WO2014171365A1 - Method for manufacturing thermoplastic film - Google Patents
Method for manufacturing thermoplastic film Download PDFInfo
- Publication number
- WO2014171365A1 WO2014171365A1 PCT/JP2014/060166 JP2014060166W WO2014171365A1 WO 2014171365 A1 WO2014171365 A1 WO 2014171365A1 JP 2014060166 W JP2014060166 W JP 2014060166W WO 2014171365 A1 WO2014171365 A1 WO 2014171365A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- mold
- film
- hole
- laminated structure
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 47
- 229920001169 thermoplastic Polymers 0.000 title claims description 40
- 239000004416 thermosoftening plastic Substances 0.000 title claims description 40
- 238000000034 method Methods 0.000 title description 22
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 39
- 238000002844 melting Methods 0.000 claims abstract description 23
- 230000008018 melting Effects 0.000 claims abstract description 23
- 230000009477 glass transition Effects 0.000 claims abstract description 21
- -1 polyethylene Polymers 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 10
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 10
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 238000000465 moulding Methods 0.000 abstract description 23
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 196
- 239000010408 film Substances 0.000 description 108
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 238000001816 cooling Methods 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000007747 plating Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000012790 adhesive layer Substances 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 238000010894 electron beam technology Methods 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000010030 laminating Methods 0.000 description 5
- 239000002344 surface layer Substances 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000004113 cell culture Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005323 electroforming Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 229920000306 polymethylpentene Polymers 0.000 description 2
- 239000011116 polymethylpentene Substances 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000003856 thermoforming Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013039 cover film Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
- B01D39/1692—Other shaped material, e.g. perforated or porous sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
- B29C43/021—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles characterised by the shape of the surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/10—Filtering material manufacturing
Definitions
- the present invention relates to a method for producing a thermoplastic film having a through hole.
- the film having through-holes obtained by this method should be used as a member that requires micron-sized to nano-sized through-holes having functions such as filtration, cell culture, cell separation, gas permeation, and moisture permeability. Can do.
- a thermoplastic film having through-holes whose hole shape and arrangement are controlled with high accuracy is particularly preferably used for the purpose of improving performance.
- thermoplastic film having a through-hole As a method for producing a thermoplastic film having a through-hole in which the shape and arrangement of the holes are controlled with high accuracy, injection molding, electron beam processing on the film, etching, thermal imprinting and the like can be mentioned.
- injection molding a film having through holes can be formed by filling a molten resin into a mold in which protrusions are formed.
- electron beam processing through holes can be formed by applying an electron beam to the film surface and melting it from the surface toward the inside.
- etching a through-hole is formed by chemically or physically removing the resin by bringing an etching material made of gas or liquid into contact with an opening other than a region shielded by a mask on the film surface. Can be formed.
- Patent Documents 1 and 2 disclose a thermal imprint technique in which a through-hole is formed in a film by pressing a mold having a heated projection structure on the surface of the thermoplastic film. Furthermore, as means for improving the through hole molding accuracy, by applying a molten resin to the surface of the mold having protrusions formed on the surface, and then cooling the mold while applying pressure with a pressure plate. A method for producing a film having through holes is disclosed.
- the manufacturing method based on the melt transfer technique disclosed in Patent Document 3 requires the steps of applying a resin to the mold, heating and cooling the mold, and taking out the product, and does not require processing into a roll-to-roll film. There is a problem that productivity is low because it is possible.
- the present invention provides the following method for producing a thermoplastic film.
- a protruding structure is provided on the surface of a laminated structure in which an A layer containing a thermoplastic resin P1 having a melting point Tm1 and a B layer containing a thermoplastic resin P2 having a glass transition temperature Tg2 are laminated.
- the mold is heated to a temperature of Tm1 or more and Tg2 or more and pressed against the A layer side of the laminated structure, thereby forming a through hole in the A layer and forming a recess communicating with the through hole in the B layer.
- a method for producing a thermoplastic film comprising: (2) A protruding structure is provided on the surface of the laminated structure in which the A layer containing the thermoplastic resin P1 having the melting point Tm1 and the B layer containing the thermoplastic resin P2 having the glass transition temperature Tg2 are laminated.
- the mold is heated to a temperature of Tm1 or more and Tg2 or more and pressed against the A layer side of the laminated structure, thereby forming a through hole in the A layer and forming a recess communicating with the through hole in the B layer. Then, after that, the A layer and the B layer are peeled off to obtain a thermoplastic film having a through hole including the A layer.
- thermoplastic film according to (1) or (2) wherein a difference (Tm1 ⁇ Tg2) between the melting point Tm1 and the glass transition temperature Tg2 is ⁇ 30 to 60 ° C.
- thermoplastic film according to (3) wherein a difference (Tm1 ⁇ Tg2) between the melting point Tm1 and the glass transition temperature Tg2 is ⁇ 10 to 0 ° C.
- thermoplastic resin P1 is polyethylene or polypropylene.
- thermoplastic resin P2 is polymethyl methacrylate or polycarbonate.
- thermoplastic film according to any one of (1) to (6) wherein the diameter of the through hole is 1 to 100 ⁇ m.
- a protruding structure is formed on a laminated structure in which an A layer containing a thermoplastic resin P1 having a melting point Tm1 and a B layer containing a thermoplastic resin P2 having a glass transition temperature Tg2 are laminated.
- the mold on the surface is heated to a temperature of Tm1 or more and Tg2 or more, and pressed against the A layer side of the laminated structure, thereby being disposed in the A layer at a desired position and density distribution and having a desired shape Holes can be formed.
- FIG. 2 is a surface photograph of a film produced by the production method of the present invention described in Example 1 using a scanning electron microscope.
- 2 is a cross-sectional photograph of a film produced by the production method of the present invention described in Example 1 using a scanning electron microscope.
- 2 is a surface photograph of a film produced by the production method of the present invention described in Example 2 using a scanning electron microscope.
- 3 is a cross-sectional photograph taken by a scanning electron microscope of a film produced by the production method of the present invention described in Example 2.
- FIG. 2 is a surface photograph of a film produced by the production method of the present invention described in Comparative Example 1 using a scanning electron microscope.
- 2 is a cross-sectional photograph of a film produced by the production method of the present invention described in Comparative Example 1 using a scanning electron microscope.
- the present invention relates to a method for producing a thermoplastic film having a through hole.
- One of the production methods according to the present invention is for a laminated structure in which an A layer containing a thermoplastic resin P1 having a melting point Tm1 and a B layer containing a thermoplastic resin P2 having a glass transition temperature Tg2 are laminated. Then, a mold having a protruding structure on the surface is heated to a temperature of Tm1 or more and Tg2 or more and pressed against the A layer side of the laminated structure, thereby forming a through hole in the A layer, and the B layer It is a manufacturing method of a thermoplastic film characterized by forming a crevice connected to a penetration hole.
- Another manufacturing method is a laminated structure in which an A layer containing a thermoplastic resin P1 having a melting point Tm1 and a B layer containing a thermoplastic resin P2 having a glass transition temperature Tg2 are laminated.
- a mold having a protruding structure on the surface is heated to a temperature of Tm1 or more and Tg2 or more and pressed against the A layer side of the laminated structure, thereby forming a through hole in the A layer, and the B layer Forming a recess communicating with the through hole, and then peeling off the A layer and the B layer to obtain a thermoplastic film having a through hole containing the A layer.
- a mold having a protruding structure on the surface is heated to a temperature of Tm1 or more and Tg2 or more and pressed against the A layer side of the laminated structure, thereby forming a through hole in the A layer, and the B layer Forming a recess communicating with the through hole, and then peeling off the A layer and the
- FIG. 1 and 2 are flowcharts showing an example of an embodiment according to the method for producing a thermoplastic film having a through hole of the present invention.
- FIG. 3 is a perspective view showing an example of a mold applied to the manufacturing method of the present invention.
- a laminated structure 10 in which an A layer 11 and a B layer 12 are laminated, and a mold 20 in which independent protrusion structures are arranged at predetermined positions on the surface are prepared.
- the A layer 11 includes a thermoplastic resin P1 having a melting point Tm1
- the B layer includes a thermoplastic resin P2 having a glass transition temperature Tg2.
- each layer may contain an additive or a coating component for imparting moldability and releasability.
- an upper limit is not specifically limited, 100 mass% becomes a substantial upper limit.
- the interface between the A layer and the B layer can be peeled off, and the interface between the A layer and the B layer is laminated by using the action of an adhesive formed by coating or the like.
