JP4325973B2 - Gas permeable material for oxygen replenisher in water and its structure - Google Patents

Description

BACKGROUND OF THE INVENTION
[0001]
The present invention, aquarium tank, supplies gas such as oxygen in water, such as live fish for fish preserve, to a gas permeable material used for oxygen or the like discharge portion such as oxygen supply devices.
[Prior art]
[0002]
Conventionally, electric air pumps, oxygen cylinders, oxygen generators, etc. have been mainly used as methods for supplying oxygen and other gases into water such as ornamental fish tanks and live fish cages. An electric air pump is generally widely used from the viewpoint of convenience and the like. The supply of oxygen in the water by the electric air pump is performed by discharging the air taken into the air pump into the water through a micro hole provided in the oxygen discharge unit.
[Problems to be solved by the invention]
[0003]
However, the foam discharged into the water through the micropores provided in the oxygen discharge section is released into the atmosphere approximately in proportion to the size of the foam by buoyancy without being effectively replenished with oxygen. .
[Means for Solving the Problems]
[0004]
The water to gas supplies such as oxygen supplementation dexterity gas transmitting material such as oxygen according to claim 1, compressed air that fills the oxygen or the like replenishing vessel, to limit transmission of compressed oxygen of very fine bubbles state In order to discharge into the water, a breathable film in which a striped craze region is provided on a polymer resin film and a foam material intended to separate the fine bubbles stagnant in the ejection part It is a gas permeable material characterized.
【Example】
[0005]
A foam material was superposed on the surface of a breathable film (hereinafter referred to as a craze-containing breathable resin film), which is one of the present invention, in which a striped craze region is provided on a polymer resin film. As shown in FIG. 1 as an example, a gas permeable material for supplying oxygen or the like into water is provided with a permeable material fixing frame in an oxygen etc. discharge portion 4 of the oxygen etc. replenisher 2. 10, the packing 12 or the like, fitted with a gas permeable material F made by superimposing craze containing breathable resin film 14 and Awakiri member 16, the compressed air that fills the oxygen or the like replenishing device, the transmission amount of compressed oxygen, etc. It is restricted and discharged into water.
[0006]
Compressed air filled in oxygen like replenishing device, compressed oxygen or the like is used may vary depending on the type of the resin, generally ^{0.3~100,000 × 10 4 cm 3 / m} 2 · gas permeability of oxygen and nitrogen gas Within a range of 24 hr · atm, the amount of permeation is limited by the crazed breathable resin film and discharged into water in the form of fine bubbles. When only the permeable breathable resin film is used as the gas permeable material, the discharged fine bubbles are stagnant on the surface, and the bubbles are released into the water in a combined state and fused with the water intended by the present invention. It becomes impossible to replenish air, oxygen, etc. into the water effectively by discharging into the water in the form of fine bubbles that are easy to do.
[0007]
The fine foam discharged with limited permeability by overlaying foaming material on the crazed breathable resin film and imparting hydrophilicity to the surface of the crazed breathable resin film is the crazed breathable resin film. It is discharged into the water in the form of fine foam that is easy to fuse with water through the foamed material that is superimposed on the surface of the water.
[0008]
As the foam material used in the present invention, a cotton woven fabric is also suitable, but a composite nonwoven fabric of pulp and synthetic fiber is most suitable, and the synthetic fiber material is polyethylene, polypropylene, polyamide, polyester, acrylic, Vinylon or the like is used. Moreover, as long as it has corrosion resistance in addition to hydrophilicity and breathability, it may be a composite nonwoven fabric or a composite woven fabric with glass fiber, metal fiber, etc., and the material, composition, and weaving method are particularly limited. It is not something. One method is to perform foaming by applying a hydrophilic treatment to the surface of the breathable resin film containing craze.
[0009]
The gas permeable material of the present invention is mainly formed by superposing a breathable resin film and a foam material, and the superposition is performed by placing the foam material on the surface of the breathable resin film. . Moreover, it has an easy-to-handle form by adhering, welding, or adhering the peripheral edge of the gas permeable material formed by using plastic, rubber or the like.
[0010]
Further, as shown in FIGS. 2 and 3 as an embodiment, the gas permeable material is prevented from being deformed by pressurization on the surface of the gas permeable material F formed by superposing the permeable permeable resin film 14 and the foaming material 16. By placing the target reinforcing material 18 and fixing the peripheral edge portion thereof with rubber 20 or the like, a gas permeable material having a stable shape and having a sealing function at the peripheral edge portion is obtained. The reinforcement is not particularly limited as long as it has a mesh shape, but is not particularly limited as long as it is suitable for use.
