Source: http://www.google.com/patents/US6890373?dq=6,034,652
Timestamp: 2017-02-23 12:36:28
Document Index: 629932055

Matched Legal Cases: ['in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine']

Patent US6890373 - Adsorbents, process for producing the same, and applications thereof - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsAn adsorbent includes core particles containing an adsorbing material; a porous coating layer including a polymer material that coats the core particles; and an underlying layer containing a metal compound and disposed between the core particles and the porous coating layer. The porous coating layer...http://www.google.com/patents/US6890373?utm_source=gb-gplus-sharePatent US6890373 - Adsorbents, process for producing the same, and applications thereofAdvanced Patent SearchTry the new Google Patents, with machine-classified Google Scholar results, and Japanese and South Korean patents.Publication numberUS6890373 B2Publication typeGrantApplication numberUS 10/296,163PCT numberPCT/JP2001/005010Publication dateMay 10, 2005Filing dateJun 13, 2001Priority dateJun 19, 2000Fee statusLapsedAlso published asUS20030153457, WO2001097965A1Publication number10296163, 296163, PCT/2001/5010, PCT/JP/1/005010, PCT/JP/1/05010, PCT/JP/2001/005010, PCT/JP/2001/05010, PCT/JP1/005010, PCT/JP1/05010, PCT/JP1005010, PCT/JP105010, PCT/JP2001/005010, PCT/JP2001/05010, PCT/JP2001005010, PCT/JP200105010, US 6890373 B2, US 6890373B2, US-B2-6890373, US6890373 B2, US6890373B2InventorsYasushi Nemoto, Hisashi Mori, Tadashi KuwaharaOriginal AssigneeBridgestone CorporationExport CitationBiBTeX, EndNote, RefManPatent Citations (30), Referenced by (63), Classifications (79), Legal Events (4) External Links: USPTO, USPTO Assignment, EspacenetAdsorbents, process for producing the same, and applications thereof
Increasing capacity of and miniaturization of hard disk (hereinafter called as “HD”), one of storage devices, are rapidly advanced in recent years, and the levels of the requirements for the hard disk drive (hereinafter called as “HDD”), finished products of the HD, are increasing from year to year. The required performances for the HDD include better dehumidifying and maintaining cleanliness within the HDD. These performances are required because a contamination within the HDD generally leads to disk errors, damages of HD and damages of magnetic heads thereof. Therefore, it would be ideal to eliminate the contamination source such as organic gases from the interior of the HDD. However in reality, since the HDD includes a number of parts therein that contain adhesives for assembling thereof, contamination particles and gases are generated from the parts assembled therein or adhesives, thereby generally contaminating the interior of the HDD.
Similar problems related to the adsorbing material and the container occur in other applications. Plants such as fruits, vegetables, flowers and so on (hereinafter called as “vegetables”) emit a trace amount of ethylene gas. The presence of ethylene gas in the storage atmosphere accelerates aging of vegetables, thereby deteriorating the freshness of the vegetables.
FIG. 1 is a scanning electron microscope photograph (magnitude: ×15,000) of the adsorbent that was obtained in Example 3;
FIG. 3 is a scanning electron microscope photograph (magnitude: ×1,500) of the coated activated carbon particle that was obtained in Example 4;
FIG. 4 is a scanning electron microscope photograph (magnitude: ×350) of the adsorbent that was obtained in Example 4;
FIG. 5 is a scanning electron microscope photograph (magnitude: ×15,000) of the adsorbent that was obtained in Example 4;
FIG. 6 is a scanning electron microscope photograph (magnitude: ×15,000) of the adsorbent that was obtained in Example 5;
FIG. 7 is a scanning electron microscope photograph (magnitude: ×15,000) of the adsorbent that was obtained in Example 6;
FIG. 8 is a scanning electron microscope photograph (magnitude: ×15,000) of the adsorbent that was obtained in Example 7;
When the thermal processing is carried out after the processing of the coating layer, the thermal processing may be preferably carried out at a lower temperature than the melting point of the polymer material of the porous coating layer, since the processing at such temperature can provide higher rate of hole area over the surface and higher porosity can be maintained to provide higher air permeability, i.e., higher adsorbability. The temperature for the thermal processing may preferably be selected to a temperature between the melting point of the polymer material (mp) and a temperature of 100° C. lower than the melting point (mp−100° C.)
A circular cylinder of a diameter of 300 mm and having a mesh having opening dimension of 0.297 mm at the bottom thereof was set standing normally. Core particles of activated carbon of between 20-mesh and 10-mesh were introduced into the circular cylinder, and thereafter dry air of 160° C. was flowed from the bottom thereof at a volumetric flow rate of 3 L/sec., to promote the convection movements of the activated carbon particles. A spray nozzle having a nozzle diameter of 2.5 mm was mounted to the central portion of the bottom mesh. A suspension containing: 6 parts by weight of polytetrafluoroethylene; 5 parts by weight of nonionic surfactant (e.g., oxy ethylene oxy propylene co-polymer and so on); and 89 parts by weight of water was sprayed to the convection-moving activated carbon from the nozzle for 0.2 second, and then the sprayed activated carbon was dried for 60 seconds. The operation was repeated for 100 times to form the coating layer having an average film thickness of about 50 μm onto the surface of the activated carbon. The activated carbon particles were immersed into a water-methanol solution mixture (containing 30 parts by weight of water and 70 parts by weight of methanol) for 10 minutes to extract and remove the nonionic surfactant that had been mixed into the suspension therefrom. Thereafter, the activated carbon was dried within an atmosphere of 110° C. Then, the activated carbon was introduced into a powder dryer, where the activated carbon was heated at a condition in which the particle surface temperature of the activated carbon was increased from 110° C. to approximately 325° C. at a heating rate of 10° C./min., and the activated carbon was held at the temperature of 325° C. for 3 minutes so that polytetrafluoroethylene of the surface of the activated carbon particles was baked out. After that, the activated carbon was washed with methanol and ultra pure water to obtain the adsorbent of the present invention.
