CN101001686A - Oxygen-permeable film, oxygen-permeable sheet and electric cell comprising the same - Google Patents

Abstract

An oxygen-permeable film, which comprises an aggregate of water-repellent particles having an average particle diameter of 0.01 to 50 mum. The above oxygen-permeable film exhibits a contact angle with water of 120 DEG or more and has super water-repellency, and therefore exhibits excellent capability to inhibit the permeation of steam. A fluororesin such as polytetrafluoroethylene, polyvinyl fluoride or polyvinylidene fluoride is suitable as the material of the above particle. It is preferred that the oxygen-permeable film has a specific surface area of 0.1 to 500 m<2>.

Description

Oxygen-permeable film, oxygen see through sheet and comprise their battery

Technical field

The present invention relates generally to a kind of oxygen-permeable film, is specifically related to a kind of oxygen that optionally allows and sees through, suppresses simultaneously the film that steam sees through.Oxygen-permeable film for example can be used for sucking the air cell of oxygen of atmosphere and air inlet (oxygen) mechanism of fuel cell.In other words, the present invention relates to a kind of air cleaning film of from atmosphere, removing steam.

Background technology

In order to prevent moisture, the many element of airborne oxygen and devices of utilizing many invention designs have been carried out as air cell and fuel cell along with oxygen enters together.Under the situation of air cell, for example vapor in the atmosphere enters battery, causes the change in concentration or the Volume Changes of electrolyte, thereby flash-over characteristic is descended.

Therefore, proposed to provide a kind of oxygen selective permeation film and a kind of oxygen permeability solution layer that comprises the siloxy group compound, thereby prevented that vapor in the atmosphere from entering battery (patent documentation 1) at the air inlet place of air cell.

In addition, also proposed a kind of air cell, wherein uniform films etc. is provided with and is used to a plurality of holes that see through that are no more than 300 μ m that air is passed through, and uses it as the selective permeation film (patent documentation 2) that is used to prevent that steam from seeing through.

In addition, although be not in field of batteries, under the situation of the employed wireless antenna of many snowfields band, the snow or the ice that are attached to antenna surface may reduce electric-field intensity, thereby the quality of radio communication is descended.For preventing this point, can use the technology (non-patent literature 1) that PTFE (polytetrafluoroethylene (PTFE)) particle is applied to antenna surface as anti-snow material by adhesive.

Patent documentation 1: Japanese laid-open patent communique No.Sho 59-75582

Patent documentation 2: Japanese laid-open patent communique No.Hei 6-44954

Non-patent literature 1:Super water-repellency and super water-repellenttechnology, Technical Information Institute Co.Ltd. distribution, 155-163 page or leaf.

Summary of the invention

Problem to be solved by this invention

According to the proposal of patent documentation 1, can expect that oxygen is optionally imported in the battery.Yet, owing to use the double-layer structure that comprises oxygen selective permeation film and oxygen permeability solution layer, so gas permeation is slow.Therefore, although during low rates of discharge, can realize effect, during high rate discharge, be difficult to guarantee the oxygen of necessary amount, thereby flash-over characteristic descends significantly.

In addition, the proposal of expectability patent documentation 2 does not realize suppressing the very large effect that steam sees through, and is linear through hole because see through the hole, so the water proofing property deficiency of the inner surface in hole.

The means of dealing with problems

Therefore, inventor of the present invention conscientiously studies through the relation between the phenomenon the structure and the steam of air penetrating film, finds following result.Promptly, inventor of the present invention finds a kind of phenomenon, when by constituting air penetrating film by predetermined particle, thereby when making air penetrating film be in super water proofing property state (wherein the contact angle of air penetrating film and water is not less than 120 ℃ state), air sees through air penetrating film, but steam is through being suppressed.

Usually, when freely spread and during by the hole in the film in the hole of air in film, the inwall in the hole in airborne molecular collision film surface and the film.Similarly, the inwall in the hole in film surface and the film is collided in airborne steam (hydrone) diffusion simultaneously.Yet when film was in super water proofing property state, in the inwall process in the hole in collision film surface and film, steam was subjected to big repulsive force from the surface that quilt is collided, thereby can not diffuse into (by) hole.On the other hand, be not subjected to big repulsive force during the inwall in molecule in the air except steam such as oxygen and the nitrogen hole in collision film surface and film, therefore can diffuse into (by) hole.

Therefore, when air is not less than 120 ℃ film by the contact angle with water, optionally remove airborne steam, thereby can obtain dry air.

In addition, the mean free path that freely spreads molecule is about 100nm (=0.1 μ m).Therefore, when the aperture in the film is no more than about 100nm, the inwall in the hole when airborne steam passes through film in most of meeting collision film.Therefore, suppress the effect increase that steam sees through.That is, when realizing the Knudsen diffusion, suppress the effect increase that steam sees through.

In view of foregoing, the present invention proposes a kind of oxygen-permeable film that comprises the aggregation of water proofing property particle.Yet, with non-patent literature 1 propose being applied to antenna surface and not form the composite of the adhesive in any space and PTFE particle different, oxygen-permeable film of the present invention allows oxygen to see through.

Particularly, be 0.01～50 μ m by the average grain diameter that the water proofing property particle is set, formation is suitable for the space that oxygen passes through between particle.Because oxygen-permeable film of the present invention all or basically all is made of the water proofing property particle, so the inwall in the hole in film surface and the film has many concavo-convex.This concavo-convex water proofing property of improving film, thus obtained wherein being not less than 120 ° super water proofing property state with the contact angle of water.Therefore, when having suppressed steam during by oxygen-permeable film of the present invention, atmosphere sees through.

Is that 0.01～50 μ m and the particle with water proofing property are made oxygen-permeable film of the present invention by the whole bag of tricks in conjunction with average grain diameter.For example, wait fusion and incorporate particle agglomeration can be used as oxygen-permeable film by heating.Particle kind by change constituting film, particle diameter and in conjunction with the method for particle etc. can controlling diaphragm physical property.

As the water proofing property particle, preferably use fluorocarbon resin.As fluorocarbon resin, be preferably selected from least a of polytetrafluoroethylene (PTFE), polyvinyl fluoride and polyvinylidene fluoride.

The specific area of preferred oxygen-permeable film of the present invention is not less than 0.1m ²/ g and be not more than 500m ²/ g.In addition, although the thickness of oxygen-permeable film is not particularly limited, thickness for example can be not less than 0.1 μ m and be not more than 1000 μ m.

The invention still further relates to a kind of oxygen that comprises above-mentioned oxygen-permeable film and support the porous substrate of oxygen-permeable film and see through sheet, also relate to a kind of have comprise that above-mentioned oxygen-permeable film and a pair of oxygen that oxygen-permeable film is clipped in the three-decker of porous substrate therebetween see through sheet.In the present invention, preferred oxygen is not less than 0.5 second and is not more than 50000 seconds through the Gurley number of sheet.

As the material of porous substrate, be preferably selected from least a of polyethylene, polypropylene, polytetrafluoroethylene (PTFE), vinylon, polyphenylene sulfide (PPS), polybutylene terephthalate (PBT) (PBT) and nylon.

Preferred porous substrate has net, nonwoven or micro-porous film form.Can also use the material of metal as porous substrate.That is, can also use the metal forming and the wire netting of perforation.

The aggregation of preferred water proofing property particle has the hole that diameter is no more than 0.5 μ m.For example, the ratio of the accumulation pore volume S1 of diameter in 0.01 μ m～0.5 mu m range and the accumulation pore volume S2 of diameter in 0.01 μ m～10 mu m ranges: S1/S2 preferably is not less than 0.01 and be not more than 0.8, more preferably is not less than 0.02 and be not more than 0.75.

In addition, be no more than in the oxygen-permeable film of the present invention in hole of 0.5 μ m porosity preferred 20%～90% having diameter.

The invention still further relates to a kind of air cell, it comprises positive pole, negative pole, electrolyte and is used for supplying to positive pole the admission gear of air that wherein this admission gear comprises that above-mentioned oxygen-permeable film or oxygen see through sheet.

The invention still further relates to a kind of fuel cell, it comprises negative electrode, anode, electrolyte and is used for supplying to negative electrode the admission gear of air that wherein this admission gear comprises that above-mentioned oxygen-permeable film or oxygen see through sheet.

It is concavo-convex on a small quantity to should be noted that the polytetrafluoroethylene (PTFE) perforated membrane that generally can get often exists in its surface, and the contact angle of film and water is no more than 110 °, so they almost can not realize blocking the effect of steam.

The invention effect

Comprise that by use the aggregation of water proofing property particle and the average grain diameter of particle are the oxygen-permeable film of 0.01～50 μ m, can suppress airborne steam and see through, thereby obtain drier air.Use this oxygen-permeable film can suppress steam for the air inlet of air cell or fuel cell and enter in the battery, oxygen that will be a large amount of relatively imports in the battery simultaneously.Therefore, for air cell, even after under open mode, preserving, also can realize good high-rate discharge characteristic.In addition,, can suppress the water slug at negative electrode place, thereby enlarge the opereating specification of allowing for fuel cell.

In addition, using under the situation of oxygen-permeable film of the present invention, can prevent that also airborne steam from entering element and device for element except battery and device.Therefore, the function of the adverse effect that prevents that steam from causing can be provided for element and device.For example,, make room air and outdoor air exchange, can keep indoor humidity by oxygen-permeable film of the present invention at the device that is used for room air except steam and outdoor air exchange.

The present invention can also be used for the food association area.For example, when seeing through the sheet packaged food, can suppress airborne moisture and enter in store food, thereby improve keeping quality with oxygen of the present invention.

Description of drawings

Fig. 1 has the front view that oxygen sees through the Coin shape air cell of sheet, partly shows with the cross section.

Fig. 2 A has the front view that oxygen sees through the AA type air-zinc battery of sheet, partly shows with the cross section.

Fig. 2 B is the part enlarged drawing of Fig. 2 A.

Fig. 3 is a graph of pore diameter distribution, shows the aperture of oxygen-permeable film and the relation between the log differential pore volume.

Fig. 4 is a graph of pore diameter distribution, shows the aperture of oxygen-permeable film and the relation between the accumulation pore volume.

The specific embodiment

Oxygen-permeable film of the present invention comprises the aggregation of water proofing property particle, and the average grain diameter of particle is 0.01～50 μ m.Because the shape of particle, on the inwall in the hole in film surface and film formation many concavo-convex, thereby film is in the water proofing property state.In addition, the inside of oxygen-permeable film is occupied by the particle that merges or partly mutually combine by means of adhesive by its surface.Therefore, the inside of oxygen-permeable film presents fractal structure (fractal structure), and has many spaces.

When air passed through these spaces, only Comparatively speaking entering of strong inhibition steam, promoted seeing through of oxygen.Although oxygen and nitrogen by film diffuse in the film, bump has the inwall in the film surface and the hole in the film of water proofing property simultaneously, only has steam to be subjected to diffusion-restricted, because the inwall in its hole from film surface and film receives strong repulsive force.Should be noted that in the present invention, be not less than 120 ° film with the contact angle of water and be defined as super water proofing property.

When oxygen-permeable film of the present invention for example placed the inlet channel place of air cell or fuel cell, when air is only removed steam contained in the air during by this film, and dry air was imported in the battery.Therefore, Comparatively speaking can promote to import oxygen.

When the average grain diameter of water proofing property particle during, the concavo-convex minimizing on the inwall in the hole in film surface and the film, thereby can not obtain repelling the effect of steam fully greater than 50 μ m.On the other hand, when the average grain diameter of water proofing property particle during less than 0.01 μ m, the aperture in the film becomes quite little, thereby in the effect that the steam that is inhibited sees through, seeing through of oxygen is slack-off.Therefore, be difficult to guarantee apace the oxygen of necessary amount.

As previously mentioned, in the present invention, the average grain diameter that constitutes the water proofing property particle of oxygen-permeable film is limited to 0.01 μ m～50 μ m.Should be noted that preferably the average grain diameter of water proofing property particle is set to 0.1 μ m～15 μ m from obtain having the viewpoint of well balanced oxygen-permeable film between the effect of repelling steam and oxygen permeation rate.In addition, the contact angle between film and the water preferably is not less than 140 °.

Wherein use the state of adhesive although oxygen-permeable film of the present invention can be in, more preferably do not use adhesive that particle is merged each other by heat treated etc. in conjunction with the particle that constitutes film.Merge and increased film-strength, thereby can keep steam to see through the inhibition effect for more time.In addition, also can be to wherein realizing the further heat treatment of oxygen-permeable film of combination with adhesive, thus particle is merged each other.

