[0001] The present invention relates to a process for producing a water-soluble article
comprising a water-soluble, primary (or "first") thermoformed component and a water-soluble,
secondary (or "second") component attached thereto. It also relates to an article
obtainable by such a process.
[0002] Thermoforming is a well-known technique for preparing articles from a polymer. It
generally comprises heating a polymeric composition, which can be in the form of,
for example, a film, to above its softening temperature and thermally deforming the
composition in a male or female mould.
[0003] It is also known to package chemical compositions, particularly those which may be
of a hazardous or irritant nature, in films. If such compositions are held within
water-soluble films forming a container around the compositions, the containers can
simply be added to water in order to dissolve or disperse the composition into the
water.
[0004] WO 92/17382 discolses a package which corresponds to the preamble of claim 17 containing
an agrochemical comprising a first sheet of non-planar water-soluble or water-dispersible
material and a second sheet of water-soluble or water-dispersible material superposed
on the first sheet and sealed to it.
[0005] A difficulty with this package, however, is that it can only contain a single composition
which is compatible with the film. It cannot be used for two compositions which are
incompatible with each other or for compositions which are incompatible with the water-soluble
or water-dispersible material. For example, WO 92/17382 states that when the package
contains the liquid, the liquid must be an organic liquid which contains less than
2 to 3% of water to ensure that it does not attack the film forming the package and
cause leakage.
[0006] The present invention provides a process for preparing a water-soluble article comprising
a water-soluble primary thermoformed component and a water-soluble secondary component
attached to the outside thereof, which comprises placing the secondary component in
the cavity of a thermoforming mould, thereafter placing a primary component in or
over the thermoforming mould, forming the primary thermoformed component by thermoforming
the primary component in the mould, and removing the article from the mould.
[0007] The present invention also provides a water-soluble article comprising a water-soluble
primary component which is a thermoformed container containing a primary composition,
and a water-soluble secondary component attached to the outside thereof.
[0008] The present invention provides a convenient process for preparing an article comprising
a thermoformed primary component, which has a secondary component attached thereto.
While it may well be possible to prepare an article by preparing the initial primary
component by thermoforming and then attaching the secondary component thereto using,
for example, an adhesive, the process of the present invention provides a process
which can be carried out in a single step, thus eliminating the need to use separate
machines.
[0009] Advantageously the present invention also, if desired, allows for the primary component
and secondary component to be attached without the need for an adhesive, which may
cause problems in some uses.
[0010] The primary component, prior to being placed in or over the thermoforming mould,
may be of any shape or form. The primary component may, for example, be in the form
of a rigid sheet or a flexible film. The primary component and the secondary component
may together form in the finally formed water-soluble article, for example, a strip
of a sheet or film (the primary thermoformed component) with one or more compositions
such as solid balls or pills (the secondary component) spaced apart along the sheet
or film. Individual compositions may then be removed from the sheet or film for individual
use. Perforations in the sheet or film may be used to assist separation. The secondary
component(s) may be held on the primary component by, for example, mechanical adhesion
caused by thermoforming the primary component around the secondary component(s), or
by use of an adhesive.
[0011] Desirably, however, in the present invention the primary thermoformed component comprises
a polymeric film that has been thermoformed into a desired shape.
[0012] Ideally the primary component is a film which is thermoformed in the mould, thus
becoming the primary thermoformed component. Preferably the film of the primary component
is formed into a pocket surrounded by a sealing portion. Preferably the process additionally
comprises the following process steps thereafter; filling the pocket with a primary
composition and closing the pocket, for example by placing a film on top of the filled
pocket and across the sealing portion and sealing the films together at the sealing
portion.
[0013] Most desirably in the present invention the primary component is a container. The
secondary component is then attached to the outside of the container. Such a container
can be prepared by thermoforming a film into a pocket surrounded by a sealing portion,
filling the pocket with a primary composition and closing the pocket, for example
by placing a film on top of the filled pocket and across the sealing portion and sealing
the films together at the sealing portion.
[0014] The film may be a single film, or a laminated film as disclosed in GB-A-2,244,258.
While a single film may have pinholes, the two or more layers in a laminate are unlikely
to have pinholes which coincide. The film is water-soluble (which term is taken to
include water-dispersible).
[0015] The term "water-soluble" when used herein means that when used in a washing machine,
such as a fabric or dish washing machine, the water-soluble aspects of the article
are substantially (greater than 70%, ideally greater than 85%) dissolved or dispersed
into the water. This can be tested by placing the article in 10 litres of agitated
water at 45°C for 40 minutes and measuring any undissolved or non-disintegrated pieces
of the parts of the article, which are water-soluble, that are left.
[0016] The film may be produced by any process, for example by extrusion and blowing or
by casting. The film may be unoriented, monoaxially oriented or biaxially oriented.
If the layers in the film are oriented, they usually have the same orientation, although
their planes of orientation may be different if desired.
[0017] The layers in a laminate may be the same or different. Thus they may each comprise
the same polymer or a different polymer. If it is desired to have a water-soluble
laminated film, each of the layers should be water-soluble.
[0018] Examples of water-soluble polymers which may be used in a single layer film or in
one or more layers of a laminate are poly(vinyl alcohol) (PVOH) and cellulose derivatives
such as hydroxypropyl methyl cellulose (HPMC). An example of a preferred PVOH is ethoxylated
PVOH. The PVOH may be partially or fully alcoholised or hydrolysed. For example it
may be from 40 to 100%, preferably from 70 to 92%, more preferably about 88% or about
92%, alcoholised or hydrolysed. The degree of hydrolysis is known to influence the
temperature at which the PVOH starts to dissolve in water. 88% hydrolysis corresponds
to a film soluble in cold (ie room temperature) water, whereas 92% hydrolysis corresponds
to a film soluble in warm water.
[0019] The thickness of the film used to produce the pocket is preferably 40 to 300 µm,
more preferably 70 to 200 µm, especially 80 to 160 µm, more especially 90 to 150 µm
and most especially 90 to 120 µm.
