WO2011145216A1 - 乾燥セルロースゲル及びその製造方法 - Google Patents
乾燥セルロースゲル及びその製造方法 Download PDFInfo
- Publication number
- WO2011145216A1 WO2011145216A1 PCT/JP2010/058657 JP2010058657W WO2011145216A1 WO 2011145216 A1 WO2011145216 A1 WO 2011145216A1 JP 2010058657 W JP2010058657 W JP 2010058657W WO 2011145216 A1 WO2011145216 A1 WO 2011145216A1
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- WO
- WIPO (PCT)
- Prior art keywords
- cellulose
- gel
- electron beam
- cellulose gel
- water
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/005—Crosslinking of cellulose derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
- B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
- B01F27/805—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis wherein the stirrers or the receptacles are moved in order to bring them into operative position; Means for fixing the receptacle
- B01F27/806—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis wherein the stirrers or the receptacles are moved in order to bring them into operative position; Means for fixing the receptacle with vertical displacement of the stirrer, e.g. in combination with means for pivoting the stirrer about a vertical axis in order to co-operate with different receptacles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/70—Mixers specially adapted for working at sub- or super-atmospheric pressure, e.g. combined with de-foaming
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/10—Crosslinking of cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
Definitions
- the present invention relates to a dry cellulose gel, and particularly to a dry cellulose gel excellent in water absorption and a method for producing the same.
- Patent Documents 1 and 2 A method for producing a self-crosslinking alkylcellulose derivative using radiation irradiation has been proposed (Patent Documents 1 and 2).
- Patent Document 2 is an improvement of the method described in Patent Document 1 by the present inventors.
- the irradiation is performed.
- a method is proposed in which the gel after the formation of particles is dried.
- cellulose powder and water are kneaded with an extruder, and in particular, ⁇ -rays, X-rays, and electron beams from cobalt 60 are irradiated and crosslinked to form a cellulose gel, which is then cut. , Granulate and dry.
- the present inventors repeated the experiment it was found that the water absorption of the obtained cellulose gel was not uniform and could not be mass-produced.
- the dry cellulose gel obtained by the methods described in Patent Documents 1 and 2 has a problem that the water absorption is low, the water absorption varies, and mass production cannot be achieved. Then, the objective of this invention aims at providing the manufacturing method for mass-producing the dry cellulose gel excellent in water absorption, and the said dry cellulose gel.
- the cause of the decrease in water absorption and variation is the heterogeneity of the alkylcellulose derivative-water mixture during irradiation and the presence of bubbles.
- the invention has been completed.
- 15 to 25 wt% cellulose powder is added to a kneader containing water while spraying mist-like water, and then the water and cellulose powder are kneaded under vacuum, Including a step of obtaining a paste-like cellulose kneaded product, a step of irradiating the cellulose kneaded product with an electron beam to obtain a crosslinked cellulose gel, and a step of drying the crosslinked cellulose gel to obtain a dried cellulose gel.
- a method for producing a dry cellulose gel is provided.
- the cellulose powder rises, and not only a predetermined amount of cellulose powder cannot be introduced, but also the cellulose powder is sucked in vacuum when kneading under vacuum. .
- mist water can be sprayed onto the cellulose powder to prevent the cellulose powder from flying up. The wettability between water and cellulose powder can be improved.
- the powdered cellulose is preferably carboxyalkylcellulose, particularly preferably sodium carboxymethylcellulose.
- the water directly introduced into the kneading machine and the water to be sprayed are preferably water that does not contain chlorine or alcohol, and is water that has been desalted and deaerated. Is more preferable.
- the water and powdered cellulose used for vacuum kneading are adjusted so that the content of powdered cellulose is 15 to 25 wt%.
- the crosslinking reaction by electron beam irradiation will not advance, but the decomposition reaction of cellulose will have priority.
- the content of powdered cellulose is too small, a large amount of electron beam irradiation is required to cause a crosslinking reaction by electron beam irradiation, resulting in an increase in cost.
