JP2001031159A - Aerosol product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent an adsorptive material from being jetted out to the outside by fixedly providing the adsorptive material removing water content increasing with elapsed time in an aerosol composition, in an aerosol product that an aerosol composition composed of nonaqueous undiluted solution and a jet agent is enclosed in a pressure resistant container. SOLUTION: An aerosiol product that a nonaqueous aerosol composition such an insecticide or hair spray is filling an aerosol container in a compressed condition is constituted of an actuator 1, a valve 2, a container 3 filled with an aerosol composition (a jet agent/an undiluted solution 5), a stem 7, a mounting cup 8, a spring 10, a dip tube, etc. In this case, an adsorptive substance, silicagel 12 for exsample is fixed to a passage of the composition, the dip tube 11 for example. The adsorptive substance is not especially limitted as long as it is a material capable of removing water content increasing with elapsed time in the aerosol composition, and besides silica, synthetic zeolite, activated alumina, activated clay, etc., can be enumerated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an aerosol product for improving the stability of the aerosol product. More specifically, by removing the water that increases with time in the aerosol composition consisting of a non-aqueous stock solution and a propellant, corrosion of the container and hydrolysis of the active ingredient in the aerosol composition are prevented, and the like. The present invention relates to an aerosol product that improves the stability of an aerosol product.

[0002]

2. Description of the Related Art Aerosol products have a higher pressure than the outside (atmospheric pressure) and are highly airtight, so that even if the composition leaks from the inside, moisture or the like is mixed into the inside from the outside. I could not imagine that.

However, a non-aqueous aerosol composition such as an insecticide or a hair spray is hermetically sealed in an aerosol container under a pressurized state, and even if air is not mixed in from outside, the metal container corrodes with time. Or the active ingredient may be reduced. Such corrosion is caused by an increase in the water content of the aerosol composition over time, and the increase in the water content causes corrosion of the container, or the active ingredient in the aerosol composition is hydrolyzed to cause corrosion. It is thought that it has turned into a substance and promoted corrosion.

Japanese Patent Publication No. 2-30952 discloses the use of silica gel as a means for improving the stability of aerosol products. This publication describes an aerosol product in which halon (digestive agent) that generates halogens when absorbed moisture and corrodes the container is enclosed together with silica gel. This product is a simple fire extinguisher and sprays a large amount toward the source of fire. For this reason, there is no particular problem if the silica gel is sprayed together with the digestive agent, and there is no particular description on the means for fixing the silica gel.

[0005] Although there are aerosol products containing silica gel, there are the following problems when silica gel is simply added to general products not containing silica gel (such as hair sprays, insecticides, disinfectants, anti-inflammatory analgesics, etc.). There was a point.

(1) Since the silica gel is sprayed together with the aerosol composition, it has an adverse effect on the spraying state, such as inability to uniformly spray the active ingredient and the like.

(2) When used as a body product, the silica gel adheres to the skin, causing the skin to become white or unnecessarily rough and slippery.

(3) Since silica gel is solid, it is easy to cake at the bottom of the container or to be clogged with a valve or a spray button.

In order to prevent the silica gel from being clogged with the valve or the injection button, it is conceivable to increase the hole diameter of the valve or the injection button. However, if the hole diameter of the valve or the injection button is increased, the injection amount becomes unnecessarily large. However, there were problems in terms of safety such as cooling performance and flammability.

[0010]

DISCLOSURE OF THE INVENTION The present invention relates to an aerosol product containing an adsorbent substance for preventing corrosion of an aerosol container filled with a non-aqueous aerosol composition.
It is intended to prevent the adsorbing substance from being sprayed together with the aerosol composition. Further, the object is to improve the stability of aerosol products (containers, compositions).

