Technical field of the invention
[0001] The present invention relates to water-soluble, liquid-containing pouches, especially
to pouches containing cleaning liquids such as detergents and hard surface cleaners.
More specifically, the invention is directed to water-soluble pouches which exhibit
improved compatibility when used in combination with selected levels of water and
ionic components selected from the group consisting of carboxylates, phosphonates,
and mixtures thereof, and metal salts selected from magnesium salts and calcium salts.
Background of the Invention
[0002] Liquid-filled pouches are known as a convenient form of packaging consumer products
as well as industrial products. The liquid can be provided in premeasured quantities
intended for use as "unit doses". The film enveloping the liquid product, which forms
the wall of the pouch, is soluble in water. A particularly suitable water-soluble
film for this purpose is made from polyvinyl alcohol, and, in this context, this invention
is particularly suited to packaging unit doses of liquid detergent. Commonly known
water-soluble pouches are generally formed by using either a vertical form-fill-seal
(VFFS) or horizontal form-fill-seal (HFFS) processes or by directly thermoforming
water soluble envelopes.
[0003] Liquid products have been packaged in water-soluble films wherein the film is made
from a water-soluble co-polymer comprising vinyl alcohol and carboxylic acid groups.
However most of such water-soluble films exhibit poor compatibility when used in combination
with compositions packed therein and comprising dissolved ionic components selected
from the group consisting of carboxylates, phosphonates, and mixtures thereof. Such
ionic components are desirable in liquid detergents as they generally act as builders
or chelants. The aforementioned incompatibility translates into a substantial solubility
loss of water-soluble pouches made from a film comprising a co-polymer of vinyl alcohol
and a carboxylic acid. This solubility loss which is particularly pronounced upon
prolonged storage of the water-soluble pouches, can lead to water-soluble film polymeric
residues on fabric after the wash.
It is believed that the insolubilization phenomenon is due to the undesirable formation
of lactone rings in and/or on the water-soluble film. The lactone formation which
already takes place in the film comprising a co-polymer of vinyl alcohol and a carboxylic
acid per se, is particularly enhanced when the composition packed within the pouch
comprises dissolved ionic components. It is thought that the presence of such dissolved
ionic components favourizes exchange between the counter-ion associated with the carboxylate
groups in the film and hydrogen ions in the liquid composition, and thus facilitates
the lactone formation. It has further surprisingly been observed that the additional
amount of water, which is generally needed in the detergent composition to stably
dissolve these ionic components, detrimentally exacerbates the effect of ionic components
on the solubility of the water-soluble pouches made from a film comprising a co-polymer
of vinyl alcohol and a carboxylic acid.
[0004] WO 01/79417 discloses a water-soluble package formed from a polymeric film, containing a non-aqueous
liquid composition comprising an ionic ingredient and an excess of a stabilizing compound
which is allegedly effective for reducing the formation of lactones within the film.
US 6,185,410 describes a pouch made of a water-soluble film, containing a liquid composition comprising
a solid builder/chelant and an anionic surfactant.
WO 2004/085586 discloses a water-soluble pouch containing a liquid comprising dissolved ionic components
selected from the group of carboxylates, phosphonates and mixtures thereof, and wherein
the pouch is manufactured from a water-soluble film which has been specifically modified.
[0005] Although the systems described in the prior art provide solutions for achieving improved
compatibility of water-soluble pouches with ionic components, there is still a need
for simpler and cheaper alternative systems.
[0006] It is therefore an objective of the present invention to provide a water-soluble
liquid-containing pouch which exhibits excellent compatibility with dissolved ionic
components selected from the group consisting of carboxylates, phosphonates, and mixtures
thereof, whilst ensuring excellent stability for said dissolved ionic components and
therefore providing improved water solubility of the liquid-containing pouch upon
prolonged storage.
[0007] It has now been found that this objective can be met by providing a liquid-containing
water-soluble pouch comprising dissolved ionic components selected from the group
consisting of carboxylates, phosphonates, and mixtures thereof and metal salts selected
from magnesium salts and calcium salts and wherein said pouch is made by using a horizontal
form-fill-seal process (HFFS) and comprises a liquid composition having a carefully
selected level of water.
[0008] Advantageously, the water-soluble liquid-containing pouch according to the present
invention provides enhanced dissolution and disintegration profiles even after prolonged
storage. Additionally, as the water-soluble pouches of the instant invention provide
stable dissolution of the ionic components, the latter may perform their function
with a significant improvement and fewer amounts of such components may be required.
[0009] A further advantage of the water-soluble pouches according to the present invention
is that they may be manufactured using commercially available water-soluble films
without any further modifications required.
Summary of the Invention
[0010] The present invention encompasses a water-soluble pouch containing a liquid composition
wherein the water-soluble pouch is made from a film comprising a co-polymer of vinyl
alcohol and a carboxylic acid, wherein the liquid composition contained within said
pouch comprises at least one dissolved ionic component selected from the group consisting
of carboxylates, phosphonates and mixtures thereof, and from 5% to 15 % by weight
of the liquid composition of waterand and metal salts select from magnesium salts
and calcium salts, preferably from magnesium salts and wherein said pouch is processed
using a vacuum formed, horizontal form-fill-seal process.
