CN103046145B - The device of continuous production nano fibrous membrane - Google Patents
The device of continuous production nano fibrous membrane Download PDFInfo
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- CN103046145B CN103046145B CN201110314014.7A CN201110314014A CN103046145B CN 103046145 B CN103046145 B CN 103046145B CN 201110314014 A CN201110314014 A CN 201110314014A CN 103046145 B CN103046145 B CN 103046145B
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- jet head
- shower nozzle
- head sets
- shuttling movement
- roll dies
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- 239000012528 membrane Substances 0.000 title claims abstract description 28
- 238000010924 continuous production Methods 0.000 title claims abstract description 9
- 230000033001 locomotion Effects 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 239000002121 nanofiber Substances 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 238000007599 discharging Methods 0.000 claims abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 7
- 230000005540 biological transmission Effects 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 8
- 238000010041 electrostatic spinning Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 238000007747 plating Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- 230000005684 electric field Effects 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000001523 electrospinning Methods 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 244000309464 bull Species 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Landscapes
- Nonwoven Fabrics (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The present invention relates to the device of continuous production nano fibrous membrane, comprise DC high-voltage power supply, high-order barrel with a scale, rotate material storage tube, charging pump, connect roll dies, material receiving roller, to it is characterized in that: the jet head sets of many shower nozzles is arranged on can in the transmission base of shuttling movement; And constant liquid level in described rotation storage tank, the centre-height of groove circumferentially each discharging opening is identical, and by groove, circumferentially each discharging opening causes the material length of tube of each shower nozzle of jet head sets, caliber is identical.Device of the present invention can prepare composition and the uniform nano-fiber film of thickness, the nano-fiber film obtained is due to composition and thickness is homogeneous, film nano structural molecule orientation is even, thus causing the film mechanical strength that obtains high, percent thermal shrinkage is low, and face is without bright spot; Be suitable for preparing various extraordinary nano fibrous membrane, especially for the polymer nanofiber film of lithium ion battery separator.
Description
Technical field
The present invention relates to a kind of device preparing film in substrate, more particularly, the present invention relates to a kind of preparation facilities with the nano fibrous membrane of many shower nozzles constant voltage feeding system.
Background technology
Electrostatic spinning, also known as electrospinning, was researched and developed out in 1934 by American Formhals.Electrostatic spinning refers to by applying to polymer solution (or melt) spining technology that extra electric field manufactures polymer fiber.The fibre diameter obtained with electrospinning process can reach nanoscale, compared to the little several order of magnitude of fibre diameter adopting conventional method obtained, and has the advantages such as specific area is large, porosity is high, aperture is little, draw ratio is large.Be widely used in the specific function such as conductive fiber, biological medical polymer Material Field at present; And due to unique texture and the advantageous characteristic of Electrospun nano-fibers, at bio-medical and nanoscale electric instrument field, there is wide and tempting application prospect.Therefore the design and development functionalized nano-fiber of electrospinning device and technique thereof is the study hotspot of emerging field of functional materials.
Although various countries' researcher has carried out large quantifier elimination to the basic theories of electrostatic spinning, equipment and application, make electrostatic spinning technique development perfect; But above-mentioned research is mostly confined to the laboratory of colleges and universities or the use for laboratory equipment of scientific research institution.And at present about the basic research work of nanofiber form and material behavior is still in initial stage, the technique that electrospun nanofibers is in depth studied in systematization is very urgent: how to realize the control of nanofiber yardstick, guiding and other expection features on the one hand and repeat, being still the main bugbear that electrostatic spinning produces nanofiber field; On the other hand, tying up to that fluid instability in electrostatic field carries out accurately describing to polymeric acceptor is the key preparing nanofiber.