- an electron beam for the cellulose kneaded product by using an electron beam for the cellulose kneaded product, it can be crosslinked by irradiation for a very short time.
- the irradiation amount of the electron beam varies depending on the content of powdered cellulose, but it is preferably 9 to 16 kGy in the range of 15 to 25 wt% of powdered cellulose.
- the amount of electron beam irradiation is large, the network of the crosslinked structure becomes small, and when the amount of electron beam irradiation is small, the network of the crosslinked structure becomes large. If it is in the said range, the water absorption of a dry cellulose gel can be raised.
- the production method of the present invention preferably further includes a step of molding the cellulose kneaded product under vacuum.
- a step of molding the cellulose kneaded product under vacuum By forming under vacuum, it is possible to avoid generating excess bubbles in the cellulose kneaded product containing water.
- a dried cellulose gel having a water absorption ratio of 150 or more obtained by dividing the gel absorbed for 24 hours by the initial weight before water absorption is obtained.
- an apparatus for enforcing the manufacturing method of the dry cellulose gel of this invention Comprising: The kneading pot provided with the stirring blade, the flowing water pipe provided along the inner peripheral part, and the said flowing water
- a vacuum kneading device comprising a lid provided with water spraying portions provided at equal intervals on the tube, and a vacuum suction unit; a belt conveyor for conveying the cellulose kneaded material taken out from the vacuum kneading device, and an electron beam irradiation unit
- An electron beam irradiation device comprising: an electron beam source; a breathable belt conveyor that conveys the cellulose gel taken out from the electron beam irradiation device; and a circulation fan that blows hot air from above the belt conveyor.
- An apparatus for producing a dry cellulose gel comprising a drying apparatus is also provided.
- FIG. 1 is a schematic flowchart showing the manufacturing process of the present invention.
- FIG. 2 is an explanatory view schematically showing the entire manufacturing apparatus used in the present invention.
- FIG. 3 (A) is a schematic front view showing a vacuum kneading apparatus used in the present invention
- FIG. 3 (B) is a schematic side view thereof
- FIG. 3 (C) is an A line in FIG. 3 (B).
- FIG. 4a is a schematic sectional view showing an electron beam irradiation apparatus used in the present invention.
- FIG. 4b is a schematic plan view of the same.
- FIG. 5 is a schematic sectional view showing an extrusion apparatus used in the present invention.
- FIG. 1 is a schematic flowchart showing the manufacturing process of the present invention.
- FIG. 2 is an explanatory view schematically showing the entire manufacturing apparatus used in the present invention.
- FIG. 3 (A) is a schematic front view showing a vacuum kneading apparatus used in the present invention
- FIG. 6 is a schematic sectional view showing a drying apparatus used in the present invention.
- FIG. 7 a is a bar graph showing measurement results of water absorption magnification according to Example 1.
- FIG. 7 b is a bar graph showing the measurement results of the water absorption magnification according to Example 1.
- FIG. 7 c is a bar graph showing measurement results of water absorption magnification according to Example 1.
- the manufacturing apparatus of the present invention includes a vacuum kneading apparatus 10, an electron beam irradiation apparatus 100, and a drying apparatus 200.
- the vacuum kneading apparatus 10 includes a kneading pot 20, a lid 30, a lifting cylinder 40 that raises and lowers the lid 30, a hydraulic / vacuum unit 50, and a kneading motor 60.
- the lid 30 includes a stirring blade 31, a raw material inlet 32, a water pipe 34 provided on the inner periphery of the lid above the raw material inlet 32, and water spray provided at equal intervals on the water pipe 34. Part 33.
- the lid 30 is lowered to the position of the kneading pot 20 by the lifting cylinder 40.
- the inside of the kneading vessel 20 is vacuumed by the hydraulic / vacuum unit 50, and the stirring blade 31 is driven by the kneading motor 60.
