
Alternatively it may be heated
indirectly, for example by heating the surface or applying a hot item onto the
film. Most preferably
the film is heated using an infra red light. The film is preferably heated to
a temperature of 50 to
120 C, or even 60 to 90 C. Alternatively, the film can be wetted by any mean,
for example directly
by spraying a wetting agent (including water, solutions of the film material
or plasticizers for the
film material) onto the film, prior to feeding it onto the surface or once on
the surface, or indirectly
by wetting the surface or by applying a wet item onto the film.
Once a film has been heated/wetted, it is drawn into an appropriate mould,
preferably using a
vacuum. The filling of the moulded film can be done by any known method for
filling (preferably
moving) items. The most preferred method will depend on the product form and
speed of filling
required. Preferably the moulded film is filled by in-line filling techniques.
The filled, open
pouches are then closed, using a second film, by any suitable method.
Preferably, this is also done
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while in horizontal position and in continuous, constant motion. Preferably
the closing is done by
continuously feeding a second film, preferably water-soluble film, over and
onto the open pouches
and then preferably sealing the first and second film together, typically in
the area between the
moulds and thus between the pouches.
Preferred methods of sealing include heat sealing, solvent welding, and
solvent or wet sealing. It is
preferred that only the area which is to form the seal, is treated with heat
or solvent. The heat or
solvent can be applied by any method, preferably on the closing material,
preferably only on the
areas which are to form the seal. If solvent or wet sealing or welding is
used, it may be preferred
that heat is also applied. Preferred wet or solvent sealing/ welding methods
include applying
selectively solvent onto the area between the moulds, or on the closing
material, by for example,
spraying or printing this onto these areas, and then applying pressure onto
these areas, to form the
seal. Sealing rolls and belts as described above (optionally also providing
heat) can be used, for
example.
The formed pouches can then be cut by a cutting device. Cutting can be done
using any known
method. It may be preferred that the cutting is also done in continuous
manner, and preferably with
constant speed and preferably while in horizontal position. The cutting device
can, for example, be a
sharp item or a hot item, whereby in the latter case, the hot item 'burns'
through the film/ sealing
area.
The different compartments of a multi-compartment pouch may be made together
in a side-by-side
style and consecutive pouches are not cut. Alternatively, the compartments can
be made separately.
According to this process and preferred arrangement, the pouches are made
according to the process
comprising the steps of:
a) forming an first compartment (as described above);
b) forming a recess within some or all of the closed compartment formed in
step (a), to generate a
second moulded compartment superposed above the first compartment;
c) filling and closing the second compartments by means of a third film;
d) sealing said first, second and third films; and
e) cutting the films to produce a multi-compartment pouch.
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Said recess formed in step b is preferably achieved by applying a vacuum to
the compartment
prepared in step a).
Alternatively the second, and optionally third, compartment(s) can be made in
a separate step and
5 then combined with the first compartment as described in our co-pending
application EP
08101442.5. A particularly preferred process comprises
the steps of:
a) forming a first compartment, optionally using heat and/or vacuum, using a
first film on a first
forming machine;
10 b) filling said first compartment with a first composition;
c) on a second forming machine, deforming a second film, optionally using heat
and vacuum, to
make a second and optionally third moulded compartment;
d) filling the second and optionally third compartments;
e) sealing the second and optionally third compartment using a third film;
15 f) placing the sealed second and optionally third compartments onto the
first compartment;
g) sealing the first, second and optionally third compartments; and
h) cutting the films to produce a multi-compartment pouch
The first and second forming machines are selected based on their suitability
to perform the above
20 process. The first forming machine is preferably a horizontal forming
machine. The second forming
machine is preferably a rotary drum forming machine, preferably located above
the first forming
machine.
It will be understood moreover that by the use of appropriate feed stations,
it is possible to
manufacture multi-compartment pouches incorporating a number of different or
distinctive
compositions and/or different or distinctive liquid, gel or paste
compositions.
Optional Detergent Composition Components
The composition of the present invention is preferably a liquid. By the term
'liquid' it is meant to
include liquid, paste, waxy or gel compositions. The liquid composition may
comprise a solid.
Solids may include powder or agglomerates, such as micro-capsules, beads,
noodles or one or more
pearlised balls or mixtures thereof. Such a solid element may provide a
technical benefit, through
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the wash or as a pre-treat, delayed or sequential release component.