[0011]
The crazed breathable resin film used as one member of the gas permeable material is partly described in Japanese Patent Application Laid-Open No. 7-256676 and Japanese Patent No. 3156058 by the applicant of the present invention. By providing a striped craze region in the film, a gas such as air can pass through in a slightly pressurized state, but it can have a characteristic of not passing a liquid such as water or a gel-like solution.
[0012]
The polymer resin used as the material of the polymer resin film can be formed into a film or a sheet, such as polyolefin, polyester, polyamide, styrene resin, polycarbonate, halogen-containing thermoplastic resin, nitrile resin, etc. A thermoplastic resin can be mentioned.
[0013]
The polyolefin is an α-olefin homopolymer or a copolymer with another α-olefin and / or α-olefin as a main component and another ethylenically unsaturated monomer. Here, the copolymer may be a block, random, graft, or a composite thereof. Examples of the ethylenically unsaturated monomer include unsaturated carboxylic acids or anhydrides such as methacrylic acid, methyl methacrylate, and maleic acid.
[0014]
Specific examples of useful polyolefins include low density branched polyethylene, high density linear polyethylene, low density linear polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly (1-butene), poly (4-methyl-1 -Pentene) and the like.
[0015]
Polyamide is a condensation product containing, as an essential component, a repeating unit having an aromatic or / and aliphatic amide group. Useful polyamides include nylon-4, nylon-6, nylon-6,6, nylon-4,6, nylon-12, amorphous nylon and the like. Among these, preferred polyamides are nylon-6, nylon-6,6, and amorphous nylon.
[0016]
Examples of the polyester include, for example, a thermoplastic polyester produced by condensing a dicarboxylic acid or a lower alkyl ester thereof, an acid halide or an acid anhydride derivative and a glycol or a dihydric phenol according to a usual method. Can do. Among these polyesters, it is preferable to use saturated polyesters, particularly polyethylene terephthalate, polybutylene terephthalate, and polynaphthalene terephthalate.
[0017]
The styrene resin is a polymer of a vinyl aromatic compound, and specific examples of the vinyl aromatic compound include styrene, α-methylstyrene, paramethylstyrene, vinyl toluene, vinyl xylene, and the like. Styrenic resins are homopolymers and copolymers of these vinyl aromatic compounds. Among these, polystyrene is preferable, and rubber graft polystyrene (HIPS) and acrylonitrile / butadiene / styrene copolymer are preferably used.
[0018]
Examples of the polycarbonate include aromatic polycarbonate, aliphatic polycarbonate, and aliphatic / aromatic polycarbonate. Among these, aromatic polycarbonates composed of 2,2-bis (4-oxyphenyl) alkane-based, bis (4-oxyphenyl) ether-based, bis (4-oxyphenyl) sulfone, sulfide or sulfoxide-based bisphenols are used. It is preferable to use it.
[0019]
Examples of the halogen-containing thermoplastic resin include homopolymers and copolymers such as tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, and vinyl fluoride. In addition, homopolymers and copolymers derived from vinylidene chloride can be mentioned. Among these, preferable halogen-containing thermoplastic resins include homopolymers of polyvinylidene fluoride, copolymers with tetrafluoroethylene, hexafluoropropylene, and chlorotrifluoroethylene, and vinylidene chloride.
[0020]
The nitrile resin contains 50% by weight or more of α-β olefinic unsaturated mononitrile. Among these unsaturated mononitriles, it is preferable to use acrylonitrile and methacrylonitrile and mixtures thereof.
[0021]
Among the thermoplastic resins, polyolefin, polyester, styrene resin, and halogen-containing thermoplastic resin are preferably used from the viewpoint of moldability to a film or sheet and economical efficiency. These thermoplastic resins may be used alone, combined and used as a composition, or may be blended with another polymer resin, and two or more types of resins may be multilayered. It may be used.
[0022]
In view of the ease of formation of crazes, it is desirable to use a resin having a glass transition temperature of −45 ° C. or higher, preferably −30 ° C. or higher, particularly preferably −15 ° C. or higher. When used as a composition or in a multilayered form, it is preferable that the glass transition temperature of the thermoplastic resin, which is the main component, is within the above range. In the case of a thermoplastic resin exhibiting a glass transition temperature lower than this, it is difficult to efficiently form a craze because it is too flexible.