[0020] In a thermoforming process the primary component, preferably a film, may be drawn
down or blown down into a mould. Thus, for example, the primary component is heated
to the thermoforming temperature using a thermoforming heater plate assembly, and
then drawn down under vacuum or blown down under pressure into the mould. In the present
invention it is preferred that the film is blown down since the presence of the secondary
component in the mould may inhibit the effective use of a vacuum. Plug-assisted thermoforming
and pre-stretching the film, for example by blowing the film away from the mould before
thermoforming, may, if desired, be used. One skilled in the art can choose an appropriate
temperature, pressure or vacuum and dwell time to achieve an appropriate pocket. The
amount of vacuum or pressure and the thermoforming temperature used depend on the
thickness and porosity of the film and on the polymer or mixture of polymers being
used. Thermoforming of PVOH films is known and described in, for example, WO 00/55045.
[0021] A suitable forming temperature for PVOH or ethoxylated PVOH is, for example, from
90 to 130°C, especially 90 to 120°C. A suitable forming pressure is, for example,
69 to 138kPa (10 to 20 p.s.i.), especially 83 to 117 kPa (12 to 17 p.s.i.). A suitable
forming vacuum is 0 to 4 kPa (0 to 40 mbar), especially 0 to 2 kPa (0 to 20 mbar).
A suitable dwell time is, for example, 0.4 to 2.5 seconds, especially 2 to 2.5 seconds.
[0022] While desirably conditions are chosen within the above ranges, it is possible to
use one or more of these parameters outside the above ranges, although it may be necessary
to compensate by changing the values of the other two parameters.
[0023] Where a pocket is formed from the primary component it may be filled with a desired
composition. The pocket may be completely filled or only partially filled. The composition
may be a solid. For example, it may be a particulate solid or granulated solid, or
a tablet. It may also be a liquid, which may be thickened or gelled if desired. The
liquid composition may be non-aqueous or aqueous, for example comprising less than
or more than 5% total or free water. The composition may have more than one phase.
For example it may comprise an aqueous composition and a liquid composition which
is immiscible with the aqueous composition. It may also comprise a liquid composition
and a separate solid composition, for example in the form of a ball, pill or speckles.
[0024] After the pocket has been filled it is closed, for example by placing a film on top
of the filled pocket and across the sealing portion, and sealing the films together
at the sealing portion. This film may be a single-layered film but is desirably laminated
to reduce the possibility of pinholes allowing leakage through the film. The film
may be the same or different as the film forming the pocket. Examples of suitable
films are those given for the film forming the pocket.
[0025] Desirably the covering film has a thickness which is less than that of the film used
for forming a pocket because it would not generally be stretched so localised thinning
of the sheet will not occur. It is also desirable to have a thickness which is less
than that of the film used to form a pocket to ensure a sufficient heat transfer through
the film to soften the pocket film if heat sealing is used.
[0026] The thickness of the covering film is generally from 20 to 160 µm, preferably from
40 to 100 µm, such as 40 to 80 µm or 50 to 60 µm.
[0027] The films may be sealed together by any suitable means, for example by means of an
adhesive or by heat sealing. Other methods of sealing include infra-red, radio frequency,
ultrasonic, laser, solvent, vibration and spin welding. An adhesive such as an aqueous
solution of PVOH may also be used. The seal desirably is water-soluble if the containers
are water-soluble. The presence of a coating on the sealing portion of the film could
hinder or prevent sealing and could cause a reduction in seal strength. Therefore,
in the present invention, the sealing portion is preferably left uncoated by the coating
composition.
[0028] If heat sealing is used, a suitable sealing temperature is, for example, 120 to 195°C,
for example 140 to 150°C. A suitable sealing pressure is, for example, from 250 to
600 kPa. Examples of sealing pressures are 276 to 552 kPa (40 to 80 p.s.i.), especially
345 to 483 kPa (50 to 70 p.s.i.) or 400 to 800 kPa (4 to 8 bar), especially 500 to
700 kPa (5 to 7 bar) depending on the heat sealing machine used. Suitable sealing
dwell times are 0.4 to 2.5 seconds.
[0029] One skilled in the art can use an appropriate temperature, pressure and dwell time
to achieve a seal of the desired integrity. While desirably conditions are chosen
within the above ranges, it is possible to use one or more of these parameters outside
the above ranges, although it might be necessary to compensate by changing the values
of the other two parameters.
[0030] The secondary component may be any water-soluble components. The term "water-soluble"
again includes water-dispersible. Desirably it is not deformed, or is substantially
not deformed, during the step wherein the primary component is thermoformed.
[0031] Thus, for example, the secondary component may be in the form of a solid, such as
a compressed solid, for example in the form of a ball or pill. It may also itself
be a container containing a secondary composition. For example it may comprise a polymeric
film containing a secondary composition such as a solid, a gel or a liquid. Such a
container may be previously prepared by a thermoforming technique such as that discussed
above. It may also be prepared by other means, for example by vertical form fill sealing,
injection moulding or blow moulding.
[0032] If the primary composition or secondary composition is incompatible with the films
enclosing them, steps have to be taken to improve the compatibility. For example,
if the films are water-soluble, the amount of free water in the compositions may be
reduced. In particular, an electrolyte or gelling agent may be added. Alternatively
a coating may be applied on the inside of the films, for example as disclosed in WO
00/64667 or by coating the inside of the pockets after they have been thermoformed
but before they have been filled.
[0033] The primary composition and the composition constituting the secondary component
may be the same or different. If they are different they may, nevertheless, have one
or more individual components in common. The present invention is especially advantageous
when the primary composition and the secondary composition are incompatible with each
other since they are separated. It is also advantageous if one of the compositions
is incompatible with the components contacting the other composition. For example,
the secondary composition may be a composition which is incompatible with the film
forming the container containing the primary composition when the secondary composition
is itself held within a film. Similarly the primary composition may be a composition
which is incompatible with the secondary component or the film containing the secondary
composition.
[0034] The secondary component should be chosen such that it does not adversely affect the
thermoforming process used to prepare the primary component. In the process of the
present invention it is placed in the cavity of the thermoforming mould as an initial
step, for example, by a robot.
[0035] In a thermoforming process air must be evacuated from underneath the primary component
as it is being thermoformed. Unless the secondary component is permeable, it will
prevent air from being withdrawn from underneath it.