- an adhesive formed by coating or the like preferable.
- a two-layer stacked configuration of the A layer and the B layer is described, but another layer may be provided on the side opposite to the A layer with the B layer interposed therebetween. It is preferable to apply a material having the same configuration as that of the A layer to the coating on the surface of the A layer because the flatness after the molding becomes high.
- a laminated structure refers to a structure in which two or more layers containing different components are laminated.
- the continuous structure film conveyed by roll to roll may be sufficient as a laminated structure, and a single wafer sheet may be sufficient as it.
- the glass transition temperature is a method according to the method described in JIS K 7244-4 (1999).
- the sample dynamic amplitude speed (driving frequency) is 1 Hz
- the tensile mode is 5 mm
- the heating rate is 2 ° C. This is the temperature at which tan ⁇ is maximized when measuring the temperature dependence (temperature dispersion) in / min.
- the melting point here is a melting point Tm in a temperature rising process (temperature rising rate: 20 ° C./min) obtained by DSC (differential calorimetry), and based on JIS K 7121 (1999) as described above.
- Heat at a rate of temperature increase from 25 ° C. to 300 ° C. at a rate of 20 ° C./min (1stRUN), hold in that state for 5 minutes, then rapidly cool to below 25 ° C., and then increase again from room temperature to 20 ° C./min.
- the melting point of the resin is determined by the temperature at the peak top in the 2ndRun crystal melting peak obtained by raising the temperature to 300 ° C. at a temperature rate.
- the mold 20 having the protruding structure 21 on the surface is heated. Heating is performed so that the mold has a temperature range of Tm1 or more and Tg2 or more. Heating may be performed in a state where the mold and the laminated structure are in contact with each other. By keeping the contact, the planarity of the laminated structure can be maintained in a good state.
- the upper limit of the heating temperature of the mold is not limited, it is preferably below the thermal decomposition point of the thermoplastic resin P1 and below the thermal decomposition point of the thermoplastic resin P2.
- the mold 20 is pressed and pressed so that the protruding structure surface is in contact with the surface of the layer A 11 of the laminated structure 10 in a heated state.
- the protrusion structure 21 has an appropriate height by being pressurized, the protrusion structure penetrates the A layer 11 and penetrates to the B layer 12. And as FIG.1 (c) shows, it will be in the state which the metal mold
- the required pressure and pressing time at this time depend on the material of the film, the transfer shape, particularly the aspect ratio of the unevenness, and the preferable range of the press pressure is generally 1 to 100 MPa, and the preferable range of the molding time is 0.01. ⁇ 60 seconds.
- a more preferable range of the pressing pressure is 10 to 80 MPa, and a more preferable range is 30 to 60 MP.
- a more preferable range of the molding time is 1 to 50 seconds, and a more preferable range is 3 to 30 seconds.
- the mold 20 may be pressed against the laminated structure 10 by position control. That is, the mold 20 may be moved to a preset position and pressed against the laminated structure 10.
- the preset position is a position where the plane including the protrusion structure of the mold can be in contact with the surface of the A layer without any gap.
- the pressure may be removed while maintaining the position of the mold, and the contact state between the mold 20 and the laminated structure 10 may be maintained.
- the mold is cooled while maintaining the pressurized state or the contacted state. Cooling is preferably performed to a glass transition temperature Tg2 or lower of the thermoplastic resin P2 constituting the B layer. Cooling to Tg2 or less is preferable because the resin deformation after the mold 20 is peeled from the laminated structure 10 can be suppressed, and a through hole can be formed with high accuracy.
- the laminated structure 10 is peeled from the mold 20.
- the mold and the laminated structure are moved away from each other in the direction perpendicular to the surface of the laminated structure.
- the B layer has a role as a cover film, and if it is peeled off immediately before use, the surface is hardly damaged, and since it can be handled as a thick and highly rigid film until just before use, it is preferable because workability is good.
- FIG. 2 adds the peeling process mentioned above.
- 2 (a) to 2 (d) are the same as FIGS. 1 (a) to 1 (d), and a description thereof will be omitted.
- the A layer 11 is peeled from the B layer 12. Peeling is suppressed by applying tension to the A layer or B layer in the direction perpendicular to the surface of the A layer or B layer, and peeling so that the linear peeling position moves continuously. From the viewpoint of
- the A layer 11 becomes a film having a through-hole whose shape is controlled with high accuracy. Due to the above manufacturing method, the A layer is in a molten state at the time of molding. Therefore, when the protruding structure is pressed, the A layer causes plastic deformation with a behavior close to that of a viscous material, and through holes with less burrs are formed at the end face of the opening. Is done. In addition, when the protrusion pattern (protrusion structure) is pushed in, the B layer causes viscoelastic deformation, and the protrusion structure can smoothly enter the inside of the B layer, so that there is no burrs at the interface between the A layer and the B layer. A few beautiful end faces can be formed.
- Tm1 ⁇ Tg2 which is the difference between the melting point Tm1 of the thermoplastic resin P1 contained in the A layer 11 and the glass transition temperature Tg2 of the thermoplastic resin P2 contained in the B layer is ⁇ 30 to 60 ° C.
- Tm1 ⁇ Tg2 which is the difference between the melting point Tm1 of the thermoplastic resin P1 contained in the A layer 11 and the glass transition temperature Tg2 of the thermoplastic resin P2 contained in the B layer is ⁇ 30 to 60 ° C.
- the temperature is lower than ⁇ 30 ° C., a large force is required for deformation of the B layer, and therefore, when the through hole is formed, the protrusion structure may be prevented from smoothly entering the B layer.
- the temperature is higher than 60 ° C., the elasticity of the B layer may be lowered, and the planarity of the interface between the A layer and the B layer may be lowered.
- Tm1-Tg2 is 5 to 60 ° C. That is, the material of the thermoplastic resin P1 contained in the A layer 11 is preferably 5 to 60 ° C. higher than the glass transition temperature Tg2 of the thermoplastic resin P2 contained in the B layer. More preferably, it is 20 to 50 ° C., and further preferably 30 to 40 ° C. When the temperature is lower than 5 ° C., a large force is required for deformation of the B layer, and therefore, when the through hole is formed, the protrusion structure may be prevented from smoothly entering the B layer. If the temperature is higher than 60 ° C., the elasticity of the B layer may be reduced, and the planarity of the A layer and the B layer may be reduced.
- the difference between the melting point Tm1 and the glass transition temperature Tg2 (Tm1 ⁇ Tg2). ) Is preferably ⁇ 10 to 0 ° C. If it is less than ⁇ 10 ° C., the dimensional accuracy of the opening may deteriorate. When the temperature is higher than 0 ° C., burrs may occur at the end face.
- the B layer has a certain range of hardness at the time of molding, achieving both good flatness at the interface between the A layer and the B layer and high-precision through-hole molding in which burr is suppressed at the opening.
- the storage elastic modulus of the resin contained in the B layer at the temperature of the mold at the time of molding is 0.005 to 0.5 GPa, more preferably 0.01 to 0.1 GPa.
- the burr suppression can be further enhanced by the flatness of the interface of the B layer and the opening in the through hole molding.
- the planarity of the interface between the A layer and the B layer may be deteriorated, and a through hole may not be formed in the A layer, or a burr may be easily generated at the opening of the through hole.
- it exceeds 0.5 GPa it is difficult to deform in the B layer, the protrusion structure of the mold is not inserted to the back, and it may be difficult to form a through hole with a predetermined shape accuracy.
- the main component of the thermoplastic resin constituting the A layer 11 is preferably a polyolefin resin such as polyethylene, polystyrene, polypropylene, polyisobutylene, polybutene, and polymethylpentene because mold releasability is good.
- a main component means the component which occupies 50 mass% or more when the whole resin which comprises A layer is 100 mass%.
- 50 mass% or more is preferable and, as for the main component, 80 mass% or more is more preferable.
- an upper limit is not specifically limited, 100 mass% becomes a substantial upper limit.
- thermoplastic resin P1 is polyethylene or polypropylene.
- polyethylene or polypropylene By using polyethylene or polypropylene, it is possible to mold the through-holes at a relatively low temperature, and thus it is easy to increase productivity.
- the main component of the thermoplastic resin constituting the B layer 12 is preferably a polyester resin such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene, polystyrene, polypropylene, poly Polyolefin resins such as isobutylene, polybutene, polymethylpentene, polyamide resins, polyimide resins, polyether resins, polyesteramide resins, polyetherester resins, acrylic resins, polyurethane resins, polycarbonate resins, or poly A vinyl chloride resin or the like is preferably used. Particularly preferred is polymethyl methacrylate.