[0011] In another embodiment, the present invention encompasses a process for making a water-soluble
pouch having improved water-solubility upon storage, wherein the process comprises
the steps of (a) formulating a liquid composition comprising at least one dissolved
ionic component selected from the group consisting of carboxylates, phosphonates and
mixtures thereof, and from 5% to 15 % by weight of the liquid composition of waterand
and metal salts select from magnesium salts and calcium salts, preferably from magnesium
salts and (b) processing a film comprising a copolymer of vinyl alcohol and a carboxylic
acid into a water-soluble pouch containing the liquid composition using a vacuum formed,
horizontal form-fill-seal process.
Detailed Description of the Invention
Water-soluble film
[0012] According to the present invention, the water-soluble film comprises a co-polymer
of vinyl alcohol and a carboxylic acid.
Preferably, the level of the co-polymer in the film material, is at least 60% by weight
of the film. The polymer can have any weight average molecular weight, preferably
from 1000 daltons to 1,000,000 daltons, more preferably from 10,000 daltons to 300,000
daltons, even more preferably from 15,000 daltons to 200,000 daltons, most preferably
from 20,000 daltons to 150,000 daltons.
[0013] Preferably, the co-polymer present in the film is from 60% to 98% hydrolysed, more
preferably 80% to 95% hydrolysed, to improve the dissolution of the material.
[0014] In a highly preferred execution, the co-polymer comprises from 0.1 mol% to 30 mol%,
preferably from 1 mol% to 6 mol%, of said carboxylic acid.
[0015] The water-soluble film of the present invention may further comprise additional co-monomers.
Suitable additional co-monomers include sulphonates and ethoxylates. An example of
preferred sulphonic acid is 2-acrylamido-2-methyl-1-propane sulphonic acid (AMPS).
[0016] A suitable water-soluble film for use in the context of the present invention is
commercially available under tradename M8630
™ from Mono-Sol of Indiana, US.
[0017] The water-soluble film herein may also comprise ingredients other than the polymer
or polymer material. For example, it may be beneficial to add plasticisers, for example
glycerol, ethylene glycol, diethyleneglycol, propane diol, 2-methyl-1,3-propane diol,
sorbitol and mixtures thereof, additional water, disintegrating aids, fillers, anti-foaming
agents, emulsifying/dispersing agents, and/or antiblocking agents. It may be useful
that the pouch or water-soluble film itself comprises a detergent additive to be delivered
to the wash water, for example organic polymeric soil release agents, dispersants,
dye transfer inhibitors. Optionally the surface of the film of the pouch may be dusted
with fine powder to reduce the coefficient of friction. Sodium alumino silicate, silica,
talc and amylose are examples of suitable fine powders.
Liquid composition
[0018] The term "liquid" is used herein to broadly include, for example, mixtures, solutions,
dispersions and emulsions, although homogeneous liquids are most preferred. The liquid
may have from low to very high viscosities including gels and pastes. The preferred
viscosity may be up to 10,000 mPa.s, but it is more preferably from 100 to 3000 mPa.s,
and most preferably from 300 to 1500 mPa.s when measured at 20 sec-1 and 21°C. The
liquid may contain active ingredients suitable for various applications. Examples
of such applications are domestic and consumer products, e.g. laundry cleaning and
treatment, dish and hard surface cleaning, shampoo, bath additives; agrochemicals,
e.g. pesticides, herbicides, fungicides, insecticides; industrial chemicals, e.g.
materials used in construction industries, materials used in photography, printing
and textile industries; chemicals for treating water, e.g. swimming pools, water heating
systems, sewage and drainage systems; health and beauty care products, e.g. pharmaceutical
and cosmetic applications. Particularly preferred liquids are suitable for use as
liquid detergents in the cleaning of clothes, dishes, and other household surfaces.
[0019] The liquid composition preferably has a density of 0.8 kg/l to 1.3 kg/l, preferably
about 1.0 to 1.1 kg/l. The liquid composition can be made by any method and can have
any viscosity, typically depending on its ingredients. The viscosity may be controlled,
if desired, by using various viscosity modifiers such as hydrogenated castor oil and/or
solvents. Hydrogenated castor oil is commercially available as Thixcin
®. Suitable solvents are described in more detail below.
[0020] It is preferred that the liquid compositions of the present invention are homogeneous
solutions and, in particular, that the ionic components are dissolved in the homogeneous
liquid.
[0021] The liquid of the present invention preferably has a pH of less than 9, preferably
less than 8, when measured by dissolving the liquid to a level of 1% in demineralized
water..