Under the situation of using adhesive, in addition the polysiloxane group resin also can use fluorocarbon resin such as polyvinylidene fluoride as adhesive although for example preferably use.Adhesive consumption is particle diameter that depends on the water proofing property particle etc., thus regulation adhesive consumption and it is not particularly limited utterly; Yet binder dosage can be the water proofing property particle of 2～20 weight portions/100 weight portions.

As the water proofing property particle, can use water proofing property compound such as polysiloxanes based compound and fluorine-based compound, without any special restriction.Yet, preferably use fluorocarbon resin, because it is easy to obtain, it is low to be easy to processing and cost.The example of fluorocarbon resin comprises polytetrafluoroethylene (PTFE), polytrifluorochloroethylene, polyvinyl fluoride, polyvinylidene fluoride, dichloro difluoroethylene, polychlorotrifluoroethylene, fluorinated ethylene-propylene copolymer, perfluoroalkyl vinyl ether polymer, perfluoroalkyl vinyl ester polymer and ethylene-tetrafluoroethylene copolymer.Those effects that can provide bigger inhibition steam to see through with higher water proofing property.Wherein, polytetrafluoroethylene (PTFE), polyvinyl fluoride and polyvinylidene fluoride are particularly preferred, because they have excellent especially water proofing property.

As the water proofing property particle, can also use polyolefin, as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, PETG and polystyrene etc.

The specific area of oxygen-permeable film of the present invention preferably is not less than 0.1m ²/ g and be not more than 500m ²/ g.When specific area surpasses 500m ²During/g, although suppress the effect increase that steam sees through, the aperture in the film becomes quite little.Therefore, oxygen permeation rate also descends, thereby is difficult to guarantee apace the oxygen of necessary amount.On the contrary, when specific area less than 0.1m ²During/g,, suppress the effect decline that steam sees through although oxygen permeation rate increases.From obtaining in the viewpoint that suppresses to have between effect that steam sees through and the oxygen permeation rate well balanced oxygen-permeable film, the specific area of film more preferably is not less than 1m ²/ g and be not more than 100m ²/ g.

The thickness of oxygen-permeable film of the present invention preferably is not less than 0.1 μ m and is not more than 1000 μ m.When the thickness of film during greater than 1000 μ m, suppress the effect that steam sees through and increase because gas by film the distance of process increase; Yet, be difficult to guarantee apace the oxygen of necessary amount.On the contrary, when the thickness of film during less than 0.1 μ m, although oxygen is by good, existence wherein is difficult to form the tendency of uniform films.When film is inhomogeneous, in film, cause the interparticle density contrast of water proofing property, thereby formed degree of irregularity also becomes inhomogeneous on the inwall in the hole in film surface and film.As a result, suppress the effect decline that steam sees through.From obtaining having the viewpoint of high oxygen permeation rate and uniform film, the thickness of film especially preferably is not less than 5 μ m and is not more than 500 μ m.

Oxygen-permeable film of the present invention also can be by being supported on the porous substrate as supporter, or be clipped between a pair of porous substrate and use.Should be noted that the combination of supporter and oxygen-permeable film in the present invention is known as oxygen and sees through sheet.See through under the situation of sheet at the oxygen with three-decker, wherein oxygen-permeable film is clipped between a pair of porous substrate, can prevent that oxygen-permeable film from damaging, thereby can keep suppressing the effect that steam sees through for a long time.

Porous substrate is not particularly limited, and also can support oxygen-permeable film as long as it has the ability that allows gas to pass through.Yet, for the oxygen by oxygen-permeable film mobile not had unnecessary restriction, the preferred porous substrate that has higher oxygen permeation rate than oxygen-permeable film of the present invention that uses.

The example of the material of porous substrate comprises polytetrafluoroethylene (PTFE), polypropylene (PP), polyethylene (PE), vinylon, polyphenylene sulfide (PPS), polybutylene terephthalate (PBT) (PBT) and nylon.

Preferred porous substrate has net or nonwoven form.Porous substrate also can have the form of micro-porous film.The example of micro-porous film comprise the porous resin sheet or by the resulting film of stretchable porous resin sheet, contain silica etc. particulate the porous resin sheet or have by from the resin sheet that contains particulate, removing the sheet of the resulting high porosity of fine particle (voidage) with solvent etc.

From the viewpoint that combine and improve film-strength of enhancing with oxygen-permeable film, can also use metal base as the perforation metal forming or wire netting as porous substrate, using under the situation of metal base, thickness, degree of perforation and the porosity etc. by base material are controlling diaphragm intensity relatively easily.

The Gurley number that the oxygen that comprises oxygen-permeable film of the present invention and porous substrate sees through sheet preferably is not less than 0.5 second and is not more than 50000 seconds.When Gurley number during greater than 50000 seconds, increase although suppress the effect that steam sees through, be difficult to guarantee apace the oxygen of necessary amount.On the other hand, when Gurley number during less than 0.5 second, the thickness of film needs to reduce to a large extent, thereby the effect that the inhibition steam in the film sees through is tended to inhomogeneous.From obtaining having the viewpoint of high oxygen permeation rate and uniform film, the Gurley number of film especially preferably is not less than 10 seconds and is not more than 20000 seconds.

The aggregation of preferred water proofing property particle has the hole that diameter is no more than 0.5 μ m.The existence of micro hole has further increased the effect that inhibition steam sees through.The size by changing the water proofing property particle or the ratio of water proofing property particle and adhesive can be controlled the pore size of oxygen-permeable film.Especially, by changing the ratio of water proofing property particle and adhesive, the technical staff can easily control pore size.

In addition, has the porosity more preferably 20%～90% of oxygen-permeable film that diameter is no more than the hole of 0.5 μ m and comprises the aggregation of water proofing property particle.When porosity less than 20% the time, can not fully guarantee for example in the admission gear of battery, to enter the air diffusion admittance of battery from atmosphere.As a result, when High speed battery is discharged, be difficult to suck from atmosphere fast the oxygen of necessary amount, thereby can not obtain sufficient flash-over characteristic.From the viewpoint of High speed battery discharge, porosity preferably is not less than 20%.

Although from guaranteeing that porosity is not less than 20% viewpoint, preferred porose diameter all is no more than 0.5 μ m, must all not have the diameter that is no more than 0.5 μ m in all holes.If the air by film even disposablely be no more than the hole of 0.5 μ m by diameter can obtain the effect that goodish inhibition steam sees through so.

When porosity greater than 90% the time, be difficult to keep film strength, therefore, although the speed characteristic of battery and suppress that steam sees through respond well, the ratio that can manufacture the film of product is reduced to about 10%.Therefore, porosity preferably is no more than 90%.

In pore-size distribution, the ratio of the accumulation pore volume S1 of diameter in 0.01 μ m～0.5 mu m range and the accumulation pore volume S2 of diameter in 0.01 μ m～10 mu m ranges: S1/S2 preferably is not less than 0.01 and be not more than 0.8, more preferably is not less than 0.05 and be not more than 0.8.The existence of the micro hole of diameter in 0.01 μ m～0.5 mu m range has further increased the effect that inhibition steam sees through.

When S1/S2 was no more than 0.01, the micro hole ratio of existence was little, thereby the effect that inhibition steam sees through may be insufficient.When S1/S2 greater than 0.8 the time, the micro hole ratio of existence increases, thus the total void rate of oxygen-permeable film may descend, and has hindered seeing through of oxygen.Selectively, the interparticle adhesion of water proofing property may descend, thus easier separating particles.

The hole that exists diameter to be not less than 10 μ m has not only reduced the effect that inhibition steam sees through, and has reduced the intensity of oxygen-permeable film.Therefore, preferably do not exist diameter to be not less than the hole of 10 μ m.

Suppress the effect that steam sees through in order further to improve, more preferably oxygen-permeable film has the hole that many diameters are no more than 0.1 μ m, expects that they can provide the Knudsen diffusion effect.The ratio that exists that the raising diameter is no more than the hole of 0.1 μ m has improved the effect that inhibition steam sees through widely.Therefore, the ratio of the accumulation pore volume S3 of diameter in 0.01 μ m～0.1 mu m range and the accumulation pore volume S2 of diameter in 0.01 μ m～10 mu m ranges: S3/S2 preferably is not less than 0.01 and be not more than 0.7, more preferably is not less than 0.02 and be not more than 0.7.

When S3/S2 greater than 0.7 the time, micro hole increases, thus the porosity of oxygen-permeable film descends, and has hindered seeing through of oxygen.Selectively, the interparticle adhesion of water proofing property may descend, thus easier separating particles.

Although the example of the pore-size distribution of measurement oxygen-permeable film and the method for porosity includes but not limited to mercury intrusion porosimetry, nitrogen adsorption method and porosimetry.The principle of measuring method has nothing in common with each other, thereby even for identical oxygen-permeable film, resulting pore-size distribution result also may be different.Yet, even in different measuring methods, accumulation pore volume ratio, promptly the ratio of the total pore volume in the predetermined diameter scope changes hardly.

Should be noted that mercury intrusion porosimetry and nitrogen adsorption method can provide comprises the various forms of holes pore-size distribution of (comprising through hole and non through hole).That is, the lip-deep concavo-convex pore-size distribution that also influences of film, thus can in greater than the bore region of 1 μ m, produce distribution.In mercury intrusion porosimetry and nitrogen adsorption method, the maximum peak of pore-size distribution appears at substantially the same aperture location.Yet in mercury intrusion porosimetry, possible mercury can enlarge the aperture of oxygen-permeable film, makes maximum peak also appear at than position bigger slightly in the nitrogen adsorption method.

Porosimetry is a kind of method of estimating the through-hole diameter of porous material based on bubble point method (ASTM F316-86, JIS K3832).The narrow diameter zone that this method is provided at the hole that penetrates is that the recess diameter of neck portion distributes.The penetration speed of fluid such as gas and gaseous state main body changes with the recess diameter size of through hole.Recess diameter is more little, and the penetration speed of fluid is slow more.Therefore, the recess diameter of through hole is a greatest factor of measuring gas and liquid permeability.

Import in the stage of mercury by pressure in mercury intrusion porosimetry, the pressure of mercury may enlarge the aperture, and the possibility in change aperture is less in porosimetry, because by the liquid outside pressure importing gas or the mercury.Therefore, when the pore size distribution of measuring with the same film of same procedure manufacturing, exist and compare with the pore size distribution that mercury intrusion porosimetry obtains, the pore size distribution that obtains with porosimetry has the tendency of the narrower dispersion of distribution and narrower peak width.

In addition, in mercury intrusion porosimetry and nitrogen adsorption method, non through hole also is a measuring object, thereby has reflected also that in distribution the lip-deep degree of irregularity of film is a surface roughness; Yet the hole that only penetrates in porosimetry is a measuring object.Therefore, following characteristic is arranged, i.e. the influence of surface roughness can not appear in the pore size distribution.Because the effect that supposition inhibition steam sees through is in the neck maximum of through hole, so porosimetry is suitable for the measured hole distribution most.

In above-mentioned porosimetry, absolute value that can not measurement volumes.Therefore, preferably infer the porosity of oxygen-permeable film by mercury intrusion porosimetry and nitrogen adsorption method.Should be noted that in this manual, be not less than the voidage in the hole of 10nm by mercury intrusion porosimetry measurement aperture in oxygen-permeable film.In addition, use nitrogen adsorption method to measure the voidage that the aperture is no more than the hole of 10nm.Then, the ratio of the volume of the summation of the voidage in these holes and film (apparent volume) is defined as porosity.

In that oxygen-permeable film of the present invention or oxygen are placed under the air inlet and the situation between the positive pole of air cell through sheet, when sucking air in the battery, suppressed steam and entered battery.Therefore, even the battery of preserving in open mode also can obtain excellent discharge characteristics.

Place under the situation of the passage of the negative electrode supply air of fuel cell oxygen-permeable film of the present invention or oxygen being seen through sheet, when sucking air in the fuel cell, suppressed steam and entered negative electrode, suppressed the water slug (overflow) of negative electrode.Therefore, enlarged the opereating specification of allowing of fuel cell.

Embodiment

Below, specify the present invention based on embodiment and comparative example, but the invention is not restricted to following examples.

(1) forms oxygen-permeable film

Use the listed water proofing property particle of table 1A～1G as raw material, on the listed porous substrate of table 1A～1G, form oxygen-permeable film, and making has the oxygen of predetermined form through sheet by following three kinds of film build methods.Be used as the average grain diameter of the water proofing property particle of raw material, the Gurley number of porous substrate and the thickness of formed oxygen-permeable film are shown among table 1A～1G.