[0036] Therefore the air holes in the thermoforming mould need not be positioned directly
underneath the secondary component, although if they are they may help in drawing
the primary component down over the secondary component as it is being thermoformed.
In particular the mould may, for example, be roughened to assist good air evacuation.
Preferably the secondary component should not be placed in a position where a substantial
thinning of the primary component can occur if it is in the form of a film. Desirably,
therefore, the secondary component is placed at the centre of the bottom of the thermoforming
mould, and air is withdrawn from the sides and corners of the mould as well as, optionally,
the bottom of the mould around the area on which the secondary component is positioned.
[0037] The mould may contain a recess which is dimensioned so as to accept the secondary
component. This is especially advantageous when the secondary component is in the
form of a ball since it can simply roll into the recess. The recess may be in any
part of the mould, but is desirably near the bottom of the mould, for example on the
bottom surface of the mould. It may be at the centre of the bottom surface, or may
be off-set to one side. However, the thermoforming mould does not need to contain
a recess and the secondary component can simply be placed at the bottom of the mould
or on a step positioned above the bottom of the mould.
[0038] During the thermoforming process the primary component, which is usually a polymer,
has an elevated temperature. By an appropriate choice of thermoforming temperature
and of the secondary component, the primary component will stick to the secondary
component at the same time as it is thermoformed. This is especially the case when,
for example, the secondary component itself comprises a polymeric film which will
be heated to a certain extent by the elevated temperatures within the thermoforming
machine or by the contacting of the heated primary component. The mould may also be
formed such that the cooling pipes generally used in thermoforming moulds do not cool
the area directly under the secondary component.
[0039] Alternatively the secondary component may have an adhesive applied thereto before
or after it is placed in the cavity of the thermoforming mould. A suitable adhesive
may, for example, be a polymer which is heated in the thermoforming mould, or a component
such as water which can act as an adhesive when it contacts the primary component,
especially when the primary component is water-soluble. Preferably the primary and
secondary components are formed from or are coated with the same water-soluble polymer,
this aids adhesion, especially in the presence of water. The adhesive may, for example,
be a heat activated adhesive or coating. The secondary component may also be held
on the primary component by mechanical adhesion by ensuring that the primary component
flows around and at least partially encloses the secondary component.
[0040] The primary and secondary compositions may independently be any compositions which
are intended to be released in an aqueous environment if the container is water-soluble.
Thus, for example, either or both compositions may be agrochemical compositions such
as a plant protection agent, for instance a pesticide such as an insecticide, fungicide,
herbicide, acaricide, or nematocide, a plant growth regulator or a plant nutrient.
Such compositions are generally packaged in total amounts of from 0.1 g to 7 kg, preferably
1 to 5 kg, when in solid form. When in liquid or gelled form, such compositions are
generally packaged in total amounts of from 1 ml to 10 litres, preferably 0.1 to 6
litres, especially from 0.5 to 1.5 litres.
[0041] The primary and secondary compositions may also independently be fabric care, surface
care or dishwashing compositions. Thus, for example, it may be a dishwashing, water-softening,
laundry or detergent composition, or a rinse aid. Such compositions may be suitable
for use in a domestic washing machine. The primary and secondary compositions may
also independently be a disinfectant, antibacterial or antiseptic composition, or
a refill composition for a trigger-type spray. Such compositions are generally packaged
in total amounts of from 5 to 100 g, especially from 15 to 40 g. For example, a dishwashing
composition may weigh from 15 to 30 g, a water-softening composition may weigh from
15 to 40 g.
[0042] The primary composition and the secondary composition may be appropriately chosen
depending on the desired use of the article.
[0043] If the article is for use in laundry washing, the primary composition may comprise,
for example, a detergent, and the secondary composition may comprise a bleach, stain
remover, water-softener, enzyme or fabric conditioner. The article may be adapted
to release the compositions at different times during the dish washing cycle. For
example, a bleach or fabric conditioner is generally released at the end of a wash,
and a water-softener is generally released at the start of a wash. An enzyme may be
released at the start or the end of a wash.
[0044] If the article is for use as a fabric conditioner, the primary composition may comprise
a fabric conditioner and the secondary component may comprise an enzyme which is released
before or after the fabric conditioner in a rinse cycle.
[0045] If the article is for use in dish washing the primary composition may comprise a
detergent and the secondary composition may comprise a water-softener, enzyme, rinse
aid, bleach or bleach activator. The article may be adapted to release the compositions
at different times during the wash. For example, a rinse aid, bleach or bleach activator
is preferably released at the end of a wash, and a water-softener or enzyme is generally
released at the start of a wash.
[0046] The primary and secondary compositions, if in liquid form, may independently be anhydrous
or comprise water, for example at least 5 wt %, preferably at least 10 wt% free or
total water based on the weight of the aqueous compositions. Desirably the compositions
contain less than 80 wt% water, ideally less than 50 wt% of water.
[0047] The remaining ingredients of the primary and secondary compositions depend on the
use of the compositions. Thus, for example, the compositions may independently contain
surface active agents such as an anionic, nonionic, cationic, amphoteric or zwitterionic
surface active agents or mixtures thereof.
[0048] Examples of anionic surfactants are straight-chained or branched alkyl sulfates and
alkyl polyalkoxylated sulfates, also known as alkyl ether sulfates. Such surfactants
may be produced by the sulfation of higher C
8-C
20 fatty alcohols.
[0049] Examples of primary alkyl sulfate surfactants are those of formula:
ROSO
3-M
+
wherein R is a linear C
8-C
20 hydrocarbyl group and M is a water-solubilising cation. Preferably R is C
10-C
16 alkyl, for example C
12-C
14, and M is alkali metal such as lithium, sodium or potassium.
[0050] Examples of secondary alkyl sulfate surfactants are those which have the sulfate
moiety on a "backbone" of the molecule, for example those of formula:
CH
3(CH
2)
n(CHOSO
3-M
+)(CH
2)
mCH
3
wherein m and n are independently 2 or more, the sum of m+n typically being 6 to 20,
for example 9 to 15, and M is a water-solubilising cation such as lithium, sodium
or potassium.