- the electron beam irradiation apparatus 100 includes a belt conveyor 110 that conveys the cellulose kneaded material prepared in the vacuum kneading apparatus 10, an electron beam irradiation unit 120 that irradiates the cellulose kneaded material with an electron beam, A radiation source 130.
- the electron beam irradiation unit 120 and the electron beam source 130 are accommodated in a shielding enclosure 140 for preventing the electron beam from leaking to the outside.
- the belt conveyor 110 is disposed so as to be long enough to give a desired electron beam dose.
- the belt conveyor 110 may be a straight path, a winding path, a turning path, or a three-dimensional path.
- the production apparatus of the present invention may include an extrusion apparatus 150 that forms the crosslinked cellulose gel crosslinked by the electron beam irradiation apparatus 100 into a shape that can be easily dried. As shown in FIG. 5, the extrusion apparatus 150 is formed into a spherical shape by cutting the crosslinked cellulose gel into a spherical shape, a hopper 152 that receives the crosslinked cellulose gel, a slicer 154 that is provided below the hopper 152 and cuts the crosslinked cellulose gel. An extrusion unit 156 and a discharge port 158 are provided.
- the extruding portion 156 includes a cylindrical main body 156a and an extruding screw 156b that is rotatably provided inside the cylindrical main body.
- the discharge port 158 is provided with a plate-like member 158a having a circular hole for extruding the crosslinked cellulose gel into a spherical shape.
- the feed pitch P1 of the front half of the screw 156b for extrusion is about half of the feed pitch P2 of the latter half, and the extrusion pressure on the tip end side is increased.
- a space 156d having a divergent shape is formed between the tip of the screw 156b and the die 156c.
- the die die 156c has a large number of forming holes 156e for particle formation, and each forming hole 156e is not shown, but from the rear surface of the screw 156b side to the intermediate position in the thickness direction of the forming hole 156e.
- the taper hole has a slightly tapered shape, and is a straight hole having a constant diameter from the middle position to the front surface of the die die 156c.
- the diameter of the molding hole 156e varies depending on the use of the dry gel, and a die die 156c having a desired diameter is mounted on the extrusion device in a replaceable manner.
- the drying apparatus 200 includes a breathable belt conveyor 210 that receives and conveys the crosslinked cellulose gel formed into particles by the extrusion apparatus 150, and a circulation fan that blows hot air from above the belt conveyor 210. 220, an exhaust duct 230, and an outlet 240 for taking out the crosslinked cellulose gel after drying.
- the breathable belt conveyor 210 may be made of punching metal or mesh metal as long as it is configured to vent hot air from the circulation fan 220.
- the exhaust duct 230 is provided above the circulation fan 220, and removes exhaust gas containing moisture that is removed from the crosslinked cellulose gel when hot air is applied to the crosslinked cellulose gel from the drying device 200. It is preferable to provide a plurality of circulation fans and individually adjust the temperature according to the degree of drying of the crosslinked cellulose gel.
- FIG. S1 is a vacuum kneading step in which cellulose powder and water are kneaded under vacuum, and is preferably performed in the vacuum kneading apparatus 10 shown in FIG.
- S2 is an electron beam irradiation step of irradiating the cellulose kneaded material with an electron beam, and is preferably performed in the electron beam irradiation apparatus 100 shown in FIG.
- S3 is a drying process for drying the crosslinked cellulose gel, and is preferably performed in the drying apparatus 200 shown in FIG.
- the vacuum state in the present invention can be realized by applying a pressure in the range of 500 Pa to 0.13 Pa, more preferably in the range of 130 Pa to 1 Pa with a vacuum pump, and the kneading time is 30 to 60 minutes, preferably 40 to 50. For minutes.
- the vacuum-kneaded cellulose kneaded product is formed into a size and shape suitable for electron beam irradiation.
- the molding can be performed using a vacuum press, a vacuum extruder, or the like, but the kneading pot 20 in a vacuum state may be pressurized to extrude the cellulose kneaded material from the lower extrusion port and cut it.