Film build method 1 (spraying process)

Mix predetermined water proofing property particle, adhesive, normal heptane and toluene, composition and the spraying propellant (liquefied gas) that obtains placed aerosol can, and be sprayed on the various porous substrates as supporter.Will the coating that forms on the base material in atmosphere in 80 ℃ of dryings 1 hour, thereby obtain oxygen-permeable film.Thickness by spray time control oxygen-permeable film.

Film build method 2 (rubbing method)

Mix water proofing property particle, adhesive, normal heptane and toluene, further, obtain composition like this to wherein adding the diluent that diluent (mixed solvent that comprises isooctane and normal octane) is regulated as viscosity.Use coating machine such as scraper that the composition that obtains is coated on the various porous substrates as supporter, reach desired thickness.Will the coating that forms on the base material for example in atmosphere in 80 ℃ of dryings 1 hour, thereby obtain oxygen-permeable film.

Film build method 3 (airless spraying process)

Mix predetermined water proofing property particle, adhesive, normal heptane and toluene, and, compress by exerting pressure then to composition itself with the aerosol can that the composition that obtains places no air-atomizing to use.Then, do not using under the air pressure, in composition, under the not aeriferous state, only spraying composition, and be sprayed on the various porous substrates as supporter from nozzle.Will the coating that forms on the base material in atmosphere in 80 ℃ of dryings 1 hour, thereby obtain oxygen-permeable film.Under intermittently spraying repeatedly, control the thickness of oxygen-permeable film by the spraying number of times.In airless spraying process, regulate coating layer thickness than regulating coating layer thickness by the spraying number of times by spray time, improved precision.

Table 1A

Sample number	The film form	The kind of water proofing property particle (resin)	Surface area (m 2/g)	Average grain diameter (μ m)	Film thickness (μ m)	Gurley number (s)	With the contact angle of water (°)
								A1	The aggregation of particle	Polytetrafluoroethylene (PTFE)	0.05	70	150	550	130
A2	The aggregation of particle	Polytetrafluoroethylene (PTFE)	0.09	70	150	600	130
								A3	The aggregation of particle	Polytetrafluoroethylene (PTFE)	0.1	50	150	660	130
A4	The aggregation of particle	PVF	0.5	15	150	700	140
								A5	The aggregation of particle	Vinylidene fluoride	1	10	150	750	140
A6	The aggregation of particle	Polytetrafluoroethylene (PTFE) and PVF	2	1	150	770	140
								A7	The aggregation of particle	Polytetrafluoroethylene (PTFE), PVF and vinylidene fluoride	5	0.5	150	780	150
A8	The aggregation of particle	Polytetrafluoroethylene (PTFE)	10	0.1	150	810	160
								A9	The aggregation of particle	PVF	100	0.03	150	850	120
A10	The aggregation of particle	Vinylidene fluoride	200	0.025	150	880	130
								A11	The aggregation of particle	Polytetrafluoroethylene (PTFE) and PVF	300	0.02	150	890	130
A12	The aggregation of particle	Polytetrafluoroethylene (PTFE), PVF and vinylidene fluoride	400	0.015	150	880	130
								A13	The aggregation of particle	Polytetrafluoroethylene (PTFE)	500	0.01	150	940	130
A14	The aggregation of particle	Polytetrafluoroethylene (PTFE)	600	0.009	150	950	120
								A15	The aggregation of particle	Polytetrafluoroethylene (PTFE)	700	0.009	150	1000	120
A16	Perforated membrane	Polytetrafluoroethylene (PTFE)	-	-	100	500	110
								A17	Perforated membrane	Polytetrafluoroethylene (PTFE)	-	-	100	10000	110
A18	Perforated membrane	PVF	-	-	100	2500	100
								A19	Perforated membrane	Vinylidene fluoride	-	-	100	14000	90

Table 1B

Sample number	The film form	The kind of water proofing property particle (resin)	Surface area (m 2/g)	Average grain diameter (μ m)	Film thickness (μ m)	Gurley number (s)	With the contact angle of water (°)
								B1	Partial fusion particle together	Polytetrafluoroethylene (PTFE)	0.2	30	150	600	160
B2	Partial fusion particle together	Polytetrafluoroethylene (PTFE)	0.5	10	150	810	160
								B3	Partial fusion particle together	PVF	2	1	150	850	120
B4	Partial fusion particle together	Vinylidene fluoride	4	0.5	150	880	130
								B5	Partial fusion particle together	PVF	7	0.2	150	890	140
B6	Partial fusion particle together	Vinylidene fluoride	10	0.1	150	880	150
								B7	Partial fusion particle together	Polytetrafluoroethylene (PTFE)	400	0.02	150	1000	160
C1	The aggregation of particle	Polytetrafluoroethylene (PTFE)	2.5	1	10	550	160
								C2	The aggregation of particle	Polytetrafluoroethylene (PTFE)	2.6	1.1	10	10500	160
C3	The aggregation of particle	PVF	2.55	1.2	10	3000	120
								C4	The aggregation of particle	Vinylidene fluoride	2.7	1	10	15000	130
C5	The aggregation of particle	Polytetrafluoroethylene (PTFE) and PVF	2.5	1	10	550	140
								C6	The aggregation of particle	Polytetrafluoroethylene (PTFE), PVF and vinylidene fluoride	2.6	1	10	550	150
C7	The aggregation of particle	Dimethyl polysiloxane	2	1	10	600	120

Table 1C

Sample number	The film form	The kind of water proofing property particle (resin)	Surface area (m 2/g)	Average grain diameter (μ m)	Film thickness (μ m)	Gurley number (s)	With the contact angle of water (°)
								D1	The aggregation of particle	Polytetrafluoroethylene (PTFE)	0.05	70	150	550	160
D2	Partial fusion particle together	Polytetrafluoroethylene (PTFE)	0.09	70	150	600	160
								D3	The aggregation of particle	Polytetrafluoroethylene (PTFE)	0.1	50	150	660	160
D4	The aggregation of particle	PVF	0.5	15	150	700	120
								D5	The aggregation of particle	Vinylidene fluoride	1	3	150	750	130
D6	The aggregation of particle	Polytetrafluoroethylene (PTFE) and PVF	2	1	150	770	140
								D7	The aggregation of particle	Polytetrafluoroethylene (PTFE), PVF and vinylidene fluoride	5	0.5	150	780	150
D8	Partial fusion particle together	Polytetrafluoroethylene (PTFE)	10	0.1	150	810	160
								D9	Partial fusion particle together	PVF	100	0.03	150	850	120
D10	Partial fusion particle together	Inclined to one side divinyl	200	0.025	150	880	130
								D11	Partial fusion particle together	Polytetrafluoroethylene (PTFE) and PVF	300	0.02	150	890	140
D12	Partial fusion particle together	Polytetrafluoroethylene (PTFE), PVF and vinylidene fluoride	400	0.015	150	880	150
								D13	The aggregation of particle	Polytetrafluoroethylene (PTFE)	500	0.01	150	940	160
D14	The aggregation of particle	Polytetrafluoroethylene (PTFE)	600	0.009	150	950	160
								D15	Partial fusion particle together	Polytetrafluoroethylene (PTFE)	700	0.009	150	1000	160

Table 1D

Sample number	The film form	The kind of water proofing property particle (resin)	Surface area (m 2/g)	Average grain diameter (μ m)	Film thickness (μ m)	Gurley number (s)	With the contact angle of water (°)
								E1	The aggregation of particle	Polytetrafluoroethylene (PTFE)	200	0.03	0.08	0.3	160
E2	Partial fusion particle together	Polytetrafluoroethylene (PTFE)	220	0.03	0.09	0.4	160
								E3	The aggregation of particle	Polytetrafluoroethylene (PTFE)	230	0.03	0.1	1	160
E4	The aggregation of particle	Polytetrafluoroethylene (PTFE)	8	0.2	1	8	160
								E5	The aggregation of particle	Polytetrafluoroethylene (PTFE)	10	0.3	5	10	160
E6	The aggregation of particle	Polytetrafluoroethylene (PTFE)	10	0.3	10	500	160
								E7	The aggregation of particle	Polytetrafluoroethylene (PTFE)	12	0.3	50	2000	160
E8	The aggregation of particle	Polytetrafluoroethylene (PTFE)	15	0.2	100	10000	160
								B9	Partial fusion particle together	Polytetrafluoroethylene (PTFE)	6	0.5	500	20000	160
E10	Partial fusion particle together	Polytetrafluoroethylene (PTFE)	7	0.5	600	30000	160
								E11	Partial fusion particle together	Polytetrafluoroethylene (PTFE)	8	0.5	800	40000	160
E12	The aggregation of particle	Polytetrafluoroethylene (PTFE)	15	0.2	1000	50000	160
								E13	The aggregation of particle	Polytetrafluoroethylene (PTFE)	11	0.3	1200	60000	160
E14	Partial fusion particle together	Polytetrafluoroethylene (PTFE)	10	0.3	1400	70000	160

Table 1E

Sample number	The film form	The kind of water proofing property particle (resin)	Surface area (m 2/g)	Average grain diameter (μ m)	Film thickness (μ m)	Gurley number (s)	With the contact angle of water (°)
								F1	The aggregation of particle	Polytetrafluoroethylene (PTFE)	12	0.3	2	0.5	160
F2	Partial fusion particle together	Polytetrafluoroethylene (PTFE)	4	0.2	1	1	160
								F3	The aggregation of particle	Polytetrafluoroethylene (PTFE)	13	0.3	3	5	160
F4	The aggregation of particle	Polytetrafluoroethylene (PTFE)	12	0.3	5	10	160
								F5	The aggregation of particle	PVF		11	0.3	4	40	120
F5	Partial fusion particle together	Vinylidene fluoride	5	0.2	10	100	130
								F7	The aggregation of particle	Polytetrafluoroethylene (PTFE)	10	0.4	14	300	160
F8	The aggregation of particle	Polytetrafluoroethylene (PTFE)	11	0.3	20	1000	160
								F9	The aggregation of particle	Polytetrafluoroethylene (PTFE)	13	0.2	65	5000	160
F10	Partial fusion particle together	Polytetrafluoroethylene (PTFE)	12	0.3	32	8000	160
								F11	Partial fusion particle together	Polytetrafluoroethylene (PTFE)	10	0.2	70	10000	160
F12	The aggregation of particle	PVF	9	0.4	80	20000	120
								F13	The aggregation of particle	Vinylidene fluoride		10	0.2	130	50000	130

Table 1F

Sample number	The film form	The kind of water proofing property particle (resin)	Surface area (m 2/g)	Average grain diameter (μ m)	Film thickness (μ m)	Gurley number (s)	With the contact angle of water (°)
								G1	The aggregation of particle	Polytetrafluoroethylene (PTFE)	13	0.3	12	300	160
G2	The aggregation of particle	Polytetrafluoroethylene (PTFE)	15	0.2	13	350	160
								G3	The aggregation of particle	Polytetrafluoroethylene (PTFE)	12	0.3	14	400	160
G4	Partial fusion particle together	Polytetrafluoroethylene (PTFE)	7	0.4	15	500	160
								G5	The aggregation of particle	PVF	13	0.3	18	450	120
G6	The aggregation of particle	Vinylidene fluoride	10	0.4	13	300	130
								G7	The aggregation of particle	Polytetrafluoroethylene (PTFE)	11	0.5	12	350	160
G8	The aggregation of particle	Polytetrafluoroethylene (PTFE)	14	0.3	19	500	160
								G9	The aggregation of particle	Polytetrafluoroethylene (PTFE)	12	0.4	20	450	160
G10	The aggregation of particle	Polytetrafluoroethylene (PTFE)	13	0.3	20	300	160
								G11	The aggregation of particle	Polytetrafluoroethylene (PTFE)	15	0.2	23	330	160
G12	The aggregation of particle	Polytetrafluoroethylene (PTFE)	12	0.3	24	470	160
								G13	Partial fusion particle together	Polytetrafluoroethylene (PTFE)	7	0.4	25	550	160
G14	The aggregation of particle	PVF	13	0.3	28	500	120
								G15	The aggregation of particle	Vinylidene fluoride	10	0.4	13	300	130
G16	The aggregation of particle	Polytetrafluoroethylene (PTFE)	11	0.5	12	450	160
								G17	The aggregation of particle	Polytetrafluoroethylene (PTFE)	14	0.3	29	300	160
H1	The aggregation of particle	Polytetrafluoroethylene (PTFE)	1.3	1	32	100	160
								H2	The aggregation of particle	Polytetrafluoroethylene (PTFE)	1.2	1	50	50	160
H3	The aggregation of particle	Polytetrafluoroethylene (PTFE)	1.1	1	40	60	160
								H4	The aggregation of particle	Polytetrafluoroethylene (PTFE)	1.3	1	30	40	160
H5	Partial fusion particle together	Polytetrafluoroethylene (PTFE)	1	1	40	30	160
								H6	The aggregation of particle	PVF	1.1	1	20	12	120
H7	The aggregation of particle	Vinylidene fluoride	1.2	1	10	8	130