Core particles of activated carbon of between 20-mesh and 10-mesh were immersed within water, and air trapped within the micro pores of the activated carbon particles was degassed by applying ultrasonic vibration. The activated carbon particles were recovered on a mesh, and then the particles were introduced to liquid nitrogen one by one to form a layer of water ice having layer thickness of about 10 μm on the surface of the activated carbon particles. Then, the activated carbon particles having the water ice layer thereon were immersed for 1 second within a solution comprising: 1 part by weight of polycarbonate segment thermoplastic polyurethane resin; 1 part by weight of polyvinylpyrrolidone; 1 part by weight of hydroxy methyl cellulose; and 97 parts by weight of dimethyl formaldehyde, and immediately after that, the activated carbon particles were transferred to a solution comprising 40 parts by weight of dimethyl formaldehyde and 60 parts by weight of water. It was found that a white polymer coating layer was formed on the activated carbon particles surface. The activated carbon particles were washed in the flowing water for 3 hours to extract and remove hydroxy methyl cellulose with water, and then was dried at 70° C.
350 g of core particles of crushed activated carbon (between 20-mesh and 14-mesh) produced from the palm shell were introduced to a powder coating machine (“MP-01”, commercially available from POWREX CORPORATION), and the activated carbon particles were convected at air feeding temperature of 60° C., air feeding flow rate of 80 m3/hr., and revolution speed of a tri-blade bottom rotor of 300 rpm to create convectional movement.
On the other hand, a suspension of polytetrafluoroethylene resin fine powder (“POLYFRON D-1”, commercially available from DAIKIN INDUSTRIES Co., Ltd.) was diluted with distilled water to prepare a suspension containing solid contents of 20% wt. 150 g of the suspension was sprayed along the tangential direction of the rotating bottom rotor over the convecting activated carbon particles at an injection rate of 9.5 g/min. from a dual fluid nozzle having a nozzle diameter of 1.2 mm. The first coating process was completed when the exhaust temperature was increased to 50° C. after the spraying process was completed.
These particles were baked in the auger-built-in rotary kiln at 345° C. for about 5 minutes, and 350 g of the baked particles were processed via the aforementioned coating and baking processes again, to obtain the adsorbent of the present invention. The resultant adsorbent was observed via optical microscopy and scanning electron microscopy, and it was confirmed that the particles of polytetrafluoroethylene resin fine powder having particle size of approximately 0.1 μm were mutually fused at the contacting point thereof to form the porous film. FIG. 1 shows the scanning electron microscope photograph of the adsorbent (magnitude: ×15,000).
A column was prepared by filling the glass tube having a diameter of 14 mm with 1 g of non-treated activated carbon and 1 g of the above-mentioned adsorbent. A mixed gas containing 50 ppm of toluene or 50 ppm of acetaldehyde with a carrier gas of nitrogen was flowed through the column at a volumetric flow rate of 1 L/min., and the gas concentrations both at the inlet and at the outlet were monitored by using gas detection tube “121L”, and “92M”, both of which were commercially available from GASTECH CORPORATION, and the difference of the concentrations between the inlet and the outlet was calculated to obtain removal ratio.
700 grains of the above mentioned adsorbent particles were exposed to the gas flow of ultra pure nitrogen (flow rate: 1 L/min.) within a clean circular cylindrical vessel having a diameter of 14 mm, and the number of particles within the recovered nitrogen gas was counted by a PM counter (“KG-10”, commercially available from LION CORPORATION). The result shows that any contamination carbon dust having diameter of not smaller than 0.3 μm was not found, and thus it was confirmed that the adsorbent did not cause a problem of creating contamination dust. On the other hand, non-treated activated carbon particles were also evaluated by the similar method, and 77,451+/−1,959 (per 0.1 QF) of particles having diameter of 0.3 μm to 0.5 μm were observed, and thus confirmed that the non-treated activated carbon caused a problem of creating contamination dust.
The cutting cross sectional plane of the resultant activated carbon particles coated with polytetrafluoroethylene resin fine powder was observed by scanning electron microscope, and based on the observation, the thickness of the formed coating layer was calculated to approximately 100 μm. FIG. 3 shows a scanning electron microscope photo (magnitude: ×1,500) of the coated activated carbon particle.
The coated activated carbon particles were baked at the condition identical to the condition of Example 3, and found that, although a number of mud cracks were generated in the coating layer, fibrous agglomerations of polytetrafluoroethylene resin were formed within the opened slit of the crack by the drawing effect thereof. The scanning electron microscope photographs of the coated activated carbon particles after processed by the baking processing were shown in FIG. 4 (magnitude: ×350) and FIG. 5 (magnitude: ×15,000).