Ionic components
[0022] The liquid compositions of the present invention comprise at least one dissolved
ionic component selected from the group consisting of carboxylates, phosphonates,
and mixtures thereof Such ionic components may be suitable as builder/chelant actives
used for binding metal ions in aqueous solutions.
In one execution of the present invention, the ionic component is a carboxylate, preferably
a carboxylate builder, even more preferably a polycarboxylate builder. The term carboxylate
as used herein encompasses the acid form of the salt and also encompasses "polycarboxylate"
which refers to compounds having a plurality of carboxylate groups, preferably at
least three carboxylates. Suitable polycarboxylate builder can preferably be added
to the composition in acid form, but can also be added in the form of a neutralized
salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium,
or alkanolammonium salts are preferred.
[0023] Included among the polycarboxylate builders are a variety of categories of useful
materials. One important category of polycarboxylate builders encompasses the ether
polycarboxylates, including oxydisuccinate, as disclosed in
Berg, U.S. Patent 3,128,287, issued April 7, 1964, and
Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of
U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987. Suitable ether polycarboxylates also 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.
[0024] Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers
of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2,
4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal,
ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine
tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic
acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic
acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
[0025] Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium
salt), are polycarboxylate builders of particular importance for heavy duty liquid
detergent formulations due to their availability from renewable resources and their
biodegradability. Oxydisuccinates are also especially useful in such compositions
and combinations.
[0026] Also suitable in the liquid detergent compositions of the present invention are the
3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in
U.S. Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the C
5-C
20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound
of this type is dodecenylsuccinic acid. Specific examples of succinate builders include:
laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred),
2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders
of this group, and are described in
EP-A-0 200 263, published November 5, 1986.
[0027] Specific examples of nitrogen-containing, phosphor-free aminocarboxylates 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).
[0028] Other suitable polycarboxylates are disclosed in
U.S. Patent 4,144,226, Crutchfield et al, issued March 13, 1979 and in
U.S. Patent 3,308,067, Diehl, issued March 7, 1967. See also
Diehl U.S. Patent 3,723,322. Such materials include the water-soluble salts of homo-and copolymers of aliphatic
carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid,
aconitic acid, citraconic acid and methylenemalonic acid.
[0029] In another execution of the present invention, the ionic component is a phosphonate
component. The term phosphonate as used herein encompasses the acid form of the salt.
Suitable phosphonates for use in the present invention may be selected from the group
of inorganic and organic phosphonates.
[0030] In a preferred embodiment, the phosphonate is selected from organic phosphonates.
Examples of suitable organic phosphonates for use herein are amino alkylene poly (alkylene
phosphonates), alkali metal ethane 1-hydroxy bisphosphonates and nitrilo trimethylene
phosphonates. Preferred organic phosphonates for use herein are diethylene triamine
penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene
diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate (HEDP).
In the context of the present invention, HEDP is highly preferred.
[0031] Preferably, said at least one ionic component may be incorporated at a level of from
0.2% to 4.0%, preferably from 0.5% to 3.0%, more preferably from 0.5% to 2.0% by weight
of the liquid composition.
Water content
[0032] Although the liquid compositions of the present invention are concentrated compositions,
they still contain some amount of water.
[0033] The liquid composition contained within the water-soluble liquid-containing pouches
according to the present invention shall, as a first essential requirement, comprise,
with increasing preference in the order given, from 5%, 6%, 7%, 8%, 9% to, with increasing
preference in the order given, 15 %, 14%, 13%, 12%, 11%, 10% by weight of the liquid
composition, of water.
[0034] More specifically, the liquid composition contained within the water-soluble liquid-containing
pouch according to the present invention, shall comprise from 5% to 15%, preferably
from 6% to 12 %, more preferably from 7% to 10%, most preferably from 8% to 10% by
weight of the liquid composition, of water.
[0035] It has been surprisingly found that when the water content of the liquid composition
is maintained within the range of from 5% to 15%, preferably from 6% to 12 %, more
preferably from 7% to 10%, most preferably from 8% to 10% by weight of the liquid
composition, an optimized and stable dissolution of the ionic components selected
from the group consisting of carboxylates, phosphonates, and mixtures thereof is obtained.
Horizontal form-fill-seal process
[0036] As a second essential requirement, the water-soluble liquid-containing pouches according
to the present invention shall be processed using a vacuum formed, horizontal form-fill-seal
process (HFFS).
Pouches according to the present invention may be processed according to any of the
horizontal form-fill-seal methods commonly know in the art. A suitable method is described
for example in
WO 02/60758.
[0037] A suitable HFFS process to form the water-soluble liquid-containing pouches of the
present invention is a continuous process comprising the steps of: (a) continuously
feeding a first water-soluble film onto a horizontal portion of a continuously and
rotatably moving endless surface, which comprises a plurality of moulds; (b) forming
from the film on the horizontal portion of the continuously moving surface, and in
the moulds on the surface, a continuously moving, horizontally positioned web of open
pouches, by application of a vacuum through the bottom of the moulds onto the film;
(c) filling the continuously moving, horizontally positioned web of open pouches with
a liquid, to obtain a horizontally positioned web of open, filled pouches; (d) continuously
closing the web of open pouches, to obtain closed pouches, by feeding a second water-soluble
film onto the horizontally positioned web of open, filed pouches; and (e) heat sealing
the closed pouches.