[0011]

That is, the present invention relates to an aerosol product in which an aerosol composition comprising a non-aqueous stock solution and a propellant is sealed in a pressure-resistant container. An aerosol product wherein the adsorbing substance to be removed is fixed inside the container (claim 1), wherein the aerosol composition has a dissolution parameter of 7.5 to 25 or a kauributanol value of 50 to 120. The aerosol product according to claim 1 containing a component (claim 2), having a dissolution parameter of 7.5 to 7.5.
The aerosol product (Claim 3) according to claim 2, characterized in that the aerosol composition contains 25 or a component having a Kauributanol value of 50 to 120 by weight in the aerosol composition. 4. The aerosol product according to claim 1, 2 or 3, wherein the adsorbent is fixed to a gas phase in an aerosol container, wherein the product is fixed to a passage through which the aerosol composition passes. The aerosol product according to claim 1, 2 or 3, wherein the adsorbing substance is fixed to a liquid phase portion in an aerosol container (claim 5). The aerosol product (Claim 6), and the aerosol product according to Claim 1, 2 or 3, wherein the adsorbed substance is coated on a surface inside the container (Claim 7).
About.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to an aerosol container enclosing an aerosol composition comprising a non-aqueous stock solution and a propellant. An aerosol product which is fixed in a container so as not to be sprayed.

[0013] The non-aqueous stock solution is 1% by weight of water in the stock solution.
Containing less than, for example, lower alcohols,
Examples include polyhydric alcohols, higher alcohols, hydrocarbons, ester oils, higher fatty acids, silicones, fats and oils, and waxes.

The lower alcohol includes ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol and the like.

Examples of the polyhydric alcohol include dihydric alcohols such as ethylene glycol, propylene glycol and 1,3-butylene glycol, trihydric alcohols such as glycerin and trimethylolpropane, tetrahydric alcohols such as pentaerythritol, and xylitol. 5 such as
6 such as polyhydric alcohol, sorbitol and mannitol
Alcohol, diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, diglycerin, polyethylene glycol,
Polymers of polyhydric alcohols such as triglycerin, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether,
Alcohol alkyl ethers such as ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, propylene glycol monoethyl ether, dipropylene glycol ethyl ether, and diethylene glycol dimethyl ether; ethylene glycol monoethyl ether Examples thereof include alcohols such as acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.

Examples of the higher alcohol include linear alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol and oleyl alcohol, monostearyl glycerin ether, lanolin alcohol, hexyl decanol, isostearyl alcohol, octyl dodecanol and the like. And branched alcohols.

Examples of the hydrocarbon include n-hexane, i-hexane, kerosene, petroleum ether, liquid paraffin, squalene, squalane, petrolatum, paraffin, isoparaffin and the like.

Examples of ester oils include isopropyl myristate, cetyl octanoate, octyl dodecyl myristate, isopropyl palmitate, butyl stearate, myristyl myristate, decyl oleate, cetyl lactate, myristyl lactate, isocetyl stearate, and isocetyl isostearate. Lanolin acetate, ethyl acetate, butyl acetate, oil oleate, cetostearyl alcohol, diisobutyl adipate, diisopropyl sebacate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, And 2-hexyldecyl adipate.

Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, isostearic acid, linoleic acid, linoleic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA) and the like. Can be

Examples of the silicone include dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, decamethylpolysiloxane, tetramethyltetrahydrogenpolysiloxane and the like.

Examples of fats and oils include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, rubber oil, castor oil, linseed oil, safflower oil, jojoba oil, germ oil, Palm oil, palm oil, hydrogenated castor oil and the like.

As the wax, beeswax, lanolin, lanolin acetate, candelilla wax, kaunauba wax, whale wax,
Montan wax and the like.

Further, an active ingredient can be blended according to the purpose of the product.

The active ingredients include a set agent for the hair, a treatment agent, a hair restorer, a hair dye, a cleansing agent for the scalp, a disinfectant, athlete's foot, a wound, an anti-inflammatory analgesic, a humectant,
There are no particular limitations on cleansing agents, antiperspirants, repellents, insecticides, fumigants, deodorants, fragrances, and the like. In addition, a surfactant, a thickener, a water-soluble polymer, and the like can be blended depending on the mode of spraying (fog, foam, gel, etc.).