In order to investigate the influence of the thermal processing temperature after the coating process, a process of producing polytetrafluoroethylene resin fine powder coating activated carbon particles was carried out, that is similar to Example 3 except that the processing temperature for thermal processing of the polytetrafluoroethylene resin fine powder coating layer was: 325° C. (Example 5); 365° C. (Example 6); 375° C. (Example 7); or 385° C. (Comparative Example 1). In these Examples and Comparative Example, scanning electron microscope photos of the resultant activated carbon particles were taken, and photos of these Examples and Comparative Examples were compared with the photo taken in Example 3. According to the observation and comparison of the photos, it was found that: the polytetrafluoroethylene fine powder particles were mutually fused across the entire surface in Example 3 of baking at 345° C., as shown in FIG. 1; however, in Example 5 of baking at 325° C., there were portions in which the particles were not mutually fused as shown in FIG. 6 (magnitude: ×15,000); in Example 6 of baking at 365° C., it was observed that the geometries of the particles were partially deteriorated as shown in FIG. 7 (magnitude: ×15,000); in Example 7 of baking at 375° C., it was observed that the rate of hole area over the surface and the porosity of the coating layer decreased as shown in FIG. 8 (magnitude: ×15,000); and in Comparative Example 1 of baking at 385° C., it was observed that the formed layer was a non-porous uniform film having no air permeability
350 g of core particles of crushed activated carbon particles (30-mesh size) derived by the palm shell were introduced to a powder coating machine (“MP-01”, commercially available from POWREX CORPORATION), and the activated carbon particles were convected at air feeding temperature of 60° C., air feeding flow rate of 80 m3/hr., and revolution speed of a tri-blade bottom rotor of 300 rpm to create convectional movement of the activated carbon particles.
On the other hand, a suspension containing 20 parts by weight of photocatalyst titanium oxide (“ST01”, average particle size: 0.2 μm, commercially available from ISHIHARA INDUSTRY Co. Ltd.), 1 part by weight of methyl cellulose 25 cp (commercially available from KANTO CHEMICAL), and 79 parts by weight of water (Japanese Pharmacopoeia, distilled water) was prepared, and 300 g of the prepared suspension was sprayed at an injection rate of 15 g/min. from a dual fluid nozzle at a condition of: a nozzle diameter of 1.2 mm; and nozzle position (orientation of spraying): along the tangential direction of the rotating bottom rotor.
The conventional movement of the activated carbon particles was continued under the same condition, and the drying process was ended when the exhaust temperature was reached to 60° C. The thickness of the coating layer including the titanium oxide was measured via scanning electron microscope photos of the cross sectional specimen that was prepared by being cut with using a cutter within liquid nitrogen, and the measured thickness was about 15 μm to about 50 μm.
Then, a suspension of polytetrafluoroethylene resin fine powder (“POLYFLON D-1”, commercially available from DAIKIN INDUSTRIES Co., Ltd.) was diluted with distilled water to prepare a suspension containing solid contents of 20% wt, and 200 g of the suspension was sprayed over the convecting activated carbon particles at an injection rate of 9.5 g/min. from the above mentioned dual fluid nozzle.
These particles were baked in the auger-built-in rotary kiln at 345° C. for about 5 minutes, and 350 g of the baked particles were processed via the aforementioned coating and baking processes again, to obtain the adsorbent of the present invention.
A mixed gas containing 100 ppm of toluene, 50 ppm of acetaldehyde, 30 ppm of ammonia or 10 ppm of hydrogen sulfide and a carrier gas of air was flowed through the column at a volumetric flow rate of 1 L/min., and the gas concentrations of the original gas (at the inlet) and the adsorbed gas (at the outlet) were monitored by using. gas detection tube “92M”, “3L”, “121L” and “4LL” all of which were commercially available from GASTECH CORPORATION, and the gas removal ratio was calculated via the following equation to present the gas adsorbability. The results are shown in FIGS. 9-12.
Gas removal ratio (%)=(concentration of the original gas to concentration of the adsorbed gas)/(concentration of the original gas)×100
A water suspension including 10% wt. of polystyrene resin beads having a particle size of 0.1 μm was prepared via an ordinary emulsion polymerization and an ordinary purification. Then, a cumulative 200 g of the above mentioned suspension was sprayed to 300 g of core particles of crushed activated carbon (produced from the palm shell, particle size of between 30-mesh and 20-mesh) by using a powder coating machine of an air blowing convection type, and consequently a drying process was carried out therein. It was observed via a scanning electron microscope photo of ×15,000 of the dried product that the coarse and fine coating layer of polystyrene resin particles having particle size of 0.1 μm was formed on the surface of the activated carbon particles.
The resultant particles were thermally processed at 150° C. in the powder dryer so that the polystyrene resin particles on the coating layer can be mutually fused only at the contacting point thereof to convert the coating particles to a porous film, thereby obtaining the indoor ambient cleaning material. The indoor ambient air cleaning member was deep blue, and had no surface gloss, and the porous resin coating layer that was only 7 wt. % of the activated carbon particles was formed.
A mixed dispersion liquid was prepared by mixing 30 parts by weight of the indoor ambient air cleaning member, 15 parts by weight of a binder (“AE932”, commercially available from JSR Co. Ltd.) and 5 parts by weight of a surfactant (“PEG1000”, commercially available from KANTOH CHEMICAL Co. Ltd.) and 50 parts by weight of water. The prepared mixed dispersion liquid was readily applied onto a wall by using a sponge roller, and thereafter the coated wall was dried at 120° C. by using a hot air blower, and further the indoor ambient cleaning material was fixed onto the wall surface to obtain an indoor ambient cleaning material clay wall. The surface of the obtained wall was rough touching, and a part of the deep blue colored indoor ambient cleaning material, that looked like soil particles, flaked off the wall when the wall was strongly polished. Therefore, a product having similar appearance and characteristics to the clay wall was obtained. On the contrary, generation of any fine particles such as carbon dust was not confirmed.