[0051] Especially preferred secondary alkyl sulfates are the (2,3) alkyl sulfate surfactants
of formulae:
CH
3(CH
2)
x(CHOSO
3-M
+)CH
3
and
CH
3(CH
2)
x(CHOSO
3-M
+)CH
2CH
3
for the 2-sulfate and 3-sulfate, respectively. In these formulae x is at least 4,
for example 6 to 20, preferably 10 to 16. M is cation, such as an alkali metal, for
example lithium, sodium or potassium.
[0052] Examples of alkoxylated alkyl sulfates are ethoxylated alkyl sulfates of the formula:
RO(C
2H
4O)
nSO
3-M
+
wherein R is a C
8-C
20 alkyl group, preferably C
10-C
18 such as a C
12-C
16, n is at least 1, for example from 1 to 20, preferably 1 to 15, especially 1 to 6,
and M is a salt-forming cation such as lithium, sodium, potassium, ammonium, alkylammonium
or alkanolammonium. These compounds can provide especially desirable fabric cleaning
performance benefits when used in combination with alkyl sulfates.
[0053] The alkyl sulfates and alkyl ether sulfates will generally be used in the form of
mixtures comprising varying alkyl chain lengths and, if present, varying degrees of
alkoxylation.
[0054] Other anionic surfactants which may be employed are salts of fatty acids, for example
C
8-C
18 fatty acids, especially the sodium or potassium salts, and alkyl, for example C
8-C
18, benzene sulfonates.
[0055] Examples of nonionic surfactants are fatty acid alkoxylates, such as fatty acid ethoxylates,
especially those of formula:
R(C
2H
4O)
nOH
wherein R is a straight or branched C
8-C
16 alkyl group, preferably a C
9-C
15, for example C
10-C
14, alkyl group and n is at least 1, for example from 1 to 16, preferably 2 to 12, more
preferably 3 to 10.
[0056] The alkoxylated fatty alcohol nonionic surfactant will frequently have a hydrophilic-lipophilic
balance (HLB) which ranges from 3 to 17, more preferably from 6 to 15, most preferably
from 10 to 15.
[0057] Examples of fatty alcohol ethoxylates are those made from alcohols of 12 to 15 carbon
atoms and which contain about 7 moles of ethylene oxide. Such materials are commercially
marketed under the trademarks Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company.
Other useful Neodols include Neodol 1-5, an ethoxylated fatty alcohol averaging 11
carbon atoms in its alkyl chain with about 5 moles of ethylene oxide; Neodol 23-9,
an ethoxylated primary C
12-C
13 alcohol having about 9 moles of ethylene oxide; and Neodol 91-10, an ethoxylated
C
9-C
11 primary alcohol having about 10 moles of ethylene oxide.
[0058] Alcohol ethoxylates of this type have also been marketed by Shell Chemical Company
under the Dobanol trademark. Dobanol 91-5 is an ethoxylated C
9-C
11 fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated
C
12-C
15 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.
[0059] Other examples of suitable ethoxylated alcohol nonionic surfactants include Tergitol
15-S-7 and Tergitol 15-S-9, both of which are linear secondary alcohol ethoxylates
available from Union Carbide Corporation. Tergitol 15-S-7 is a mixed ethoxylated product
of a C
11-C
15 linear secondary alkanol with 7 moles of ethylene oxide and Tergitol 15-S-9 is the
same but with 9 moles of ethylene oxide.
[0060] Other suitable alcohol ethoxylated nonionic surfactants are Neodol 45-11, which is
a similar ethylene oxide condensation products of a fatty alcohol having 14-15 carbon
atoms and the number of ethylene oxide groups per mole being about 11. Such products
are also available from Shell Chemical Company.
[0061] Further nonionic surfactants are, for example, C
10-C
18 alkyl polyglycosides, such s C
12-C
16 alkyl polyglycosides, especially the polyglucosides. These are especially useful
when high foaming compositions are desired. Further surfactants are polyhydroxy fatty
acid amides, such as C
10-C
18 N-(3-methoxypropyl) glycamides and ethylene oxide-propylene oxide block polymers
of the Pluronic type.
[0062] Examples of cationic surfactants are those of the quaternary ammonium type.
[0063] The total content of surfactants in the composition is desirably 60 to 95 wt%, especially
75 to 90 wt%. Desirably an anionic surfactant is present in an amount of 50 to 75
wt%, the nonionic surfactant is present in an amount of 5 to 50 wt%, and/or the cationic
surfactant is present in an amount of from 0 to 20 wt%. The amounts are based on the
total solids content of the composition, i.e. excluding any solvent which may be present.
[0064] The primary and secondary compositions, particularly when used as laundry washing
or dishwashing compositions, may also independently comprise enzymes, such as protease,
lipase, amylase, cellulase and peroxidase enzymes. Such enzymes are commercially available
and sold, for example, under the registered trade marks Esperase, Alcalase and Savinase
by Nova Industries A/S and Maxatase by International Biosynthetics, Inc. Desirably
the enzymes are independently present in the primary or secondary compositions in
an amount of from 0.5 to 3 wt%, especially 1 to 2 wt%, when added as commecial preparations
they are not pure and this represents an equivalent amount of 0.005 to 0.5 wt% of
pure enzyme.
[0065] The primary and secondary compositions may, if desired, independently comprise a
thickening agent or gelling agent. Suitable thickeners are polyacrylate polymers such
as those sold under the trade mark CARBOPOL, or the trade mark ACUSOL by Rohm and
Haas Company. Other suitable thickeners are xanthan gums. The thickener, if present,
is generally present in an amount of from 0.2 to 4 wt%, especially 0.5 to 2 wt%.
[0066] Primary or secondary compositions used in dishwashing independently usually comprise
a detergency builder. The builders counteract the effects of calcium, or other ion,
water hardness. Examples of such materials are citrate, succinate, malonate, carboxymethyl
succinate, carboxylate, polycarboxylate and polyacetyl carboxylate salts, for example
with alkali metal or alkaline earth metal cations, or the corresponding free acids.