- a main component means the component which occupies 50 mass% or more when the whole resin which comprises B layer is 100 mass%. In addition, 50 mass% or more is preferable and, as for the main component, 80 mass% or more is more preferable.
- the thermoplastic resin P2 is preferably polymethyl methacrylate or polycarbonate. Particularly preferred is polymethyl methacrylate. By using polymethyl methacrylate or polycarbonate, it is possible to accurately form the concave portion communicating with the through hole.
- the A layer and the B layer may be a layer made of the above-mentioned resin alone, or may be a laminated body made of a plurality of resin layers. In this case, surface characteristics such as releasability and friction resistance can be imparted as compared with a single layer. Thus, even when it is set as the laminated body which consists of a some resin layer, in each layer of A layer and B layer, the main thermoplastic resin component should just satisfy the above-mentioned requirements.
- thermoplastic resin film by melt extrusion.
- a release layer, an adhesive layer, or the like is provided on the surface layer, a method of co-extrusion and processing into a film may be used, but it may be provided by coating after film formation.
- a method of laminating by pressing with a roll and a method of heat laminating with a heated roll or the like can be applied.
- additives can be added to the film applied to the present invention at the time of polymerization or after polymerization.
- additives that can be added and blended include, for example, organic fine particles, inorganic fine particles, dispersants, dyes, fluorescent brighteners, antioxidants, weathering agents, antistatic agents, mold release agents, thickeners, Examples include plasticizers, pH adjusters, and salts.
- a releasing agent low surface tension carboxylic acids such as long chain carboxylic acids or long chain carboxylates and derivatives thereof, and low surface tension alcohols such as long chain alcohols and derivatives thereof, and modified silicone oils. It is preferable to add a small amount of a compound or the like during polymerization.
- the preferred thickness (thickness, film thickness) of the A layer applied to the present invention is preferably in the range of 5 to 50 ⁇ m, more preferably 10 to 40 ⁇ m, and still more preferably 10 to 30 ⁇ m. If it is less than 5 ⁇ m, it may be difficult to handle. On the other hand, when the thickness is larger than 50 ⁇ m, the tip temperature of the mold is likely to change when the through hole is formed, and burrs may be easily generated on the end surface during penetration.
- the hole diameter of the through hole is preferably 1 to 100 ⁇ m. More preferably, it is 20 to 80 ⁇ m, and particularly preferably 30 to 50 ⁇ m.
- the hole diameter is the hole diameter of the opening formed on the B layer side surface of the A layer. If it is a circle, it is the diameter, and if it is not a circle, it is the diameter when the opening is replaced with a circle of equal area. If the hole diameter is less than 1 ⁇ m, it may be difficult in terms of accuracy, and if it is larger than 100 ⁇ m, a large pressure may be required for forming the through-hole, and the apparatus may be enlarged. When the thickness is larger than 100 ⁇ m, mechanical processing such as punching is often suitable.
- FIG. 3 is a perspective view showing an example of a mold applied to the present invention
- FIGS. 4A and 4B are cross-sectional views showing an example of a mold applied to the present invention.
- a protrusion structure 21 is disposed at a predetermined position on the outer surface of the mold 20.
- the protruding structure refers to a convex structure provided on a mold, and the protruding structure may be provided with only the same shape on the mold, or may be provided with a plurality of different shapes.
- the arrangement and density of the protrusion structure are preferably the same as the arrangement and density of the through holes required as product specifications.
- the pitch is 100 nm to 1 mm. Note that the pitch means a repetition interval of the protrusion structure.
- the material of the mold is preferably a metal having high strength and thermal conductivity, such as nickel, steel, stainless steel, or copper. Moreover, you may use what gave the outer surface the plating in order to improve workability.
- the height and cross-sectional shape of the protrusion structure are determined by the required shape of the through hole and the thickness of the film.
- the height of the protruding structure is preferably a length that penetrates the thickness of the A layer 11. That is, it is preferable to have a height that penetrates the A layer 11 when the mold 20 is in close contact with the laminated structure 10 during molding.
- the protrusion structure shown in FIG. 4A is a protrusion structure in which a cone and a cylinder are connected.
- the protrusion structure shown in FIG. 4B is a protrusion structure having only a cone.
- the tip is preferably pointed rather than flat.
- a connection structure in which the protrusion structure has a weight shape and a cylindrical shape is preferable. This is because when the tip has a weight shape, the pressure applied to the laminated structure at the start of molding is increased to facilitate deformation.
- a through hole having a high dimensional accuracy and a constant hole diameter can be formed.
- mold and the square pillar other than the shape quoted above may be sufficient.
- Each mold with a protrusion structure on the surface is made by directly cutting, laser processing or electron beam processing on the metal surface, or by direct cutting, laser processing or electron beam processing on the plating film formed on the metal surface. And a method of electroforming these. Also, after applying the resist on the substrate, forming the resist with a predetermined patterning by photolithography technique, etching the substrate to form a recess, and removing the resist to obtain the inverted pattern by electroforming Etc. A cone-shaped pattern can be obtained by applying anisotropic etching. As the substrate, a silicon substrate or the like can be applied in addition to the metal plate.
- a through-hole is a space that penetrates from one side of the layer to the other.
- the recessed part connected to a through-hole means the recessed part of the B layer connected with the through-hole formed in the A layer by protrusion structure.
- the film having a through hole of the present invention can be manufactured by a process through an apparatus as shown in FIGS. 5 and 6, for example.
- 5 and 6 show a through hole made of the A layer by forming a through hole in the A layer of the film-like laminated structure formed by laminating the A layer and the B layer, and further peeling the A layer and the B layer.
- the cross-sectional schematic of the manufacturing apparatus for manufacturing the film which has this is shown.
- the mold 53 is pressed against the laminated structure 50 sent intermittently and pressurized, and then cooled while maintaining the contact state, thereby forming a predetermined through-hole in the A layer 50a of the laminated structure 50.
- a concave portion communicating with the through hole is formed in the B layer by the protruding structure.
- a peeling means 55 for peeling the laminated structure 50 attached to the mold 53 in the pressure transfer process from the mold 53, and the A layer 50a.
- Each film is wound around each of the winding rolls 57 and 58 through a film peeling device 56 for peeling the film formed and the film formed of the B layer 50b.
- the peeling means 55 consists of a pair of parallel arrangement rolls which hold
- One surface of the laminated structure 50 sent intermittently is thermoformed by the die 53 in the press unit 54, and after the thermoforming, the peeling means 55 is moved toward the upstream side, whereby the die 53 is moved.
- the laminated structure 50 that has been attached to is sequentially peeled off from the mold 53.
- reference numeral 59 denotes a pressure plate
- 60 and 61 denote buffer means provided to smoothly perform intermittent conveyance in the mold 53 portion of the laminated structure 50.
- films constituting the A layer 71 and the B layer 72 are drawn from the unwinding rolls 73 and 74, and the laminated structure 70 is formed by the laminating device 75. Thereafter, the laminated structure 70 is supplied by a heating roll 76 onto an endless belt-shaped mold 77 having a protrusion structure formed on the heated surface.
- a protrusion structure is formed on the outer surface of the mold 77 and is heated by the heating roll 76 immediately before coming into contact with the laminated structure 70.
- the laminated structure 70 that is continuously supplied is pressed against the surface on which the protruding structure of the mold 77 is processed by the nip roll 78, and a through hole is formed in the A layer 71 of the laminated structure. At the same time, a concave portion communicating with the through hole is formed in the B layer 72.
- the laminated structure 70 is conveyed to the outer surface position of the cooling roll 79 in a state of being in close contact with the surface of the mold 77.
- the laminated structure 70 is cooled by heat conduction through a mold 77 by a cooling roll 79 and then peeled off from the mold 77 by a peeling roll 80 and peeled into a film composed of an A layer and a film composed of a B layer.
- Each film is taken up by take-up rolls 82 and 83 through a peeling device 81.
- thermoplastic film In the method for producing a thermoplastic film described above, a shape having a fine pore size ranging from a micron size to a nano size can be freely designed, and a thermoplastic film can be produced inexpensively with high productivity.
- the thermoplastic film obtained by the production method of the present invention has micron-sized to nano-sized fine pore diameters uniformly formed. Therefore, filtration, cell culture, cell separation, gas permeation, moisture permeation that require through holes are required. Etc. are preferably used.