Table 1G

Sample number	The film form	The kind of water proofing property particle (resin)	Surface area (m 2/g)	Average grain diameter (μ m)	Film thickness (μ m)	Gurley number (s)	With the contact angle of water (°)
								I1	The aggregation of particle	Polytetrafluoroethylene (PTFE)	0.6	1	120	600	160
I2	The aggregation of particle	Polytetrafluoroethylene (PTFE)	1.8	1	121	600	160
								I3	The aggregation of particle	Polytetrafluoroethylene (PTFE)	8	1	122	590	160
I4	The aggregation of particle	Polytetrafluoroethylene (PTFE)	44	1	119	580	160
								I5	The aggregation of particle	Polytetrafluoroethylene (PTFE)	88	1	123	550	160
I6	The aggregation of particle	Polytetrafluoroethylene (PTFE)	102	1	121	600	160
								I7	The aggregation of particle	Polytetrafluoroethylene (PTFE)	0.7	0.8	120	600	160
I8	The aggregation of particle	Polytetrafluoroethylene (PTFE)	2.1	0.8	120	590	160
								I9	The aggregation of particle	Polytetrafluoroethylene (PTFE)	9.5	0.8	120	580	160
I10	The aggregation of particle	Polytetrafluoroethylene (PTFE)	53	0.8	120	570	160
								I11	The aggregation of particle	Polytetrafluoroethylene (PTFE)	107	0.8	120	580	160
I12	The aggregation of particle	Polytetrafluoroethylene (PTFE)	107	0.8	120	570	160

Particularly, make oxygen in the following manner and see through sheet.

Embodiment 1

Oxygen sees through sheet A1～A15

On porous substrate, form and comprise the water proofing property particle (average grain diameter: oxygen-permeable film 0.009 μ m～70 μ m) shown in the table 1A by the above-mentioned film method that is predetermined to be with different Gurley numbers.

(i) make A1

The Gurley number is 500 seconds and comprises that (Japan Gore-TexInc. makes: production number GF52) as porous substrate for the perforated membrane of polytetrafluoroethylene (PTFE).Comprise that average grain diameter is that the particle (particle A1) of the polytetrafluoroethylene (PTFE) of 70 μ m is as the water proofing property particle.Make oxygen by film build method 1 (spraying process) and see through sheet.Content from the position of the about 30cm of distance porous substrate with aerosol can is sprayed on the porous substrate, and spraying was carried out for 2 seconds.

The content that aerosol can is advanced in filling has following composition, and said composition comprises the normal heptane of 40wt%, the toluene of 5wt%, the liquefied gas (LPG) of 35wt%, the particle A1 of 10wt% and the polyorganosiloxane resin as adhesive (dimethyl polysiloxane) of 10wt%.

(ii) make A2

The Gurley number is 500 seconds and comprises that the perforated membrane of polyethylene (Asahi Kasei Corporation manufacturing) is used as porous substrate.Comprise that average grain diameter is that the particle (particle A2) of the polytetrafluoroethylene (PTFE) of 70 μ m is as the water proofing property particle.Make oxygen by film build method 2 (rubbing method) and see through sheet.

The composition of coating usefulness comprises the normal heptane of 63wt%, the toluene of 8wt%, the particle A2 of 16wt% and the polyorganosiloxane resin as adhesive of 13wt%.With weight is diluent (comprise be not less than 98% isooctane and less than 2% the normal octane) diluted composition of the twice of described composition, uses scraper that it is coated on the porous substrate then, makes that the thickness of film is 10 μ m.

(iii) make A3～A9

See through the used program of sheet A1 according to oxygen, the water proofing property particle that use table 1A lists is made oxygen by film build method 1 (spraying process) and is seen through sheet A3～A9.

The weight ratio that should be noted that the water proofing property particle among the A6 is set to polytetrafluoroethylene (PTFE): PVF=80: 20, and the weight ratio of water proofing property particle is set to polytetrafluoroethylene (PTFE) among the A7: PVF: vinylidene fluoride=80: 10: 10.

Following perforated membrane is as porous substrate.

A3: comprise polyacrylic perforated membrane

A4: the perforated membrane that comprises vinylon

A5: the perforated membrane that comprises polyphenylene sulfide

A6: the perforated membrane that comprises polybutylene terephthalate (PBT)

A7: the perforated membrane that comprises nylon

A8: the perforated membrane that comprises polytetrafluoroethylene (PTFE)

A9: the perforated membrane that comprises polytetrafluoroethylene (PTFE)

(iv) make A10～A15

See through the used program of sheet A2 according to oxygen, water proofing property particle that use table 1A lists and porous substrate are made oxygen by film build method 2 (rubbing method) and are seen through sheet A10～A15.

The weight ratio that should be noted that the water proofing property particle among the A11 is set to polytetrafluoroethylene (PTFE): PVF=80: 20, and the weight ratio of water proofing property particle is set to polytetrafluoroethylene (PTFE) among the A12: PVF: vinylidene fluoride=80: 10: 10.

Following perforated membrane is as porous substrate.

A10: comprise poly perforated membrane

A11: comprise polyacrylic perforated membrane

A12: the perforated membrane that comprises vinylon

A13: the perforated membrane that comprises polyphenylene sulfide

A14: the perforated membrane that comprises polybutylene terephthalate (PBT)

A15: the perforated membrane that comprises nylon

Oxygen sees through sheet A16～A19

The commercially available perforated membrane that comprises the waterproof resin that table 1A lists directly sees through sheet A16～A19 as oxygen.The Gurley number of these perforated membranes and thickness also are shown among the table 1A.

Embodiment 2

Make oxygen and see through sheet B1～B7

See through the used program of sheet A1 according to oxygen, the water proofing property particle that use table 1B lists forms coating by film build method 1 (spraying process), anneals about 10 minutes in atmosphere then.Therefore, the oxygen that obtains having oxygen-permeable film is through sheet B1～B7, and the particle that will put contact in oxygen-permeable film mutually is fused to together.By putting being fused to together of contact particle, the persistence of the effect that inhibition steam sees through increases, thereby has improved the oxygen permeability in this way.Yet, when particles melt is excessive, will not have on the inwall in the hole in film surface that comprises particle agglomeration and film concavo-convex, thereby make the water proofing property decline of film.

When polytetrafluoroethylene (PTFE) is used as the water proofing property particle, annealing temperature is set to 250 ℃～310 ℃, when using other resin, the fusing point that annealing temperature is set to than each resin hangs down about 10 ℃～60 ℃ temperature.

Following perforated membrane is as porous substrate.

B1: the perforated membrane that comprises polytetrafluoroethylene (PTFE)

B2: comprise poly perforated membrane

B3: comprise polyacrylic perforated membrane

B4: the perforated membrane that comprises vinylon

B5: the perforated membrane that comprises polyphenylene sulfide

B6: the perforated membrane that comprises polybutylene terephthalate (PBT)

B7: the perforated membrane that comprises nylon

Embodiment 3

Make oxygen and see through sheet C1～C7

See through the used program of sheet A1 according to oxygen, the water proofing property particle that use table 1B lists is made oxygen by film build method 1 (spraying process) and is seen through sheet C1～C7.

The weight ratio that should be noted that the water proofing property particle among the C5 is set to polytetrafluoroethylene (PTFE): PVF=80: 20, and the weight ratio of water proofing property particle is set to polytetrafluoroethylene (PTFE) among the C6: PVF: vinylidene fluoride=80: 10: 10.

Following perforated membrane is as porous substrate.

C1: the perforated membrane that comprises polytetrafluoroethylene (PTFE)

C2: comprise poly perforated membrane

C3: comprise polyacrylic perforated membrane

C4: the perforated membrane that comprises vinylon

C5: the perforated membrane that comprises polyphenylene sulfide

C6: the perforated membrane that comprises polybutylene terephthalate (PBT)

C7: the perforated membrane that comprises nylon

Embodiment 4

Make oxygen and see through sheet D1～D15

From the specific area that detects oxygen-permeable film and the viewpoint that suppresses the relation between the effect that steam sees through, the oxygen-permeable film that making has different specific areas.Average grain diameter by changing the water proofing property particle and change over the specific area that film method is controlled oxygen-permeable film.

(i) make D1, D3～D7 and D13～D14

See through the used program of sheet A1 according to oxygen, the water proofing property particle that use table 1C lists is made oxygen by film build method 1 (spraying process) and is seen through sheet D1, D3～D7 and D13～D14.

(ii) make D2, D8～D12 and D15

See through the used program (embodiment 2) of sheet B1 according to oxygen, the water proofing property particle that use table 1C lists is made oxygen by film build method 1 (spraying process) and is seen through sheet D2, D8～D12 and D15.

The weight ratio that should be noted that the water proofing property particle among D6 and the D11 is set to polytetrafluoroethylene (PTFE): PVF=80: 20, and the weight ratio of water proofing property particle is set to polytetrafluoroethylene (PTFE) among D7 and the D12: PVF: vinylidene fluoride=80: 10: 10.

Following perforated membrane is as porous substrate.

D1: the perforated membrane that comprises polytetrafluoroethylene (PTFE)

D2: the perforated membrane that comprises polytetrafluoroethylene (PTFE)

D3: comprise polyacrylic perforated membrane

D4: the perforated membrane that comprises vinylon

D5: the perforated membrane that comprises polyphenylene sulfide

D6: the perforated membrane that comprises polybutylene terephthalate (PBT)

D7: the perforated membrane that comprises nylon

D8: the perforated membrane that comprises polytetrafluoroethylene (PTFE)

D9: the perforated membrane that comprises polytetrafluoroethylene (PTFE)

D10: the perforated membrane that comprises polytetrafluoroethylene (PTFE)

D11: the perforated membrane that comprises polytetrafluoroethylene (PTFE)

D12: the perforated membrane that comprises polytetrafluoroethylene (PTFE)

D13: the perforated membrane that comprises polyphenylene sulfide

D14: the perforated membrane that comprises polybutylene terephthalate (PBT)

D15: the perforated membrane that comprises polytetrafluoroethylene (PTFE)

Embodiment 5

Make oxygen and see through sheet E1～E14

From the thickness that detects oxygen-permeable film and the viewpoint that suppresses the relation between the effect that steam sees through, making has the oxygen-permeable film of different-thickness.Average grain diameter (the unified polytetrafluoroethylene (PTFE) that uses) by in the scope of 0.03 μ m～0.5 μ m, changing the water proofing property particle and change over the thickness that film method is controlled oxygen-permeable film.

(i) make E1, E3～E8 and E12～E13

See through the used program of sheet A2 according to oxygen, the water proofing property particle that use table 1D lists is made oxygen by film build method 2 (rubbing method) and is seen through sheet E1, E3～E8 and E12～E13.

(ii) make E2, E9～E11 and E14

See through the used program of sheet A2 according to oxygen, the water proofing property particle that use table 1D lists forms coating by film build method 2 (rubbing method), anneals about 10 minutes in atmosphere then.Therefore, the oxygen that obtains having oxygen-permeable film is through sheet E2, E9～E11 and E14, and the particle that will put contact in oxygen-permeable film mutually is fused to together.Should be noted that because polytetrafluoroethylene (PTFE) is used as the water proofing property particle, thereby annealing temperature is set to 250 ℃～310 ℃.

In addition, following perforated membrane is as porous substrate.