Alternatively it may provide an
aesthetic effect. The compositions of the present invention may comprise one
or more of the
ingredients discussed below.
Surfactants or Detersive Surfactants
The composition of the present invention preferably comprises further
surfactants. The total
surfactant level may be in the range of from about 1% to 80% by weight of the
composition.
Further detersive surfactants utilized can be of the nonionic, zwitterionic,
ampholytic or cationic
type or can comprise compatible mixtures of these types. More preferably
surfactants are selected
from the group consisting of anionic, nonionic, cationic surfactants and
mixtures thereof. Preferably
the compositions are substantially free of betaine surfactants. Detergent
surfactants useful herein
are described in U.S. Patent 3,664,961, Norris, issued May 23, 1972, U.S.
Patent 3,919,678,
Laughlin et al., issued December 30, 1975, U.S. Patent 4,222,905, Cockrell,
issued September 16,
1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980. Anionic
and nonionic
surfactants are preferred.
Preferred nonionic surfactants are those of the formula R1(0C2H4).0H, wherein
R1 is a C10-C16
alkyl group or a C8-C12 alkyl phenyl group, and n is from 3 to about 80.
Particularly preferred are
condensation products of C12-C15 alcohols with from about 5 to about 20 moles
of ethylene oxide
per mole of alcohol, e.g., C12-C13 alcohol condensed with about 6.5 moles of
ethylene oxide per
mole of alcohol.
Fabric Care Benefit Agents
The compositions may comprise a fabric care benefit agent. As used herein,
"fabric care benefit
agent" refers to any material that can provide fabric care benefits such as
fabric softening, color
protection, pill/fuzz reduction, anti-abrasion, anti-wrinkle, and the like to
garments and fabrics,
particularly on cotton and cotton-rich garments and fabrics, when an adequate
amount of the
material is present on the garment/fabric. Non-limiting examples of fabric
care benefit agents
include cationic surfactants, silicones, polyolefin waxes, latexes, oily sugar
derivatives, cationic
polysaccharides, polyurethanes, fatty acids and mixtures thereof. Fabric care
benefit agents when
present in the composition, are suitably at levels of up to about 30% by
weight of the composition,
more typically from about 1% to about 20%, preferably from about 2% to about
10%.
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Detersive enzymes
Detersive enzymes may be incorporated into the compositions of the present
invention. Suitable
detersive enzymes for use herein include protease, amylase, lipase, cellulase,
carbohydrase including
mannanase and endoglucanase, and mixtures thereof. Enzymes can be used at
their art-taught levels,
for example at levels recommended by suppliers such as Novo and Genencor.
Typical levels in the
compositions are from about 0.0001% to about 5%. When enzymes are present,
they can be used at
very low levels, e.g., from about 0.001% or lower, in certain embodiments of
the invention; or they
can be used in heavier-duty laundry detergent formulations in accordance with
the invention at
higher levels, e.g., about 0.1% and higher. In accordance with a preference of
some consumers for
"non-biological" detergents, the present invention includes both enzyme-
containing and enzyme-free
embodiments.
Deposition Aid
Deposition aids may be incorporated into the composition of the present
invention. As used herein,
"deposition aid" refers to any cationic polymer or combination of cationic
polymers that
significantly enhance the deposition of a fabric care benefit agent onto the
fabric during laundering.
Preferably, the deposition aid is a cationic or amphoteric polymer. The
amphoteric polymers of the
present invention will also have a net cationic charge, i.e.; the total
cationic charges on these
polymers will exceed the total anionic charge. Nonlimiting examples of
deposition enhancing
agents are cationic polysaccharides, chitosan and its derivatives and cationic
synthetic polymers.
Preferred cationic polysaccharides include cationic cellulose derivatives,
cationic guar gum
derivatives, chitosan and derivatives and cationic starches.
Rheology Modifier
In a preferred embodiment of the present invention, the composition comprises
a rheology modifier.
The rheology modifier is selected from the group consisting of non-polymeric
crystalline, hydroxy-
functional materials, polymeric rheology modifiers which impart shear thinning
characteristics to
the aqueous liquid matrix of the composition. Crystalline, hydroxy-functional
materials are
rheology modifiers which form thread-like structuring systems throughout the
matrix of the
composition upon in situ crystallization in the matrix. Specific examples of
preferred crystalline,
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hydroxyl-containing rheology modifiers include castor oil and its derivatives.