- ⁇ S2> The cellulose kneaded material after molding is placed on the belt conveyor 110, conveyed into the electron beam irradiation apparatus 100, and irradiated with an electron beam from the electron beam source 130 at the electron beam irradiation unit 120.
- the cross-linked cellulose gel obtained by electron beam irradiation is transported to the hopper 152 of the extrusion apparatus 150 while being placed on the belt conveyor 110 and is put into the hopper 152.
- the crosslinked cellulose gel charged into the hopper 152 is cut by a slicer 154 at the bottom of the hopper 152 and supplied into the extrusion apparatus 150 main body.
- the cross-linked cellulose gel supplied to the extrusion unit 156 of the extrusion apparatus 150 body is pushed out of the cylindrical body 156a toward the discharge port 158 by the extrusion screw 156b, and is pushed out from the circular hole of the plate-like member 158a of the discharge port 158. And discharged as a sphere.
- the crosslinked cellulose gel is crushed by the rotating screw 156b and is pushed forward of the cylindrical main body 156a while being kneaded. Since the feed pitch P1 of the front half of the screw 156b is about half of the feed pitch P2 of the latter half, the pressing force against the kneaded product of the crosslinked cellulose gel gradually increases, and each die die 156c is molded with a predetermined pushing force.
- Cross-linked cellulose gel is extruded from the holes 156e. During the extrusion, the crosslinked cellulose gel is not continuously elongated but is cut into short particles and extruded as a particulate gel because of the moisture content and viscoelasticity of the crosslinked cellulose gel.
- the cross-linked cellulose gel discharged in a spherical shape is received by the air-permeable belt conveyor 210 of the drying device 200 and conveyed into the drying device 200.
- the spherical crosslinked cellulose gel is exposed to warm air at a predetermined temperature of 60 to 90 ° C. in each drying chamber in the drying apparatus 200 to become a dried crosslinked cellulose gel, and is taken out from the outlet 240.
- the hot air repeatedly flows from the upper side to the lower side of the breathable belt conveyor 210 and from the lower side to the upper side, so that the particulate crosslinked cellulose gel is dried to a residual moisture content of about 10 wt% while moving at a low speed. .
- Example 1 As the cellulose powder, carboxyalkyl cellulose sodium is used, the content is changed from 15 wt% to 30 wt%, the electron beam irradiation amount is changed from 7 kGy to 16 kGy, and the dried crosslinked cellulose gel is used using the production apparatus shown in FIG. Manufactured. That is, 10.5 L to 12.75 L of water was poured into the kneading pot, and 2.25 to 4.5 kg of sodium carboxyalkylcellulose powder was added while spraying mist of water. The mixture was vacuumed and kneaded for 40 minutes.
- the cellulose kneaded material kneaded under vacuum was transferred to an electron beam irradiation apparatus and irradiated with a predetermined electron beam to be crosslinked to obtain a crosslinked cellulose gel.
- the cross-linked cellulose gel was transferred to an extrusion device and formed into a spherical shape, and then transferred to a drying device and dried to obtain a dry cellulose gel.
- the amount of electron beam irradiation decreases as the cellulose powder content increases, and the optimum cellulose powder content and electrons to achieve a high water absorption ratio, although it varies depending on the type of cellulose powder used as a raw material. It can be seen that there is a combination with the irradiation dose.
- the evaluation item “ ⁇ ” has a water absorption ratio of 350 times or more, especially indicating that the water absorption capacity is required, and “ ⁇ ” has a water absorption ratio of 150 to 350 times. “ ⁇ ” indicates that it has a water absorption ratio of 90 to 150 times.
- Material No. 1350 is softer than gel No. 2200 in the raw state after irradiation. Among the three types of materials, the water absorption of the dried gel tends to vary.
- Material No. 350 shows a stable and high water absorption ratio for both the gel in the raw state after irradiation and the dried gel.
- the dry gel obtained as “ ⁇ ” in Table 1 has both flexibility and strength and is slow to decompose, and is therefore suitable as a water retention material for plants.