[0038] Alternatively, step (e) above may be performed by solvent welding (as described in
WO 03/008486), and solvent or wet sealing.
[0039] While using a vacuum formed, horizontal form-fill-seal process, the first water-soluble
film will typically have a thickness of from 20µm to 100 µm before thermoforming.
[0040] It has been surprisingly found that when water-soluble pouches containing a liquid
composition comprising from 5% to 15%, preferably from 6% to 12 %, more preferably
from 7% to 10%, most preferably from 8% to 10% by weight of the liquid composition
of water and comprising at least one dissolved ionic component selected from the group
consisting of carboxylates, phosphonates and mixtures thereof, are processed using
a vacuum formed, horizontal form-fill-seal process, significantly improved water solubility
of the liquid-containing pouch upon storage is obtained.
Enhanced water-solubility of the pouches according to the present invention is clearly
observed over similar pouches manufactured using alternative pouchproducing methods
commonly know in the art, such as for example vertical form-fill-seal process. The
improvement in water solubility is particularly noticeable after several weeks storage
of the liquid-containing pouch.
[0041] The liquid composition also comprises metal salts selected from magnesium salts and
calcium salts, preferably from magnesium salts. Without being bound by any theory,
it is believed that such metal salts further contribute in obtaining stable dissolution
of the ionic components into the liquid composition contained within the water-soluble
pouches according to the invention. The metals salts are selected from the group of
magnesium salts and calcium salts. Particularly preferred salts are magnesium chloride,
magnesium sulphate, magnesium sulfite and magnesium bisulfite. Magnesium chloride
is a highly preferred salt in the context of the present invention. However the Applicant
has found that chloride ions, especially at high temperatures, can have long term
detrimental effects on the manufacturing equipment. In this case the most preferred
metal salt is magnesium bisulfite. The use of magnesium bisulfite brings further advantages
as well. Potassium sulfite provides a known benefit of improving the aesthetics of
a composition upon ageing. The use of magnesium bisulfite, allows the detergent manufacturer
to gain two benefits from one ingredient. Magnesium stabilizes the dissolved ionic
component and the bisulfite provides the aesthetic benefit described above:
Preferably, the liquid composition comprises less than about 1%, more preferably less
than 0.5%, most preferably less than 0.3% by weight of the composition, of the metal
salts.
Preferred optional ingredients of the liquid composition
[0042] If the liquid composition is a detergent composition, it is preferred that at least
a surfactant and/or a builder be present, preferably at least an anionic surfactant
and preferably also a nonionic surfactant, and preferably at least a builder, more
preferably at least a water-soluble builder such as phosphate builder and/or fatty
acid builder. Other preferred components are enzymes and/or bleaching agents, such
as a preformed peroxyacid.
[0043] Other preferred optional ingredients are also perfume, brightener, buffering agents,
fabric softening agents, including clays and silicones, benefit agents, and suds suppressors.
[0044] In hard-surface cleaning compositions and dish wash compositions, it is preferred
that at least a water-soluble builder is present, such as a phosphate, and preferably
also surfactant, perfume, enzymes, bleach.
[0045] In fabric enhancing compositions, preferably at least a perfume and a fabric benefit
agent are present for example a cationic softening agent, silicone softening agent
or clay softening agent, anti-wrinkling agent, fabric substantive dye.
[0046] Other highly preferred optional ingredients in all above compositions are also solvents,
such as alcohols, diols, monoamine derivatives, glycerol, glycols, polyalkylane glycols,
such as polyethylene glycol, propane diol, monoethanolamine. Highly preferred are
mixtures of solvents, such as mixtures of alcohols, or mixtures of diols and alcohols.
Highly preferred may be that (at least) an alcohol, a diol, or monoethanolamine and
preferably even glycerol be present in the composition. The compositions of the invention
are preferably concentrated liquids having preferably less than 50% or even less than
40% by weight of solvent (other than water), preferably less than 30% or even less
than 20% by weight of solvent (other than water). Preferably the solvent is present
at a level of at least 5% or even at least 10% or even at least 15% by weight of the
composition.
[0047] Highly preferred is that the composition comprises a plasticiser for the water-soluble
pouch material, for example one of the plasticisers described above, for example glycerol.
Such plasticisers can have the dual purpose of being a solvent for the other ingredients
of the composition and a plasticiser for the pouch material.
[0048] Further highly preferred ingredients are other ionic ingredients selected from the
group of polycarboxylated polymers (such as polyacrylic acid, polyacrylic-maleic acid
copolymers), cationic ethoxylated amines, zwiterrionic polymers (such as those described
in
EP patent application No. 04447256), anionic soil release polymers.
