TECHNICAL FIELD
[0001] 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
[0002] 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
[0003] According to the present invention there is provided the use of a composition comprising
- a) anionic surfactant; and
- b) solvent system comprising at least one primary solvent having Hansen solubility
(δ) 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
[0004] 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.
[0005] 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.
[0006] 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
[0007] The detergent composition comprises an anionic surfactant and a solvent system. The
solvent system comprises at least one primary solvent having Hansen solubility (δ)
of less than 29.
Anionic Surfactant
[0008] 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.
[0009] 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.
[0010] 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 (C
8-C
18 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 C
11-C
13 LAS, sodium, potassium and ammonium alkyl polyethoxylate sulfates having from 12
to 18 carbon atoms and mixtures thereof.
Solvent system
[0011] The composition of the present invention comprises a solvent system. The solvent
system comprises at least one primary solvent having Hansen solubility (δ) of less
than 29, more preferably less than 28.5 and preferably greater than 10, more preferably
greater than 15.
[0012] 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 (δ
d), a hydrogen bonding component (δ
h) and a polar component (δ
p). The Hansen solubility parameter (δ) 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:

δ is achieved by finding the square root of δ
2
[0013] 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 (δ
d) 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.
[0014] 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 (δ
h) of less than 20.5, and preferably greater than 10.
[0015] 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.
Table 1: Hansen solubility component parameters
| Solvent |
δ Dispersion |
δ Polarity |
δ H-bonding |
δ |
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 |
[0016] 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.
[0017] 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.
[0018] 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
[0019] 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.
[0020] 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.
[0021] 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 OSO
3M, SO
3M, CO
2M, OCO
2M, OPO
3M
2, OPO
3HM and OPO
2M. More preferably A is selected from the group consisting of OSO
3M, SO
3M, CO
2M, and OCO
2M. Even more preferably A is selected from the group consisting of SO
3M and CO
2M. 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.
[0022] 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 1wt% or to 0.5 wt% or to 0.25wt% of the composition.
[0023] 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.
[0024] 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.
[0025] 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.
[0026] Preferred hueing dyes are selected from the group consisting of thiophene azo carboxylate
dyes having the generalized structure of Formula II:

wherein R
1 and R
2 are independently selected from [(CH
2CR'HO)
x(CH
2CR"HO)
yQ], C
1-
12 alkyl, C
6-
10 aryl, C
7-C
22 aryl alkyl, with the requirement that at least one of R
1 or R
2 is [(CH
2CR'HO)
x(CH
2CR"HO)
yQ], wherein R' is selected from the group consisting of H, C
1-
4 alkyl, CH
2O(CH
2CH
2O)
zQ, phenyl and -CH
2OR
5; wherein R" is selected from the group consisting of H, C
1-
4 alkyl, CH
2O(CH
2CH
2O)
zQ, phenyl and CH
2OR
5; 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 R
5 is selected from the group consisting of C
1-C
16 linear or branched alkyl, C
6-C
14 aryl and C
7-C
16 arylalkyl; preferably R
5 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

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)
[0027] Suitable negatively charged dyes may also be selected from the group consisting of
carboxylate dyes having the structure of Formula IV:
D-L-CO
2M 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 O and/or N, and in
the sequence of bonds starting from the carbonyl carbon of the C(O)OM group and ending
at the dye moiety, any -(C
a(O)-O
b)- groups are incorporated such that the oxygen atom O
b is encountered prior to the carbonyl carbon C
a. Preferably L is a C
1-20 alkylene chain having optionally therein ether (-O-) and/or ester and/or amide links,
the chain being optionally substituted for example with -OH, -CN, -NO
2, -SO
2CH
3 ,-Cl, -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
US61/612539 (Attorney docket CM3732).
[0029] 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 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 A1 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.
[0030] 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
WO2011/98355,
US 2012/225803 A1,
US 2012/090102 A1,
US 7,686,892 B2, and
WO2010/142503.
[0031] 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.
[0032] Preferred hueing dyes may include the whitening agents found in
WO 08/87497 A1,
WO2011/0117 and
US 2012/129752 A1. 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
WO2011/01179. Other preferred dyes are disclosed in
US 8,138,222. Other preferred dyes are disclosed in
US 7,909,890 B2.
[0033] The aforementioned fabric hueing agents can be used in combination (any mixture of
fabric hueing agents can be used).