[0023]
The polymer resin film or sheet obtained by using a thermoplastic resin is not particularly limited in its production method, and can be obtained by applying various molding methods. A product obtained by applying a molding method or a blow-up inflation molding method is industrially advantageous.
[0024]
The thickness of the polymer resin film is generally 0.5 to 1,000 μm, preferably 1 to 800 μm, particularly preferably 2 to 500 μm.
[0025]
The polymer resin film has a degree of molecular orientation having a birefringence of 0.5 × 10 ⁻³ or more, preferably 1 × 10 ⁻³ or more, particularly preferably 1.5 × 10 ⁻³ or more. This is effective for the formation of crazes. In a film having a molecular orientation whose birefringence is out of the above range, it is difficult to easily form an intended craze. The degree of orientation refers to the molecular structure such as the resin temperature, take-off speed, cooling rate, resin molecular weight, molecular weight distribution, tacticity, etc. at the time of forming the film, especially the draw ratio in the case of the T-die method, and in particular the inflation method. If there is, the film can be controlled by changing the blow-up ratio and the like, and thus a film having an orientation degree in a desired preferable range can be produced by appropriately controlling these.
[0026]
The birefringence referred to here is expressed as a difference between the main refractive indexes. For example, the difference between the refractive index (n1) in the film forming direction and the refractive index (n2) in the direction perpendicular thereto (n1-n2). ) And is one of the indexes expressing the degree of molecular orientation. In actuality, these birefringence can be measured by using a deflection microscope and a compensator, and the larger the value, the greater the anisotropy and the more likely to cause crazing.
[0027]
The striped craze of the permeable breathable film used in the present invention is basically substantially parallel to the direction of molecular orientation of the polymer resin film and generally has a width of 0.5 to 100 μm, preferably 1 to 50 μm. The ratio of the number of crazes penetrating in the thickness direction of the film is 10% or more, preferably 20% or more, particularly preferably 40% or more, and penetrating. If the ratio is less than the above range, sufficient air permeability cannot be obtained.
[0028]
The craze is formed in a direction substantially parallel to the molecular orientation direction. The craze is formed by pulling in the direction perpendicular to the molecular chain orientation direction, and the craze is formed in a direction perpendicular to the molecular chain orientation direction. Because it is difficult to do. The craze mentioned here includes a surface craze appearing on the surface of the polymer resin film and an internal craze generated inside, and refers to a region having a fine crack-like pattern. This craze is composed of molecular bundles (fibrils) and microvoids, and the gas permeability of various gases is generated in this portion.
[0029]
Although the above-mentioned permeable breathable film varies depending on the type of resin used, as an example, when a homopolymer of polyvinylidene fluoride is used, the gas permeability of oxygen and nitrogen gas is generally 0.3 to 100,000. × 10 ⁴ cm ³ / m ² · 24 hr · atm. The moisture permeability is generally 10 to 100,000 × 10 ⁴ g / m ² · 24 hr. The transparency is generally 1 to 99.5 haze, preferably 2 to 90 haze, particularly preferably 5 to 80 haze. The tensile strength is generally 50 to 500 kg / cm ² , preferably 60 to 500 kg / cm ² , particularly preferably 75 to 500 kg / cm ² .
[0030]
The craze formed on the polymer resin film is generally formed in an interval of 0.1 to 1,000 μm, preferably 1 to 800 μm, and is an amount that can be recognized as a striped region.
[0031]
Since the breathable film containing craze used in the present invention has the striped craze, it has functions of breathability and moisture permeability. As shown in FIG. 4, the craze 22 formed in a stripe shape penetrates the thickness direction of the film or sheet, and the gas 24 such as oxygen, nitrogen, or water vapor diffuses in the craze zone. Pass through and air permeability is developed.
[0032]
The degree of breathability of the crazed breathable film can be adjusted by changing the width of the craze formed in the polymer resin film, the distance between the crazes, and the ratio of the number of crazes penetrated. Specifically, by adjusting the degree of molecular orientation of the polymer resin film, the temperature at which the craze is formed, the tension of the polymer resin film (tension in the tension state), the folding angle of the film, etc. Breathability can be controlled and a breathable film can be provided according to the intended use.
[0032]
For example, increasing the tension when forming a craze or reducing the folding angle reduces the spacing between the generated crazes and increases the percentage of the number of crazes penetrated, resulting in increased breathability. . The air-permeable film with craze adjusted by changing the width of the craze, the distance between the crazes, and the ratio of the craze penetrated is the gas permeability, moisture permeability, transparency and tensile strength of the oxygen and nitrogen gas. Etc. can be controlled.