- Example 1 Laminated structure A film having a thickness of 30 ⁇ m containing a polymer mainly composed of polypropylene (melting point: 144 ° C.) in the A layer, and a polymer mainly composed of polymethyl methacrylate (PMMA) in the B layer (glass transition temperature of 105 A film having a thickness of 175 ⁇ m was used.
- One surface layer of the A layer has a 6 ⁇ m thick adhesive layer mainly composed of low density polyethylene. The adhesive layer of A layer was laminated so that it might adhere to the surface of B layer, and the laminated structure was comprised.
- the triangular pyramid is a regular triangle whose bottom is 230 ⁇ m on a side, has a height of 70 ⁇ m, and is arranged on the entire surface without any gaps.
- the region where the protrusion structure is processed is a region of 200 mm (film width direction) ⁇ 400 mm (film transport direction).
- the material of the mold was a 20 mm thick copper base metal with a nickel plating film on the surface, and a triangular pyramid pattern was formed on the plating film by machining.
- the press unit is a mechanism that is pressurized by a hydraulic pump.
- Two pressurizing plates are attached inside the press unit, and are connected to a heating device and a cooling device, respectively.
- the mold is placed on the upper surface of the lower pressure plate.
- a peeling means for peeling the film attached to the mold is installed in the press unit.
- the mold temperature at the time of molding was 150 ° C., and the pressure was 5 MPa over the entire surface.
- the pressurization time was 30 seconds.
- the mold temperature at the time of peeling was 80 ° C.
- thermoplastic film (film peeled from the mold) was continuously sent to the downstream side of the winding device, and the A layer and the B layer were peeled off and wound up. This obtained the thermoplastic film containing A layer which has a through-hole.
- FIGS. 7 is a photograph of the A layer as seen from the mold contact surface
- FIG. 8 is a photograph of the cross section of the A layer.
- Through holes having a triangular opening with a side of 45 ⁇ m were uniformly formed as designed. If the triangular shape of the opening is replaced with a circle of equal area, the hole diameter is equivalent to 33 ⁇ m.
- the film composed of the B layer was uniformly formed with recesses communicating with the through holes corresponding to the triangular pyramid protrusion shape.
- Example 2 Laminated structure A film having a thickness of 30 ⁇ m containing a polymer (melting point: 144 ° C.) mainly composed of polypropylene in the A layer and a polymer (glass transition temperature: 146 ° C.) mainly composed of polycarbonate (PC) in the B layer. A film having a thickness of 180 ⁇ m was used.
- One surface layer of the A layer has a 6 ⁇ m thick adhesive layer mainly composed of low density polyethylene. The adhesive layer of A layer was laminated so that it might adhere to the surface of B layer, and the laminated structure was comprised.
- the triangular pyramid is a regular triangle whose bottom is 230 ⁇ m on a side, has a height of 70 ⁇ m, and is arranged on the entire surface without any gaps.
- the region where the protrusion structure is processed is a region of 200 mm (film width direction) ⁇ 400 mm (film transport direction).
- the material of the mold was a 20 mm thick copper base metal with a nickel plating film on the surface, and a triangular pyramid pattern was formed on the plating film by machining.
- the press unit is a mechanism that is pressurized by a hydraulic pump.
- Two pressurizing plates are attached inside the press unit, and are connected to a heating device and a cooling device, respectively.
- the mold is placed on the upper surface of the lower pressure plate.
- a peeling means for peeling the film attached to the mold is installed in the press unit.
- the mold temperature at the time of molding was 160 ° C., and the pressure was 5 MPa over the entire surface.
- the pressurization time was 30 seconds.
- the mold temperature at the time of peeling was 80 ° C.
- thermoplastic film (released from the mold) was continuously sent to the downstream side of the winding device, and the A layer and the B layer were peeled off and wound up. This obtained the thermoplastic film containing A layer which has a through-hole.
- FIGS. 9 is a photograph of the A layer viewed from the mold contact surface
- FIG. 10 is a photograph of a cross section of the A layer. Through holes having a triangular opening with a side of 45 ⁇ m were uniformly formed as designed. When the triangular shape of the opening is replaced with a circle of equal area, the hole diameter is equivalent to 33 ⁇ m. Further, as can be seen from FIG. 10, a through-hole film having a high flatness on the lower surface of the A layer in FIG. 10 (the surface in contact with the B layer before peeling) and few burrs was obtained.
- the film composed of the B layer was uniformly formed with recesses communicating with the through holes corresponding to the triangular pyramid protrusion shape.
- the triangular pyramid is a regular triangle whose bottom is 230 ⁇ m on a side, has a height of 70 ⁇ m, and is arranged on the entire surface without any gaps.
- the region where the protrusion structure is processed is a region of 200 mm (film width direction) ⁇ 400 mm (film transport direction).
- the material of the mold was a 20 mm thick copper base metal with a nickel plating film on the surface, and a triangular pyramid pattern was formed on the plating film by machining.
- the press unit is a mechanism that is pressurized by a hydraulic pump.
- Two pressurizing plates are attached inside the press unit, and are connected to a heating device and a cooling device, respectively.
- the mold is placed on the upper surface of the lower pressure plate.
- a peeling means for peeling the film attached to the mold is installed in the press unit.
- the mold temperature during molding was 130 ° C., and the pressure was 5 MPa over the entire surface.
- the pressurization time was 30 seconds.
- the mold temperature at the time of peeling was 80 ° C.
- the peeled film was sent to the winding device side on the downstream side, the A layer and the B layer were peeled off, and each was wound up.
- FIGS. 11 is a photograph of the A layer viewed from the mold contact surface
- FIG. 12 is a photograph of the cross section of the A layer. No through hole was obtained in the A layer. Further, as can be seen from FIG. 12, the flatness of the lower surface of the A layer in FIG. 12 (the surface that was in contact with the B layer before peeling) was poor.
- Laminated structure 11 A layer 12: B layer 20: Mold 21: Protrusion structure 50: Laminated structure 50a: A layer 50b: B layer 51: Unwinding roll 52: Unwinding unit 53: Mold 54: Press unit 55: peeling means 56: film peeling device 57, 58: take-up roll 59: pressure plate 60, 61: buffer means 62: take-up unit 70: laminated structure 71: A layer 72: B layers 73, 74 : Unwinding roll 75: Laminating apparatus 76: Heating roll 77: Die 78: Nip roll 79: Cooling roll 80: Peeling roll 81: Film peeling apparatus 82, 83: Winding roll
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Laminated Bodies (AREA)
- Shaping Of Tube Ends By Bending Or Straightening (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
Description
(1)融点Tm1を有する熱可塑性樹脂P1を含むA層、および、ガラス転移温度Tg2を有する熱可塑性樹脂P2を含むB層が少なくとも積層された積層構造体に対して、突起構造を表面に有する金型を、Tm1以上かつTg2以上の温度まで加熱し、該積層構造体のA層側に押し当てることにより、A層に貫通孔を形成し、B層に前記貫通孔に連通する凹部を形成することを特徴とする熱可塑性フィルムの製造方法。
(2)融点Tm1を有する熱可塑性樹脂P1を含むA層、および、ガラス転移温度Tg2を有する熱可塑性樹脂P2を含むB層が少なくとも積層された積層構造体に対して、突起構造を表面に有する金型を、Tm1以上かつTg2以上の温度まで加熱し、該積層構造体のA層側に押し当てることにより、A層に貫通孔を形成し、B層に前記貫通孔に連通する凹部を形成し、さらにその後、前記A層と前記B層を剥離し、前記A層を含む貫通孔を有する熱可塑性フィルムを得ることを特徴とする熱可塑性フィルムの製造方法。
(3)前記融点Tm1と前記ガラス転移温度Tg2との差(Tm1-Tg2)が-30~60℃であることを特徴とする(1)または(2)に記載の熱可塑性フィルムの製造方法。
(4)前記融点Tm1と前記ガラス転移温度Tg2との差(Tm1-Tg2)が-10~0℃であることを特徴とする(3)に記載の熱可塑性フィルムの製造方法。
(5)前記熱可塑性樹脂P1がポリエチレンまたはポリプロピレンであることを特徴とする(1)~(4)のいずれかに記載の熱可塑性フィルムの製造方法。
(6)前記熱可塑性樹脂P2がポリメタクリル酸メチルまたはポリカーネートであることを特徴とする(1)~(5)のいずれかに記載の熱可塑性フィルムの製造方法。
(7)前記貫通孔の孔径が1~100μmであることを特徴とする(1)~(6)のいずれかに記載の熱可塑性フィルムの製造方法。
(8)前記A層の厚みが5~50μmであることを特徴とする(1)~(7)のいずれかに記載の熱可塑性フィルムの製造方法。
(9)前記突起構造が錘形状と円柱形状とを連結させた構造であることを特徴とする(1)~(8)のいずれかに記載の熱可塑性フィルムの製造方法。 In order to solve the above problems, the present invention provides the following method for producing a thermoplastic film.