Test Methods
I. Method for Determining Deposition for a Dye
[0034]
- a.) Unbrightened Multifiber Fabric Style 41 swatches (MFF41, 5cm x 10cm, average 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
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 λmax 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 0gpg 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:

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
[0035] A dye is considered a shading dye (also known as a hueing dye) for the purposes of
the present invention if the HD
cotton, HD
polyester or HD
nylon 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
[0036] 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
245ml ± 1ml 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.
[0037] 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.
[0038] 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.
[0039] 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.
[0040] 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. 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.
[0041] 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
US2006/0213801,
WO 2010/119022 and
US6787512.
[0042] 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 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.
[0043] 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%.
[0044] 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.
[0045] 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 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 about 45 to about
55 wt.% of the second PVA polymer.
[0046] 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 5.0.
[0047] 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.[ ] is the
viscosity for the respective PVA polymers.
[0048] 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 (w[t] \.micro.[{] - A |)/.Sigma. ((W)iMi) > wherein .micro.[(] is seventeen,
/, is the average viscosity each of the respective PVA polymers, and Wi is the weight
percentage of the respective PVA polymers.
[0049] Even more preferred films are water soluble copolymer films comprising a least one
anionically modified monomer with formula:
[Y]- [G]
n
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 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.
[0050] The anionic group of G is preferably selected from the group consisting of OSO
3M, SO
3M, CO
2M, OCO
2M, OPO
3M
2, OPO
3HM and OPO
2M. More preferably anionic group of G is selected from the group consisting of OSO
3M, SO
3M, CO
2M, and OCO
2M. Most preferably the anionic group of G is selected from the group consisting of
SO
3M and CO
2M.
[0051] 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.
[0052] 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
[0053] 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 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.
[0054] 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.
[0055] 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.
Process for Making the Pouch Unitized Dose Product
[0056] 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.
[0057] 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 300ml, or even 10 and 150ml
or even 20 and 100ml and that the mould sizes are adjusted accordingly.
[0058] 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.
[0059] 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 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.
[0060] 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.
[0061] 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.
[0062] 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.
[0063] Said recess formed in step b is preferably achieved by applying a vacuum to the compartment
prepared in step a).
[0064] Alternatively the second, and optionally third, compartment(s) can be made in a separate
step and then combined with the first compartment as described in our co-pending application
EP 08101442.5 which is incorporated herein by reference. 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;
- 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;
- 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
[0065] The first and second forming machines are selected based on their suitability to
perform the above 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.
[0066] 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
[0067] 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 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
[0068] 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.
[0069] Preferred nonionic surfactants are those of the formula R
1(OC
2H
4)
nOH, wherein R
1 is a C
10-C
16 alkyl group or a C
8-C
12 alkyl phenyl group, and n is from 3 to about 80. Particularly preferred are condensation
products of C
12-C
15 alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol,
e.g., C
12-C
13 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.
Fabric Care Benefit Agents
[0070] 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%.
Detersive enzymes
[0071] 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
[0072] 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.
[0073] 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
[0074] 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, 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
[0075] 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
[0076] 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
[0077] 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 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
[0078] 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
[0079] 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.
Secondary Packaging
[0080] 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 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
[0081] 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
[0082] 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.
[0083] 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.
[0084] The following table provides an interpretation of the corneometer value for weeping.
| 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 |
[0085] 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 |
- |
| Structurant |
0.15 |
| Solvent system |
37.8 |
| Mono-ethanolamine or NaOH (or mixture thereof) |
neutralize to pH to about 7.4 |
| Additives, Minor |
To 100% |
[0086] All levels are in weight percent of the composition.
[0087] 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 µm 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
[0088] 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 level |
Water level |
Glycerol level |
Pdiol level |
DEG level |
Corneometer value |
Weeping classification |
| Formulation 1 |
0% |
6.1% |
9.0% |
2.7% |
19.9% |
94 |
Extremely |
| (Comparative example) |
|
|
|
|
|
|
Heavy |
| 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.