Static Spinning technology of the prior art generally all concentrates on single needle electrostatic spinning, and the efficiency that this technique obtains fiber is lower, and output is little, cannot reach industrial requirement.And bull injection Static Spinning technology not only can solve the little problem of output, be also expected to reach continuous prodution and obtain large-area fibre net.But many shower nozzles equipment of the prior art or to move reciprocatingly scanning along receiving device for bull scanning constant or for bull, and above two kinds of modes all can not produce the even nano fibrous membrane that accord with the demands of the market alternate without thickness of face thin and thick.The commercial application of electrostatic spinning nano fiber film cannot be realized.
A kind of macromolecular fibre net manufacturing installation is described in Chinese patent application CN02103350.1, described feeding system adopts the feeding system of many shower nozzles, but described many shower nozzles are fixed, the nanofiber film uniformity prepared by this device is poor, can not practical requirement.Chinese patent application CN200910028078 describes a kind of automatic electrostatic spinning device, and the feed mode of what it adopted is single needle, production efficiency is low, is unsuitable for large-scale industrial and produces.
Summary of the invention
In order to overcome the problems referred to above of prior art, particularly electrospinning device preparing nano tunica fibrosa inefficiency and the uneven technical problem of nano fibrous membrane, the invention provides a kind of device of continuous production nano fibrous membrane, the device of continuous production nano fibrous membrane of the present invention has can many shower nozzles constant voltage feeding system of shuttling movement, and the nano fibrous membrane face thickness prepared is even, film thickness easily regulates, film mechanical strength is high, percent thermal shrinkage is low, face is without bright spot.The nano fibrous membrane prepared can directly use as lithium ion battery separator, solve method of electrostatic spinning produce tunica fibrosa laterally, longitudinal tensile strength is less, the technical problem that puncture strength is also low, accelerate the paces that nano fibrous membrane that method of electrostatic spinning produces enters lithium battery industry, also substantially increase quality and the reliability of dynamic lithium battery simultaneously.
In order to solve the problems of the technologies described above, present invention employs following technical scheme:
A device for continuous production nano fibrous membrane, comprises DC high-voltage power supply, high-order barrel with a scale, rotates material storage tube, charging pump, connects roll dies, material receiving roller, to it is characterized in that: the jet head sets of many shower nozzles is arranged on can in the transmission base of shuttling movement; And constant liquid level in described rotation storage tank, the centre-height of groove circumferentially each discharging opening is identical, and by groove, circumferentially each discharging opening causes the material length of tube of each shower nozzle of jet head sets, caliber is identical.
Preferably, be positioned in described device and connect roll dies both sides, the transmission base of shuttling movement can be respectively arranged with the jet head sets of shower nozzle more than a group.And then can be implemented in the two sides continuous plating nano fibrous membrane simultaneously of base material.
Preferably, in described device, constant voltage gravitation tank can carry out rotation with groove material pipe circumferentially; The direction of rotation can be identical or contrary with the direction of rotation rotating material storage tube; Preferably, the direction of rotation is contrary with the direction of rotation rotating material storage tube, and so, feed liquid can be mixed to get more even, and the nano fibrous membrane prepared is also more even.
Preferably, in described device, transmission base is shuttling movement drive, and it is by shuttling movement drive wheel, and shuttling movement driving wheel is connected with motor.
Preferably, in described device, also there is hot-air system, the solvent connect on roll dies can be remained in by evaporative removal.
Preferably, in described device, can also glow discharge device be comprised, carry out preliminary treatment for the metal base treating plating; Through the pretreated metal base of glow discharge, more uniform barrier film can be obtained further.
Preferably, in described device, the positive high voltage of DC high-voltage power supply is connected on the shower nozzle of jet head sets, and the other end is connected on roll dies, connects roll dies ground connection.
Preferably, connecing roll dies described in is that stainless steel mirror connects roll dies.