E1: the perforated membrane that comprises polytetrafluoroethylene (PTFE)

E2: the perforated membrane that comprises polytetrafluoroethylene (PTFE)

E3: comprise poly perforated membrane

E4: comprise polyacrylic perforated membrane

E5: the perforated membrane that comprises vinylon

E6: the perforated membrane that comprises polyphenylene sulfide

E7: the perforated membrane that comprises polybutylene terephthalate (PBT)

E8: the perforated membrane that comprises nylon

E9: the perforated membrane that comprises polytetrafluoroethylene (PTFE)

E10: the perforated membrane that comprises polytetrafluoroethylene (PTFE)

E11: the perforated membrane that comprises polytetrafluoroethylene (PTFE)

E12: the perforated membrane that comprises polytetrafluoroethylene (PTFE)

E13: the perforated membrane that comprises polytetrafluoroethylene (PTFE)

E14: the perforated membrane that comprises polytetrafluoroethylene (PTFE)

Embodiment 6

Make oxygen and see through sheet F1～F13

Porous substrate (support with) go up form predetermined oxygen-permeable film after, use another porous substrate (protection with) to clamp each film, protecting this film, thereby make have three-decker oxygen through sheet.Should be noted that " with contact angle of water " of table shown in the 1B be use another porous substrate clamp film before surperficial measured to each film.

(i) make F1, F3～F5, F7～F9 and F12～13

See through the used program of sheet A2 according to oxygen, the water proofing property particle that use table 1E lists is made oxygen-permeable film by film build method 2 (rubbing method).Subsequently, on formed each oxygen-permeable film, place another porous substrate, thereby obtain having the oxygen of three-decker through sheet F1, F3～F5, F7～F9 and F12～13.By on each dry oxygen-permeable film, placing another porous substrate, then by the marginal portion joint of hot weld with the about 1mm of width, make three layers integrated.

(ii) make F2, F6 and F10～F11

See through the used program of sheet A2 according to oxygen, the water proofing property particle that use table 1E lists forms coating by film build method 2 (rubbing method), anneals about 10 minutes in atmosphere then.Therefore, form the particle wherein will put contact mutually and be fused to together oxygen-permeable film.Subsequently, on formed each oxygen-permeable film, place another porous substrate, thereby obtain having the oxygen of three-decker through sheet F2, F6 and F10～F11.Should be noted that because polytetrafluoroethylene (PTFE) is used as the water proofing property particle, thereby annealing temperature is set to 250 ℃～310 ℃.

Following perforated membrane is as porous substrate.

F1: comprise the perforated membrane (support with) of polytetrafluoroethylene (PTFE) and comprise the perforated membrane (protection with) of polytetrafluoroethylene (PTFE)

F2: comprise poly perforated membrane (support and use) and comprise poly perforated membrane (protection is used)

F3: comprise polyacrylic perforated membrane (support and use) and comprise polyacrylic perforated membrane (protection is used)

F4: comprise the perforated membrane (support and use) of polytetrafluoroethylene (PTFE) and comprise poly perforated membrane (protection is used)

F5: comprise the perforated membrane (support with) of polytetrafluoroethylene (PTFE) and comprise the perforated membrane (protection with) of polytetrafluoroethylene (PTFE)

F6: comprise the perforated membrane (support with) of polytetrafluoroethylene (PTFE) and comprise the perforated membrane (protection with) of polytetrafluoroethylene (PTFE)

F7: comprise the perforated membrane (support with) of vinylon and comprise the perforated membrane (protection with) of vinylon

F8: comprise the perforated membrane (support with) of polyphenylene sulfide and comprise the perforated membrane (protection with) of polyphenylene sulfide

F9: comprise the perforated membrane (support with) of polybutylene terephthalate (PBT) and comprise the perforated membrane (protection with) of polybutylene terephthalate (PBT)

F10: comprise the perforated membrane (support with) of nylon and comprise the perforated membrane (protection with) of nylon

F11: comprise the perforated membrane (support with) of polyphenylene sulfide and comprise the perforated membrane (protection with) of nylon

F12: comprise the perforated membrane (support with) of polybutylene terephthalate (PBT) and comprise the perforated membrane (protection with) of nylon

F13: comprise the perforated membrane (support with) of vinylon and comprise the perforated membrane (protection with) of nylon

Embodiment 7

Make oxygen and see through sheet G1～G17

Various porous substrates are as supporter.

(i) make G1～G3 and G5～G9

See through the used program of sheet A1 according to oxygen, the water proofing property particle that use table 1B lists is made oxygen by film build method 1 (spraying process) and is seen through sheet G1～G3 and G5～G9.

(ii) make G4

See through the used program of sheet A1 according to oxygen, the water proofing property particle that use table 1F lists forms coating by film build method 1 (spraying process), anneals about 10 minutes in atmosphere then.Therefore, the oxygen that obtains having oxygen-permeable film is through sheet G4, and the particle that will put contact in oxygen-permeable film mutually is fused to together.Should be noted that because polytetrafluoroethylene (PTFE) is used as the water proofing property particle, thereby annealing temperature is set to 250 ℃～310 ℃.

(iii) make G10～12 and G14～17

See through the used program of sheet A1 according to oxygen, the water proofing property particle that use table 1F lists forms oxygen-permeable film by film build method 1 (spraying process).Subsequently, on formed each oxygen-permeable film, place another porous substrate, thereby obtain having the oxygen of three-decker through sheet G10～12 and G14～17.

(iv) make G13

See through the used program of sheet A1 according to oxygen, the water proofing property particle that use table 1F lists forms coating by film build method 1 (spraying process), anneals about 10 minutes in atmosphere then.Therefore, form the particle wherein will put contact mutually and be fused to together oxygen-permeable film.Subsequently, on formed oxygen-permeable film, place another porous substrate, thereby obtain having the oxygen of three-decker through sheet G13.Should be noted that because polytetrafluoroethylene (PTFE) is used as the water proofing property particle, thereby annealing temperature is set to 250 ℃～310 ℃.

Following base material is as porous substrate.

G1: comprise poly perforated membrane

G2: comprise polyacrylic perforated membrane

G3: the nonwoven that comprises polytetrafluoroethylene (PTFE)

G4: the nonwoven that comprises polytetrafluoroethylene (PTFE)

G5: the nonwoven that comprises vinylon

G6: the net that comprises polyphenylene sulfide

G7: the net that comprises polybutylene terephthalate (PBT)

G8: the nonwoven that comprises nylon

G9: the net that comprises nylon

G10: comprise the perforated membrane (support with) of polytetrafluoroethylene (PTFE) and comprise the perforated membrane (protection with) of polytetrafluoroethylene (PTFE)

G11: comprise poly perforated membrane (support and use) and comprise poly nonwoven (protection is used)

G12: comprise polyacrylic perforated membrane (support and use) and comprise polyacrylic nonwoven (protection is used)

G13: comprise the perforated membrane (support with) of polytetrafluoroethylene (PTFE) and comprise the net (protection with) of nylon

G14: comprise the nonwoven (support with) of polyphenylene sulfide and comprise the net (protection with) of nylon

G15: comprise the nonwoven (support with) of polybutylene terephthalate (PBT) and comprise the net (protection with) of nylon

G16: comprise the perforated membrane (support with) of vinylon and comprise the nonwoven (protection with) of vinylon

G17: comprise the perforated membrane (support with) of polytetrafluoroethylene (PTFE) and comprise the net (protection with) of nylon

Embodiment 8

Make oxygen and see through sheet H1～H7

The porous substrate that comprises various metals is as supporter.

(i) make H1～H4 and H6～H7

See through the used program of sheet A1 according to oxygen, the water proofing property particle that use table 1F lists is made oxygen by film build method 1 (spraying process) and is seen through sheet H1～H4 and H6～H7.

(ii) make H5

See through the used program of sheet A1 according to oxygen, the water proofing property particle that use table 1F lists forms coating by film build method 1 (spraying process), anneals about 10 minutes in atmosphere then.Therefore, the oxygen that obtains having oxygen-permeable film is through sheet H5, and the particle that will put contact in oxygen-permeable film mutually is fused to together.Should be noted that because polytetrafluoroethylene (PTFE) is used as the water proofing property particle, thereby annealing temperature is set to 250 ℃～310 ℃.

Following base material is as the porous substrate that comprises metal.

H1:KUSHIBE CO., the porous copper foil (Copper Foil of perforation) that LTD. makes, thickness 18 μ m, aperture Ф 0.3mm, spacing (distance between borehole) 0.404mm, porosity 50%

H2:KUSHIBE CO., the copper mesh paper tinsel that LTD. makes, aperture 75 μ m * 75 μ m are woven into the graticule mesh configuration by the copper cash with diameter Ф 0.2mm and obtain

H3:SUS (stainless steel) net paper tinsel has the form identical with H2

H4: the porous nickel foil has the form identical with H1

H5: the porous aluminium foil has the form identical with H1

H6: aluminium net paper tinsel has the form identical with H2

H7: the brass screen paper tinsel has the form identical with H2

Embodiment 9

Make oxygen and see through sheet I1～I10

(i) make I1

The Gurley number is 450 seconds and comprises that (Japan Gore-TexInc. makes: production number GF41) as porous substrate for the perforated membrane of polytetrafluoroethylene (PTFE).Comprise that average grain diameter is that the particle I1 of polytetrafluoroethylene (PTFE) of 1 μ m is as the water proofing property particle.Make oxygen by film build method 3 (airless spraying process) and see through sheet I1.From the position of the about 50cm of distance porous substrate the content of aerosol can was sprayed on the porous substrate that length is 30cm about 1 second.Injection is carried out three times.

The content that aerosol can is advanced in filling has following composition, and composition comprises the normal heptane of 40wt%, the toluene of 10wt%, the particle I1 of 10wt% and the polyorganosiloxane resin as adhesive (dimethyl polysiloxane) of 40wt%.

Here, by coating weight ratio dry and setting up period particle I1 and adhesive is set is 20: 80, and with the ratio of the accumulation pore volume S1 of diameter in 0.01 μ m～0.5 mu m range with the accumulation pore volume S2 of diameter in 0.01 μ m～10 mu m ranges: S1/S2 controls to 0.01.

(ii) make I2～I6

See through the used program of sheet I1 according to oxygen, make oxygen by film build method 3 (airless spraying process) and see through sheet I2～I6, except the weight ratio by dry and setting up period particle I1 and adhesive are set respectively is 40: 60,60: 40,70: 30,80: 20 or 95: 5, thereby S1/S2 is changed to 0.05,0.15,0.5,0.8 or 1 respectively.

(iii) make I7

Seeing through the used program of sheet I1 according to oxygen, make oxygen by film build method 3 (airless spraying process) and see through sheet I7, is that the particle I7 of 0.8 μ m is as the water proofing property particle except comprising polytetrafluoroethylene (PTFE) and average grain diameter.

Here, by coating weight ratio dry and setting up period particle I7 and adhesive is set is 10: 90, and with the ratio of the accumulation pore volume S3 of diameter in 0.01 μ m～0.1 mu m range with the accumulation pore volume S2 of diameter in 0.01 μ m～10 mu m ranges: S3/S2 controls to 0.01.

(iv) make I8～I12

See through the used program of sheet I7 according to oxygen, make oxygen by film build method 3 (airless spraying process) and see through sheet I8～I12, except the weight ratio by change drying respectively and setting up period particle I7 and adhesive is 20: 80,40: 60,60: 40,80: 20 or 96: 4, S3/S2 is changed to 0.02,0.05,0.4,0.7 or 1 respectively.

(2) oxygen sees through the physical property evaluation of sheet

Estimate the physical property that resulting oxygen sees through sheet in the following manner.

Measure specific area

" ASAP 2010 instruments " that use Micromeritics Instrument Corporation to make measure specific area with nitrogen adsorption method, wherein N ₂(nitrogen) is as adsorbed gas.Before the measurement, every kind of oxygen-permeable film in a vacuum in 120 ℃ predrying 5 hours, import nitrogen subsequently with measurement the specific area.The results are shown in table 1A～1G.

Measure average grain diameter

Measure the average grain diameter of the water proofing property particle that is used as the oxygen-permeable film raw material by laser particle diameter distribution measurement method.As measurement mechanism, the laser diffraction and the scattering particle diameter apparatus for measuring distribution that use HORIBA Ltd. to make.Here, measure the median particle diameter of sample as average grain diameter.The results are shown in table 1A～1G.

The thickness of oxygen-permeable film

Use micrometer or SEM to measure the thickness of oxygen-permeable film by observing the cross section.Should be noted that " film thickness " shown in table 1A～1F do not comprise the thickness of each porous substrate of support membrane.The results are shown in table 1A～1G.

Measure the Gurley number

The Ohken type air permeability test machine that uses Asahi Seiko Co. to make is measured total Gurley number that each oxygen sees through sheet.Air pressure is set to 2.5kgf/cm ², the size that measuring each oxygen sees through the test-strips (test strip) of sheet is set to Ф 2cm.The results are shown in table 1A～1G.