The propellant is a liquid or a gas having a pressure for injecting the undiluted solution out of the container.
Liquefied petroleum gas (hereinafter, referred to as "LPG"), dimethyl ether (hereinafter, referred to as "DME"), nitrogen gas, which is butane, i-butane, propane, and a mixture thereof;
Examples include carbon dioxide, nitrogen suboxide, compressed air, and helium. The ratio of the stock solution in the composition comprising these stock solution and the propellant is preferably 5 to 99.9% by weight.
If the amount exceeds 99.9% by weight, the pressure required for injecting the entire amount of the undiluted solution cannot be obtained, and the undiluted solution remaining in the container increases,
If the amount is less than 5% by weight, the amount of the active ingredient that can be blended becomes small, and the desired effect tends not to be obtained.

In the present invention, the aerosol composition comprising a non-aqueous stock solution and a propellant has a solubility parameter (SP value).
Is 7.5 to 25, or kauributanol value (KB)
(Value) is 50 to 120.

10% by weight of a component satisfying the above conditions is used.
Since the composition contained above has a high solubility in water, it absorbs (dissolves) water over time. Therefore, when the solubility parameter is less than 7.5 and the Kauributanol value is less than 50, the water dissolving ability is poor,
It is stable with little water absorption over time.

The solubility parameter δ is defined by the following equation:

Δ = (ΔE^V/ V)^1/2(Cal / cm^Three)^1/2 Here, V is the molecular volume at each temperature of the liquid, ΔE^VIs steamed
Represents the energy generated. ΔE^VAbout the saturated steam of liquid
If the pressure is not very high, the gas
ΔE^V= (ΔH^V-RT)
From the heat of evaporation ΔH ^VCan be determined by measuring
it can. The evaporation energy at the boiling point is known.
At the temperature (25 ° C) where the solubility is to be determined.
Heat of evaporation ΔH ^VIf you don't know,
It can be obtained by conversion using the equation of n.

H ₂ = H ₁ × {(1−T _r2 ) / (1−T _r1 )} ^0.38 where _{Tr 1} = T ₁ / T _c , and T _c is a critical temperature.

On the other hand, kauributanol value (KB value)
Can be calculated by a test method according to “ASTM-D1133-61”.

The kauri-butanol value KB is determined by adding 20 g of a 20% by weight butanol solution of kauri gum (natural resin) to 25 g.
It is defined by the following formula from the titration amount of the solvent added until the kauri gum precipitates and becomes cloudy at 0 ° C. with a hydrocarbon solvent.

KB = 65 × (CB) / (AB) +40 where A is the titer when toluene is used, and B is n-
The titer when a heptane: toluene = 75: 25 mixed solvent is used, and C is the titer of the sample solvent. When the measurement temperature T is not 25 ° C., the amount is calculated from the titer C ′ at that temperature using C obtained by the following equation.

C = C ′ × (25−T) × 0.0009 As a component having a solubility parameter of 7.5 to 25 or a Kauributanol value of 50 to 120, for example, D
ME (SP value 7.9, KB value 91), ethanol (SP
Value 13.2), n-propanol (SP value 12.1),
i-propanol (SP value 12), n-butanol (S
P value 11.4), i-butanol (SP value 11.3),
Ethylene glycol (SP value 15.6), propylene glycol (SP value 13.3), butanediol (SP value 13.6), glycerin (SP value 14.1), diethylene glycol (SP value 12.9), triethylene Glycol (SP value 11.3), ethylene glycol monoethyl ether (SP value 11), ethylene glycol monobutyl ether (SP value 9.2), ethylene glycol monoethyl ether acetate (SP value 8.8), lauryl alcohol (SP Value 9.1), n-hexane (SP value 7.6), n-heptane (SP value 7.7) and the like.

When the component having a solubility parameter of 7.5 to 25 or a kauributanol value of 50 to 120 is contained in the aerosol composition in an amount of 10% by weight or more, the water absorption of the aerosol composition is high. Must be installed. When the content is less than 10% by weight, the composition is stable over time due to a small amount of the water-absorbing component, and the necessity of installing an adsorbing substance is small.