Specific examples are sodium, potassium and lithium salts of oxydisuccinic acid, mellitic
acid, benzene polycarboxylic acids, C
10-C
22 fatty acids and citric acid. Other examples are organic phosphonate type sequestering
agents such as those sold by Monsanto under the trade mark Dequest and alkylhydroxy
phosphonates. Citrate salts and C
12-C
18 fatty acid soaps are preferred. Further builders are; phosphates such as sodium,
potassium or ammonium salts of mono-, di- or tri-poly or oligo-phosphates; zeolites;
silicates, amorphous or structured, such as sodium, potassium or ammonium salts.
[0067] Other suitable builders are polymers and copolymers known to have builder properties.
For example, such materials include appropriate polyacrylic acid, polymaleic acid,
and polyacrylic/polymaleic and copolymers and their salts, such as those sold by BASF
under the trade mark Sokalan.
[0068] The builder is desirably present in an amount of up to 90 wt%, preferably 15 to 90
wt%, more preferable 15 to 75 wt%, relative to the total weight of the composition.
Further details of suitable components are given in, for example, EP-A-694,059, EP-A-518,720
and WO 99/06522.
[0069] The primary and secondary compositions can also independently optionally comprise
one or more additional ingredients. These include conventional detergent composition
components such as further surfactants, bleaches, bleach enhancing agents, builders,
suds boosters or suds suppressors, anti-tarnish and anti-corrosion agents, organic
solvents, co-solvents, phase stabilisers, emulsifying agents, preservatives, soil
suspending agents, soil release agents, germicides, pH adjusting agents or buffers,
non-builder alkalinity sources, chelating agents, clays such as smectite clays, enzyme
stabilizers, anti-limescale agents, colourants, dyes, hydrotropes, dye transfer inhibiting
agents, brighteners, and perfumes. If used, such optional ingredients will generally
constitute preferably no more than 15 wt%, for example from 1 to 6 wt%, the total
weight of the compositions.
[0070] Primary or secondary compositions which comprise an enzyme may optionally contain
materials which maintain the stability of the enzyme. Such enzyme stabilizers include,
for example, polyols such as propylene glycol, boric acid and borax. Combinations
of these enzyme stabilizers may also be employed. If utilized, the enzyme stabilizers
generally constitute from 0.1 to 5 wt%, ideally 0.1 to 1 wt% of the compositions.
[0071] The primary and secondary compositions may independently optionally comprise materials
which serve as phase stabilizers and/or co-solvents. Example are C
1-C
3 alcohols such as methanol, ethanol and propanol. C
1-C
3 alkanolamines such as mono-, di- and triethanolamines can also be used, by themselves
or in combination with the alcohols. The phase stabilizers and/or co-solvents can,
for example, constitute 0 to 1 wt%, preferably 0.1 to 0.5 wt%, of the composition.
[0072] The primary and secondary compositions may independently optionally comprise components
which adjust or maintain the pH of the compositions at optimum levels. The pH may
be from, for example, 1 to 13, such as 8 to 11 depending on the nature of the composition.
For example a dishwashing composition desirably has a pH of 8 to 11, a laundry composition
desirable has a pH of 7 to 9, and a water-softening composition desirably has a pH
of 7 to 9. Examples of pH adjusting agents are NaOH and citric acid.
[0073] The above examples may be used for dish or fabric washing. In particular dish washing
formulations are preferred which are adapted to be used in automatic dish washing
machines. Due to their specific requirements specialised formulation are required
and these are illustrated below
[0074] Amounts of the ingredients can vary within wide ranges, however preferred automatic
dishwashing detergent compositions herein (which typically have a 1% aqueous solution
pH of above 8, more preferably from 9.5 to 12, most preferably from 9.5 to 10.5) are
those wherein there is present: from 5% to 90%, preferably from 5% to 75%, of builder;
from 0.1% to 40%, preferably from 0.5% to 30%, of bleaching agent; from 0.1% to 15%,
preferably from 0.2% to 10%, of the surfactant system; from 0.0001% to 1%, preferably
from 0.001% to 0.05%, of a metal-containing bleach catalyst; and from 0.1% to 40%,
preferably from 0.1% to 20% of a water-soluble silicate. Such fully-formulated embodiments
typically further comprise from 0.1% to 15% of a polymeric dispersant, from 0.01%
to 10% of a chelant, and from 0.00001% to 10% of a detersive enzyme, though further
additional or adjunct ingredients may be present. Detergent compositions herein in
granular form typically limit water content, for example to less than 7% free water,
for better storage stability.
[0075] Non-ionic surfactants useful in ADW (Automatic Dish Washing) compositions of the
present invention desirably include surfactant (s) at levels of from 2% to 60% of
the composition. In general, bleach-stable surfactants are preferred. Non-ionic surfactants
generally are well known, being described in more detail in Kirk Othmer's Encyclopedia
of Chemical Technology, 3rd Ed., Vol. 22, pp. 360-379, "Surfactants and Detersive
Systems", incorporated by reference herein.
[0076] Preferably the ADW composition comprises at least one non-ionic surfactant. One class
of non-ionics are ethoxylated non-ionic surfactants prepared by the reaction of a
monohydroxy alkanol or alkylphenol with 6 to 20 carbon atoms with preferably at least
12 moles particularly preferred at least 16 moles, and still more preferred at least
20 moles of ethylene oxide per mole of alcohol or alkylphenol.
[0077] Particularly preferred non-ionic surfactants are the non-ionic from a linear chain
fatty alcohol with 16-20 carbon atoms and at least 12 moles particularly preferred
at least 16 and still more preferred at least 20 moles of ethylene oxide per mole
of alcohol.
[0078] According to one preferred embodiment the non-ionic surfactant additionally comprise
propylene oxide units in the molecule. Preferably this PO units constitute up to 25%
by weight, preferably up to 20% by weight and still more preferably up to 15% by weight
of the overall molecular weight of the non-ionic surfactant. Particularly preferred
surfactants are ethoxylated mono-hydroxy alkanols or alkylphenols, which additionally
comprises polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol
portion of such surfactants constitutes more than 30%, preferably more than 50%, more
preferably more than 70% by weight of the overall molecular weight of the non-ionic
surfactant.
[0079] Another class of non-ionic surfactants includes reverse block copolymers of polyoxyethylene
and polyoxypropylene and block copolymers of polyoxyethylene and polyoxypropylene
initiated with trimethylolpropane.