Especially preferred
are hydrogenated castor oil derivatives such as hydrogenated castor oil and
hydrogenated castor
wax. Commercially available, castor oil-based, crystalline, hydroxyl-
containing rheology modifiers
include THIXCIN from Rheox, Inc. (now Elementis). Polymeric rheology
modifiers are preferably
selected from polyacrylates, polymeric gums, other non-gum polysaccharides,
and combinations of
these polymeric materials. Preferred polymeric gum materials include pectine,
alginate,
arabinogalactan (gum Arabic), carrageenan, gellan gum, xanthan gum, guar gum
and mixtures
thereof.
Builder
The compositions of the present invention may optionally comprise a builder.
Suitable builders
include polycarboxylate builders include cyclic compounds, particularly
alicyclic compounds,
such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635;
4,120,874 and
4,102,903. Particularly preferred are citrate builders, e.g., citric acid and
soluble salts thereof
(particularly sodium salt
Other preferred builders include ethylene diamine disuccinic acid and salts
thereof
(ethylene diamine disuccinates, EDDS), ethylene diamine tetraacetic acid and
salts thereof
(ethylene diamine tetraacetates, EDTA), and diethylene triamine penta acetic
acid and salts
thereof (diethylene triamine penta acetates, DTPA), aluminosilicates such as
zeolite A, B or MAP;
fatty acids or salts, preferably sodium salts, thereof, preferably C12-C18
saturated and/or
unsaturated fatty acids; and alkali or alkali earth metal carbonates
preferably sodium carbonate.
Bleaching System
Bleaching agents suitable herein include chlorine and oxygen bleaches,
especially inorganic
perhydrate salts such as sodium perborate mono-and tetrahydrates and sodium
percarbonate
optionally coated to provide controlled rate of release (see, for example, GB-
A-1466799 on
sulfate/carbonate coatings), preformed organic peroxyacids and mixtures
thereof with organic
peroxyacid bleach precursors and/or transition metal-containing bleach
catalysts (especially
manganese or cobalt). Inorganic perhydrate salts are typically incorporated at
levels in the range
from about 1% to about 40% by weight, preferably from about 2% to about 30% by
weight and
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more preferably from abut 5% to about 25% by weight of composition. Peroxyacid
bleach
precursors preferred for use herein include precursors of perbenzoic acid and
substituted perbenzoic
acid; cationic peroxyacid precursors; peracetic acid precursors such as TAED,
sodium
acetoxybenzene sulfonate and pentaacetylglucose; pernonanoic acid precursors
such as sodium
3,5,5-trimethylhexanoyloxybenzene sulfonate (iso-NOBS) and sodium
nonanoyloxybenzene
sulfonate (NOBS); amide substituted alkyl peroxyacid precursors (EP-A-
0170386); and benzoxazin
peroxyacid precursors (EP-A-0332294 and EP-A-0482807). Bleach precursors are
typically
incorporated at levels in the range from about 0.5% to about 25%, preferably
from about 1% to
about 10% by weight of composition while the preformed organic peroxyacids
themselves are
typically incorporated at levels in the range from 0.5% to 25% by weight, more
preferably from 1%
to 10% by weight of composition. Bleach catalysts preferred for use herein
include the manganese
triazacyclononane and related complexes (US-A-4246612, US-A-5227084); Co, Cu,
Mn and Fe
bispyridylamine and related complexes (US-A-5114611); and pentamine acetate
cobalt(III) and
related complexes (US -A-4810410).
Other adjuncts
Examples of other suitable cleaning adjunct materials include, but are not
limited to; enzyme
stabilizing systems; antioxidants, opacifier, pearlescent agent, hueing dye,
scavenging agents
including fixing agents for anionic dyes, complexing agents for anionic
surfactants, and mixtures
thereof; optical brighteners or fluorescers; soil release polymers;
dispersants; suds suppressors; dyes;
colorants; hydrotropes such as toluenesulfonates, cumenesulfonates and
naphthalenesulfonates;
color speckles; perfumes and perfume microcapsules, colored beads, spheres or
extrudates; clay
softening agents and mixtures thereof.
Composition Preparation
The compositions herein can generally be prepared by mixing the ingredients
together. If a
pearlescent material is used it should be added in the late stages of mixing.
If a rheology modifier is
used, it is preferred to first form a pre-mix within which the rheology
modifier is dispersed in a
portion of the water and optionally other ingredients eventually used to
comprise the compositions.