[0049] In another embodiment of the present invention, it is provided a process for making
a water-soluble pouch having improved water-solubility upon storage, comprising the
steps of (a) formulating a liquid composition comprising at least one dissolved ionic
component selected from the group consisting of carboxylates, phosphonates and mixtures
thereof, and from 5% to 15 % by weight of the liquid composition of water, and (b)
processing a film comprising a copolymer of vinyl alcohol and a carboxylic acid into
a water-soluble pouch containing said liquid composition, using a vacuum formed, horizontal
form-fill-seal process.
Test Method
Polymer Residue Grading Test
[0050] In order to assess the in-wash solubility of liquid detergent pouches, the so-called
"Black Pouch Solubility Method" has been developed. The method provides a relative
assessment of the solubility of liquid detergent pouches under specified consumer
relevant conditions. Data are generated by visual grading of PVA residues, relative
to a defined grading scale.
[0051] Equipment needed: 4 Miele washing machines type W467, connected to a water temperature control system
and 16 black velvet pouches made by folding and stitching a piece of black velvet
(23.5 x 47 cm) with the velvet on the inside. The fabric used is Black Cotton Pie
Velvet, quality 8897, commercially available from Denholme Velvets, Denholme, England.
[0052] Preparation of the Test: Liquid detergent-containing PVA pouches (at recommended dosage for normal conditions)
are added, in a standardized way, inside the black velvet pouches. The resulting black
pouches are thereafter closed by stitching. Each of the 4 washing machines is loaded
with 4 black pouches in a standardized way. Different liquid detergent pouches may
be added into a single washing machine, however at least 4 external replicates for
each of the products are needed.
[0053] Test conditions: wool wash program at 40°C, using city water of 14°C +/- 1°C via the water temperature
control system.
[0054] Visual grading: At the end of the washing cycle, the black pouches are opened and visual grading
of the polymer residues on fabric is immediately performed by at least 2 persons,
according to a pre-defined grading scale. The overall grade is a statistical average
of the different replicates. The grading scale ranges from 0, meaning no noticeable
PVA residues on fabric after the wash, to 7, meaning that substantially no PVA pouch
is noticeably dissolved. In the context of the present test, good pouch dissolution
is obtained for a score below 3. A score of 3 means that no opaque PVA residues with
a largest average diameter greater than 2 cm are visible on fabric after the wash.
Ideally, the score should be as low as possible.
Examples
[0055] The following examples will further illustrate the present invention. The compositions
are made by combining the listed ingredients in the listed proportions (weight % unless
otherwise specified). Example compositions 1 to 4 are meant to exemplify compositions
according to the present invention but are not necessarily used to limit or otherwise
define the scope of the present invention.
Ingredients: (% by weight) |
1 |
2* |
3 |
4* |
Dodecylbenzene sulphonic acid |
21 |
23 |
19 |
25 |
C12-14 alcohol, ethoxylated |
21 |
19 |
22 |
18 |
C8-C10 amido propyl dimethylamine |
1.1 |
- |
- |
- |
Citric acid |
1.7 |
2.0 |
- |
1.7 |
C12-C18 alkyl fatty acid |
14 |
15 |
18 |
14 |
Hydroxyethane diphosphonic acid |
0.75 |
0.45 |
0.90 |
- |
Diethylene Triamine Penta methylene phosponic acid |
- |
- |
- |
0.41 |
Protease/amylase enzymes |
1.6 |
1.6 |
1.6 |
1.6 |
Magnesium chloride |
0.10 |
- |
0.11 |
- |
Potassium sulfite |
0.12 |
0.14 |
0.16 |
- |
Polyethyleneimine, 20x ethoxylated |
1.3 |
1.3 |
1.6 |
1.3 |
Zwitterionic polyamine |
2.5 |
1.2 |
2.8 |
2.5 |
Optical brightener |
0.22 |
0.21 |
0.22 |
0.19 |
Hydrogenated castor oil |
0.21 |
0.20 |
0.21 |
- |
Propylene Glycol |
4.0 |
5.2 |
7.0 |
15 |
Glycerine |
9.5 |
7.5 |
7.5 |
- |
Polydimethylsiloxane |
- |
2.0 |
- |
- |
Monoethanolamine |
9.8 |
10.7 |
9.0 |
10.6 |
Perfume, dyes, minors, Sodium hydroxide |
2.4 |
2.4 |
2.4 |
2.2 |
Water |
8.7 |
8.1 |
7.5 |
7.5 |
[0056] Dodecylbenzene sulphonic acid is commercially available from Ifrachem.
C12-14 alcohol, 7x ethoxylated is commercially available from Sasol.
C8-C10 amido propyl dimethylamine is commercially available from Akzo Nobel Chemicals
LTD.
Citric acid is commercially available from Citrique Belge NV.
C12-C18 alkyl fatty acid is commercially available from Akzo Nobel Chem. GMBH.
Hydroxyethane diphosphonic acid is commercially available from Solutia Europe NV.