Measure contact angle

Use Kyowa Interface Science Co., the dynamic contact angle system " ZR-21 " that Ltd. makes is by the contact angle between each oxygen-permeable film of topical application method and the water.Particularly, water droplet is dropped on each film of made, gather water droplet wherein and form water droplet image under the spherical state because of himself surface tension.Then, the bottom side length (base length) that obtains observed from the side water droplet image (2r) and high (h), formula calculates contact angle θ (θ/2 methods) below using.The results are shown in table 1A～1G.

θ＝2tan ^-1(h/r)

Measurement volumes pore-size distribution and accumulation pore volume

For the oxygen-permeable film of oxygen, measure pore-size distribution and accumulation pore volume by porosimetry through sheet I1～I10.The CapillaryFlow Porometer CFP-1200-AEXL that uses POROUS MATERIALS INC. to make carries out porosimetry and measures.The results are shown in table 10.

In case of necessity, measure through sheet for the oxygen of the combination that is porous substrate and oxygen-permeable film, and obtain the pore-size distribution of each oxygen-permeable film by the pore-size distribution that deducts porous substrate.

The representative instance of the measurement result of pore-size distribution is shown in Fig. 3.In addition, the representative instance of the measurement result of accumulation pore volume is shown in Fig. 4.In Fig. 4, S1 is the accumulation pore volume in the hole of diameter 0.01 μ m～0.5 μ m, and S2 is that the accumulation pore volume and the S3 in the hole of diameter 0.01 μ m～10 μ m is the accumulation pore volume in the hole of diameter 0.01 μ m～0.1 μ m.

The measured hole voidage

(a) use Autopore III 9410 instruments of SHIMADZU CORPORATION manufacturing according to mercury intrusion porosimetry measured hole voidage.Condition is as follows.

Pressure limit: 0.5～60000 pound/square inch

Sample: about 3cm * 2cm * 1 slice

(b) use ASAP 2010 instruments of Micromeritics Instrument Corporation manufacturing according to nitrogen adsorption method measured hole voidage.Condition is as follows.

Predrying (degassing condition): in the vacuum 24 hours

Sample size: 1g

Adsorbed gas: N ₂(nitrogen)

(3) make air cell

The Coin shape air cell

Use predetermined oxygen to see through the Coin shape air cell shown in the partial cross section figure of sheet shop drawings 1.

This air cell comprise negative electrode casing 11, filling advance in the negative electrode casing and comprise zinc negative pole 12, place the negative electrode casing periphery ring-type insulating washer 13, be inserted in barrier film 14 between positive pole and the negative pole, a side to the air pole (positive pole) 15 of dividing plate, be fixed to the air pole opposite side water proofing property film 16, see through the diaphragm seal 111 that sheet 17, inner bottom surface fixed oxygen see through the anode cover 18 of sheet and be fixed to the anode cover outer bottom facing to the oxygen of water proofing property film.

See through at fixed oxygen between the inner bottom surface of anode cover 18 of sheet 17 and the water proofing property film 16 air diffuser casing 19 is set.In anode cover 18 bottoms air inlet 110 is set.Water proofing property film 16 is used for oxygen supply air pole 15, prevents that simultaneously electrolyte leakage is to outside batteries.

When not using battery, be sealed into gas port 110 with diaphragm seal 111, when using battery, peel off diaphragm seal 111.This is for blocks air enters in the battery, thereby prevents that battery is because of the self discharge deterioration.On the other hand, oxygen sees through sheet 17 and is sealed into gas port 110 always.

As air pole 15, pressurization will be attached to and will obtain air pole on the reticulated collectors as the catalyst of principal component by containing metal oxide, graphite, active carbon and fluorine-based adhesive.

Make air pole 15 as follows.

At first, 25kg water is added in the material blends that comprises 1.5kg carbon black, 4.5kg active carbon, 6kg Mn oxide and 0.88kg fluorocarbon resin powder, mediates the whole mixture of gained, be squeezed into the flat belt-like sheet then.The sheet that pushed is rolled being heated to pass between two about 60 ℃ rollers, thereby obtains the sheet that thickness is 0.6mm.

Next, this pressurization is attached to a side of collector.As collector, use the collector that comprises that by graphite is applied to line directly obtains on the nickel plating sheet that is equivalent to 40 sieve meshes of the stainless steel wire of about 0.15mm.

With Daikin Industries, the D1 (dispersion that contains the PTFE of 60wt%) that Ltd. makes is applied to the afflux side that has by pressurization bonding pad and the formed structure of collector, then 250 ℃ of dryings 1 hour.Subsequently, be attached on the side that is coated with D1 in conjunction with the PTFE perforated membrane (the Gurley number is 500 seconds) that Japan Gore-Tex Inc. is made by pressurization, thereby obtain air pole 15.

Make negative pole 12 as follows.

As the zinc that constitutes negative pole, use by the synthetic Zinc alloy powder that contains Al, Bi and In of atomization method.This zinc powder of 1.3g is added in the negative electrode casing 11, will comprises that the 34wt% potassium hydroxide aqueous solution of 400 μ L of the zinc oxide of 3wt% adds wherein, thereby obtain negative pole 12.

Although should be noted that and use the alkaline electrolyte of KOH concentration in this test, can working concentration be the interior any alkaline electrolyte of 30wt%～45wt% scope as 34wt%.

ZnO can be dissolved in the electrolyte, to suppress the self discharge of zinc.The amount of the ZnO of dissolving can suitably be adjusted to ZnO to the saturated degree of various alkaline concentration.In addition, the organic anti-corrosive agent also can be dissolved in the electrolyte, to suppress the generation of hydrogen.Can use and suppress any organic anti-corrosive agent that hydrogen produces, the example comprises Asahi Glass Co., the fluoroalkyl polyoxyethylene (SURFLON #S-161 (trade name)) that Ltd. makes.

Also can be by making electrolyte be in gel state to wherein adding gelling agent.Can use any gelling agent that alkaline electrolyte can be converted to gel.For example can use Sodium Polyacrylate, carboxymethyl cellulose, polyvinyl alcohol, PEO, polyacrylic acid and chitosan gel rubber with the various degree of polymerization, the degree of cross linking or molecular weight.

The cylindrical shape air cell

Use predetermined oxygen to see through sheet and make AA type air-zinc battery shown in Figure 2.Fig. 2 A is the partial cross section figure of air-zinc battery.Fig. 2 B is the part enlarged drawing of Fig. 2 A, shows the cross section of the air pole 24 with the three-decker that comprises catalyst layer 21, collector 22 and gas diffusion layers 23.

This air-zinc battery comprises the barrier film 25 that contacts with the inner surface of air pole, the zinc negative pole 26 as a form of gel of barrier film inner surface is advanced in filling, the oxygen that contacts with the outer surface of air pole sees through sheet 27, and the inner surface fixed oxygen sees through the anode cover 28 of sheet, cover the pitch tube 219 of anode cover outer surface, using the sealing sticker of peeling off before the battery 211, ware paper (tray paper) 212, the collector exposed portions serve of air pole is clipped in therebetween crown cap 213 and 214, be applied to the organic encapsulant 215 on the part of the inside 1mm of anode cover openend, the resin sealing body 216 of sealing anode cover opening, with incorporate negative terminal lid 217 of resin sealing body and the spike negative pole current collection element 218 that is connected with the negative terminal lid.

Air inlet 210 is arranged on the sidepiece of anode cover 28, on pitch tube 219.Lid 213 spots weld the bottom of anode cover 28.Obtain barrier film 25 by laminated vinylon nonwoven and cellophane.

When not using battery, be sealed into gas port 210 with sealing sticker 211, when using battery, peel off sealing sticker 211.On the other hand, oxygen sees through sheet 27 and is sealed into gas port 210 always.

Make air pole 24 as follows.

At first, 25kg water is added in the material blends that comprises 1.5kg carbon black, 4.5kg active carbon, 6kg Mn oxide and 0.88kg fluorocarbon resin powder, mediates the whole mixture that obtains, be squeezed into the flat belt-like sheet then.The sheet that pushed is rolled being heated to pass between two about 60 ℃ rollers, thereby obtains the sheet that thickness is the catalyst layer 1 of 0.6mm.

Next, the sheet pressurization of a pair of catalyst layer 21 is attached to each side of collector 22.As collector 22, use by to comprising the directly resulting collector of nickel plating on the sheet that is equivalent to 40 sieve meshes of the stainless steel wire of about 0.15mm of line.Be bent into the flat board that comprises catalyst layer 21 and collector 22 that obtains cylindric.Subsequently, partly remove catalyst layer 21, thereby expose collector 22, thereby form the part that is connected with anode cover.

Next, will comprise carbon black, fluorocarbon resin, water and the moulding of polyxyethylated ester group surfactant mixtures plate shape, obtain the sheet of gas diffusion layers 23 into about 200 μ m.With this sheet from the cylinder outer felt around cylinder two week or week how, thereby obtain having the air pole 24 of three-decker.

Make zinc negative pole 26 as a form of gel as follows.

By the Sodium Polyacrylate of adding 3wt% and the carboxymethyl cellulose of 1wt%, make the 40wt% potassium hydroxide aqueous solution of the zinc oxide that comprises 3wt% form gel.In the gel that obtains, add the zinc powder (Zinc alloy powder that contains element al, Bi and In) of 2 times of amounts of gel, thereby obtain shape zinc negative pole 26 with fixed attention.The theoretical capacity that coagulates shape zinc negative pole 26 is 3700mAh.

In addition, use the identical alkaline electrolyte used with the Coin shape air cell.

Although constituting the zinc of negative pole can be simple substance, can also use the kirsite that comprises the various metals outside the zinc.The Zinc alloy powder of using from the raw mix synthesis of air battery of the predetermined-element that comprises scheduled volume by atomization method is to carrying out classification.As kirsite, preferred use for example comprises the alloy of Zn and Al and comprises Zn and Al and also comprise at least a alloy that is selected from Bi, In, Ca, Sn and Ph.The amount of the element outside the Zn that is comprised in the kirsite is preferably 20～5000ppm.

Zinc and kirsite can use in any form, for example can powder, the form of porous material or plate uses.Porous material for example can by Zinc alloy powder is shaped to bead and in 350～500 ℃ scope in reducing atmosphere with its sintering, or carry out moulding and sintering simultaneously by hot pressing and make.Usually, make flat bead for Coin-shaped battery, and make the tubulose bead for cylindrical battery.

Use roll presses etc. are by being molded into block alloy the tabular tabular kirsite that obtains.Plate thickness is arbitrarily, because according to battery case plate thickness is regulated.The plate surface can be level and smooth, perforation, maybe can have concavo-convex.

(4) evaluation of air cell

, the air scoop of battery makes under extraneous air and the state that air pole communicates that each battery was preserved 10 days in that being opened in 20 ℃, the constant temperature bath of relative humidity 60%.Subsequently, each battery obtains the discharge capacity C1 (mAh) of battery with various current discharges.With discharge capacity C1 that obtains and theoretical capacity C2 (mAh) the substitution following formula (1) that included zinc weight is calculated from each battery, obtain the discharging efficiency (P (%)) of battery.The results are shown in table 2～9.P value that we can say battery is big more, and flash-over characteristic is excellent more.

P(％)＝(C1/C2)×100 (1)

(5) suppress the ability assessment that steam sees through

Owing to produce water, therefore, exist air duct by the problem of water slug when the air mass flow that is fed to negative electrode (flow velocity) hour or when battery temperature hangs down at the cathode side electrode of mobile fuel cell (DMFC).This phenomenon is called overflow, has increased the possibility of power generation characteristics deterioration.Especially, when air has high humility, tend to take place overflow, because the tolerance of saturated steam is little.

On the other hand, place when the negative electrode of fuel cell is supplied the passage place of air, dry air can be supplied with fuel cell, thereby can suppress overflow phenomena and improve power generation characteristics when oxygen of the present invention sees through sheet.Therefore, suppose to see through sheet by oxygen and be supplied to the negative electrode of fuel cell from extraneous air institute inhaled air, so the dew-point spread T of air (℃) value is by as giving a definition.Higher T value means that oxygen sees through sheet and has more excellent performance.

T (℃)=(see through the dew point (℃)) of air before the sheet-(see through the dew point (℃)) of air after the sheet by oxygen by oxygen

See through sheet from extraneous air institute inhaled air by predetermined oxygen, obtain then seeing through before the sheet and afterwards dew point, and use following formula to measure the T value by oxygen.The results are shown in table 2～10.In addition, be set at 0 ℃ from the dew point unification of extraneous air institute inhaled air before seeing through sheet by oxygen.