In this space, one BALB mouse (male, 6 week-aged), commercially available from CHARLES RIVER LABORATORIES JAPAN Co. was bred within a commercially available cage having a bottom area of 300 mm×300 mm that was disposed within the space. The bottom of the cage was a grating, and a smooth polypropylene tray was disposed under the grating bottom, and no other object was installed over the bottom of the cage except a tray for containing a feeding stuff and a piping for feeding water.
The feeding stuff was “CR-LPF”, commercially available from ORIENTAL YEAST Co. Ltd. 30 g of the feeding stuff was fed twice a day, and all of uneaten feeding stuff was removed at the next feeding. Water was suitably fed to the mouse, which was a commercially available mineral water (“Minami Alps Ten-nen sui”, commercially available from SUNTORY Co. Ltd). Air ventilation was performed once an hour, in which a side wall was removed and the side was released for 1 minute. Lighting cycle was programmed so that light was on for 12 hours and off for next 12 hours and the lightning cycles were repeated.
These three colored indoor ambient air cleaning members, as well as the indoor ambient air cleaning members of Example 9, were fixed onto the adhesive tape (using EVA type adhesives) of 300 mm×300 mm and four paintings of flowers, mountains, starry sky and abstract painting of a person were painted thereon to present indoor ambient air cleaning paintings.
In this case, the manner of the movements of the adsorbent particles can be that the particulate adsorbent particles only vibrate within the air flow tube, and in such case, better adsorbability may be instantaneously obtainable only when the air to be adsorbed passes the instantaneously created clearances between the particulate adsorbent particles that are instantaneously created by the vibration. Here, we include this type of movements into the “free” movement.
The results indicated that the adsorbability of the particulate adsorbent was equivalent to 70 to 90% of that of the pre-coated activated carbon, depending on the types of gases. Further, 700 grains of the particulate adsorbent were exposed to the gas flow of ultra pure nitrogen (flow rate: 1 L/min.) within a clean circular cylindrical vessel of 14 φ, and the number of particles within the recovered nitrogen gas was counted by the PM counter (“KC-10 C”, commercially available from LION CORPORATION), and the result shows that any contamination carbon dust having diameter of not smaller than 0.3 μm was not found.
The crushed activated carbon particles of 20-mesh size produced from the palm shell were transferred onto the sieve of 30-mesh opening size, and the particles were washed with an injection solvent water of the Japanese Pharmacopoeia, and then the particles were dried by being left at 110° C. 700 grains of these particles were also used to clean the nitrogen gas as in Example 11, and the results of the evaluation showed that 77,451+/−1,959 particles (per 0.1 QF) having diameter of 0.3 μm to 0.5 μm were found within the recovered gas.
Thereafter, the particles were baked by using a rotary kiln for 3 minutes at about 350° C., and after cooling the particles the process from the coating process by spraying to the baking process by using the rotary kiln was repeated for two times in total to obtain the dehumidifying material for the inner gas of the dual-glass window according to the present invention. The obtained dehumidifying material was silica gel particles, on the surface of which polytetrafluoroethylene resin coating layer of about 10 μm thick was formed. The polytetrafluoroethylene resin beads itself were mutually fused only at the contacting point thereof, thereby providing the porous layer having a size of the opening equivalent to about 0.2 μm.
Next, 700 grains of the obtained dehumidifying material were exposed to the gas flow of ultra pure nitrogen (flow rate: 1 L/min.) within a clean circular cylindrical vessel of 14 φ, and the number of particles within the recovered nitrogen gas was counted by the PM counter (“KC-10C”, commercially available from LION CORPORATION), and the result shows that any contamination dust having diameter of not smaller than 0.3 μm was not found. Thus, it was confirmed that the adsorbent itself did not cause a problem of creating contamination dust.
Consequently, the dehumidifying ability was evaluated as follows. First, a saturated solution of inorganic compounds listed in TABLE-1 was poured into a tray having a dimension of 200 mm×200 mm (height: 20 mm) to a level of 80% of the height of the tray, and the tray was then transferred to a desiccator having a built-in hygrometer (width 300 mm×length 500 mm×height 500 mm), and the desiccator was transferred to a thermostat and left for 3 hours as it was. Here, three temperatures of the thermostat were selected as shown in TABLE-1. Also, the humidity within the desiccator was shown in TABLE-1.
Then, 100 g of silica gel particles that were not coated by the porous coating layer and 100 g of dehumidifying material according to the present invention were fed to the trays having a dimension of 200 mm×200 mm (height: 20 mm), and the trays were then transferred to a desiccator where the humidity change was measured. The results of the measurements show that both of the uncoated silica gel and the dehumidifying material of the present invention exhibit substantially same behavior, and thus it is found that the dehumidifying material according to the present invention retains the dehumidifying characteristic which the silica gel originally has.
Next, a window sash (size: 900 mm×1,800 mm) of a dual-glass window comprising two transparent glass sheets of 3 mm thick and containing an air layer of 6 mm thick between the two glass sheets was prepared. 20 g of the dehumidifying material according to the present invention was disposed in a space for positioning the conventional dehumidifying material within the window frame of aluminum alloy.
The dual-glass window was stored in a laboratory, in which the room temperature was set to 25° C. for 1 hour, and thereafter the dual-glass window was transferred into a refrigerator of 4° C., where no condensation or no haze was observed. In addition, no foreign object such as fine dust was observed within the glasses.