This pre-mix is formed in such a way that it forms a structured liquid. To
this structured pre-mix can
then be added, while the pre-mix is under agitation, the surfactant(s) and
essential laundry adjunct
materials, along with water and whatever optional detergent composition
adjuncts are to be used.
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Secondary Packaging
The multi-compartment pouches of the present invention are preferably further
packaged in an outer
package. Said outer package may be a see-through or partially see-through
container, for example a
5 transparent or translucent bag, tub, carton or bottle. The pack can be
made of plastic or any other
suitable material, provided the material is strong enough to protect the
pouches during transport.
This kind of pack is also very useful because the user does not need to open
the pack to see how
many pouches there are left. Alternatively, the pack can have non-see-through
outer packaging,
perhaps with indicia or artwork representing the visually-distinctive contents
of the pack.
Process of washing
The pouches of the present invention are suitable for laundry cleaning
applications. The pouches
are suitable for hand or machine washing conditions. When machine washing, the
pouch may be
delivered from the dispensing drawer or may be added directly into the washing
machine drum.
Method for Measuring Weeping
Migration of liquid compounds through the film to the outside of the water
soluble package can be
quantified using a Corneometer CM825 equipped with CM-825 probe, manufactured
by Courage-
Khazaka Electronic, Koln, Germany. The equipment is calibrated according to
the supplier
recommendation. The equipment provides a corneometer value which is recorded.
The
Corneometer can detect even slightest changes in weeping level since change in
the dielectric
constant (i.e. presence of fluid on the outside of the pouch) alters the
Corneometer value.
The equipment is placed in a conditioned laboratory at 20 C +/- 3C and 50% +/-
10 relative
humidity. The pouches are brought to temperature of 20+/- 3C prior to the
measurement. The probe
is cleaned with a dry and clean paper tissue; then blank measurements are made
by slowly wiping
the sensor on the clean paper tissue (VWR International bvba, Leuven, Belgium,
Cat. No. 115-
0600), to ensure there is no contamination on the probe, until the instrument
reads a Corneometer
value of zero. The probe is placed vertically on the pouch, as per the usage
instructions. Ten
replicates are measured for each pouch. The center and corners of the top and
bottom face of the
pouch are tested. Measurement are repeated on 5 different pouches. The data is
thus the average of
50 measurements. The probe is cleaned in between each measurement.
The following table provides an interpretation of the corneometer value for
weeping.
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Weeping classification Corneometer value
Extremely light <50
Very light 50-59
Light 60-64
Light/Medium 65-59
Medium 70-74
Medium/Heavy 75-79
Heavy 80-84
Very heavy 85-89
Extremely heavy >90
10
The following are examples of the present invention. The following detergent
compositions (as set
out below, composition A) were prepared comprising differing combinations and
levels of solvents.
Ingredients A
Linear C9-C15 Alkylbenzene sulfonic acid 18.3
C12-14 alkyl 9-ethoxylate 14.7
Citric Acid 0.7
Fatty acid 6.0
C12-14 alkyl ethoxy 3 sulfate 8.7
Chelant 0.6
Polymer 5.9
Enzymes -
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Structurant 0.15
Solvent system 37.8
neutralize to pH to
Mono-ethanolamine or NaOH (or mixture thereof)
about 7.4
Additives, Minor To 100%
All levels are in weight percent of the composition.
Mono compartment pouches are filled with liquid detergents of composition A,
wherein the solvent
system is selected as below from formulations 1 to 9. The pouches are made
using M8779 film,
available from Monosol using standard thermoforming techniques. Specifically,
0.7g of a 76 pm
thick film M8779 are thermoformed to a single compartment pouch measuring 41mm
by 43 mm.
The pouch is filled with 23.7 mL (25.4 g) of composition A, above.
Example 1
The following solvent system formulations 1 to 4 were prepared comprising
differing combinations
and levels of solvents. The Corneometer value was measured after 4 weeks
storage at 32 C and 80%
relative humidity. Based on the value, the weeping profile is classified.
DPG Water Glycerol Pdiol DEG Corneometer Weeping
level level level level level value classification
Formulation 1
Extremely
(Comparative 0% 6.1% 9.0% 2.7% 19.9% 94
Heavy
example)
Formulation 2 2.7% 6.1% 9.0% 0% 19.9% 85 Very Heavy
Formulation 3 6.9% 10.9% 0% 0% 19.9% 81 Heavy
Formulation 4 8.1% 6.1% 3.6% 0% 19.9% 79 Medium/Heavy
DPG (dipropylene glycol) was supplied by Ineos Manufacturing, Koln, Germany.