The main operational steps of device of the present invention is as follows: the polymer solution as spray silk raw material is delivered to rotation stock chest from high-order barrel with a scale, constant liquid level in stock chest, and rotation can ensure that feed liquid mixes; High voltage electric field is produced by DC high-voltage power supply, DC high-voltage power supply one end export positive high voltage be connected on can shuttling movement jet head sets shower nozzle on, other end ground wire is connected on roll dies.Charged polymer solution overcomes the surface tension of spininess spray silk needle tip under the effect of electric field force, splits into nano silk and sprays on the base material of continuous motion connecing godet roll surface.Device of the present invention, by creatively, the design of the jet head sets of shuttling movement and the design of rotation material storage tube combine, composition and the uniform nano-fiber film of thickness can be prepared, the nano-fiber film obtained is due to composition and thickness is homogeneous, film nano structural molecule orientation is even, thus causing the film mechanical strength that obtains high, percent thermal shrinkage is low, and face is without bright spot.Thus achieve under the scale of suitability for industrialized production, high-quality nano-fiber film can be obtained equally.
Device of the present invention is suitable for preparing various extraordinary nano fibrous membrane, the application such as nm-class conducting fibre, biological medical polymer nanofiber, submicron order special filtering base material of such as specific function.Especially, device of the present invention is also specially adapted to the polymer nanofiber film of lithium ion battery separator, and described polymer includes but are not limited to Kynoar (PVDF), polyacrylonitrile, Kynoar, and hexafluoropropene, polyacrylonitrile are total to methacrylate etc. altogether.
Compared with prior art, the present invention has following useful technique effect: device of the present invention can realize the industrially scalable continuous seepage of nano fibrous membrane, prepare composition and the uniform nano-fiber film of thickness simultaneously, the nano-fiber film obtained is due to composition and thickness is homogeneous, film nano structural molecule orientation is even, thus cause the film mechanical strength that obtains high, percent thermal shrinkage is low, and face is without bright spot.Adopt device of the present invention can prepare various extraordinary nano fibrous membrane of the prior art; And be specially adapted to the preparation of the polymer nanofiber film of lithium ion battery separator, the barrier film obtained can meet safety and the charge-discharge performance requirement of lithium ion battery and power lithium-ion battery completely.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the device of the continuous production nano fibrous membrane of one embodiment of the invention.
Implication in figure representated by each Reference numeral is as follows: 1-high-order barrel with a scale, 2-rotate stock chest, the total delivery tube of 3-, 4-delivery tube, 5-motor, 6-shower nozzle, 7-high-tension cable, 8-material receiving roller, 9-connects roll dies driver, 10-connects roll dies, 11-DC high-voltage power supply, 12-rotate stock chest driving wheel, 13-metallic sealing section rotary feeding joint, 14-jet head sets shuttling movement drive, 15-jet head sets shuttling movement driving wheel.
Detailed description of the invention
Below in conjunction with accompanying drawing and specific embodiment, the present invention will be further explained.Following examples are only to further illustrate technical scheme of the present invention, can not be interpreted as the restriction to invention protection domain.