(1) A protruding structure is provided on the surface of a laminated structure in which an A layer containing a thermoplastic resin P1 having a melting point Tm1 and a B layer containing a thermoplastic resin P2 having a glass transition temperature Tg2 are laminated. The mold is heated to a temperature of Tm1 or more and Tg2 or more and pressed against the A layer side of the laminated structure, thereby forming a through hole in the A layer and forming a recess communicating with the through hole in the B layer. A method for producing a thermoplastic film, comprising:
(2) A protruding structure is provided on the surface of the laminated structure in which the A layer containing the thermoplastic resin P1 having the melting point Tm1 and the B layer containing the thermoplastic resin P2 having the glass transition temperature Tg2 are laminated. The mold is heated to a temperature of Tm1 or more and Tg2 or more and pressed against the A layer side of the laminated structure, thereby forming a through hole in the A layer and forming a recess communicating with the through hole in the B layer. Then, after that, the A layer and the B layer are peeled off to obtain a thermoplastic film having a through hole including the A layer.
(3) The method for producing a thermoplastic film according to (1) or (2), wherein a difference (Tm1−Tg2) between the melting point Tm1 and the glass transition temperature Tg2 is −30 to 60 ° C.
(4) The method for producing a thermoplastic film according to (3), wherein a difference (Tm1−Tg2) between the melting point Tm1 and the glass transition temperature Tg2 is −10 to 0 ° C.
(5) The method for producing a thermoplastic film as described in any one of (1) to (4), wherein the thermoplastic resin P1 is polyethylene or polypropylene.
(6) The method for producing a thermoplastic film according to any one of (1) to (5), wherein the thermoplastic resin P2 is polymethyl methacrylate or polycarbonate.
(7) The method for producing a thermoplastic film according to any one of (1) to (6), wherein the diameter of the through hole is 1 to 100 μm.
(8) The method for producing a thermoplastic film according to any one of (1) to (7), wherein the thickness of the A layer is 5 to 50 μm.
(9) The method for producing a thermoplastic film according to any one of (1) to (8), wherein the protrusion structure is a structure in which a weight shape and a columnar shape are connected.
以上の熱可塑性フィルムの製造方法では、ミクロンサイズからナノサイズの微細な孔径の形状を自由に設計することができ、さらに熱可塑性フィルムを安価に生産性良く製造することができる。本発明の製造方法により得られた熱可塑性フィルムは、ミクロンサイズからナノサイズの微細な孔径が均一に形成されているため、通孔が必要な濾過、細胞培養、細胞分離、ガス透過、透湿等において好適に用いられる。 [Application example]
In the method for producing a thermoplastic film described above, a shape having a fine pore size ranging from a micron size to a nano size can be freely designed, and a thermoplastic film can be produced inexpensively with high productivity. The thermoplastic film obtained by the production method of the present invention has micron-sized to nano-sized fine pore diameters uniformly formed. Therefore, filtration, cell culture, cell separation, gas permeation, moisture permeation that require through holes are required. Etc. are preferably used.
(1)積層構造体
A層にポリプロピレンを主体としたポリマー(融点が144℃)を含む厚み30μmのフィルムを、B層にポリメタクリル酸メチル(PMMA)を主体としたポリマー(ガラス転移温度が105℃)を含む厚み175μmのフィルムを用いた。なお、A層の一方の表層には低密度ポリエチレンを主体とした厚さ6μmの粘着層を有する。A層の粘着層をB層の表面に貼り合わせるようにラミネートし、積層構造体を構成した。 (Example 1)
(1) Laminated structure A film having a thickness of 30 μm containing a polymer mainly composed of polypropylene (melting point: 144 ° C.) in the A layer, and a polymer mainly composed of polymethyl methacrylate (PMMA) in the B layer (glass transition temperature of 105 A film having a thickness of 175 μm was used. One surface layer of the A layer has a 6 μm thick adhesive layer mainly composed of low density polyethylene. The adhesive layer of A layer was laminated so that it might adhere to the surface of B layer, and the laminated structure was comprised.
三角錐の突起構造が全面に配置された金型を用いた。三角錐は底面が一辺が230μmの正三角形で、高さが70μmであり、全面に隙間なく配置されている。突起構造が加工されている領域は200mm(フィルム幅方向)×400mm(フィルム搬送方向)の領域である。金型の材質は厚さ20mmの銅を母材として表面にニッケル鍍金膜を施したものに、鍍金膜に三角錐パターンを機械加工により形成した。 (2) Mold A mold having a triangular pyramid protrusion structure disposed on the entire surface was used. The triangular pyramid is a regular triangle whose bottom is 230 μm on a side, has a height of 70 μm, and is arranged on the entire surface without any gaps. The region where the protrusion structure is processed is a region of 200 mm (film width direction) × 400 mm (film transport direction). The material of the mold was a 20 mm thick copper base metal with a nickel plating film on the surface, and a triangular pyramid pattern was formed on the plating film by machining.
装置は図5に示すような装置を適用した。プレスユニットは油圧ポンプで加圧される機構で、内部に加圧プレートが上下に2枚取り付けられ、それぞれ、加熱装置、冷却装置に連結されている。金型は下側の加圧プレートの上面に設置される。また、金型に貼りついたフィルムを剥離するための剥離手段がプレスユニット内に設置されている。 (3) Molding apparatus and conditions The apparatus as shown in FIG. 5 was applied. The press unit is a mechanism that is pressurized by a hydraulic pump. Two pressurizing plates are attached inside the press unit, and are connected to a heating device and a cooling device, respectively. The mold is placed on the upper surface of the lower pressure plate. A peeling means for peeling the film attached to the mold is installed in the press unit.
成形したフィルム(A層)の走査型電子顕微鏡((株)キーエンス VE-7800)で撮影した写真を図7、図8に示す。図7はA層を金型接触面から見た写真で、図8はA層の断面を見た写真である。設計どおり一辺が45μmの三角形の開口部を有する貫通孔が均一に形成された。開口部の三角形の形状を等面積の円に置き換えると孔径は33μm相当となる。また、B層からなるフィルムには、三角錐の突起形状に対応した貫通孔に連通する凹部が均一に形成されていた。 (4) Molding results Photographs taken with a scanning electron microscope (Keyence VE-7800, Inc.) of the molded film (A layer) are shown in FIGS. FIG. 7 is a photograph of the A layer as seen from the mold contact surface, and FIG. 8 is a photograph of the cross section of the A layer. Through holes having a triangular opening with a side of 45 μm were uniformly formed as designed. If the triangular shape of the opening is replaced with a circle of equal area, the hole diameter is equivalent to 33 μm. Further, the film composed of the B layer was uniformly formed with recesses communicating with the through holes corresponding to the triangular pyramid protrusion shape.
(1)積層構造体
A層にポリプロピレンを主体としたポリマー(融点が144℃)を含む厚み30μmのフィルムを、B層にポリカーボネート(PC)を主体としたポリマー(ガラス転移温度が146℃)を含む厚み180μmのフィルムを用いた。なお、A層の一方の表層には低密度ポリエチレンを主体とした厚さ6μmの粘着層を有する。A層の粘着層をB層の表面に貼り合わせるようにラミネートし、積層構造体を構成した。 (Example 2)
(1) Laminated structure A film having a thickness of 30 μm containing a polymer (melting point: 144 ° C.) mainly composed of polypropylene in the A layer and a polymer (glass transition temperature: 146 ° C.) mainly composed of polycarbonate (PC) in the B layer. A film having a thickness of 180 μm was used. One surface layer of the A layer has a 6 μm thick adhesive layer mainly composed of low density polyethylene. The adhesive layer of A layer was laminated so that it might adhere to the surface of B layer, and the laminated structure was comprised.