Thereafter, the particles were baked by using a rotary kiln for 3 minutes at about 350° C. while air was fed therein, and after cooling the baked particles, the process from the coating process by spraying to the baking process by using the rotary kiln was repeated for three times in total to obtain the drying agent for organic solvents according to the present invention. The obtained drying agent was silica gel particles in a coarse and fine state, on the surface of which polytetrafluoroethylene resin coating layer of about 20 μm thick was formed. The polytetrafluoroethylene resin beads itself were mutually fused only at the contacting points thereof, thereby providing the porous polymer layer having an average size of the opening equivalent to 0.1 μm.
Next, 700 grains of the obtained drying agent were exposed to the gas flow of ultra pure nitrogen (flow rate: 1 L/min.) within a clean circular cylindrical vessel of 14 φ, and the number of particles within the recovered nitrogen gas was counted by the PM counter (“KC-10C”, commercially available from LION CORPORATION), and the result shows that any contamination dust having diameter of not smaller than 0.3 μm was not found. Thus, it was confirmed that the adsorbent itself did not cause a problem of creating contamination dust.
Thereafter, the container was opened in a dry box of dry nitrogen atmosphere, and 100 mL of the anhydrous benzene contained therein was heated in a 200° C. oven for 1 hour, and was transferred to a 200 mL eggplant type flask that had been dried by exposing burner flame. Then, 10 mL of titanium tetra (iso-propoxide) purified via vacuum distillation was aliquoted by using a syringe and injected therein, and after the injections, the flask was sealed and the liquid was stirred by using a magnet stirrer for 30 minutes.
an ordinary purification. Then, a cumulative 200 g of the above mentioned suspension was sprayed to 300 g of core particles of crushed activated carbon (produced from the palm shell, particle size of between 30-mesh and 20-mesh) by using a powder coating machine of a type of air blowing convection processing, and consequently a drying process was carried out therein. It was observed via a scanning electron microscope image photo of ×15,000 of the dried product that the coarse and fine coating layer of polystyrene resin particles having particle size of 0.1 μm was formed on the surface of the activated carbon particles.
The resultant particles were thermally processed at 150° C. in the powder dryer so that the polystyrene resin particles on the coating layer can be mutually fused only at the contacting point thereof to convert the coating particles to a porous film, thereby obtaining the particulate adsorbent. 60 particles of the obtained particulate adsorbent were fixed onto one side of a double-sided adhesive tape of 10 mm×10 mm in a single particle layer to obtain the adsorbent according to the present invention.
350 g of core particles of crushed activated carbon (between 20-mesh and 14 mesh) derived by the palm shell were introduced to the powder coating machine (“MP-01”, commercially available from POWREX CORPORATION), and the activated carbon particles were convected at air feeding temperature of 60° C., air feeding flow rate of 80 m3/hr., and revolution speed of a tri-blade bottom rotor of 300 rpm to create convectional movement of the activated carbon particles.
On the other hand, a suspension of polytetrafluoroethylene resin fine powder (“POLYFRON D-1”, commercially available from DAIKIN INDUSTRIES Co., Ltd.) was diluted with distilled water to prepare a suspension containing solid contents of 20% wt, and 150 g of the suspension was sprayed along the tangential direction of the rotating bottom rotor over the convecting activated carbon particles at an injection rate of 9.5 g/min. from a dual fluid nozzle having a nozzle diameter of 1.2 mm. The first coating process was completed when the exhaust temperature was increased to 50° C. after the spraying process was completed.
These particles were baked in the auger-built-in rotary kiln at 345° C. for about 5 minutes, and 350 g of the baked particles were processed via the aforementioned coating and baking processes again, to obtain the freshness keeping member of the present invention. The resultant freshness keeping member was observed via optical microscopy and scanning electron microscopy, and it was confirmed that the particles of polytetrafluoroethylene resin fine powder having diameter of approximately 0.1 μm were mutually fused at the contacting point thereof to form the porous film.
A flexible polyurethane foam having no film and having flexibility (“SF#06”, commercially available from BRIDGESTONE CORPORATION) was cut to a size of 25 mm×25 mm×5 mm thick, and the piece was coated with acrylic type binder, then after the surplus binder was removed, the particulate freshness keeping member particles obtained above were sprinkled on the surface of the foam and pressurized to adhere thereto, thereby fixing the freshness keeping member particles on one surface of the foam at a density of 0.1 g (350 particles) per 1 cm2 to obtain the freshness keeping member of the present invention.
Spinach was selected to be a vegetable sample, and 60 g of the spinach and 5 g of water were fed into a polyethylene bag of 120 μm thick together with the above mentioned freshness keeping member, and the bag was left for 4 days at a room temperature (25° C.). Three spinach samples were simultaneously evaluated. After 4 days had passed, appearance, level of foreign odor and green color level were evaluated for these spinach samples.
Sodium sulfate anhydrous salt powder was agglomerated via the fluidized bed method to form core particles having an average particle size of 0.6 mm. 150 g of the core particles were introduced to the powder coating machine (“MP-01”, commercially available from POWREX CORPORATION), and the core particles were convected at air feeding temperature of 60° C., air feeding flow rate of 80 m3/hr., and revolution speed of a tri-blade bottom rotor of 300 rpm to create convectional movement of the core particles.
On the other hand, a suspension of polytetrafluoroethylene resin fine powder (“POLYFRON D-1”, commercially available from DAIKIN INDUSTRIES Co., Ltd.) was diluted with distilled water to prepare a suspension containing solid contents of 20% wt, and 150 g of the suspension was sprayed along the tangential direction of the rotating bottom rotor over the convecting core particles at an injection rate of 9.5 g/min. from a dual fluid nozzle having a nozzle diameter of 1.2 mm. The first coating process was completed when the exhaust temperature was increased to 50° C. after the spraying process was completed.
