[0001] The present invention relates to a semipermeable venting cap according to the preamble
of the independent claim. It permits the selective passage of gases but not of the
liquids, suitable to seal plastic bottles, containing liquids which could create positive
or negative pressure by producing gaseous products or by absorbing air from the headspace,
and to compensate pressure differences. Examples of such liquids are housecleaning
and sanitation solutions, cosmetics, biochemicals, agrochemicals, beverages and liquid
food products. The creation of positive or negative pressure in the plastic container
causes unwanted deformation of the container.
[0002] Venting caps must be able to function properly in a wide spun of end uses and storage
and transportation conditions. For a wide group of consumer packages the following
major prerequisites are required: (a) The caps must vent air at low pressure difference
built-up. (b) They must not permit liquid exit even at high pressure built-up in the
container. (c) They must retain these properties in the most extreme conditions of
transportation and storage. (d) Their cost of production must be low and the materials
and parts required for their manufacturing must be readily available. From the evaluation
of vented cap technology available at present it was found that in all cases the vented
caps proposed or offered in the market do not conform sufficiently to one or more
of the above prerequisites.
[0003] Up to now the following arrangements have been tried to overcome this problem.
[0004] A first attempt was the creation of plastic bottles with very thick walls and specially
design features to prevent deformation. Such bottles are expensive and environmentally
non suitable because of the need to use excessive plastic material (see for example
Packaging Techn. & Sci., 6 (1993), 23-29).
[0005] A second attempt was the capping of the bottles with caps fitted with porous semipermeable
membranes, which permit the passage of gazes but not of liquids. The caps have suitable
openings permitting the gas to exit to the environment. The major problem of this
arrangement consists in the need of a much higher pressure difference to guarantee
functionality, when the membrane is wet. Such caps are described in the following
patents and patent applications: EP-0 408 378 (W.L. Gore), WO 94/26614 (Procter&Gamble),
WO 94/22553 (W.L. Gore), DE-2 341 414 (Hesser). There are two main problems related
to such caps. One is the high cost of the semipermeable membrane used and the limited
sources of their supply. The other and most important problem is that when the membranes
come in contact with the liquid contents (which almost always happens when the packages
are transported or stored in tilted or in horizontal position) there is a change in
their permeation characteristics. Thus, instead of permitting the gases to flow at
low pressure differences, the once moistened membranes require much higher pressure
differences to permit gas flow. There are cases where a membrane is specified to permit
gas flow at 5 mbar pressure difference which rises to 250 mbar when the membrane is
wetted. To overcome this second problem, a protective cap of the membrane is proposed
in EP-0 110 046 (Rhein-Conti) and in Greek patent application 960100443. Such attempts
increase excessively the cost of caps.
[0006] A third attempt was the use of caps containing an outlet covered by an elastic membrane
with a thin split which would permit the exit of gas above certain pressure but impermeable
to the liquid contents. Such caps are described in EP-0 555 623 GB-1 534 570, US-5,143,236
(L'Oreal), US-4,896,789 and Greek patent application 96011443. The drawback of such
caps is the lack of complete selectivity in permitting the exit of gas but not of
the liquid. Normally one can see liquid bubbles coming out of such caps during storage.
It has been found in our experiments that the size and shape of the slit, the geometry
of the elastic membrane, and the characteristics of the elastic material of the membrane
are so critical that even the slightest deviation creates this non selectivity problem.
[0007] A fourth attempt where caps containing an inside elastic sealing disc, seated on
a ribbed or grooved non flat surface on the underside of the cap. In theory a gas
under pressure inside the bottle deforms the elastic disc and escapes through the
openings created between the deformed disc and the non flat surface of the cap (US-5,242,069
(Henkel), DE-3 611 089 (Henkel), WO 94/13549 (Wazel), EP-0 241 780 (Henkel), US-5,457,943
(Hertramf)). The main drawback in such caps, in addition to their non-selectivity,
is the fact that very high pressure differences are required to deform the disc (200
mbar or more). At such high pressures the plastic bottle is already deformed before
the escape of gas.
[0008] The aim of the present invention is to overcome the above limitations of the up to
now existing venting caps. The aim is solved by the invention as defined in the independent
claims.
[0009] The herein disclosed cap is designed to permit gas escape from the contents to the
environment and vice versa at very low pressure differences, even when the cap is
wet. In the same time the cap is not permeable to liquid even at high pressure differences.
The distinguished characteristic of the venting cap described in the present invention
is the foolproof selective permeation of gas but not of liquid. The venting properties
of such a cap remain unaltered even at extreme conditions of transportation and storage.