三角錐の突起構造が全面に配置された金型を用いた。三角錐は底面が一辺が230μmの正三角形で、高さが70μmであり、全面に隙間なく配置されている。突起構造が加工されている領域は200mm(フィルム幅方向)×400mm(フィルム搬送方向)の領域である。金型の材質は厚さ20mmの銅を母材として表面にニッケル鍍金膜を施したものに、鍍金膜に三角錐パターンを機械加工により形成した。 (2) Mold A mold having a triangular pyramid protrusion structure disposed on the entire surface was used. The triangular pyramid is a regular triangle whose bottom is 230 μm on a side, has a height of 70 μm, and is arranged on the entire surface without any gaps. The region where the protrusion structure is processed is a region of 200 mm (film width direction) × 400 mm (film transport direction). The material of the mold was a 20 mm thick copper base metal with a nickel plating film on the surface, and a triangular pyramid pattern was formed on the plating film by machining.
装置は図5に示すような装置を適用した。プレスユニットは油圧ポンプで加圧される機構で、内部に加圧プレートが上下に2枚取り付けられ、それぞれ、加熱装置、冷却装置に連結されている。金型は下側の加圧プレートの上面に設置される。また、金型に貼りついたフィルムを剥離するための剥離手段がプレスユニット内に設置されている。 (3) Molding apparatus and conditions The apparatus as shown in FIG. 5 was applied. The press unit is a mechanism that is pressurized by a hydraulic pump. Two pressurizing plates are attached inside the press unit, and are connected to a heating device and a cooling device, respectively. The mold is placed on the upper surface of the lower pressure plate. A peeling means for peeling the film attached to the mold is installed in the press unit.
成形したフィルム(A層)の走査型電子顕微鏡((株)キーエンス VE-7800)で撮影した写真を図9、図10に示す。図9はA層を金型接触面から見た写真で、図10はA層の断面をみた写真である。設計どおり一辺が45μmの三角形の開口部を有する貫通孔が均一に形成された。開口部の三角形の形状を等面積の円に置き換えると孔径は33μm相当となる。また、図10からわかるように、図10におけるA層の下側の表面(剥離前にB層と接触していた面)の平面性が高く、バリの少ない貫通孔フィルムが得られた。 (4) Molding results Photographs taken with a scanning electron microscope (Keyence VE-7800, Inc.) of the molded film (A layer) are shown in FIGS. FIG. 9 is a photograph of the A layer viewed from the mold contact surface, and FIG. 10 is a photograph of a cross section of the A layer. Through holes having a triangular opening with a side of 45 μm were uniformly formed as designed. When the triangular shape of the opening is replaced with a circle of equal area, the hole diameter is equivalent to 33 μm. Further, as can be seen from FIG. 10, a through-hole film having a high flatness on the lower surface of the A layer in FIG. 10 (the surface in contact with the B layer before peeling) and few burrs was obtained.
(1)積層構造体
A層にポリプロピレンを主体としたポリマー(融点が144℃)を含む厚み30μmのフィルムを、B層にポリメタクリル酸メチル(PMMA)を主体としたポリマー(ガラス転移温度が105℃)を含む厚み175μmのフィルムを用いた。なお、A層の一方の表層には低密度ポリエチレンを主体とした厚さ6μmの粘着層を有する。A層の粘着層をB層の表面に貼り合わせるようにラミネートし、積層構造体を構成した。 (Comparative Example 1)
(1) Laminated structure A film having a thickness of 30 μm containing a polymer mainly composed of polypropylene (melting point: 144 ° C.) in the A layer, and a polymer mainly composed of polymethyl methacrylate (PMMA) in the B layer (glass transition temperature of 105 A film having a thickness of 175 μm was used. One surface layer of the A layer has a 6 μm thick adhesive layer mainly composed of low density polyethylene. The adhesive layer of A layer was laminated so that it might adhere to the surface of B layer, and the laminated structure was comprised.
三角錐の突起構造が全面に配置された金型を用いた。三角錐は底面が一辺が230μmの正三角形で、高さが70μmであり、全面に隙間なく配置されている。突起構造が加工されている領域は200mm(フィルム幅方向)×400mm(フィルム搬送方向)の領域である。金型の材質は厚さ20mmの銅を母材として表面にニッケル鍍金膜を施したものに、鍍金膜に三角錐パターンを機械加工により形成した。 (2) Mold A mold having a triangular pyramid protrusion structure disposed on the entire surface was used. The triangular pyramid is a regular triangle whose bottom is 230 μm on a side, has a height of 70 μm, and is arranged on the entire surface without any gaps. The region where the protrusion structure is processed is a region of 200 mm (film width direction) × 400 mm (film transport direction). The material of the mold was a 20 mm thick copper base metal with a nickel plating film on the surface, and a triangular pyramid pattern was formed on the plating film by machining.
装置は図5に示すような装置を適用した。プレスユニットは油圧ポンプで加圧される機構で、内部に加圧プレートが上下に2枚取り付けられ、それぞれ、加熱装置、冷却装置に連結されている。金型は下側の加圧プレートの上面に設置される。また、金型に貼りついたフィルムを剥離するための剥離手段がプレスユニット内に設置されている。 (3) Molding apparatus and conditions The apparatus as shown in FIG. 5 was applied. The press unit is a mechanism that is pressurized by a hydraulic pump. Two pressurizing plates are attached inside the press unit, and are connected to a heating device and a cooling device, respectively. The mold is placed on the upper surface of the lower pressure plate. A peeling means for peeling the film attached to the mold is installed in the press unit.
成形したフィルム(A層)の走査型電子顕微鏡((株)キーエンス VE-7800)で撮影した写真を図11、図12に示す。図11はA層を金型接触面から見た写真で、図12はA層の断面を見た写真である。A層に貫通孔が得られなかった。また、図12からわかるように、図12におけるA層の下側の表面(剥離前にB層と接触していた面)の平面性が不良であった。 (4) Molding results Photographs taken with a scanning electron microscope (Keyence VE-7800, Inc.) of the molded film (A layer) are shown in FIGS. FIG. 11 is a photograph of the A layer viewed from the mold contact surface, and FIG. 12 is a photograph of the cross section of the A layer. No through hole was obtained in the A layer. Further, as can be seen from FIG. 12, the flatness of the lower surface of the A layer in FIG. 12 (the surface that was in contact with the B layer before peeling) was poor.
11:A層
12:B層
20:金型
21:突起構造
50:積層構造体
50a:A層
50b:B層
51:巻出ロール
52:巻出ユニット
53:金型
54:プレスユニット
55:剥離手段
56:フィルム剥がし装置
57、58:巻取ロール
59:加圧プレート
60、61:バッファ手段
62:巻取ユニット
70:積層構造体
71:A層
72:B層
73、74:巻出ロール
75:ラミネート装置
76:加熱ロール
77:金型
78:ニップロール
79:冷却ロール
80:剥離ロール
81:フィルム剥がし装置
82、83:巻取ロール 10: Laminated structure 11: A layer 12: B layer 20: Mold 21: Protrusion structure 50:
Claims (9)
- 融点Tm1を有する熱可塑性樹脂P1を含むA層、および、ガラス転移温度Tg2を有する熱可塑性樹脂P2を含むB層が少なくとも積層された積層構造体に対して、突起構造を表面に有する金型を、Tm1以上かつTg2以上の温度まで加熱し、該積層構造体のA層側に押し当てることにより、A層に貫通孔を形成し、B層に前記貫通孔に連通する凹部を形成することを特徴とする熱可塑性フィルムの製造方法。 A mold having a protruding structure on the surface of a laminated structure in which an A layer containing a thermoplastic resin P1 having a melting point Tm1 and a B layer containing a thermoplastic resin P2 having a glass transition temperature Tg2 are laminated. Heating to a temperature of Tm1 or higher and Tg2 or higher and pressing against the A layer side of the laminated structure, thereby forming a through hole in the A layer and forming a recess in the B layer communicating with the through hole. A method for producing a thermoplastic film.
- 融点Tm1を有する熱可塑性樹脂P1を含むA層、および、ガラス転移温度Tg2を有する熱可塑性樹脂P2を含むB層が少なくとも積層された積層構造体に対して、突起構造を表面に有する金型を、Tm1以上かつTg2以上の温度まで加熱し、該積層構造体のA層側に押し当てることにより、A層に貫通孔を形成し、B層に前記貫通孔に連通する凹部を形成し、さらにその後、前記A層と前記B層を剥離し、前記A層を含む貫通孔を有する熱可塑性フィルムを得ることを特徴とする熱可塑性フィルムの製造方法。 A mold having a protruding structure on the surface of a laminated structure in which an A layer containing a thermoplastic resin P1 having a melting point Tm1 and a B layer containing a thermoplastic resin P2 having a glass transition temperature Tg2 are laminated. Heating to a temperature of Tm1 or higher and Tg2 or higher, and pressing the laminated structure against the A layer side, thereby forming a through hole in the A layer, forming a recess in the B layer communicating with the through hole, and Then, the said A layer and the said B layer are peeled, The thermoplastic film which has a through-hole containing the said A layer is obtained, The manufacturing method of the thermoplastic film characterized by the above-mentioned.