- ⁇ Swelling degree> Moreover, 1 g of the dry cellulose gel of the present invention was immersed in 1600 g of well water for 18 hours, and the mass before and after swelling was measured to calculate the degree of swelling ( mass after immersion / mass before immersion). Table 2 shows the measurement results of representative examples.
- Example 1 A dry cellulose gel was obtained in the same manner as in Example 1 except that the kneading was performed in the air, and the water absorption ratio and the degree of swelling were measured. The results are shown in Tables 3 and 4. Although the water absorption ratio was evaluated as “ ⁇ ”, the water retention was poor, and it was sometimes decomposed overnight under high temperature and high humidity exceeding 30 ° C. such as summer night.
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
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- Polymers & Plastics (AREA)
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020127033212A KR101778826B1 (ko) | 2010-05-21 | 2010-05-21 | 건조 셀룰로오스 겔 및 그 제조 방법 |
CN201080068153.XA CN103025763B (zh) | 2010-05-21 | 2010-05-21 | 干燥纤维素凝胶及其制造方法 |
PCT/JP2010/058657 WO2011145216A1 (ja) | 2010-05-21 | 2010-05-21 | 乾燥セルロースゲル及びその製造方法 |
JP2010534170A JP5416709B2 (ja) | 2010-05-21 | 2010-05-21 | 乾燥セルロースゲル及びその製造方法 |
TW099118147A TWI496821B (zh) | 2010-05-21 | 2010-06-04 | Dried cellulose gel and its manufacturing method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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PCT/JP2010/058657 WO2011145216A1 (ja) | 2010-05-21 | 2010-05-21 | 乾燥セルロースゲル及びその製造方法 |
Publications (1)
Publication Number | Publication Date |
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WO2011145216A1 true WO2011145216A1 (ja) | 2011-11-24 |
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Family Applications (1)
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PCT/JP2010/058657 WO2011145216A1 (ja) | 2010-05-21 | 2010-05-21 | 乾燥セルロースゲル及びその製造方法 |
Country Status (5)
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JP (1) | JP5416709B2 (ko) |
KR (1) | KR101778826B1 (ko) |
CN (1) | CN103025763B (ko) |
TW (1) | TWI496821B (ko) |
WO (1) | WO2011145216A1 (ko) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014070194A (ja) * | 2012-09-28 | 2014-04-21 | Uni Charm Corp | 吸収性材料の製造方法 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106993813B (zh) * | 2017-03-31 | 2020-05-15 | 宝健(北京)生物技术有限公司 | 一种益生菌微胶囊的制备方法 |
CN106916230B (zh) * | 2017-03-31 | 2019-07-19 | 宝健(北京)生物技术有限公司 | 一种利用电子辐照技术制备微胶囊包埋壁材的方法 |
KR102432556B1 (ko) * | 2021-10-05 | 2022-08-16 | 주식회사 이너시아 | 친환경 고흡수성 카르복시메틸 셀룰로오스 수지 및 그 제조방법 |
WO2023058897A1 (ko) * | 2021-10-05 | 2023-04-13 | 주식회사 이너시아 | 친환경 고흡수성 카르복시메틸 셀룰로오스 수지 및 그 제조방법 |
Citations (12)
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JPS63201708U (ko) * | 1987-06-17 | 1988-12-26 | ||
JPH07303824A (ja) * | 1994-05-12 | 1995-11-21 | Hironobu Matsumura | 加圧型ニーダ |