The solvent has
an HSP of 28.5 and a clog P of -0.6.
DEG (diethylene glycol) was supplied by Sabic Petrochemicals, Sittard, The
Netherlands.
Glycerol was supplied by Brenntag Sa, Orleans, France.
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Pdiol (propanediol) was supplied by Ineos Manufacturing, Koln, Germany.
Example 2
The following solvent system formulations 2 to5 were prepared comprising
differing combinations
and levels of solvents. The Corneometer value was measured after 4 weeks
storage at 32 C and 80%
relative humidity. Based on the value, the weeping profile is classified.
DPG Water Glycerol Pdiol DEG Corneometer Weeping
level level level level level value classification
Formulation 2 2.7% 6.1% 9.0% 0.0% 19.9% 85 Very Heavy
Formulation 3 6.9% 10.9% 0.0% 0.0% 19.9% 81 Heavy
Formulation 4 8.1% 6.1% 3.6% 0.0% 19.9% 79
Medium/Heavy
Formulation 5 19.9% 6.1% 9.0% 0.0% 2.7% 66
Light/Medium
Example 3
The following solvent system formulations 1, 2, 5 and 7 were prepared
comprising differing
combinations and levels of solvents. The Corneometer value after 4 weeks
storage at 32 C and 80%
relative humidity. Based on the value, the weeping profile is classified.
DPG Water Glycerol Pdiol DEG Corneometer Weeping
level level level level level value classification
Formulation 1
Extremely
(Comparative 0.0% 6.1% 9.0% 2.7% 19.9% 94
Heavy
example)
Formulation 2 2.7% 6.1% 9.0% 0.0% 19.9% 85 Very Heavy
Formulation 6 15.7% 6.1% 9.0% 7.0% 0.0% 79
Medium/Heavy
Formulation 5 19.9% 6.1% 9.0% 0.0% 2.7% 66
Light/Medium
Example 4
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The following solvent system formulations 1 to8 were prepared comprising
differing combinations
and levels of solvents. The Corneometer value was measured after 4 weeks
storage at 32 C and 80%
relative humidity. Based on the value, the weeping profile is classified.
DPG Water Glycerol Pdiol DEG Corneometer Weeping
level level level level level value
classification
Formulation 1
Extremely
(Comparative 0.0% 6.1% 9.0% 2.7% 19.9% 94
Heavy
example)
Formulation 2 2.7% 6.1% 9.0% 0.0% 19.9% 85 Very
Heavy
Formulation 4 8.1% 6.1% 3.6% 0.0% 19.9% 79
Medium/Heavy
Formulation 6 15.7% 6.1% 9.0% 7.0% 0.0% 79
Medium/Heavy
Formulation 5 19.9% 6.1% 9.0% 0.0% 2.7% 66
Light/Medium
Formulation 7 19.9% 6.1% 4.7% 7.0% 0.0% 64 Light
Formulation 3 6.9% 10.9% 0.0% 0.0% 19.9% 81 Heavy
Formulation 8 19.9% 10.9% 0.0% 7.0% 0.0% 59 Very
Light
Example 5
The following solvent system formulations 5, 7, 8 and 9 were prepared
comprising differing
combinations and levels of solvents. The Corneometer value was measured after
4 weeks storage at
32 C and 80% relative humidity. Based on the value, the weeping profile is
classified.
DPG Water Glycerol Pdiol DEG Corneometer
Weeping
level level level level level value
classification
Formulation 9 19.9% 8.8% 9.0% 0.0% 0.0% 72 Medium
Formulation 5 19.9% 6.1% 9.0% 0.0% 2.7% 66
Light/Medium
Formulation 7 19.9% 6.1% 4.7% 7.0% 0.0% 64 Light
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Formulation 8 19.9% 10.9% 0.0% 7.0% 0.0% 59
Very Light
The dimensions and values disclosed herein are not to be understood as being
strictly limited to the
exact numerical values recited. Instead, unless otherwise specified, each such
dimension is intended
to mean both the recited value and a functionally equivalent range surrounding
that value. For
5 example, a dimension disclosed as "40 mm" is intended to mean "about 40
mm."