- 前記融点Tm1と前記ガラス転移温度Tg2との差(Tm1-Tg2)が-30~60℃であることを特徴とする請求項1または2に記載の熱可塑性フィルムの製造方法。 3. The method for producing a thermoplastic film according to claim 1, wherein a difference (Tm1−Tg2) between the melting point Tm1 and the glass transition temperature Tg2 is −30 to 60 ° C.
- 前記融点Tm1と前記ガラス転移温度Tg2との差(Tm1-Tg2)が-10~0℃であることを特徴とする請求項3に記載の熱可塑性フィルムの製造方法。 The method for producing a thermoplastic film according to claim 3, wherein the difference (Tm1-Tg2) between the melting point Tm1 and the glass transition temperature Tg2 is -10 to 0 ° C.
- 前記熱可塑性樹脂P1がポリエチレンまたはポリプロピレンであることを特徴とする請求項1~4のいずれかに記載の熱可塑性フィルムの製造方法。 The method for producing a thermoplastic film according to any one of claims 1 to 4, wherein the thermoplastic resin P1 is polyethylene or polypropylene.
- 前記熱可塑性樹脂P2がポリメタクリル酸メチルまたはポリカーボネートであることを特徴とする請求項1~5のいずれかに記載の熱可塑性フィルムの製造方法。 The method for producing a thermoplastic film according to any one of claims 1 to 5, wherein the thermoplastic resin P2 is polymethyl methacrylate or polycarbonate.
- 前記貫通孔の孔径が1~100μmであることを特徴とする請求項1~6のいずれかに記載の熱可塑性フィルムの製造方法。 The method for producing a thermoplastic film according to any one of claims 1 to 6, wherein the through-hole has a diameter of 1 to 100 µm.
- 前記A層の厚みが5~50μmであることを特徴とする請求項1~7のいずれかに記載の熱可塑性フィルムの製造方法。 The method for producing a thermoplastic film according to any one of claims 1 to 7, wherein the layer A has a thickness of 5 to 50 袖 m.
- 前記突起構造が錘形状と円柱形状とを連結させた構造であることを特徴とする請求項1~8のいずれかに記載の熱可塑性フィルムの製造方法。 The method for producing a thermoplastic film according to any one of claims 1 to 8, wherein the protrusion structure is a structure in which a weight shape and a columnar shape are connected.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201480021206.0A CN105121114B (en) | 2013-04-18 | 2014-04-08 | The manufacture method of thermoplastic film |
JP2014523119A JP6380102B2 (en) | 2013-04-18 | 2014-04-08 | Method for producing thermoplastic film |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013-087076 | 2013-04-18 | ||
JP2013087076 | 2013-04-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014171365A1 true WO2014171365A1 (en) | 2014-10-23 |
Family
ID=51731309
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/060166 WO2014171365A1 (en) | 2013-04-18 | 2014-04-08 | Method for manufacturing thermoplastic film |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP6380102B2 (en) |
CN (1) | CN105121114B (en) |
TW (1) | TWI624370B (en) |
WO (1) | WO2014171365A1 (en) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015166725A1 (en) * | 2014-04-28 | 2015-11-05 | シャープ株式会社 | Filter having sterilizing activity, and container |
JP2016517362A (en) * | 2013-03-12 | 2016-06-16 | スリーエム イノベイティブ プロパティズ カンパニー | Polymer multilayer film and method for producing the same |
JP2017030357A (en) * | 2015-07-31 | 2017-02-09 | 東レ株式会社 | Method for producing thermoplastic resin film |
WO2017111148A1 (en) | 2015-12-26 | 2017-06-29 | 東レ・メディカル株式会社 | Cell sorting, culture, and growth vessel; and cell sorting, culture, and growth method |
US9781926B2 (en) | 2014-04-22 | 2017-10-10 | Sharp Kabushiki Kaisha | Synthetic polymer film whose surface has microbicidal activity, multilayer structure having synthetic polymer film, sterilization method with the use of surface of synthetic polymer film, method for reactivating surface of synthetic polymer film, mold for production of synthetic polymer film, and mold manufacturing method |
US10251393B2 (en) | 2014-11-20 | 2019-04-09 | Sharp Kabushiki Kaisha | Synthetic polymer film having surface provided with bactericidal activity |
JP2019084744A (en) * | 2017-11-07 | 2019-06-06 | 東レ株式会社 | Mold, method of producing thermoplastic resin film using the same, and thermoplastic film |
US10375953B2 (en) | 2015-07-17 | 2019-08-13 | Sharp Kabushiki Kaisha | Synthetic polymer film having surface that is provided with bactericidal action, and film comprising same |
JP2020515369A (en) * | 2017-04-03 | 2020-05-28 | ザ・ユナイテッド・ステイツ・ガバメント・アズ・リプレゼンティッド・バイ・ザ・デパートメント・オヴ・ヴェテランズ・アフェアズ | Microfluidic diffusion devices and systems, and methods of making and using same |
US10907019B2 (en) | 2015-06-23 | 2021-02-02 | Sharp Kabushiki Kaisha | Synthetic polymer film provided with surface having sterilizing activity |
US10934405B2 (en) | 2018-03-15 | 2021-03-02 | Sharp Kabushiki Kaisha | Synthetic polymer film whose surface has microbicidal activity, plastic product which includes synthetic polymer film, sterilization method with use of surface of synthetic polymer film, photocurable resin composition, and manufacturing method of synthetic polymer film |
US10968292B2 (en) | 2017-09-26 | 2021-04-06 | Sharp Kabushiki Kaisha | Synthetic polymer film whose surface has microbicidal activity, photocurable resin composition, manufacturing method of synthetic polymer film, and sterilization method with use of surface of synthetic polymer film |
US10980255B2 (en) | 2014-12-25 | 2021-04-20 | Sharp Kabushiki Kaisha | Food preservation method, food film, food container, and food handling method |
US11364673B2 (en) | 2018-02-21 | 2022-06-21 | Sharp Kabushiki Kaisha | Synthetic polymer film and production method of synthetic polymer film |
US11883999B2 (en) | 2015-09-17 | 2024-01-30 | Sharp Kabushiki Kaisha | Synthetic polymer film provided with surface having sterilizing effect, method for manufacturing synthetic polymer film and sterilization method using surface of synthetic polymer film |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN209388796U (en) * | 2017-10-30 | 2019-09-13 | 伊利诺斯工具制品有限公司 | A kind of insulated compound film and electric component |
CN116100738A (en) * | 2023-01-03 | 2023-05-12 | 嘉兴和雄服饰有限公司 | A kind of preparation method of metal texture label |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050118393A1 (en) * | 2002-01-18 | 2005-06-02 | Corcoran Craig S. | Sheet having microsized architecture |
JP2006326860A (en) * | 2005-05-23 | 2006-12-07 | Asia Genshi Kk | Perforated film and its manufacturing method |
JP2009090538A (en) * | 2007-10-09 | 2009-04-30 | Sumitomo Electric Ind Ltd | Plastic thin film manufacturing method |
JP2009090615A (en) * | 2007-10-12 | 2009-04-30 | Sumitomo Electric Ind Ltd | Manufacturing method of plastic thin film |
JP2009113461A (en) * | 2007-10-18 | 2009-05-28 | Ricoh Elemex Corp | Apparatus for manufacturing fine through-hole structural body, method for manufacturing fine through-hole structural body, fine through-hole structural body, liquid droplet nozzle, liquid droplet filter, liquid droplet head and liquid droplet apparatus |
JP2010046598A (en) * | 2008-08-21 | 2010-03-04 | Panasonic Corp | Method for manufacturing gas adsorbing filter and gas adsorbing filter |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006015523A (en) * | 2004-06-30 | 2006-01-19 | Konica Minolta Holdings Inc | Molding method and molding apparatus |
JP4591053B2 (en) * | 2004-11-22 | 2010-12-01 | 住友電気工業株式会社 | Processing method and processing apparatus |
JP2010125843A (en) * | 2008-12-01 | 2010-06-10 | Ricoh Elemex Corp | Manufacturing method for minute through hole structure, minute through hole structure, liquid droplet ejection head, and liquid droplet ejector |
US20100193469A1 (en) * | 2009-02-05 | 2010-08-05 | National Cheng Kung University | Method for manufacturing micro/nano three-dimensional structure |
JP5072899B2 (en) * | 2009-04-17 | 2012-11-14 | 株式会社日本製鋼所 | Manufacturing method and manufacturing apparatus for microstructured body having through hole |
JP5152935B2 (en) * | 2010-04-28 | 2013-02-27 | 株式会社日本製鋼所 | Manufacturing method of microstructured molded body having through-hole and microstructured molded body material |