Diethylene Triamine Penta methylene phosponic acid is commercially available from
Albright & Wilson LTD.
[0057] Enzymes are proteolitic and amylolytic enzyme solutions commercially available from
respectively Genencor and Novozymes.
Magnesium chloride is commercially available from Nedmag.
Potassium sulfite is commercially available from BASF.
Polyethyleneimine ethoxylate PEI600 E20, is commercially available from BASF.
Zwitterionic polyamine is Lutensit Z96
™, commercially available from BASF.
Optical brightener is disodium 4,4'-bis-(2-sulphostyryl) biphenyl, commercially available
from Ciba AG.
Hydrogenated castor oil is commercially available from Brazil Oleo De Mamona.
Propylene glycol is commercially available from BASF.
Glycerine is commercially available from NAT OLEO.
Polydimethylsiloxane is commercially available from Dow Coming.
Monoethanolamine is commercially available from Sasol.
[0058] The liquid compositions
1, 2, 3 and
4 were packed into film pouches using vacuum-formed, horizontal form-fill-seal process,
each pouch containing about 50 ml of liquid. The film was made from a polyvinyl alcohol
/ carboxylate copolymer resin (M8630
™, Mono-Sol, Indiana, US). The resulting pouches comprise completely homogeneous liquids.
The dissolution and disintegration profiles of each of the pouched compositions is
good; the pouches dissolve/disintegrate rapidly in water without leaving any residue
even after prolonged storage (eight weeks) at 35°C.
Comparative data
[0059] The following examples will further illustrate the present invention. The compositions
are made by combining the listed ingredients in the listed proportions (weight % unless
otherwise specified). Example composition
5 is meant to exemplify compositions according to the present invention but is not
necessarily used to limit or otherwise define the scope of the present invention.
Example compositions
A, B, and
C are comparative examples. Example composition
6 is a reference example, which is outside the scope of the claims.
Ingredients: (% by weight) |
5 |
A |
B |
6/C |
Dodecylbenzene sulphonic acid |
24 |
23 |
20 |
21.8 |
C12-14 alcohol, 7x ethoxylated |
19 |
19 |
20 |
18.5 |
C8-C10 amido propyl dimethylamine |
- |
1.9 |
1.6 |
1.7 |
Citric acid |
1.7 |
1.7 |
0.67 |
1.5 |
C12-C18 alkyl fatty acid |
14 |
17 |
6.4 |
16.4 |
Hydroxyethane diphosphonic acid |
0.74 |
0.84 |
1.8 |
- |
Diethylene Triamine Penta methylene phosponic acid |
- |
- |
0.46 |
0.85 |
Protease/amylase Enzymes |
1.6 |
1.5 |
- |
1.5 |
Magnesium chloride |
0.10 |
- |
0.10 |
- |
Potassium sulfite |
0.15 |
- |
0.15 |
- |
Polyethyleneimine, 20x ethoxylated |
1.3 |
1.6 |
- |
1.5 |
Formic acid |
- |
- |
0.17 |
1.1 |
Ethoxylated tetraethylene pentamine |
|
1.6 |
- |
1.5 |
Zwitterionic polyamine |
2.8 |
- |
2.7 |
- |
Optical brightener 1 |
0.21 |
0.26 |
0.17 |
0.25 |
Hydrogenated castor oil |
0.20 |
- |
0.18 |
- |
Propylene Glycol |
6.3 |
17 |
16 |
15 |
Glycerine |
7.5 |
- |
- |
- |
Monoethanolamine |
10.2 |
8 |
7.3 |
11.4 |
Perfume, dyes, minors, Na-hydroxide |
2.4 |
3.5 |
4.8 |
1.7 |
Water |
7.8 |
3.1 |
17.5 |
5.3 |
[0060] Formic acid is commercially available from BASF.
Ethoxylated tetraethylene pentamine is commercially available from BASF.
Optical brightener is disodium 4,4'-bis-(2-sulphostyryl) biphenyl, commercially available
as from Ciba AG, in compositions
5 and
B and is a disulphated di-amino stilbene based fluorescent whitening agent, commercially
available from Hickson & Welch LTD, in compositions
6, A and
C.
Experiment 1: Effect of the water content of the liquid composition on physical stability and solubility
of various PVA pouches after storage.
[0061] The liquid compositions
5, A, and
B were packed into film pouches using vacuum-formed, horizontal form-fill-seal process,
each pouch containing about 50ml of liquid. The film was made from a polyvinyl alcohol
/ carboxylate copolymer resin (sold under the trade reference M8630
™ by Mono-Sol of Indiana, US). The corresponding pouches were stored for 8 weeks at
35°C.
The physical stability after storage has been assessed by visual observation of the
corresponding pouches. The in-wash solubility of the liquid-containing pouches has
been assessed using the "Black Pouch Solubility Method" as described herein above.