JPH09155173A (ja) * | 1995-12-08 | 1997-06-17 | Kansai Electric Power Co Inc:The | 加湿混練機 |
JPH11104404A (ja) * | 1997-10-01 | 1999-04-20 | Eme:Kk | 混練脱泡方法とその装置 |
JPH11300188A (ja) * | 1998-04-17 | 1999-11-02 | Takahashi Kikan:Kk | 加湿混練装置 |
JP2001002703A (ja) * | 1999-06-23 | 2001-01-09 | Japan Atom Energy Res Inst | 自己架橋型アルキルセルロース誘導体、及びそれらの製造方法 |
JP2001179072A (ja) * | 1999-12-28 | 2001-07-03 | Toyo Chem Co Ltd | 真空混練機 |
JP2002355542A (ja) * | 2001-05-30 | 2002-12-10 | Sumitomo Heavy Ind Ltd | 加湿混練装置 |
JP2005126599A (ja) * | 2003-10-24 | 2005-05-19 | Japan Atom Energy Res Inst | 生分解性材料および生分解性材料の製造方法 |
JP2008069315A (ja) * | 2006-09-15 | 2008-03-27 | Japan Atomic Energy Agency | カルボキシメチルセルロースゲルの製造方法 |
JP2008144007A (ja) * | 2006-12-08 | 2008-06-26 | Japan Atomic Energy Agency | 多糖類を原料とするゲルの製造方法 |
JP2009179706A (ja) * | 2008-01-30 | 2009-08-13 | Takeshi Shimizu | 乾燥ゲル粒子ならびにその製造方法 |
-
2010
- 2010-05-21 WO PCT/JP2010/058657 patent/WO2011145216A1/ja active Application Filing
- 2010-05-21 JP JP2010534170A patent/JP5416709B2/ja not_active Expired - Fee Related
- 2010-05-21 CN CN201080068153.XA patent/CN103025763B/zh not_active Expired - Fee Related
- 2010-05-21 KR KR1020127033212A patent/KR101778826B1/ko active IP Right Grant
- 2010-06-04 TW TW099118147A patent/TWI496821B/zh not_active IP Right Cessation
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS63201708U (ko) * | 1987-06-17 | 1988-12-26 | ||
JPH07303824A (ja) * | 1994-05-12 | 1995-11-21 | Hironobu Matsumura | 加圧型ニーダ |
JPH09155173A (ja) * | 1995-12-08 | 1997-06-17 | Kansai Electric Power Co Inc:The | 加湿混練機 |
JPH11104404A (ja) * | 1997-10-01 | 1999-04-20 | Eme:Kk | 混練脱泡方法とその装置 |
JPH11300188A (ja) * | 1998-04-17 | 1999-11-02 | Takahashi Kikan:Kk | 加湿混練装置 |
JP2001002703A (ja) * | 1999-06-23 | 2001-01-09 | Japan Atom Energy Res Inst | 自己架橋型アルキルセルロース誘導体、及びそれらの製造方法 |
JP2001179072A (ja) * | 1999-12-28 | 2001-07-03 | Toyo Chem Co Ltd | 真空混練機 |
JP2002355542A (ja) * | 2001-05-30 | 2002-12-10 | Sumitomo Heavy Ind Ltd | 加湿混練装置 |
JP2005126599A (ja) * | 2003-10-24 | 2005-05-19 | Japan Atom Energy Res Inst | 生分解性材料および生分解性材料の製造方法 |
JP2008069315A (ja) * | 2006-09-15 | 2008-03-27 | Japan Atomic Energy Agency | カルボキシメチルセルロースゲルの製造方法 |
JP2008144007A (ja) * | 2006-12-08 | 2008-06-26 | Japan Atomic Energy Agency | 多糖類を原料とするゲルの製造方法 |
JP2009179706A (ja) * | 2008-01-30 | 2009-08-13 | Takeshi Shimizu | 乾燥ゲル粒子ならびにその製造方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014070194A (ja) * | 2012-09-28 | 2014-04-21 | Uni Charm Corp | 吸収性材料の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
TWI496821B (zh) | 2015-08-21 |
KR20130095196A (ko) | 2013-08-27 |
JP5416709B2 (ja) | 2014-02-12 |
CN103025763A (zh) | 2013-04-03 |
CN103025763B (zh) | 2015-06-24 |
KR101778826B1 (ko) | 2017-09-14 |
TW201141918A (en) | 2011-12-01 |
JPWO2011145216A1 (ja) | 2013-07-22 |
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