Embodiment 1
As shown in Figure 1, the device of the continuous production nano fibrous membrane shown in the present embodiment, its feeding system comprise high-order barrel 1 with a scale, rotate stock chest 2 and for respectively to rotation stock chest 2 supply total delivery tube 3 of feed liquid and the delivery tube 3 for supplying feed liquid to jet head sets shower nozzle 6; By rotating the driving of storage tank driving wheel 12, rotating stock chest and can realize rotating, thus sedimentation and the segregation of each component in feed liquid can be prevented, can ensure that feed liquid supplies shower nozzle 7 uniformly; Feed liquid supply rotation stock chest in high-order barrel 1 with a scale also ensures to rotate the constant liquid level in stock chest 2 by metallic sealing section rotary feeding joint 13 by total delivery tube 3 in addition; Centre-height in addition owing to rotating stock chest 2 groove circumferentially each discharging opening is identical, and circumferentially each discharging opening causes the length of the delivery tube 4 of each shower nozzle of jet head sets 6, caliber is identical by groove; Thus can ensure that the material liquid component that makes to be supplied to each shower nozzle 6 is homogeneous and the pressure of feed liquid is also consistent; Under the condition of continuous plating, give the feed liquid that each shower nozzle 6 provides composition identical with pressure, thus be conducive to obtaining composition and the uniform nano fibrous membrane of thickness.Further, described delivery tube 4 self can rotation, further ensures the homogeneous of material liquid component and pressure; On the other hand, electrode 5 moves for driving jet head sets shuttling movement driving wheel 15, jet head sets shuttling movement driving wheel 15 drives jet head sets shuttling movement drive 14 shuttling movement, thus realize the shuttling movement of the shower nozzle 6 be located thereon, shower nozzle 6 can be transmitted pedestal and drive and shuttling movement (such as circular motion), thus shower nozzle 6 can be made to produce relative motion relative to the base material of motion continuously; High voltage electric field is produced by DC high-voltage power supply 11, DC high-voltage power supply 11 one end export positive high voltage be connected on can shuttling movement jet head sets shower nozzle 6 on, other end ground wire is connected on roll dies 10; Charged polymer solution overcomes the surface tension of spininess spray silk needle tip under the effect of electric field force, splits into nano silk and sprays on the base material of continuous motion connecing godet roll surface, and pass through the base material of material receiving roller rolling plating nano fibrous membrane; Connect roll dies 10 to drive by connecing roll dies driver 9.We show by experiment: ensureing under the prerequisite that each shower nozzle 6 feed liquid component is consistent with pressure, the shuttling movement of shower nozzle 6 (such as circular motion or move along elliptic orbit) can strengthen the scrambling screw of the feed liquid injection stream sprayed from shower nozzle 6, further enhancing the random motion of jetting fluid, can guarantee to obtain composition and the homogeneous nano fibrous membrane of thickness.
In addition, device of the present invention can also comprise glow discharge device, carries out preliminary treatment for the electrode slice treating plating.Unforeseeable, compared with the sandblasting pre-treatment of routine, adopt glow discharge process to improve adhesion strength, also help the uniformity improving plating, and the utilization rate of the polymer solution of spray silk raw material can be improved.
Embodiment 2
Schematically, the device of the present invention described in embodiment 1 is adopted to prepare the electrode slice of plating PVDF barrier film.The present embodiment is only schematic, except PVDF nano fibrous membrane, and can also other nano fibrous membrane of plating.
Preparation is the Kynoar solution of 9.0wt% containing weight concentration, and the viscosity of solution is between 600-700mPaS.Base material transfer rate is 100cm/min.Shower nozzle and meet the speed 20-50cm/min that the electric-field intensity applied between roll dies is 1500V/cm, distance 15cm, shower nozzle shuttling movement; The speed of rotation rotating stock chest is that 50-3000 turns/min, and the rotary speed of delivery tube is that 50-3000 turns/min; In device of the present invention, feeding system effectively can ensure that the material liquid component being supplied to shower nozzle is consistent with pressure.Open device of the present invention, Kynoar solution carries out plating by shower nozzle to electrode slice, obtains the nano fibrous membrane of Kynoar.Actually record the clean thickness of one side 12 μm, gained film thickness in the thickness difference of length and width lower than 3%; And by observation by light microscope, the nano-fiber film even pore distribution obtained, Mechanics Performance Testing show that the tensile strength of nano fibrous membrane is high; And the Heat stability is good of film, 90 DEG C keep 4h way contracting < 0.5%.
The above; be only the preferred embodiments of the present invention; can not be interpreted as limiting scope of the present invention with this, the equivalent distortion made in all scopes claimed at claims of the present invention and the embodiment of change are all in the present invention's scope required for protection.