These particles were baked in the auger-built-in rotary kiln at 345° C. for about 5 minutes, and 150 g of the baked particles was processed via the aforementioned coating and baking processes again, to obtain the ambiance humidity regulating member of the present invention. The resultant ambiance humidity regulating member was observed via optical microscopy and scanning electron microscopy, and it was confirmed that the particles of polytetrafluoroethylene resin fine powder having particle size of approximately 0.1 μm were mutually fused at the contacting point thereof to form the porous film.
A front edge of a gas detection tube for water vapor (“Gas detection tube No. 6”, commercially available from GASTECH CORPORATION) was inserted into the desiccator via the gas collecting opening of the desiccator, and 100 ml of the internal gas was sucked and the obtained gas was tested to measure a water vapor concentration thereof. Relative humidity was calculated by using a temperature at the time of measurement, and the calculated results indicated that the relative humidity varied as shown in FIG. 20. According to FIG. 20, it was confirmed that this ambiance humidity regulating member had a dehumidifying effect, and that the relative humidity in the desiccator was stable within a range of 30% to 40% and did not decrease from this level.
Next, the polypropylene sheet having the fixed ambiance humidity regulating member thereon was transferred into a desiccator that had been dried at 110° C., and water vapor concentration was measured in the similar manner, and the results of the measurements indicated the humidity variation as shown in FIG. 21.
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS2375008 *Sep 19, 1942May 1, 1945Hercules Powder Co LtdCarbonaceous materialUS2638179 *Jan 6, 1950May 12, 1953Edward M YardDrying capsuleUS3544507 *Aug 23, 1967Dec 1, 1970Calgon C0RpDedusting and agglomerating activated carbonUS3953657 *Jan 28, 1974Apr 27, 1976Mitsui Toatsu Kagaku Kabushiki KaishaMethod for coating particulate solids with polymersUS4076892Jul 24, 1974Feb 28, 1978T. J. Smith & Nephew LimitedTreatment of particulate carbonUS4126433 *Oct 12, 1976Nov 21, 1978Forssberg Knut S EMethod of and apparatus for removing aerosols of hydrocarbons from a gas streamUS4248736 *Jan 2, 1979Feb 3, 1981Kuraray Co., Ltd.Fibrous adsorbent for hemoperfusionUS4337294 *May 2, 1980Jun 29, 1982Phillips Petroleum CompanyRubber covered carbon black pelletsUS4687573 *Aug 13, 1984Aug 18, 1987Pall CorporationSorbing apparatusUS4764424 *Mar 31, 1986Aug 16, 1988AtochemPolyamide-coated particles and process for their preparationUS5182016 *Sep 18, 1991Jan 26, 1993Regents Of The University Of MinnesotaPolymer-coated carbon-clad inorganic oxide particlesUS5224972 *Apr 18, 1991Jul 6, 1993Frye Gregory CCoatings with controlled porosity and chemical propertiesUS5281478 *Dec 3, 1992Jan 25, 1994Th. Goldschmidt AgMethod for modifying the surface of finely divided particles by the application of organofunctional polysiloxanesUS5639550 *Jun 21, 1995Jun 17, 1997Specialty Media CorporationComposite particulate material and process for preparing sameUS5721187 *Dec 27, 1995Feb 24, 1998Sumitomo Chemical Company, LimitedOxygen absorberUS5853690Feb 24, 1997Dec 29, 1998Toyota Jidosha Kabushiki KaishaMethod for decomposing water using an activated carbon catalystUS6030704 *Jun 18, 1997Feb 29, 2000Ecc International Ltd.Granular materials comprising inorganic silicon-containing materialUS6059860 *Jun 21, 1996May 9, 20003M Innovative Properties CompanySorptive articlesUS6277179 *Jun 23, 1999Aug 21, 2001Ceca S.A.Agglomerates based on active charcoal, their process of preparation and their use as adsorption agentsUS6391429 *Jan 9, 1997May 21, 20023M Innovative Properties CompanyPermeable shaped structures of active particulate bonded with PSA polymer microparticulateUS6395678 *Sep 1, 1999May 28, 2002Aero-Terra-Aqua Technologies CorporationBead and process for removing dissolved metal contaminantsUS6429165 *Oct 27, 1999Aug 6, 2002Auergesellschaft GmbhPolymer-bonded materialUS6458458 *May 24, 1999Oct 1, 2002Cabot CorporationPolymer coated carbon products and other pigments and methods of making same by aqueous media polymerizations or solvent coating methodsUS20030226443 *Jun 7, 2002Dec 11, 2003Shyamala RajagopalanAir-stable metal oxide nanoparticlesEP0635301A2 *Mar 15, 1991Jan 25, 1995Regents Of The University Of MinnesotaCarbon-clad inorganic oxide particles with a polymer coating thereonJPH0790168A Title not availableJPH02233140A Title not availableJPH04367722A Title not availableJPH09225299A Title not availableJPS5062884A Title not available* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS7367997 *Jul 11, 2005May 6, 2008Donaldson Company, Inc.Electronic