[0080] Another preferred non-ionic surfactant can be described by the formula:
R
1O[CH
2CH(CH
3)O]
X[CH
2CH
2O]
Y[CH
2CH(OH)R
2]
wherein
R1 represents a linear or branched chain aliphatic hydrocarbon group with 4-18 carbon
atoms or mixtures thereof,
R2 represents a linear or branched chain aliphatic hydrocarbon rest with 2-26 carbon
atoms or mixtures thereof, x is a value between 0.5 and 1.5 and y is a value of at
least 15.
[0081] Another group of preferred nonionic surfactants are the end-capped polyoxyalkylated
non-ionics of formula:
R
1O[CH
2CH(R
3)O]
x[CH
2]
kCH(OH)[CH
2]
jOR
2
wherein R
1 and R
2 represent linear or branched chain, saturated or unsaturated, aliphatic or aromatic
hydrocarbon groups with 1-30 carbon atoms, R
3 represents a hydrogen atom or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl
or 2-methyl-2-butyl group , x is a value between 1 and 30 and, k and j are values
between 1 and 12, preferably between 1 and 5. When the value of x is ≥2 each R
3 in the formula above can be different. R
1 and R
2 are preferably linear or branched chain, saturated or unsaturated, aliphatic or aromatic
hydrocarbon groups with 6-22 carbon atoms, where group with 8 to 18 carbon atoms are
particularly preferred. For the group R
3 H, methyl or ethyl are particularly preferred. Particularly preferred values for
x are comprised between 1 and 20, preferably between 6 and 15.
[0082] As described above, in case x≥2, each R
3 in the formula can be different. For instance, when x=3, the group R
3 could be chosen to build ethylene oxide (R
3=H) or propylene oxide (R
3=methyl) units which can be used in every single order for instance (PO) (EO) (EO),
(EO) (PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and
(PO) (PO) (PO) . The value 3 for x is only an example and bigger values can be chosen
whereby a higher number of variations of (EO) or (PO) units would arise.
[0083] Particularly preferred end-capped polyoxyalkylated alcohols of the above formula
are those where k=1 and j=1 originating molecules of simplified formula:
R
1O[CH
2CH(R
3)O]
XCH
2CH(OH)CH
2OR
2
[0084] The use of mixtures of different non-ionic surfactants is particularly preferred
in ADW formulations for example mixtures of alkoxylated alcohols and hydroxy group
containing alkoxylated alcohols.
[0085] In the present invention, if more than one article, for example a container, is formed
at the same time from the same sheet, the articles may then be separated from each
other by cutting the portions between them, for example the sealing portions or flanges.
Alternatively, they may be left conjoined and, for example, perforations provided
between the individual articles so that they can be easily separated a later stage,
for example by a consumer. If the articles are separated, the flanges may be left
in place. However, desirably the flanges are partially removed in order to provide
an even more attractive appearance. Generally the flanges remaining should be as small
as possible for aesthetic purposes while bearing in mind that some flange is required
if the articles are in the form of thermoformed containers to ensure the two films
remain adhered to each other. A flange having a width of 1 mm to 8 mm is desirable,
preferably 2 mm to 7 mm, most preferably about 5 mm.
[0086] The articles, for example containers, may be packaged in outer containers if desired,
for example non-water soluble containers which are removed before the water-soluble
articles are used.
[0087] The containers produced by the process of the present invention, especially when
used for a fabric care, surface care or dishwashing composition, may have a maximum
dimension of 5 cm, excluding any flanges. For example, a container may have a length
of 1 to 5 cm, especially 3.5 to 4.5 cm, a width of 1.5 to 3.5 cm, especially 2 to
3 cm, and a height of 1 to 2 cm, especially 1.25 to 1.75 cm.
1. A process for preparing a water-soluble article comprising a water-soluble primary
thermoformed component and a water-soluble secondary component attached to the outside
thereof, which comprises placing the secondary component in the cavity of a thermoforming
mould, thereafter placing a primary component in or over the thermoforming mould,
forming the primary thermoformed component by thermoforming the primary component
in the mould, and removing the article from the mould.
2. A process according to claim 1 wherein the primary component is a film.
3. A process according to claim 1 wherein the primary thermoformed component comprises
a film.
4. A process according to any claim from 1 to 3 wherein the primary component is thermoformed
into a pocket surrounded by a sealing portion and wherein the process additionally
comprises the steps of filling the pocket with a primary composition and closing the
pocket, for example by placing a film on top of the filled pocket and across the sealing
portion and sealing the polymeric films together at the sealing portion.
5. A process according to claim 1 or 3 wherein the primary component is a sealed container
containing a primary composition.
6. A process according to claim 5 wherein the sealed container is prepared by thermoforming
a film into a pocket surrounded by a sealing portion, filling the pocket with a primary
composition and closing the pocket, for example by placing a film on top of the filled
pocket and across the sealing portion and sealing the films together at the sealing
portion.
7. A process according to any claim from 4 to 6 wherein the composition is a solid, a
gel or a liquid.
8. A process according to any one of the preceding claims wherein the secondary component
is a compressed solid or a container containing a secondary composition.
9. A process according to claim 8 wherein the secondary component is a container comprising
a polymeric film containing a solid, a gel or a liquid.
10. A process according to any one of the preceding claims wherein the primary component
and/or the secondary component comprises a poly(vinyl alcohol).
11. A process according to any one of the preceding claims wherein the article is for
use in dishwashing, fabric care or surface care.
12. A process according to claim 11 wherein the primary component comprises a dishwashing,
water-softening, laundry or detergent composition.
13. A process according to claim 11 or 12 wherein the secondary component comprises a
dishwashing, water-softening, laundry or detergent composition or a rinse-aid.
14. A process according to any one of claims 1 to 10 wherein the primary component and/or
secondary component comprises a disinfectant, antibacterial or antiseptic composition.
15. A process according to any one of claims 1 to 10 or 14 wherein the article comprises
a refill composition for a trigger-type spray.
16. A process according to any one of claims 1 to 10 wherein the article comprises an
agricultural composition.
17. A water-soluble article comprising a water-soluble primary component which is a thermoformed
container containing a primary, composition, characterized in that a water-soluble secondary component is attached to the outside of the thermoformed
container.