Pdiol (propanediol) was supplied by Ineos Manufacturing, Koln, Germany. |
Example 2
[0089] The following solvent system formulations 2 to 5 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 level |
Water level |
Glycerol level |
Pdiol level |
DEG level |
Corneometer value |
Weeping 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
[0090] 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 level |
Water level |
Glycerol level |
Pdiol level |
DEG level |
Corneometer value |
Weeping classification |
| Formulation 1 (Comparative example) |
0.0% |
6.1% |
9.0% |
2.7% |
19.9% |
94 |
Extremely Heavy |
| 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
[0091] 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 level |
Water level |
Glycerol level |
Pdiol level |
DEG level |
Corneometer value |
Weeping classification |
| Formulation 1 (Comparative example) |
0.0% |
6.1% |
9.0% |
2.7% |
19.9% |
94 |
Extremely Heavy |
| 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
[0092] 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 level |
Water level |
Glycerol level |
Pdiol level |
DEG level |
Corneometer value |
Weeping 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 |
| Formulation 8 |
19.9% |
10.9% |
0.0% |
7.0% |
0.0% |
59 |
Very Light |
[0093] 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 example, a dimension disclosed as "40
mm" is intended to mean "about 40 mm."
1. The use of a composition comprising
a) anionic surfactant; and
b) solvent system comprising at least one primary solvent having Hansen solubility
(δ) of less than 29, said composition being encapsulated in a water soluble film,
for reducing migration and weeping of said composition through said film.
2. A use according to the preceding claim wherein the primary solvent has molecular weight
of less than 1500, more preferably less than 1000, even more preferably less than
700.
3. A use according to any preceding claim wherein the primary solvent has a cLog P of
greater than -1.0.
4. A use according to any preceding claim wherein the primary solvent has a Hydrogen
bonding component of less than 20.5.
5. A use according to any preceding claim wherein the water soluble film is selected
from those having Formula V:
[Y]- [G]n Formula V
wherein Y represents a vinyl alcohol monomer and G represents a monomer comprising
an anionic group selected from the group consisting of OSO3M, SO3M, CO2M, OCO2M, OPO3M2, OPO3HM and OPO2M and the index is n is from 1 to X.
6. A use according to claim 5 wherein G is selected from the group consisting of carboxylic
acids, more preferably G is selected from the group consisting of maleic acid, itaconic
acid, coAMPS, acrylic acid, vinyl acetic 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.
7. A use according to any preceding claim wherein the anionic surfactant is present at
a level of from 2% to 60%, preferably from 7% to 50%, most preferably from 10% to
40%.
8. A use according to any preceding claim wherein 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.
9. A use according to any preceding claim wherein the primary solvent is present at a
level of from 1 to 25%, preferably from 2.5 to 20%, more preferably from 4 to 19%.
10. A use according to any preceding claim wherein the solvent system additionally comprises
a secondary solvent selected from the group consisting of glycerol, water and mixtures
thereof.
11. A use according to claim 11 wherein the secondary solvent is glycerol and is present
at a level of less than 5%, more preferably less than 4%, most preferably less than
3% by weight of the composition.
12. A use according to claim 11 wherein the secondary solvent is water and is present
at a level of less than 20%, more preferably less than 15%, most preferably less than
10% by weight of the composition.
13. A use according to claims 10 to 12 wherein the ratio of primary solvent to glycerol
is from 7:1 to 1:5, more preferably from 6.5:1 to 1:3, most preferably 3:1 to 1:1.
14. A use according to any preceding claim wherein the composition comprises a hueing
dye.
15. A use according to claim 14 wherein the hueing dye is selected from the group having
Formula I below:
[D]-[A]n Formula I
wherein D represents the residue of a dye comprising a chromophore and A is a moiety
selected from the group consisting of OSO3M, SO3M, CO2M, OCO2M, OPO3M2, OPO3HM and OPO2M, M is selected from the group consisting of Hydrogen, an alkali or alkali earth
metal ion and the index n is an integer from 1 to 6.
16. The use according to claim 15 wherein in formula I, A is selected from the group consisting
of OSO3M, SO3M, CO2M, and OCO2M.
17. The use according to either of claims 15 or 16 wherein M is selected from the group
consisting of hydrogen, sodium or potassium ion.
18. The use according to either of claims 15 to 17 wherein the index n is from 1 to 4,
preferably n is 1 or 2.
19. The use according to any of claims 15 to 18 wherein the chromophore group of dye residue,
D, provides the negatively charged hueing dye with a maximum extinction coefficient
in methanol solution greater than about 1000 liter/mol/cm in the wavelength range
of about 400 nm to about 750 nm, preferably from about 10,000 to 100,000 liter/mol/cm
in the wavelength range of about 540 nm to about 630 nm, even more preferably from
about 20,000 to 70,000 liter/mol/cm in the wavelength range of about 560 nm to about
610 nm.
20. The use according to any of claims 15 to 19 wherein chromophore group of dye residue,
D, 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, azo chromophores and mixtures thereof.