enclosure filter for very small spacesUS7393381 *Mar 8, 2005Jul 1, 2008Applied Filter Technology, Inc.Removing siloxanes from a gas stream using a mineral based adsorption mediaUS7410524Sep 21, 2005Aug 12, 2008Tower Paul MRegenerable purification system for removal of siloxanes and volatile organic carbonsUS7514010 *Jul 9, 2007Apr 7, 2009Salmon Daniel JWater filtering method and apparatusUS7553355 *Jun 23, 2004Jun 30, 2009Matheson Tri-GasMethods and materials for the reduction and control of moisture and oxygen in OLED devicesUS7811539Nov 3, 2006Oct 12, 2010Seagate Technology LlcDevice and method for filtering contaminantsUS7812188 *Dec 7, 2006Oct 12, 2010American Air Liquide, Inc.Preparation of adsorbents for purifying organosilicon compoundsUS7947111May 21, 2009May 24, 2011Matheson Tri-GasMethods and materials for the reduction and control of moisture and oxygen in OLED devicesUS7955418Sep 11, 2006Jun 7, 2011Abela Pharmaceuticals, Inc.Systems for removing dimethyl sulfoxide (DMSO) or related compounds or odors associated with sameUS8002877 *Dec 7, 2006Aug 23, 2011Lawrence SadlerMethod of trapping ethyleneUS8033304Jul 13, 2008Oct 11, 2011Donaldson Company, Inc.Contaminant control filter with fill portUS8137438Feb 9, 2011Mar 20, 2012Matheson Tri-GasMethods and materials for the reduction and control of moisture and oxygen in OLED devicesUS8298320May 2, 2011Oct 30, 2012Abela Pharmaceuticals, Inc.Systems for removing dimethyl sulfoxide (DMSO) or related compounds, or odors associated with sameUS8309484 *May 31, 2007Nov 13, 2012Carrier CorporationPreparation and manufacture of an overlayer for deactivation resistant photocatalystsUS8404204 *Mar 31, 2008Mar 26, 2013Rockwood Italia SpaGranulate having photocatalytic activity and methods for manufacturing the sameUS8435224Sep 11, 2006May 7, 2013Abela Pharmaceuticals, Inc.Materials for facilitating administration of dimethyl sulfoxide (DMSO) and related compoundsUS8440001Oct 24, 2012May 14, 2013Abela Pharmaceuticals, Inc.Systems for removing dimethyl sulfoxide (DMSO) or related compounds, or odors associated with sameUS8480797May 2, 2011Jul 9, 2013Abela Pharmaceuticals, Inc.Activated carbon systems for facilitating use of dimethyl sulfoxide (DMSO) by removal of same, related compounds, or associated odorsUS8496739 *Aug 22, 2011Jul 30, 2013Corning IncorporatedOrganic antioxidant based filtration apparatus and methodUS8500887 *Feb 25, 2011Aug 6, 2013Exxonmobil Research And Engineering CompanyMethod of protecting a solid adsorbent and a protected solid adsorbentUS8513157Jun 30, 2011Aug 20, 2013Carrier CorporationDeactivation resistant photocatalystsUS8535426Aug 22, 2011Sep 17, 2013Lawrence R. SadlerApparatus, system, and method for removing ethylene from a gaseous environmentUS8628669 *Jun 20, 2011Jan 14, 2014Global Green Products, LlcMethods to recover and reclaim hydrocarbons or hydrophobic substances in an aqueous environmentUS8651773 *Mar 6, 2007Feb 18, 2014Basf SeProcess for pneumatic conveying of water-absorbing polymer particlesUS8673061May 2, 2011Mar 18, 2014Abela Pharmaceuticals, Inc.Methods for facilitating use of dimethyl sulfoxide (DMSO) by removal of same, related compounds, or associated odorsUS8795588May 31, 2007Aug 5, 2014Carrier CorporationSystems and methods for removal of contaminants from fluid streamsUS8805616 *Dec 21, 2010Aug 12, 2014Schlumberger Technology CorporationMethod to characterize underground formationUS8814985 *Dec 22, 2009Aug 26, 2014Glatt Systemtechnik GmbhComposite adsorbent bead, process for its production, gas separation process and gas adsorption bedUS8864884Oct 7, 2011Oct 21, 2014Donaldson Company, Inc.Contaminant control filter with fill portUS8927078Feb 14, 2012Jan 6, 2015Reynolds Consumer Products Inc.Encapsulated activated carbon and the preparation thereofUS9186297May 3, 2013Nov 17, 2015Abela Pharmaceuticals, Inc.Materials for facilitating administration of dimethyl sulfoxide (DMSO) and related compoundsUS9186472May 10, 2013Nov 17, 2015Abela Pharmaceuticals, Inc.Devices for removal of dimethyl sulfoxide (DMSO) or related compounds or associated odors and methods of using sameUS9198457Mar 7, 2009Dec 1, 2015Paper-Pak IndustriesAbsorbent pads for food packagingUS9247851Sep 11, 2009Feb 2, 2016Paper-Pak IndustriesAbsorbent pad to preserve freshness for consumer food storageUS9364119Sep 11, 2009Jun 14, 2016Paper-Pak IndustriesAbsorbent pad to preserve freshness for consumer food storageUS9427419Sep 11, 2006Aug 30, 2016Abela Pharmaceuticals, Inc.Compositions comprising dimethyl sulfoxide (DMSO)US9484123Sep 10, 2012Nov 1, 2016Prc-Desoto International, Inc.Conductive sealant compositionsUS20050186123 *Jun 23, 2004Aug 25, 2005Torres Robert Jr.Methods and materials for the reduction and control of moisture and oxygen