Claims (4)
1. the device of a continuous production nano fibrous membrane, it is characterized in that: for the preparation of the polymer nanofiber film of lithium ion battery separator, described device comprises DC high-voltage power supply, high-order barrel with a scale, rotates stock chest, charging pump, connects roll dies, material receiving roller, each shower nozzle of jet head sets, and for supplying total delivery tube of feed liquid and the delivery tube for supplying feed liquid to each shower nozzle of jet head sets to rotating stock chest; Wherein be arranged on can in the transmission base of shuttling movement for each shower nozzle of jet head sets; Constant liquid level in described rotation stock chest, the centre-height rotating stock chest circumferentially each discharging opening is identical, and by described rotation stock chest, circumferentially each discharging opening causes the delivery tube length of each shower nozzle of jet head sets, caliber is identical; And the described delivery tube to jet head sets each shower nozzle supply feed liquid can carry out rotation; And it is contrary with the direction of rotation rotating stock chest to the sense of rotation of the delivery tube of jet head sets each shower nozzle supply feed liquid; Transmission base is shuttling movement drive, and it is by shuttling movement drive wheel, and shuttling movement driving wheel is connected with motor; The positive high voltage of described DC high-voltage power supply is connected on the shower nozzle of jet head sets, and the other end is connected on roll dies, connects roll dies ground connection.
2. device according to claim 1, is characterized in that also having hot-air system in described device, can remain in the solvent connect on roll dies by evaporative removal.
3. device according to claim 1, connecing roll dies described in it is characterized in that is that stainless steel mirror connects roll dies.
4. device according to claim 1, is characterized in that described shuttling movement is circular motion or along elliptical orbit shuttling movement.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110314014.7A CN103046145B (en) | 2011-10-17 | 2011-10-17 | The device of continuous production nano fibrous membrane |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110314014.7A CN103046145B (en) | 2011-10-17 | 2011-10-17 | The device of continuous production nano fibrous membrane |
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| CN103046145A CN103046145A (en) | 2013-04-17 |
| CN103046145B true CN103046145B (en) | 2016-01-27 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1760411A (en) * | 2004-10-11 | 2006-04-19 | 财团法人纺织产业综合研究所 | Electrospinning device |
| CN201024236Y (en) * | 2007-04-13 | 2008-02-20 | 华南理工大学 | Liquid supply device for continuous electrospinning |
| CN101586256A (en) * | 2009-07-06 | 2009-11-25 | 江苏泰灵生物科技有限公司 | Preparation of porosity electrospun fiber |
| CN101709535A (en) * | 2009-11-17 | 2010-05-19 | 天津工业大学 | Device and method for manufacturing melting electrostatic spinning nano-fiber non-woven fabrics |
-
2011
- 2011-10-17 CN CN201110314014.7A patent/CN103046145B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1760411A (en) * | 2004-10-11 | 2006-04-19 | 财团法人纺织产业综合研究所 | Electrospinning device |
| CN201024236Y (en) * | 2007-04-13 | 2008-02-20 | 华南理工大学 | Liquid supply device for continuous electrospinning |
| CN101586256A (en) * | 2009-07-06 | 2009-11-25 | 江苏泰灵生物科技有限公司 | Preparation of porosity electrospun fiber |
| CN101709535A (en) * | 2009-11-17 | 2010-05-19 | 天津工业大学 | Device and method for manufacturing melting electrostatic spinning nano-fiber non-woven fabrics |
Non-Patent Citations (1)
| Title |
|---|
| A new electrospinning method to control the number and a diameter of uniaxially aligned polymer fibers;Yuya Ishii等;《Materials Letters》;20080326(第62期);第3370-3372段 * |
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Effective date of registration: 20171121 Address after: Suzhou City, Jiangsu province Longqiao road 215200 Wujiang economic and Technological Development Zone No. 883 Patentee after: Suzhou ranked membrane material Co., Ltd. Address before: 472000 road of Sanmenxia Development Zone, Sanmenxia, Sanmenxia, Henan Patentee before: Sanmenxia Xingbang Special Film Technology Development Co., Ltd. |