This selective permeation is achieved by forcing the fluid contents, liquid or gas,
to pass through a swellable liquid-absorbing mass preferably made of polymeric matrix
before finding an outlet to the outside environment. No liquid is permitted to pass
through this polymeric matrix after its expansion by absorption of water, contrary
to the free passage of gas. The selective free passage of gas is further improved
by the inclusion of granules of a porous material in the swollen polymeric mass.
[0010] The venting cap according to the invention comprises a cavity, at least one first
passage for fluids connecting the cavity with the inside of the container, at least
one second passage for fluids connecting the cavity with the outside of the container,
and a liquid-absorbing mass arranged within the cavity. The liquid-absorbing mass
acts, after absorption of liquid, as a selective filter prohibiting the passage of
liquid, but permits the passage of gas.
[0011] Further characteristics and advantages of the present invention will become apparent
from the following detailed description of one preferred embodiment of the invention,
illustrated by the accompanying drawings, wherein;
- Fig. 1
- shows a cross-section through the cap according to the invention in perspective three-dimensional
view;
- Fig. 2
- shows a cross-section through the cap according to the invention in a front view;
- Fig. 3
- shows the cap according to the invention in a top view; and
- Fig. 4-6
- show the function of the cap according to the invention in three cross-sections.
[0012] Figure 1 shows a preferred embodiment of a semipermeable venting cap 1 according to the invention.
The cap 1 is preferably made of polypropylene or other thermoplastic or thermo set
materials. An inside 11 of the cap 1, comprises at least one narrow venting channel
5.1, 5.2 restricting the passage of liquid; such venting channels 5.1, 5.2 may also
form a network. The inside 11 of the cap 1 is designed to form a cavity 7 for storing
a liquid-absorbing mass 8 (see Fig. 2) and the fastening of an undercap 3. In the
embodiment shown in Fig. 1, the cavity 7 is formed by a cylindrical ring 12 connected
to the cap 1, and the undercap 3 is fitted over the ring 12. The undercap 3 is preferably
made of low-density PE or other flexible material. It comprises a venting hole 4 with
a diameter in the range of 0.1 to 1.5 mm which is small enough to slow down the passage
of liquid contents. A cut or slot or a slot having a length in the range of 2 to 10
mm and a width in the range of width 0.01 to 0.2 mm would also be suitable to serve
as the venting hole 4. In the undercap 3 a sealing ring 6 is incorporated to create
air-tight sealing between the cap 2 and a container 9 (see Fig. 4).
[0013] Figure 2 shows the venting cap 1 in a front view. The cavity 7 is filled with the liquid-absorbing
mass 8, e.g., water-absorbing polymeric granules. The undercap 3 acts as a cover which
prevents the water-absorbing granules 8 from falling out of the cavity 7. The narrow
venting channels 5.1, 5.2 are arranged in such a manner that the adjustment of pressure
difference by gas flow is supported and the flow of liquid is restricted. The cavity
7 can also be arranged in a different way but it is preferably located in a place
where normally it is surrounded by gas. The venting cap 1 permits therefore the selective
passage of gases but not of liquids. The water-absorbing granules 8 in the cavity
7 act as a selective filter prohibiting the passage of liquid, but permitting the
passage of gas. The following swellable polymers are preferred as liquid absorbing
polymeric mass: Crosslinked acrylic acid polymers and copolymers polymerized in organic
solvents. Other carboxylic acids and salts used to create such polymers are metacrylic
acid, malcic acid and itaconic acid. To improve the rate of water absorbency, these
acrylic acid polymers can be polymerized in presence of dispersed nitrogen or CO
2 so that polymer porous particles are formed. The liquid-absorbing mass 8 in the cavity
7 preferably has a bulk volume of 5-70 % of the volume of the cavity 7.
[0014] To further improve the selective free passage of gas, an inert organic or inorganic
porous material can be included in the cavity 7. This porous material with a open
surface structure creates a continuous network of channels, when in contact to each
other. The ensuring of free passage of gas is guaranteed. As an example good results
are obtained by the following porous materials: Aluminosilicate molecular sieve with
a preferred bulk density of 750 kg/m
3, a bead size of 95 % between 1 and 0.5 mm and an average pore size of 3 µm; Porous
polyolefin with a preferred bulk density of 300 kg/m
3, a bead size of 1-3 mm, a porosity of > 50 vol% and an average pore size of 3 µm.
[0015] Figure 3 shows the venting cap 1 in a top view. The hidden edges are dashed. The narrow venting
channels 5.1, 5.2 connect the cavity 7 with the outer environment of the cap 1. As
shown here the narrow channels 5.1, 5.2 are arranged in a way that their existence
is not visible from the outside, which may be an advantage due to design reasons.