in OLED devicesUS20060000352 *Mar 8, 2005Jan 5, 2006Tower Paul MRemoving siloxanes from a gas stream using a mineral based adsorption mediaUS20060144224 *Sep 21, 2005Jul 6, 2006Applied Filter Technology, Inc.Regenerable purification system for removal of siloxanes and volatile organic carbonsUS20080009645 *Dec 7, 2006Jan 10, 2008Mindi XuPreparation Of Adsorbents For Purifying Organosilicon CompoundsUS20080178738 *Jan 29, 2007Jul 31, 2008Foamex L.P.Absorbent and/or filter materials comprising open cell foams coated with photocatalytic titanium dioxide, and methods of making and using the sameUS20080217230 *Jul 9, 2007Sep 11, 2008Salmon Daniel JWater filtering method and apparatusUS20080236397 *May 5, 2008Oct 2, 2008Donaldson Company, Inc.Electronic Enclosure Filter for Very Small SpacesUS20090005842 *Oct 12, 2007Jan 1, 2009Alpharma Inc., Animal Health DivisionCooling SystemUS20090025561 *Jul 13, 2008Jan 29, 2009Tuma Daniel LContaminant control filter with fill portUS20090060660 *Mar 6, 2007Mar 5, 2009Basf SeProcess for Pneumatic Conveying of Water-Absorbing Polymer ParticlesUS20090155508 *Dec 14, 2007Jun 18, 2009Pactiv CorporationEncapsulated Activated Carbon and the Preparation ThereofUS20090185966 *May 31, 2007Jul 23, 2009Carrier CorporationPreparation and manufacture of an overlayer for deactivation resistant photocatalystsUS20090278455 *May 21, 2009Nov 12, 2009Matheson Tri-GasMethods and materials for the reduction and control of moisture and oxygen in oled devicesUS20100047405 *Sep 11, 2009Feb 25, 2010Sayandro VersteylenAbsorbent pad to preserve freshness for consumer food storageUS20100086460 *Nov 3, 2006Apr 8, 2010Deeken John SDevice and method for filtering contaminantsUS20110091367 *Mar 31, 2008Apr 21, 2011Rockwood Italia SpaGranulate having photocatalytic activity and methods for manufacturing the sameUS20110117002 *May 31, 2007May 19, 2011Carrier CorporationSystems and methods for removal of contaminants from fluid streamsUS20110127660 *Feb 9, 2011Jun 2, 2011Matheson Tri-GasMethods and materials for the reduction and control of moisture and oxygen in oled devicesUS20110165294 *Mar 7, 2009Jul 7, 2011Sayandro VersteylenAbsorbent pads for food packagingUS20110232493 *Feb 25, 2011Sep 29, 2011Exxonmobil Research And Engineering CompanyMethod of protecting a solid adsorbent and a protected solid adsorbentUS20110315637 *Jun 20, 2011Dec 29, 2011Koskan Larry PMethods to recover and reclaim hydrocarbons or hydrophobic substances in an aqueous environmentUS20120048110 *Aug 22, 2011Mar 1, 2012Steven Bruce DawesOrganic antioxidant based filtration apparatus and methodUS20120152115 *Dec 22, 2009Jun 21, 2012Air Products And Chemicals, Inc.Composite adsorbent bead, process for its production, gas separation process and gas adsorption bedUS20120152548 *Dec 21, 2010Jun 21, 2012Schlumberger Technology CorporationMethod to characterize underground formationUS20140251927 *May 19, 2014Sep 11, 2014Nathan T. StarbardPorous Polymeric Particles and Methods of Making and Using ThemWO2007091911A1 *Feb 9, 2006Aug 16, 2007Institut Problem Pererabotki Uglevodorodov Sibirskogo Otdeleniya Rossiiskoi Akademii NaukSorbent a method for the production thereof and hydrocarbon drying method* Cited by examinerClassifications U.S. Classification95/90, 428/407, 96/118, 210/504, 95/143, 96/135, 55/524, 95/116, 96/117.5, 502/402, G9B/33.043, G9B/33.044, 55/385.6, 95/91, 96/154International ClassificationB01D53/04, B01J47/00, B01J20/20, B01J20/32, G11B33/14Cooperative ClassificationB01J47/018, Y10T428/2998, B01J20/261, B01J20/262, B01J20/264, B01J20/28004, B01J20/327, B01J20/3272, B01J20/3276, B01J20/3289, B01J2220/49, B01J20/305, B01D2253/102, B01D53/02, B01J20/3236, B01J20/3293, B01D2253/112, B01D2253/108, B01J20/20, B01J20/3204, B01D2253/308, B01D2259/4508, B01D2259/4146, B01J20/06, B01D2257/90, B01D2253/206, B01J20/08, G11B33/146, G11B33/1453, B01D2253/304, B01D2253/202, B01D2257/80, B01D2253/104, B01J20/103, B01D2253/106, B01J20/16, B01J20/2805, B01J20/28078, B01J20/14, B01J20/28019European ClassificationB01J20/28F12, B01J20/10B, B01J20/08, B01J20/32B4, B01J20/32F8F, B01J20/28D36, B01J20/14, B01J20/32H4, B01J20/28D4B, B01J20/30K, B01J20/16, B01J20/32F4D, B01J20/06, B01J20/20, G11B33/14C2, B01J47/00M, B01J20/32, G11B33/14C4, B01D53/02Legal EventsDateCodeEventDescriptionJan 17, 2003ASAssignmentOwner name: BRIDGESTONE CORPORATION, JAPANFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:NEMOTO, YASUSHI;MORI, HISASHI;KUWAHARA, TADASHI;REEL/FRAME:013675/0403Effective date: 20030106Nov 17, 2008REMIMaintenance fee reminder mailedMay 10, 2009LAPSLapse for failure to pay maintenance feesJun 30, 2009FPExpired due to failure to pay maintenance feeEffective date: 20090510RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services