(6) air cell evaluation result and suppress the ability assessment result that steam sees through

(i) embodiment's 1 the results are shown in table 2.

Table 2

	Sheet	P under the discharge current 100mA in the Coin shape air cell	P under the discharge current 1A in the cylindrical shape air cell (%)	The T value (℃)
					Sample number 1	A1	58	57	14
Sample number 2	A2	58	57	13
					Sample number 3	A3	67	65	18
Sample number 4	A4	70	71	20
					Sample number 5	A5	70	71	21
Sample number 6	A6	71	70	20
					Sample number 7	A7	70	71	21
Sample number 8	A8	70	70	20
					Sample number 9	A9	67	67	17
Sample number 10	A10	67	66	18
					Sample number 11	A11	66	67	17
Sample number 12	A12	66	66	18
					Sample number 13	A13	65	65	17
Sample number 14	A14	56	57	13
					Sample number 15	A15	57	56	14
Comparative example 1	A16	5	3	0
					Comparative example 2	A17	15	12	0
Comparative example 3	A18	13	12	0
					Comparative example 4	A19	11	12	0

(ii) embodiment's 2 the results are shown in table 3.

Table 3

	Sheet	P under the discharge current 100mA in the Coin shape air cell (%)	P under the discharge current 1A in the cylindrical shape air cell (%)	The T value (℃)
					Sample number 16	B1	58	57	14
Sample number 17	B2	58	57	13
					Sample number 18	B3	67	65	18
Sample number 19	B4	66	66	18
					Sample number 20	B5	70	71	21
Sample number 21	B6	71	70	20
					Sample number 22	B7	70	71	21
Comparative example 5	A16	5	3	0
					Comparative example 6	A17	15	12	0
Comparative example 7	A18	13	12	0
					Comparative example 8	A19	11	12	0

(iii) embodiment's 3 the results are shown in table 4.

Table 4

	Sheet	P under the discharge current 102mA in the Coin shape air cell (%)	P under the discharge current 1.02A in the cylindrical shape air cell (%)	The T value (℃)
					Sample number 23	C1	68	65	15
Sample number 24	C2	62	59	16
					Sample number 25	C3	60	58	15
Sample number 26	C4	59	58	16
					Sample number 27	C5	61	57	14
Sample number 28	C6	62	59	13
					Sample number 29	C7	42	41	10
Comparative example 9	A16	5	3	0
					Comparative example 10	A17	13	12	0
Comparative example 11	A18	11	11	0
					Comparative example 12	A19	11	12	0

(iv) embodiment's 4 the results are shown in table 5.

Table 5

	Sheet	P under the discharge current 105mA in the Coin shape air cell (%)	P under the discharge current 1.05A in the cylindrical shape air cell (%)	The T value (℃)
					Sample number 30	D1	56	55	12
Sample number 31	D2	55	54	13
					Sample number 32	D3	68	65	17
Sample number 33	D4	66	64	18
					Sample number 34	D5	70	71	20
Sample number 35	D6	71	71	21
					Sample number 36	D7	70	70	20
Sample number 37	D8	72	71	21
					Sample number 38	D9	70	70	20
Sample number 39	D10	66	64	18
					Sample number 40	D11	64	65	17
Sample number 41	D12	63	63	18
					Sample number 42	D13	63	63	18
Sample number 43	D14	56	55	12
					Sample number 44	D15	55	54	12
Comparative example 13	A16	4	3	0
					Comparative example 14	A17	14	11	0
Comparative example 15	A18	13	12	0
					Comparative example 16	A19	10	11	0

(v) embodiment's 5 the results are shown in table 6.

Table 6

	Sheet	P under the discharge current 107mA in the Coin shape air cell (%)	P under the discharge current 1.07A in the cylindrical shape air cell (%)	The T value (℃)
					Sample number 45	E1	56	55	12
Sample number 46	E2	55	54	13
					Sample number 47	E3	68	65	17
Sample number 48	E4	66	64	18
					Sample number 49	E5	70	71	20
Sample number 50	E6	71	71	21
					Sample number 51	E7	70	70	20
Sample number 52	E8	72	71	21
					Sample number 53	E9	70	70	20
Sample number 54	E10	66	64	18
					Sample number 55	E11	64	65	17
Sample number 56	E12	63	63	18
					Sample number 57	E13	56	55	13
Sample number 58	E14	56	55	12
					Comparative example 17	A16	4	3	0
Comparative example 18	A17	13	10	0
					Comparative example 19	A18	11	10	0
Comparative example 20	A19	10	11	0

(vi) embodiment's 6 the results are shown in table 7.

Table 7

	Sheet	P under the discharge current 110mA in the Coin shape air cell (%)	P under the discharge current 1.1A in the cylindrical shape air cell (%)	The T value (℃)
					Sample number 59	F1	65	65	14
Sample number 60	F2	70	71	18
					Sample number 61	F3	71	70	21
Sample number 62	F4	74	75	20
					Sample number 63	F5	75	76	20
Sample number 64	F6	74	75	21
					Sample number 65	F7	76	77	21
Sample number 66	F8	75	76	20
					Sample number 67	F9	75	76	21
Sample number 68	F10	74	75	20
					Sample number 69	F11	75	76	20
Sample number 70	F12	70	71	21
					Sample number 71	F13	65	65	14
Comparative example 21	A16	3	3	0
					Comparative example 22	A17	12	10	0
Comparative example 23	A18	11	9	0
					Comparative example 24	A19	9	11	0

(vii) embodiment's 7 the results are shown in table 8.

Table 8

	Sheet	P under the discharge current 112mA in the Coin shape air cell (%)	P under the discharge current 1.12A in the cylindrical shape air cell (%)	The T value (℃)
					Sample number 72	G1	55	55	14
Sample number 73	G2	63	63	19
					Sample number 74	G3	61	62	18
Sample number 75	G4	62	62	19
					Sample number 76	G5	63	64	19
Sample number 77	G6	62	62	20
					Sample number 78	G7	64	65	18
Sample number 79	G8	63	63	19
					Sample number 80	G9	55	56	14
Sample number 81	G10	63	63	19
					Sample number 82	G11	61	62	18
Sample number B3	G12	62	62	19
					Sample number 84	G13	63	64	19
Sample number 85	G14	62	62	20
					Sample number 86	G15	64	65	18
Sample number 87	G16	63	63	19
					Sample number 88	G17	55	56	14
Comparative example 25	A16	3	3	0
					Comparative example 26	A17	11	8	0
Comparative example 27	A18	9	9	0
					Comparative example 28	A19	9	9	0

(viii) embodiment's 8 the results are shown in table 9.

Table 9

	Sheet	P under the discharge current 115mA in the Coin shape air cell (%)	P under the discharge current 1.15A in the cylindrical shape air cell (%)	The T value (℃)
					Sample number 89	H1	66	65	18
Sample number 90	H2	67	66	17
					Sample number 91	H3	68	65	16
Sample number 92	H4	65	65	17
					Sample number 93	H5	64	67	15
Sample number 94	H6	67	66	17
					Sample number 95	H7	67	68	14
Comparative example 29	A16	3	2	0
					Comparative example 30	A17	8	7	0
Comparative example 31	A18	9	9	0
					Comparative example 32	A19	6	6	0

(viii) embodiment's 9 the results are shown in table 10.

Table 10

	Sheet	P under the discharge current 100mA in the Coin shape air cell (%)	P under the discharge current 1A in the cylindrical shape air cell (%)	The T value (℃)	S1/S2(No. 96-101)	Porosity (%)
							Sample number 96	I1	58	57	14	0.01	15
Sample number 97	I2	67	65	17	0.05	20
							Sample number 98	I3	68	66	18	0.15	40
Sample number 99	I4	69	69	19	0.5	65
							Sample number 100	I5	72	71	20	0.8	90
Sample number 101	I6	71	71	20	1	93
								Sheet	P under the discharge current 100mA in the Coin shape air cell (%)	P under the discharge current 1A in the cylindrical shape air cell (%)	The T value (℃)	S3/S2(No. 102-107)	Porosity (%)
Sample number 102	I7	60	59	14	0.01	16
							Sample number 103	I8	69	67	19	0.02	20
Sample number 104	I9	70	69	20	0.05	40
							Sample number 105	I10	72	71	21	0.4	70
Sample number 106	I11	74	73	23	0.7	90
							Sample number 107	I12	73	72	22	1	94

(7) result investigates

The result of embodiment 1 investigates

The ability assessment that the evaluation result of air cell and inhibition steam see through the results are shown in table 2.

In table 2, at sample number 1～15 (under the situation of A1～A15), the discharging efficiency P (%) that obtains when the Coin shape air cell discharges with discharge current 100mA is not less than 56%, the discharging efficiency P (%) that obtains when the cylindrical shape air cell discharges with discharge current 1A is not less than 56%, dew-point spread T (℃) be not less than 13 ℃, so they are better than comparative example 1～4 (A16～A19).

Because the average grain diameter of the water proofing property particle of sample number 3～13 is 0.01～50 μ m, their P value all be not less than 65% and the T value be not less than 17 ℃, so they are more excellent.In addition, when the average grain diameter of water proofing property particle was 0.1～15 μ m, the P value was not less than 70%, and the T value is not less than 20 ℃.

Equally, the average grain diameter that comprises the aggregation of water proofing property particle and particle is that the oxygen-permeable film of 0.01～50 μ m shows the ability that high inhibition steam sees through, and the result has improved the oxygen permeability, thereby shows good result at aspects such as battery behaviors.In addition, under the situation of sample number 1～15, the contact angle between oxygen-permeable film and the water is not less than 120 °, and under the situation of comparative example 1～4, the contact angle between film and the water is not more than 110 °.Therefore, can see that the aggregation of water proofing property particle and the contact angle between the water preferably are not less than 120 °.In addition, when the aggregation of water proofing property particle and the contact angle between the water were not less than 140 °, the P value was not less than 70%, and the T value is not less than 20 ℃.

The result of embodiment 2 investigates

The ability assessment that the evaluation result of air cell and inhibition steam see through the results are shown in table 3.

In table 3, at sample number 16～22 (under the situation of B1～B7), the discharging efficiency P (%) that obtains when the Coin shape air cell discharges with discharge current 100mA is not less than 58%, the discharging efficiency P (%) that obtains when the cylindrical shape air cell discharges with discharge current 1A is not less than 57%, and dew-point spread T (℃) be not less than 13 ℃, so they are better than comparative example 5～8 (A16～A19).On the other hand, the P value of comparative example 5～8 is low to moderate for all batteries and is no more than 15%, and the T value is 0 ℃.As mentioned above, find that wherein by merging integrated average grain diameter be that the oxygen-permeable film of aggregation of the water proofing property particle of 0.01～50 μ m has the ability that more excellent inhibition steam sees through.

The result of embodiment 3 investigates

The ability assessment that the evaluation result of air cell and inhibition steam see through the results are shown in table 4.

In table 4, at sample number 23～29 (under the situation of C1～C7), the discharging efficiency P (%) that obtains when the Coin shape air cell discharges with discharge current 102mA is not less than 42%, the discharging efficiency P (%) that obtains when the cylindrical shape air cell discharges with discharge current 1.02A is not less than 41%, and dew-point spread T (℃) be not less than 10 ℃, so they are better than comparative example 9～12 (A16～A19).On the other hand, the P value of comparative example 9～12 is low to moderate for all batteries and is no more than 13%, and the T value is 0 ℃.

The P value of sample number 23～28 is near 60%, and the T value is near 15 ℃, so they are more excellent.On the other hand, the P value of sample number 29 is about 40%, and the T value is 10 ℃.Therefore, find that fluorocarbon resin is more effective than polyorganosiloxane resin as the water proofing property particle that constitutes oxygen-permeable film.In addition, as fluorocarbon resin, the discovery polytetrafluoroethylene (PTFE),, polyvinyl fluoride and polyvinylidene fluoride etc. is preferred.

The result of embodiment 4 investigates

The ability assessment that the evaluation result of air cell and inhibition steam see through the results are shown in table 5.

In table 5, at sample number 30～44 (under the situation of D1～D15), the discharging efficiency P (%) that obtains when the Coin shape air cell discharges with discharge current 105mA is not less than 55%, the discharging efficiency P (%) that obtains when the cylindrical shape air cell discharges with discharge current 1.05A is not less than 54%, and dew-point spread T (℃) be not less than 12 ℃, so they are better than comparative example 13～16 (A16～A19).