Results are presented in the table below.
|
Pouched composition 5 |
Pouched composition A |
Pouched composition B |
Physical stability |
Translucent, homogeneous |
Solid precipitate of HEDP present |
Translucent, Homogeneous |
Black pouch solubility score |
1.5 (good solubility) |
n.a. |
3.6 (poor solubility) |
[0062] The above results clearly show the improved physical stability and solubility after
storage of a water-soluble pouch according to the present invention (pouched composition
5), versus comparative water-soluble pouches (pouched compositions
A and
B).
Experiment 2: Effect of the water-soluble pouch manufacturing process on the in-wash solubility
of the liquid-containing pouches after storage.
[0063] Liquid compositions
6 and
C have the same chemical composition but were packed into two different types of film
pouches, both containing about 50ml of liquid composition but processed using two
different manufacturing processes. A first set of pouches was manufactured using vacuum-formed,
horizontal form-fill-seal process (HFFS) (pouched composition
6), and a second set of pouches was manufactured using vertical form-fill-seal process
(VFFS) (pouched composition
C). The films were made from a polyvinyl alcohol / carboxylate copolymer resin (commercially
available under tradename M8630
™ from Mono-Sol of Indiana, US). The corresponding pouches were stored for 10 months
at room temperature.
The in-wash solubility of the liquid-containing pouches has been assessed using the
"Black Pouch Solubility Method" as described herein above.
Results are presented in the table below.
|
Composition 6 pouched via HFFS |
Composition C pouched via WFS |
Black pouch solubility score |
1.0 (good solubility) |
3.0 (poor solubility) |
[0064] The above results clearly show the improved solubility after storage of a water-soluble
pouch processed using vacuum-formed, horizontal form-fill-seal process (pouched composition
6), when compared to a water-soluble using a vertical form-fill-seal process (pouched
composition
C).
1. Wasserlöslicher Beutel, der eine flüssige Zusammensetzung enthält, wobei der wasserlösliche
Beutel aus einer Folie gefertigt ist, die ein Copolymer von Vinylalkohol und einer
Carbonsäure umfasst, wobei die flüssige Zusammensetzung, die in dem Beutel enthalten
ist, mindestens einen gelösten ionischen Bestandteil umfasst, der ausgewählt ist aus
der Gruppe bestehend aus Carboxylaten, Phosphonaten und Mischungen davon, dadurch gekennzeichnet, dass die flüssige Zusammensetzung von 5 Gew.-% bis 15 Gew.-% der flüssigen Zusammensetzung
Wasser und Metallsalze umfasst, die ausgewählt sind aus Magnesiumsalzen und Kalziumsalzen,
vorzugsweise aus Magnesiumsalzen, und der Beutel mittels eines vakuumgeformten, horizontalen
Form-Füll-Siegel-Verfahrens verarbeitet wird.
2. Wasserlöslicher Beutel nach Anspruch 1, wobei der mindestens eine ionische Bestandteil
ein Phosphonat ist.
3. Wasserlöslicher Beutel nach Anspruch 2, wobei der mindestens eine ionische Bestandteil
Hydroxy-ethylen-1,1-diphosphonat ist.
4. Wasserlöslicher Beutel nach einem der vorstehenden Ansprüche, wobei die flüssige Zusammensetzung
von 6 Gew.-% bis 12 Gew.-%, vorzugsweise von 7 Gew.-% bis 10 Gew.-%, mehr bevorzugt
von 8 Gew.-% bis 10 Gew.% der flüssigen Zusammensetzung Wasser umfasst.
5. Wasserlöslicher Beutel nach einem der vorstehenden Ansprüche, wobei die flüssige Zusammensetzung
von 0,2 Gew.-% bis 4,0 Gew.-%, vorzugsweise von 0,5 Gew.-% bis 3,0 Gew.-%, mehr bevorzugt
von 0,5 Gew.-% bis 2,0 Gew.-% der flüssigen Zusammensetzung den mindestens einen ionischen
Bestandteil umfasst.
6. Wasserlöslicher Beutel nach Anspruch 6, wobei das Metallsalz ausgewählt ist aus Magnesiumchlorid,
Magnesiumbisulfit oder Mischungen davon.
7. Wasserlöslicher Beutel nach Anspruch 6, wobei die flüssige Zusammensetzung zu weniger
als 1 Gew.-%, vorzugsweise weniger als 0,5 Gew.-%, mehr bevorzugt weniger als 0,3
Gew.-% der flüssigen Zusammensetzung die Metallsalze umfasst.
8. Wasserlöslicher Beutel nach einem der vorstehenden Ansprüche, wobei die flüssige Zusammensetzung
ferner einen oder mehrere Bestandteile umfasst, die ausgewählt sind aus der Gruppe
aus Polycarbonsäuren, Polycarboxylatsalzen, Polyphosphonsäuren, Polyphosphonatsalzen,
kationischen ethoxylierten Aminen, zwitterionischen Polymeren, Enzymen und Mischungen
davon.