The adsorbing substance in the present invention is not particularly limited as long as it can remove moisture that increases with time in the aerosol composition. Examples of the adsorbing substance include silica gel, synthetic zeolite, activated alumina, and activated clay. And so on. Among them, silica gel and zeolite are preferred because they have excellent water adsorption performance and are stable (inactive) with respect to solvents and propellants.

The amount of the adsorbent used is preferably 0.1 to 20% by weight of the aerosol composition. 20% by weight
When the pressure is higher than the above range, the bulk density of the adsorbed substance is large, so that it is difficult to fix the adsorbed substance inside the container, so that the adsorbed substance is easily ejected to the outside. On the other hand, when the content is less than 0.1% by weight, when the increase of water increases, the adsorbed substance is in a saturated adsorption state, and there is a tendency that water cannot be completely adsorbed.

The aerosol container of the present invention is characterized in that the adsorbing substance is fixed, and the adsorbing substance needs to be in contact with either or both of the gas phase and the liquid phase of the aerosol composition. The fixing method will be described below with reference to the accompanying drawings.

Embodiment 1 In this embodiment, an adsorbed substance is fixed to a passage of a composition. Examples of the passage include a dip tube and a housing of a valve. When fixing to a dip tube, the adsorbing substance may be fixed to the tip of the tube, or the entire tube may be filled with the adsorbing substance and fixed.

FIGS. 1 and 2 are cross-sectional views of an aerosol product in which an adsorbent is fixed to a dip tube. Here, 1 is an actuator, 2 is a valve, 3 is a container for containing the aerosol composition (propellant / stock solution 5), 6 is a stem gasket, 7 is a stem, 8 is a mounting cup, 9 is a housing, and 10 is a housing. spring,
11 is a dip tube, and 12 is silica gel.

The particle size of the adsorbing substance used in the present embodiment is not particularly limited, but is preferably 1 to 20 mm. If it exceeds 20 mm, the performance of the adsorbed substance cannot be sufficiently exhibited, for example, the contact area with water becomes small, and the adsorption speed becomes slow. On the other hand, if it is less than 1 mm, clogging or blockage tends to occur in the lower hole or stem hole of the valve, and when it is particularly fine, it tends to be sprayed together with the composition.

By fixing the adsorbed substance in the passage of the aerosol composition in this way, there is an effect that the adsorbed substance can be easily fixed.

Embodiment 2 In this embodiment, the adsorbed substance is fixed by molding and enclosing it in a container.

FIG. 3 shows a method for enclosing in a container.
FIG. 3 is a cross-sectional view of a product in which a storage unit is provided at a tip of a tube and a silica molded product is fixed in the storage unit. 13 represents a silica molded product. In the present embodiment, the silica molded product can be covered with a net so as not to come off from the accommodation portion installed at the tip of the tube. FIG. 4 is a cross-sectional view of a container fixed by installing a silica molded article inside the container.

Examples of a method for obtaining a molded article of an adsorbing substance such as a silica molded article include a method of compressing the adsorbed substance as it is or by mixing a binder such as a resin.
The shape of the silica molded product used here is not particularly limited, and includes a cube, a rectangular parallelepiped, a sphere, a cylinder, a cone, a triangular pyramid, and the like.In terms of the ease of molding and the strength of the molded product, a cube, A cuboid, a sphere, or a cylinder is preferred. Further, the size of such a molded product is preferably larger than at least the diameter of the dip tube. It should be noted that a plurality of silica molded products can be provided in the container.

By shaping the adsorbed substance and enclosing it in a container as described above, it plays the role of a stirring ball when the product is shaken and can move through the composition. This has the effect of increasing the adsorption activity.

Embodiment 3 In this embodiment, the molded adsorbent is fixed by attaching it to a valve. FIG. 5 shows a cross-sectional view of a product in which an adsorbent is formed and fixed to a housing portion of a valve. As shown in FIG. 5, when the aerosol product is held upright, moisture can pass through the stem, the stem gasket, the housing, and / or the seal (gasket) between the container opening and the fixed portion of the mounting cup. ), And the moisture in the gas phase first increases. By fixing the adsorbed substance to the valve portion as in the present embodiment, it is possible to adsorb water in the gas phase, prevent corrosion in the gas phase, and prevent water from being dissolved in the liquid phase. It has the effect that can be done.