The P value of sample number 32～42 be not less than 63% and the T value be not less than 17 ℃, so they are better.On the other hand, sample number 30,31,43 and 44 P value are near 55%, and the T value is near 12 ℃.In addition, the P value of sample number 34～38 is about 70%, and the T value is not less than 20 ℃, so they show good especially result.

As mentioned above, find to be not less than 0.1m when the specific area of oxygen-permeable film of the present invention ²/ g and be not more than 500m ²During/g, steam sees through the inhibition effect and is improved.In addition, find to be not less than 1m when specific area ²/ g and be not more than 100m ²During/g, steam sees through the inhibition effect and further improves.

The result of embodiment 5 investigates

The ability assessment that the evaluation result of air cell and inhibition steam see through the results are shown in table 6.

In table 6, at sample number 45～58 (under the situation of E1～E14), the discharging efficiency P (%) that obtains when the Coin shape air cell discharges with discharge current 107mA is not less than the 55% discharging efficiency P (%) that obtains and is not less than 54% when the cylindrical shape air cell discharges with discharge current 1.07A, and dew-point spread T (℃) be not less than 12 ℃, so they are better than comparative example 17～20 (A16～A19).

The P value of comparative sample numbers 47～56 is not less than 63%, and the T value is not less than 17 ℃, so they are better.On the other hand, sample number 45,46,57 and 58 P value are near 55%, and the T value is near 12 ℃.In addition, the P value of sample number 49～53 is not less than 70%, and the T value is not less than 20 ℃, so they show good especially result.

As mentioned above, find when the thickness of oxygen-permeable film of the present invention is not less than 0.1 μ m and is not more than 1000 μ m that the effect that inhibition steam sees through is improved.In addition, find when thickness is not less than 5 μ m and is not more than 500 μ m that the effect that inhibition steam sees through is further improved.

The result of embodiment 6 investigates

The ability assessment that the evaluation result of air cell and inhibition steam see through the results are shown in table 7.

In table 7, at sample number 59～71 (under the situation of F1～F13), the discharging efficiency P (%) that obtains when the Coin shape air cell discharges with discharge current 110mA is not less than 65%, the discharging efficiency P (%) that obtains when the cylindrical shape air cell discharges with discharge current 1.1A is not less than 65%, and dew-point spread T (℃) be not less than 14 ℃, so they are better than comparative example 21～24 (A16～A19).

The reason that obtains above-mentioned excellent effect is, sees through sheet at oxygen and has wherein that oxygen-permeable film is clipped under the situation of the three-decker between a pair of porous substrate, can prevent when air during by film the water proofing property particle separate gradually, thereby prevent drainage effect decline.

The result of embodiment 7 investigates

The ability assessment that the evaluation result of air cell and inhibition steam see through the results are shown in table 8.

In table 8, at sample number 72～88 (under the situation of G1～G17), the discharging efficiency P (%) that obtains when the Coin shape air cell discharges with discharge current 112mA is not less than 55%, the discharging efficiency P (%) that obtains when the cylindrical shape air cell discharges with discharge current 1.12A is not less than 55%, and dew-point spread T (℃) be not less than 14 ℃, so they are better than comparative example 25～28 (A16～A19).

When relatively using porous resin film as the sample number 72,73 of porous substrate and 81 and when using net or nonwoven as the sample number 74～80 of porous substrate and No.82～88, their characteristic is at similar level, and good.Therefore, oxygen also can be net or nonwoven etc. through the form of the porous substrate in the sheet.

In addition, find that from above-mentioned evaluation polyethylene, polypropylene, polytetrafluoroethylene (PTFE), vinylon, polyphenylene sulfide (PPS), polybutylene terephthalate (PBT) (PBT) and nylon etc. can be preferably used as porous substrate.

The result of embodiment 8 investigates

The ability assessment that the evaluation result of air cell and inhibition steam see through the results are shown in table 9.

In table 9, at sample number 89～95 (under the situation of H1～H7), the discharging efficiency P (%) that obtains when the Coin shape air cell discharges with discharge current 115mA is not less than 64%, the discharging efficiency P (%) that obtains when the cylindrical shape air cell discharges with discharge current 1.15A is not less than 65%, and dew-point spread T (℃) be not less than 14 ℃, so they are better than comparative example 29～32 (A16～A19).

As if when the porous substrate that comprises metal was used for the supporter of oxygen-permeable film, the water proofing property particle can be fixed firmly to the metal part of base material, suppressed the effect that steam sees through thereby more effectively keep.About metal species, can use all metals that can be processed to multi-hole state, except the listed metal of table 1B, also comprise for example iron and titanium.

In addition, (among the E1～E14), (the Gurley number that the oxygen of E3～E12) sees through sheet is not less than 0.5 second and is not more than 50000 seconds to show the sample number 47～56 of superperformance more at the sample number 45～58 of table 6.In addition, (the Gurley number that the oxygen of E5～E9) sees through sheet is not less than 10 seconds and is not more than 20000 seconds to show the sample number 49～53 of good much better characteristic.In addition, (among the F1～F13), (the Gurley number of E4～E12) is not less than 10 seconds and is not more than 20000 seconds to show the sample number 62～70 of superperformance more at the sample number 59～71 of table 7.

The result of embodiment 9 investigates

The ability assessment that the evaluation result of air cell and inhibition steam see through the results are shown in table 10.

In table 10, under the situation of sample number 96～101, the discharging efficiency P (%) that when the Coin shape air cell discharges with discharge current 100mA, obtains, the discharging efficiency P (%) that when the cylindrical shape air cell discharges with discharge current 1A, obtains and dew-point spread T (℃), all show as high value.Therefore, can think, when S1/S2 is not less than 0.01, realize this effect.Yet S1/S2 is under the situation of 1 sample number 101 therein, because amount of binder is few, so in the layer of water proofing property particle fracture takes place and separate.In sample number 96～101, do not observe fracture and separate.Therefore, S1/S2 preferably is not less than 0.01 and be not more than 0.8.

In addition, by S1/S2 is changed to 0.05 from 0.01, observing P value and T value significantly increases.Have at oxygen-permeable film under the situation of these samples of same thickness, observe wherein specific area changes the tendency that increases with S1/S2.Because the thickness of oxygen-permeable film is identical, thereby the increase of specific area is owing to the increase of micropore in the film.Therefore, can see that when the ratio of the micropore that exists is increased to certain level, the effect that inhibition steam sees through will become remarkable.Therefore, the ratio of the accumulation pore volume S1 of diameter in 0.01 μ m～0.5 mu m range and the accumulation pore volume S2 of diameter in 0.01 μ m～10 mu m ranges: S1/S2 preferably is not less than 0.05 and be not more than 0.8,

Under the situation of sample number 102～107, P value and T value all show as high value.Therefore, can think, when the ratio of the accumulation pore volume S3 of diameter in 0.01 μ m～0.1 mu m range: when S3/S2 is not less than 0.01, realize this effect with the accumulation pore volume S2 of diameter in 0.01 μ m～10 mu m ranges.Yet S3/S2 is under the situation of 1 sample number 107 therein, because amount of binder is few, so in the layer of water proofing property particle fracture takes place and separate.In sample number 102～106, do not observe fracture and separate.Therefore, S3/S2 preferably is not less than 0.01 and be not more than 0.7.

In addition, by S3/S4 is changed to 0.02 from 0.01, observe remarkable increase.Therefore, can think that S3/S2 preferably is not less than 0.02 and be not more than 0.7.

In addition, when sample that relatively S1/S2 value is identical with the S3/S2 value (for example comparative sample numbers 96 and sample number 102, sample number 97 and sample number 104), sample number 102 and sample number 104 are all showing high value aspect P value and the T value.Therefore, can see, can further increase by the ratio that increase to exist and suppress the effect that steam sees through than the hole of minor diameter.

In addition, the porosity of sample number 96～107 is shown in table 10.Under the situation of porosity less than 20% sample number 96 and 102, discharging efficiency P (%) that obtains when the Coin shape air cell discharges with discharge current 100mA and the discharging efficiency P (%) that obtains when the cylindrical shape air cell discharges with discharge current 1A show and are no more than 60% value; Yet, being no more than in porosity under the situation of 20% sample number 97～101 and No.103～107, above-mentioned P (%) value is not less than 65%.Equally, the porosity that can see oxygen-permeable film preferably is not less than 20%.

On the other hand, under the situation of sample number 101 and 107, because amount of binder is few, thus in the layer of water proofing property particle fracture takes place and separate, and the ratio of actual available no defective product is about 10%.In sample number 96～100 and No.102～106, do not observe fracture and separate.

Can see that from The above results the porosity of oxygen-permeable film is preferably 20～90%.

Industrial applicibility

Oxygen of the present invention sees through film and has high inhibition steam through ability, therefore can develop being used in the various application. Application example comprises following instance.

(1) is used for removing moisture to produce the purifier of dry air or oxygen from air.

(2) for the device with the room air outside the steam and outdoor air exchange.

(3) be used for suppressing the packaging material that airborne moisture enters in store food.

(4) admission gear of air cell and fuel cell, wherein admission gear is used for sucking airborne oxygen with generating. Should be noted that these application only are examples, and applicable scope of the present invention is not limited to this.

Claims (20)

1. oxygen-permeable film, it comprises the aggregation of water proofing property particle, the average grain diameter of wherein said particle is 0.01～50 μ m.

2. oxygen-permeable film as claimed in claim 1, the contact angle of wherein said oxygen-permeable film and water are not less than 120 °.

3. oxygen-permeable film as claimed in claim 1, the aggregation of wherein said particle is integrated by merging.

4. oxygen-permeable film as claimed in claim 1, wherein said particle comprises fluorocarbon resin.

5. oxygen-permeable film as claimed in claim 4, wherein said fluorocarbon resin are be selected from polytetrafluoroethylene (PTFE), polyvinyl fluoride and polyvinylidene fluoride at least a.

6. oxygen-permeable film as claimed in claim 1, the specific area of wherein said oxygen-permeable film is not less than 0.1m ²/ g and be not more than 500m ²/ g.

7. oxygen-permeable film as claimed in claim 1, the thickness of wherein said oxygen-permeable film are not less than 0.1 μ m and are not more than 1000 μ m.

8. an oxygen sees through sheet, and it comprises that the described oxygen-permeable film of claim 1 and at least one support the porous substrate of described film.

9. oxygen as claimed in claim 8 sees through sheet, and wherein said oxygen-permeable film is clipped between a pair of described porous substrate, thereby has three-decker.

10. oxygen as claimed in claim 8 sees through sheet, and the material of wherein said base material is be selected from polyethylene, polypropylene, polytetrafluoroethylene (PTFE), vinylon, polyphenylene sulfide, polybutylene terephthalate (PBT) and nylon at least a.

11. oxygen as claimed in claim 8 sees through sheet, wherein said base material has net or nonwoven form.

12. oxygen as claimed in claim 8 sees through sheet, wherein said base material comprises the metal forming or the wire netting of perforation.

13. oxygen as claimed in claim 8 sees through sheet, wherein said base material has the micro-porous film form.

14. oxygen as claimed in claim 8 sees through sheet, the aggregation of wherein said water proofing property particle has the hole that diameter is no more than 0.5 μ m.

15. oxygen as claimed in claim 14 sees through sheet, wherein the ratio of the accumulation pore volume S1 of diameter in 0.01 μ m～0.5 mu m range and the accumulation pore volume S2 of diameter in 0.01 μ m～10 mu m ranges: S1/S2 is not less than 0.01 and be not more than 0.8.

16. oxygen as claimed in claim 8 sees through sheet, the Gurley number that wherein said oxygen sees through sheet is not less than 0.5 second and is not more than 50000 seconds.

17. an air cell, it comprises positive pole, negative pole, electrolyte and is used for to the described anodal admission gear that supplies air that wherein said admission gear comprises the described oxygen-permeable film of claim 1.

18. an air cell, it comprises positive pole, negative pole, electrolyte and is used for to the described anodal admission gear that supplies air that wherein said admission gear comprises that the described oxygen of claim 8 sees through sheet.

19. a fuel cell, it comprises negative electrode, anode, electrolyte and is used for supplying to described negative electrode the admission gear of air that wherein said admission gear comprises the described oxygen-permeable film of claim 1.

20. a fuel cell, it comprises negative electrode, anode, electrolyte and is used for supplying to described negative electrode the admission gear of air that wherein said admission gear comprises that the described oxygen of claim 8 sees through sheet.

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