9. Wasserlöslicher Beutel nach einem der vorstehenden Ansprüche, wobei der Beutel nach
einer 8-wöchigen Lagerung bei 35 °C eine Wasserlöslichkeit gemäß dem "Black Pouch
Solubility"-Verfahren aufweist, so dass keine Folienreste mit einem größten mittleren
Durchmesser von größer als 2 cm nach dem Waschen auf dem Stoff sichtbar sind.
10. Verfahren zum Herstellen eines wasserlöslichen Beutels mit verbesserter Wasserlöslichkeit
nach der Lagerung, wobei das Verfahren die folgenden Schritte umfasst:
(a) Formulieren einer flüssigen Zusammensetzung, die mindestens einen ionischen Bestandteil
umfasst, der ausgewählt ist aus der Gruppe bestehend aus Carboxylaten, Phosphonaten
und Mischungen davon, von 5 Gew.-% bis 15 Gew.-% der flüssigen Zusammensetzung Wasser
und Metallsalze umfasst, die ausgewählt sind aus Magnesiumsalzen und Kalziumsalzen,
vorzugsweise aus Magnesiumsalzen.
(b) Verarbeiten einer Folie, die ein Copolymer von Vinylalkohol und einer Carbonsäure
umfasst, zu einem wasserlöslichen Beutel, der die flüssige Zusammensetzung enthält,
durch ein vakuumgeformtes, horizontales Form-Füll-Siegel-Verfahren.
1. Sachet hydrosoluble contenant une composition liquide, où le sachet hydrosoluble est
constitué d'un film comprenant un copolymère d'alcool vinylique et un acide carboxylique,
dans lequel la composition liquide contenue au sein dudit sachet comprend au moins
un composant ionique dissous choisi dans le groupe constitué de carboxylates, phosphonates
et leurs mélanges, caractérisé en ce que ladite composition liquide comprend de 5 % à 15 % en poids de la composition liquide
d'eau, et des sels métalliques choisis parmi les sels de magnésium et sels de calcium,
de préférence parmi les sels de magnésium et ledit sachet est réalisé en utilisant
un procédé de formage-remplissage-scellage horizontal formé sous vide.
2. Sachet hydrosoluble selon la revendication 1, dans lequel ledit au moins un composant
ionique est un phosphonate.
3. Sachet hydrosoluble selon la revendication 2, dans lequel ledit au moins un composant
ionique est l'hydroxy-éthylène 1,1 diphosphonate.
4. Sachet hydrosoluble selon l'une quelconque des revendications précédentes, dans lequel
ladite composition liquide comprend de 6 % à 12 %, de préférence de 7 % à 10 %, plus
préférablement de 8 % à 10 % en poids de la composition liquide, d'eau.
5. Sachet hydrosoluble selon l'une quelconque des revendications précédentes, dans lequel
ladite composition liquide comprend de 0,2 % à 4,0 %, de préférence de 0,5 % à 3,0
%, plus préférablement de 0,5 % à 2,0 % en poids de la composition liquide, dudit
au moins un composant ionique.
6. Sachet hydrosoluble selon la revendication 6, dans lequel ledit sel métallique est
choisi parmi le chlorure de magnésium, le bisulfite de magnésium ou leurs mélanges
7. Sachet hydrosoluble selon la revendication 6, dans lequel ladite composition liquide
comprend moins de 1 %, de préférence moins de 0,5 %, plus préférablement moins de
0,3 % en poids de la composition liquide, desdits sels métalliques.
8. Sachet hydrosoluble selon l'une quelconque des revendications précédentes, dans lequel
ladite composition liquide comprend en outre un ou plusieurs ingrédients choisis parmi
le groupe des acides polycarboxyliques, sels de polycarboxylate, acides polyphosphoniques,
sels de polyphosphonate, amines éthoxylées cationiques, polymères zwittérioniques,
enzymes, et leurs mélanges.
9. Sachet hydrosoluble selon l'une quelconque des revendications précédentes, où ledit
sachet après un stockage de 8 semaines à 35 °C présente une hydrosolubilité selon
le « procédé de solubilité du sachet noir » de telle sorte qu'aucun résidu de film
avec le diamètre moyen le plus grand de plus de 2 cm n'est visible sur le tissu après
lavage.
10. Procédé de fabrication d'un sachet hydrosoluble ayant une hydrosolubilité améliorée
lors du stockage, où ledit procédé comprend les étapes consistant à :
(a) formuler une composition liquide comprenant au moins un composant ionique dissous
choisi dans le groupe constitué de carboxylates, phosphonates et leurs mélanges, de
5 % à 15 % en poids de la composition liquide d'eau, et des sels métalliques choisis
parmi les sels de magnésium et sels de calcium, de préférence parmi les sels de magnésium.
(b) traiter un film comprenant un copolymère d'alcool vinylique et un acide carboxylique
en un sachet hydrosoluble contenant ladite composition liquide, en utilisant un procédé
de formage-remplissage-scellage horizontal formé sous vide.