18. An article according to claim 17 wherein the primary composition is a solid, a gel
or a liquid.
19. An article according to claim 17 or 18 wherein the secondary component is a compressed
solid or a container containing a secondary composition.
20. An article according to claim 19 wherein the secondary component is a container comprising
a polymeric film containing a solid, a gel or a liquid.
21. An article according to any one of claims 17 to 20 wherein the primary component and/or
the secondary component comprises a poly(vinyl alcohol).
22. An article according to any one of claims 17 to 21 wherein the article is for use
in dishwashing, fabric care or surface care.
23. An article according to claim 22 wherein the primary composition is a dishwashing,
water-softening, laundry or detergent composition.
24. An article according to claim 22 or 23 wherein the secondary component comprises a
dishwashing, water-softening, laundry or detergent composition or a rinse-aid.
25. An article according to any one of claims 18 to 21 wherein the primary composition
and/or secondary component comprises a disinfectant, antibacterial or antiseptic composition.
26. An article according to any one of claims 18 to 21 or 25 wherein the article comprises
a refill composition for a trigger-type spray.
27. An article according to any one of claims 17 to 21 wherein the article comprises an
agricultural composition.
1. Procédé de fabrication d'un article hydrosoluble comprenant un composant primaire
thermoformé hydrosoluble et un composant secondaire hydrosoluble attaché à l'extérieur
de celui-ci, qui comprend les étapes consistant à placer le composant secondaire dans
la cavité d'un moule de thermoformage, puis à placer un composant primaire dans ou
sur le moule de thermoformage, à former le composant primaire thermoformé par thermoformage
du composant primaire dans le moule, et à retirer l'article du moule.
2. Procédé selon la revendication 1, dans lequel le composant primaire est un film.
3. Procédé selon la revendication 1, dans lequel le composant primaire thermoformé comprend
un film.
4. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel le composant
primaire est thermoformé en une poche entourée d'une zone de scellage et dans lequel
le procédé comprend de plus les étapes consistant à remplir la poche avec une composition
primaire et à fermer la poche, par exemple en plaçant un film sur le dessus de la
poche remplie et en travers de la zone de scellage et à sceller les films polymères
ensemble au niveau de la zone de scellage.
5. Procédé selon la revendication 1 ou 3, dans lequel le composant primaire est un récipient
scellé contenant une composition primaire.
6. Procédé selon la revendication 5, dans lequel le récipient scellé est fabriqué en
thermoformant un film en une poche entourée d'une zone de scellage, en remplissant
la poche avec une composition primaire et en fermant la poche, par exemple en plaçant
un film sur le dessus de la poche remplie et en travers la zone de scellage et en
scellant les films ensemble au niveau de la zone de scellage.
7. Procédé selon l'une quelconque des revendications 4 à 6, dans lequel la composition
est un solide, un gel ou un liquide.
8. Procédé selon l'une quelconque des revendications précédentes, dans lequel le composant
secondaire est un solide comprimé ou un récipient contenant une composition secondaire.
9. Procédé selon la revendication 8, dans lequel le composant secondaire est un récipient
comprenant un film polymère contenant un solide, un gel ou un liquide.
10. Procédé selon l'une quelconque des revendications précédentes, dans lequel le composant
primaire et/ou le composant secondaire comprennent un poly(alcool vinylique).
11. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'article
est destiné à être utilisé dans le lavage de la vaisselle, l'entretien de tissus ou
l'entretien de surfaces.
12. Procédé selon la revendication 11, dans lequel le composant primaire comprend une
composition pour le lavage de la vaisselle, l'adoucissement de l'eau, le lavage du
linge ou détergente.
13. Procédé selon la revendication 11 ou 12, dans lequel le composant secondaire comprend
une composition pour lavage de la vaisselle, l'adoucissement de l'eau, le lavage du
linge ou détergente ou un adjuvant de rinçage.
14. Procédé selon l'une quelconque des revendications 1 à 10, dans lequel le composant
primaire et/ou le composant secondaire comprennent une composition désinfectante,
antibactérienne ou antiseptique.
15. Procédé selon l'une quelconque des revendications 1 à 10 ou 14 dans lequel l'article
comprend une composition de recharge pour un pulvérisateur du type à gâchette.
16. Procédé selon l'une quelconque des revendications 1 à 10, dans lequel l'article comprend
une composition à usage agricole.
17. Article hydrosoluble comprenant un composant primaire hydrosoluble qui est un récipient
thermoformé contenant une composition primaire, caractérisé en ce qu'un composant secondaire hydrosoluble est attaché à l'extérieur du récipient thermoformé.
18. Article selon la revendication 17, dans lequel la composition primaire est un solide,
un gel ou un liquide.
19. Article selon la revendication 17 ou 18, dans lequel le composant secondaire est un
solide comprimé ou un récipient contenant une composition secondaire.
20. Article selon la revendication 19, dans lequel le composant secondaire est un récipient
comprenant un film polymère contenant un solide, un gel ou un liquide.
21. Article selon l'une quelconque des revendications 17 à 20, dans lequel le composant
primaire et/ou le composant secondaire comprennent un poly(alcool vinylique).
22. Article selon l'une quelconque des revendications 17 à 21, dans lequel l'article est
destiné à être utilisé dans le lavage de la vaisselle, l'entretien de tissus ou l'entretien
de surfaces.
23. Article selon la revendication 22, dans lequel la composition primaire est une composition
pour le lavage de la vaisselle, l'adoucissement de l'eau, le lavage du linge ou détergente.
24. Article selon la revendication 22 ou 23, dans lequel le composant secondaire comprend
une composition pour le lavage de la vaisselle, l'adoucissement de l'eau, le lavage
du linge ou détergente ou un adjuvant de rinçage.
25. Article selon l'une quelconque des revendications 18 à 21, dans lequel la composition
primaire et/ou le composant secondaire comprennent une composition désinfectante,
antibactérienne ou antiseptique.
26. Article selon l'une quelconque des revendications 18 à 21 ou 25, dans lequel l'article
comprend une composition de recharge pour un pulvérisateur du type à gâchette.
27. Article selon l'une quelconque des revendications 17 à 21, dans lequel l'article comprend
une composition à usage agricole.