Embodiment 4 In this embodiment, the adsorbed substance is fixed by forming it on the surface inside the aerosol container. As the surface inside the aerosol container, not only the container itself, but also the surface of the valve mounting cup, the surface of the housing,
Examples include the surface of a dip tube. Examples of a method for forming the adsorbed substance on the surface include vapor deposition and electrostatic powder coating. By fixing the adsorbing substance on the surface inside the aerosol container in this manner, there is an effect that the contact area with moisture is large and moisture can be quickly adsorbed.

FIG. 6 is a sectional view of a container having an adsorbing substance formed on the inner surface of the container, and FIG. 7 is a sectional view of a container having a layer made of the adsorbing substance formed on the surface of a housing or a mounting cup. 14 indicates a silica coating.

The thickness of the formed layer composed of the adsorbing substance is
It is preferably from 10 to 300 μm. Even if the thickness exceeds 300 μm, the performance of removing moisture does not change and the cost increases. If the thickness is less than 10 μm, the film strength tends to be weak and the film tends to peel off from the inner surface.

In the present embodiment, since the contact between the adsorbed substance and the aerosol composition is large and the water in both the gas phase and the liquid phase can be removed, the adsorption of the water is fast and the stability is high.

[0052]

EXAMPLES Next, the aerosol container of the present invention and a method for maintaining the quality of an aerosol composition using the same will be specifically described based on examples, but the present invention is not limited thereto.

Examples 1 and 2 and Comparative Example 1 99% denatured ethanol as a stock solution and LPG as a propellant
Was mixed with 30% by volume of the stock solution and 70% by volume of the propellant to prepare an alcohol-LPG-based non-aqueous aerosol composition. In addition, the solubility parameter of ethanol is
It is 13.2 at 25 ° C., and ethanol is contained in the aerosol composition at 37.2% by weight.

Using the prepared alcohol-LPG-based non-aqueous aerosol composition, a container containing no adsorbed substance (Comparative Example 1), a container having molded silica gel fixed to a valve (Example 1, the amount of silica gel added was aerosol) 5% by weight with respect to the composition, FIG. 5) and a container (Example 2, the amount of silica gel added was 5% by weight with respect to the aerosol composition, FIG. 4) in which spherical silica gel was inserted into the container. It was sealed in various types of aerosol containers. The spherical silica gel used in Example 2 had a diameter of 10 mm.
It is.

The above three types of aerosol containers were stored upright at room temperature, and the amount of water in the aerosol composition was measured at the start of storage, three months, six months, one year, and two years. The amount of water in the aerosol composition was measured by measuring 0.1 g of the sample with a water measuring device (trace water measuring device AQ-6,
(Hiranuma Sangyo Co., Ltd.). The results are shown in Table 1 and the amount of water plotted against the storage time is shown in FIG. The results in Table 1 are the average values of three measurements.

[0056]

[Table 1]

As is clear from Table 1, alcohol-L
Even in the aerosol container using the PG-based non-aqueous aerosol composition, the amount of water increases over time, and by containing silica gel as an adsorbent, the increase in the amount of water in the aerosol composition is suppressed. You can see that there is.

Examples 3 and 4 and Comparative Example 2 Using kerosene as a stock solution, 75% by weight of LPG and 25% by weight of DME as propellants,
The mixture was mixed with 40% by volume of the stock solution and 60% by volume of the propellant to prepare a kerosene-LPG / DME-based non-aqueous aerosol composition. The DME had a solubility parameter of 7.9 at 25 ° C. and a Kauri-butanol value of 91.
Is contained in the aerosol composition at 13.2% by weight.