[0034]
A gas permeable material for an oxygen replenisher for supplying a gas such as oxygen into water characterized by using a breathable resin film having a porous membrane, which is one of the present invention, is a breathable resin having a porous membrane. By using the film as a gas permeable material in the oxygen discharge part of the oxygen replenisher, the permeability of air, oxygen, etc. filled in the oxygen replenisher is limited and discharged into water in the form of foam.
[0035]
The porous film of the resin film having air permeability is generated by heating and stretching a polymer resin film such as baked polytetrafluoroethylene (PTFE). Striped fibrils are generated by stretching uniaxially, and granular nodes and radial fibrils are generated by stretching biaxially, forming pores in the film and having air permeability.
[0036]
When the porous membrane is described in more detail with reference to polytetrafluoroethylene (hereinafter referred to as PTFE), PTFE is a filamentous crystalline polymer (about 98.5% or more) having a molecular weight of about 0.15 μm. Then, melt extrusion molding is not possible. Therefore, about 15 to 25% of kerosene or naphtha is mixed as a lubricant, and then thinly stretched with a calender roll at 80 ° C. and heated to remove the lubricant. Here, uniaxial or biaxial stretching is performed and sintering is performed at 327 ° C.
[0037]
At this time, the amorphous capacity increases and is fixed. In this way, a porous membrane having fine pores having a pore diameter of 0.02 to 15 μm and a porosity of 25 to 95% can be formed. When heated and uniaxially stretched, striped fibrils are generated, and biaxially stretched to generate granular nodes and radial fibrils, expanding fine pores in the film and venting. It has a sex.
[0038]
A gas permeable material for an oxygen replenisher for supplying a gas such as oxygen into water, characterized in that one of the present invention, wherein a foam material is superimposed on the surface of a breathable resin film having a porous membrane, The foam discharged with a limited permeability by superposing a foaming material on the surface of the air-permeable resin film having the porous membrane so as to have hydrophilicity, the air-permeable resin film having the porous membrane It is discharged into the water in the form of a foam that can be easily fused with water through the foamed material overlapped without stagnation on the surface.
[0039]
An oxygen replenisher gas permeable material for supplying a gas such as oxygen into water, which is one of the present invention, characterized in that a breathable resin film is used. By using it as a gas permeable material, the permeability of air, oxygen, etc. filled in the oxygen replenisher is limited and discharged into water in the form of bubbles. It can pass through, but it can have the characteristics of not allowing liquid such as water or gel-like solution to pass through.
[0040]
A gas permeable material for oxygen replenisher for supplying a gas such as oxygen into water, characterized in that one of the present invention, wherein a foam material is superimposed on the surface of a breathable resin film, The foam discharged on the surface of the breathable resin film with a limited permeability is superposed on the surface of the breathable resin film having a porous film by superimposing a foam material on the surface of the film to impart hydrophilicity. It is discharged into the water in the form of foam that is easy to fuse with water through the cutting material.
【The invention's effect】
[0041]
The present invention as described above, a resin film having air permeability, a gas permeable material made by overlapping Awakiri material, is attached to the oxygen or the like discharge portion such as oxygen supply devices. Compressed air filled in oxygen such as replenishing vessel, compressed oxygen or the like is limit transmission of oxygen, such as a resin film having air permeability, by giving hydrophilic by superimposing Awakiri material, gas permeability It is discharged into the water in the form of fine bubbles that are easy to fuse with water without stagnation on the surface of the material.
[Brief description of the drawings]
FIG. 1 is a perspective view showing an embodiment of a gas permeable material.
FIG. 2 is a perspective view showing a configuration of a gas permeable material and a reinforcing material.
FIG. 3 is an explanatory diagram of a gas permeable material having a sealing function.
FIG. 4 is an explanatory view of a breathable resin film containing craze.
[Explanation of symbols]
Repeated Awakiri material 2 such as oxygen supply device 4 such as oxygen discharge portion 10 transmitting material fixed frame 12 Packing 14 craze containing breathable resin film 16 Awakiri member 18 reinforcing member 20 Rubber 22 Craze 24 gas F craze filled breathable resin film Combined gas permeable material

Claims (1)

By superimposing a hydrophilic and air-permeable foam material on the surface of a breathable film in which a craze region is provided in a polymer resin film, fine bubbles generated through the breathable film can be quickly removed. A gas permeable material for a replenisher for oxygen and the like for supplying a gas such as oxygen into water, characterized by being discharged into water.

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