1. Verfahren zur Herstellung eines wasserlöslichen Gegenstands, umfassend einen wasserlöslichen
ersten warmgeformten Bestandteil und einen an der Außenseite davon angebrachten wasserlöslichen
zweiten Bestandteil, welches das Positionieren des zweiten Bestandteils in den Hohlraum
einer Warmformungsform umfasst, wonach ein erster Bestandteil in oder auf die Warmformungsform
positioniert wird, der erste warmgeformte Bestandteil durch Warmformen des ersten
Bestandteils in der Form geformt wird und der Gegenstand aus der Form entfernt wird.
2. Verfahren nach Anspruch 1, wobei der erste Bestandteil eine Folie ist.
3. Verfahren nach Anspruch 1, wobei der erste warmgeformte Bestandteil eine Folie umfasst.
4. Verfahren nach einem der Ansprüche 1 bis 3, wobei der erste Bestandteil zu einem von
einem Versiegelungsteil umgebenen Beutel warmgeformt wird und das Verfahren zusätzlich
die Schritte des Füllens des Beutels mit einer ersten Zusammensetzung und Verschließen
des Beutels z.B. durch Positionieren einer Folie auf dem gefüllten Beutel und über
dem Versiegelungsteil und Versiegeln der Polymerfolien miteinander umfasst.
5. Verfahren nach Anspruch 1 oder 3, wobei der erste Bestandteil ein versiegelter Behälter
ist, der eine erste Zusammensetzung umfasst.
6. Verfahren nach Anspruch 5, wobei der versiegelte Behälter durch Warmformen einer Folie
zu einem von einem Versiegelungsteil umgebenen Beutel, Füllen des Beutels mit einer
ersten Zusammensetzung und Verschießen des Beutels z.B. durch Positionieren einer
Folie auf dem gefüllten Beutel und über dem Versiegelungsteil und Versiegeln der Folien
miteinander am Versiegelungsteil umfasst.
7. Verfahren nach einem der Ansprüche 4 bis 6, wobei die Zusammensetzung ein Feststoff,
ein Gel oder eine Flüssigkeit ist.
8. Verfahren nach einem der vorangehenden Ansprüche, wobei der zweite Bestandteil ein
komprimierter Feststoff oder ein eine zweite Zusammensetzung enthaltender Behälter
ist.
9. Verfahren nach Anspruch 8, wobei der zweite Bestandteil ein Behälter ist, der eine
einen Feststoff, ein Gel oder eine Flüssigkeit enthaltende Polymerfolie umfasst.
10. Verfahren nach einem der vorangehenden Ansprüche, wobei der erste Bestandteil und/oder
der zweite Bestandteil einen Poly(vinylalkohol) umfassen.
11. Verfahren nach einem der vorangehenden Ansprüche, wobei der Gegenstand beim Geschirrspülen,
bei der Gewebepflege oder Oberflächenpflege verwendet wird.
12. Verfahren nach Anspruch 11, wobei der erste Bestandteil eine Geschirrspül-, Wasserenthärter-,
Wäschewasch- oder Detergenszusammensetzung umfasst.
13. Verfahren nach Anspruch 11 oder 12, wobei der zweite Bestandteil eine Geschirrspül-,
Wasserenthärter-, Wäschewasch- oder Detergenszusammensetzung oder eine Spülhilfe umfasst.
14. Verfahren nach einem der Ansprüche 1 bis 10, wobei der erste Bestandteil und/oder
der zweite Bestandteil eine desinfizierende, antibakterielle oder antiseptische Zusammensetzung
umfassen.
15. Verfahren nach einem der Ansprüche 1 bis 10 oder 14, wobei der Gegenstand eine Nachfüllzusammensetzung
für ein Pumpspray umfasst.
16. Verfahren nach einem der Ansprüche 1 bis 10, wobei der Gegenstand eine landwirtschaftliche
Zusammensetzung umfasst.
17. Wasserlöslicher Gegenstand, umfassend einen wasserlöslichen ersten Bestandteil, bei
welchem es sich um einen warmgeformten Behälter handelt, der eine erste Zusammensetzung
enthält, dadurch gekennzeichnet, dass ein wasserlöslicher zweiter Bestandteil an der Außenseite des warmgeformten Behälters
angebracht ist.
18. Gegenstand nach Anspruch 17, wobei die erste Zusammensetzung ein Feststoff, ein Gel
oder eine Flüssigkeit ist.
19. Gegenstand nach Anspruch 17 oder 18, wobei der zweite Bestandteil ein komprimierter
Feststoff oder ein eine zweite Zusammensetzung enthaltender Behälter ist.
20. Gegenstand nach Anspruch 19, wobei der zweite Bestandteil ein Behälter ist, der eine
einen Feststoff, ein Gel oder eine Flüssigkeit enthaltende Polymerfolie umfasst.
21. Gegenstand nach einem der Ansprüche 17 bis 20, wobei der erste Bestandteil und/oder
der zweite Bestandteil einen Poly(vinylalkohol) umfassen.
22. Gegenstand nach einem der Ansprüche 17 bis 21, wobei der Gegenstand beim Geschirrspülen,
bei der Gewebepflege oder Oberflächenpflege verwendet wird.
23. Gegenstand nach Anspruch 22, wobei der erste Bestandteil eine Geschirrspül-, Wasserenthärter-,
Wäschewasch- oder Detergenszusammensetzung umfasst.
24. Gegenstand nach Anspruch 22 oder 23, wobei der zweite Bestandteil eine Geschirrspül-,
Wasserenthärter-, Wäschewasch- oder Detergenszusammensetzung oder eine Spülhilfe umfasst.
25. Gegenstand nach einem der Ansprüche 18 bis 21, wobei die erste Zusammensetzung und/oder
der zweite Bestandteil eine desinfizierende, antibakterielle oder antiseptische Zusammensetzung
umfassen.
26. Gegenstand nach einem der Ansprüche 18 bis 10 oder 21, wobei der Gegenstand eine Nachfüllzusammensetzung
für ein Pumpspray umfasst.
27. Gegenstand nach einem der Ansprüche 17 bis 21, wobei der Gegenstand eine landwirtschaftliche
Zusammensetzung umfasst.