The narrow venting channels 5.1, 5.2 can also be arranged in a different way or have
a different design than in the embodiment of Fig. 1. They are optimized as to the
liquid stored in the container closed by the cap 1. If more gas has to be transferred,
they are designed wider. It is also possible that the narrow channels 5.1, 5.2 are
temporarily sealed, if this is necessary. For certain high-quality beverages it is
an advantage if they are completely sealed during a certain period. Young wines in
bottles as an example need a cap which allows to equalize pressure differences during
storing because of gas production. The narrow channels 5.1, 5.2 in a combination with
the water-absorbing granules 8 can be designed to guarantee optimal storing to obtain
best quality.
[0016] Figures 4-6 explain the operation of the invention. A container 9 is filled with a liquid product
10 (e.g., a disinfectant solution of hydrogen peroxide) and capped with the venting
cap 1. In the embodiment shown in the Figures 4-6 an opening 5 has the same function
as the narrow channels 5.1, 5.2 of Figs. 1 and 2. In case where the container 9 is
stored upside-down or side-down (see Fig. 5), the liquid 10 starts slowly entering
into the cavity 7 through the small opening 4 of the undercap 3. This is displayed
by an arrow P. The first small quantity of water solution entering the cavity 7 between
cap 2 and undercap 3 swells the granules 8 of polymer, creating a mass which fills
the cavity 7. This is displayed in Figs. 5 and 6, where the water absorbing granules
8 are starting to swell (see Fig. 5) filling the cavity 7 until it is completely filled
(see Fig. 6). This swollen mass 8 acts from this point on as selective filter prohibiting
the flow of liquid 10, but permitting the passage of gas in both directions, which
is indicated by an arrow F.
[0017] Another application of this cap is the following. A container 9 is filled with a
hot liquid 10 e.g., a hot sauce, and capped with a venting cap 1. With a normal sealing
cap (not shown in detail) the walls of the bottle will be deformed after cooling.
The use of the venting cap 1 according to the invention will create equalization of
outside and inside pressures by permitting air to enter the bottle 9. In case that
the bottle is stored side-down, the cap becomes liquid-tight due to the mechanism
described in the previous example.
[0018] An alternative possibility is the use of the venting cap 1 with already swollen water-absorbing
granules 8. A bottle 9 is filled, for an example, with an agrochemical product in
organic solvent, e.g., xylene. In case that the liquid-absorbing mass 8 absorbs only
water but not xylene, this embodiment would not work. In this case the problem is
solved by using the venting cap 1 with pre-swollen water-absorbing granules 8. This
is achieved by adding to the cavity 7 of the cap 1 the proper amount of water together
with the swollen water-absorbing granules 8 before fastening the undercap 3 to the
ring 12.
1. A venting cap for a container (9) comprising
a cavity (7),
at least one first passage (4) for fluids connecting the cavity (7) with the inside
of the container (9),
at least one second passage (5.1, 5.2, 5) for fluids connecting the cavity (7) with
the outside of the container (9), and
a liquid-absorbing mass (8) arranged within the cavity (7), the liquid-absorbing mass
(8) acting, after absorption of liquid, as a selective filter prohibiting the passage
of liquid, but permitting the passage of gas.
2. The venting cap according to claim 1 wherein the liquid-absorbing mass (8) is swellable
by absorption of liquid.
3. The venting cap according to claims 1 or 2 wherein the liquid-absorbing mass (8) consists
of crosslinked acrylic acid polymers and/or copolymers polymerized in organic solvents
and/or other carboxylic acids and salts used to create polymers such as metacrylic
acid, malcic acid or itaconic acid.
4. The venting cap according to either of claims 1-3 wherein the liquid-absorbing mass
(8) is polymerized in presence of dispersed nitrogen or CO2 so that polymer porous particles are formed to improve the rate of water absorbency.
5. The venting cap according to either of claims 1-4 wherein the cavity (7) contains
granules of an inert organic or inorganic porous material in addition to the liquid-absorbing
mass (8).
6. The venting cap according to either of claims 1-5 wherein the liquid-absorbing mass
(8) in the cavity (7) has a bulk volume of 5-70 % of the volume of the cavity (7).
7. The venting cap according to either of claims 1-6 wherein the first passage (4) is
designed in such a way that passage of liquid is slowed.
8. The venting cap according to claim 7 wherein the first passage (4) is an opening with
a diameter in the range of 0.1 to 1.5 mm or a slot having a length in the range of
2 to 10 mm and a width in the range of width 0.01 to 0.2 mm.
9. A venting cap according to either of claims 1-8 wherein the liquid-absorbing mass
(8) is swollen by previously added liquid.
10. Use of the above described venting cap (1) for capping containers for cleaning fluids,
sanitation solutions, agro chemicals, cosmetics, food and biological products.