Using the prepared kerosene-LPG / DME-based non-aqueous aerosol composition, a container containing no adsorbed substance (Comparative Example 2), a container having molded silica gel fixed to a valve (Example 3, amount of silica gel added) Is 1% by weight based on the aerosol composition, FIG. 5) and a container in which spherical shaped silica gel is inserted into the container (Example 4, the amount of silica gel added is 1% by weight based on the aerosol composition, FIG. 4). 3
It was sealed in various types of aerosol containers. The spherical silica gel used in Example 2 had a diameter of 6 mm.
It is.

The three types of aerosol containers were stored upright at room temperature, and the amount of water in the aerosol composition was measured at the start of storage, three months, six months, one year, and two years. The measurement of the amount of water in the aerosol composition was performed in Example 1.
The measurement was carried out in the same manner as in the case of. Table 2 shows the results, and FIG. 9 shows a plot of the amount of water with respect to the storage time. In addition,
The results in Table 2 are the average of three measurements.

[0061]

[Table 2]

As is clear from Table 2, kerosene-LPG /
Although the amount of water increases with time even in an aerosol container using a DME-based non-aqueous aerosol composition, the increase in the amount of water in the aerosol composition is suppressed by containing silica gel as an adsorbent. You can see that there is.

[0063]

The stability of the aerosol container can be improved by removing the increased water in the aerosol container, and the adsorbing substance for removing the water is not ejected to the outside, thereby affecting the ejection form. Nothing.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an aerosol container in which an adsorbing substance is fixed to a tip portion of a dip tube according to an embodiment of the present invention.

FIG. 2 is a cross-sectional view of an aerosol container in which an adsorbent is fixed to the entire dip tube according to one embodiment of the present invention.

FIG. 3 is a cross-sectional view of an aerosol container in which an accommodating portion is provided at a tip of a dip tube according to an embodiment of the present invention and a silica molded product is fixed in the container.

FIG. 4 is a sectional view of an aerosol container in which a silica molded product according to one embodiment of the present invention is installed inside an aerosol.

FIG. 5 is a cross-sectional view of an aerosol container in which an adsorbent according to one embodiment of the present invention is molded and fixed to a valve housing.

FIG. 6 is a cross-sectional view of an aerosol container having a container surface coated with an adsorbent substance according to one embodiment of the present invention.

FIG. 7 is a cross-sectional view of an aerosol container having a valve portion coated with an adsorbing substance according to one embodiment of the present invention.

FIG. 8 is a diagram showing a change in the amount of water in an alcohol-LPG non-aqueous aerosol composition with respect to a storage time.

FIG. 9 is a diagram showing a change in the amount of water in a kerosene-LPG / DME non-aqueous aerosol composition with respect to storage time.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Actuator 2 Valve 3 Container 4 Propellant (gas phase) 5 Propellant / Undiluted solution 6 Stem gasket 7 Stem 8 Mounting cup 9 Housing 10 Spring 11 Dip tube 12 Silica gel 13 Silica molded product 14 Silica coating 15 Gasket

Claims (7)

[Claims] 1. In an aerosol product in which an aerosol composition comprising a non-aqueous stock solution and a propellant is hermetically sealed in a pressure-resistant container, an adsorbent for removing water that increases with time in the aerosol composition contains an adsorbent substance inside the container. An aerosol product characterized by being fixed. 2. The aerosol composition according to claim 1, which has a solubility parameter of 7.5 to 25 or a Kauributanol value of 50.
The aerosol product according to claim 1, comprising a component that is 〜120. 3. The aerosol product according to claim 2, wherein a component having a solubility parameter of 7.5 to 25 or a kauributanol value of 50 to 120 is contained in the aerosol composition by 10% by weight or more. 4. The aerosol product according to claim 1, wherein the adsorbing substance is fixed in a passage through which the aerosol composition passes during injection. 5. The aerosol product according to claim 1, wherein the adsorbed substance is fixed to a gas phase in an aerosol container. 6. The aerosol product according to claim 1, wherein the adsorbed substance is fixed to a liquid phase portion in an aerosol container. 7. The aerosol product according to claim 1, wherein the adsorbing substance is coated on a surface inside the container.