-
2014
- 2014-04-08 WO PCT/JP2014/060166 patent/WO2014171365A1/en active Application Filing
- 2014-04-08 JP JP2014523119A patent/JP6380102B2/en active Active
- 2014-04-08 CN CN201480021206.0A patent/CN105121114B/en active Active
- 2014-04-14 TW TW103113507A patent/TWI624370B/en active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050118393A1 (en) * | 2002-01-18 | 2005-06-02 | Corcoran Craig S. | Sheet having microsized architecture |
JP2006326860A (en) * | 2005-05-23 | 2006-12-07 | Asia Genshi Kk | Perforated film and its manufacturing method |
JP2009090538A (en) * | 2007-10-09 | 2009-04-30 | Sumitomo Electric Ind Ltd | Plastic thin film manufacturing method |
JP2009090615A (en) * | 2007-10-12 | 2009-04-30 | Sumitomo Electric Ind Ltd | Manufacturing method of plastic thin film |
JP2009113461A (en) * | 2007-10-18 | 2009-05-28 | Ricoh Elemex Corp | Apparatus for manufacturing fine through-hole structural body, method for manufacturing fine through-hole structural body, fine through-hole structural body, liquid droplet nozzle, liquid droplet filter, liquid droplet head and liquid droplet apparatus |
JP2010046598A (en) * | 2008-08-21 | 2010-03-04 | Panasonic Corp | Method for manufacturing gas adsorbing filter and gas adsorbing filter |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016517362A (en) * | 2013-03-12 | 2016-06-16 | スリーエム イノベイティブ プロパティズ カンパニー | Polymer multilayer film and method for producing the same |
US10278387B2 (en) | 2014-04-22 | 2019-05-07 | Sharp Kabushiki Kaisha | Synthetic polymer film whose surface has microbicidal activity, multilayer structure having synthetic polymer film, sterilization method with the use of surface of synthetic polymer film, method for reactivating surface of synthetic polymer film, mold for production of synthetic polymer film, and mold manufacturing method |
US11641854B2 (en) | 2014-04-22 | 2023-05-09 | Sharp Kabushiki Kaisha | Synthetic polymer film whose surface has microbicidal activity, multilayer structure having synthetic polymer film, sterilization method with the use of surface of synthetic polymer film, method for reactivating surface of synthetic polymer film, mold for production of synthetic polymer film, and mold manufacturing method |
US11638423B2 (en) | 2014-04-22 | 2023-05-02 | Sharp Kabushiki Kaisha | Synthetic polymer film whose surface has microbicidal activity, multilayer structure having synthetic polymer film, sterilization method with the use of surface of synthetic polymer film, method for reactivating surface of synthetic polymer film, mold for production of synthetic polymer film, and mold manufacturing method |
US9781926B2 (en) | 2014-04-22 | 2017-10-10 | Sharp Kabushiki Kaisha | Synthetic polymer film whose surface has microbicidal activity, multilayer structure having synthetic polymer film, sterilization method with the use of surface of synthetic polymer film, method for reactivating surface of synthetic polymer film, mold for production of synthetic polymer film, and mold manufacturing method |
US9781924B2 (en) | 2014-04-22 | 2017-10-10 | Sharp Kabushiki Kaisha | Synthetic polymer film whose surface has microbicidal activity, multilayer structure having synthetic polymer film, sterilization method with the use of surface of synthetic polymer film, method for reactivating surface of synthetic polymer film, mold for production of synthetic polymer film, and mold manufacturing method |
US9781925B2 (en) | 2014-04-22 | 2017-10-10 | Sharp Kabushiki Kaisha | Synthetic polymer film whose surface has microbicidal activity, multilayer structure having synthetic polymer film, sterilization method with the use of surface of synthetic polymer film, method for reactivating surface of synthetic polymer film, mold for production of synthetic polymer film, and mold manufacturing method |
US10136638B2 (en) | 2014-04-22 | 2018-11-27 | Sharp Kabushiki Kaisha | Synthetic polymer film whose surface has microbicidal activity, multilayer structure having synthetic polymer film, sterilization method with the use of surface of synthetic polymer film, method for reactivating surface of synthetic polymer film, mold for production of synthetic polymer film, and mold manufacturing method |
JP5851076B1 (en) * | 2014-04-28 | 2016-02-03 | シャープ株式会社 | Bactericidal filter |
US10071175B2 (en) | 2014-04-28 | 2018-09-11 | Sharp Kabushiki Kaisha | Filter and container having microbicidal activity |
WO2015166725A1 (en) * | 2014-04-28 | 2015-11-05 | シャープ株式会社 | Filter having sterilizing activity, and container |
US10251393B2 (en) | 2014-11-20 | 2019-04-09 | Sharp Kabushiki Kaisha | Synthetic polymer film having surface provided with bactericidal activity |
US10980255B2 (en) | 2014-12-25 | 2021-04-20 | Sharp Kabushiki Kaisha | Food preservation method, food film, food container, and food handling method |
US10907019B2 (en) | 2015-06-23 | 2021-02-02 | Sharp Kabushiki Kaisha | Synthetic polymer film provided with surface having sterilizing activity |
US10375953B2 (en) | 2015-07-17 | 2019-08-13 | Sharp Kabushiki Kaisha | Synthetic polymer film having surface that is provided with bactericidal action, and film comprising same |
JP2017030357A (en) * | 2015-07-31 | 2017-02-09 | 東レ株式会社 | Method for producing thermoplastic resin film |
US11883999B2 (en) | 2015-09-17 | 2024-01-30 | Sharp Kabushiki Kaisha | Synthetic polymer film provided with surface having sterilizing effect, method for manufacturing synthetic polymer film and sterilization method using surface of synthetic polymer film |
WO2017111148A1 (en) | 2015-12-26 | 2017-06-29 | 東レ・メディカル株式会社 | Cell sorting, culture, and growth vessel; and cell sorting, culture, and growth method |
JP2020515369A (en) * | 2017-04-03 | 2020-05-28 | ザ・ユナイテッド・ステイツ・ガバメント・アズ・リプレゼンティッド・バイ・ザ・デパートメント・オヴ・ヴェテランズ・アフェアズ | Microfluidic diffusion devices and systems, and methods of making and using same |
US10968292B2 (en) | 2017-09-26 | 2021-04-06 | Sharp Kabushiki Kaisha | Synthetic polymer film whose surface has microbicidal activity, photocurable resin composition, manufacturing method of synthetic polymer film, and sterilization method with use of surface of synthetic polymer film |
JP2019084744A (en) * | 2017-11-07 | 2019-06-06 | 東レ株式会社 | Mold, method of producing thermoplastic resin film using the same, and thermoplastic film |
US11364673B2 (en) | 2018-02-21 | 2022-06-21 | Sharp Kabushiki Kaisha | Synthetic polymer film and production method of synthetic polymer film |
US10934405B2 (en) | 2018-03-15 | 2021-03-02 | Sharp Kabushiki Kaisha | Synthetic polymer film whose surface has microbicidal activity, plastic product which includes synthetic polymer film, sterilization method with use of surface of synthetic polymer film, photocurable resin composition, and manufacturing method of synthetic polymer film |
Also Published As
Publication number | Publication date |
---|---|
TWI624370B (en) | 2018-05-21 |
TW201446517A (en) | 2014-12-16 |
CN105121114B (en) | 2016-11-30 |
JP6380102B2 (en) | 2018-08-29 |
CN105121114A (en) | 2015-12-02 |
JPWO2014171365A1 (en) | 2017-02-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6380102B2 (en) | Method for producing thermoplastic film | |
JP5833592B2 (en) | Protective film with release surface | |
TW200831274A (en) | A device for intermittently forming films and a method of forming films | |
JP4135768B2 (en) | Intermittent film forming apparatus and method | |
JP5622733B2 (en) | Molding method | |
JP6787779B2 (en) | Method for manufacturing polymer multilayer film | |
JP2015051629A (en) | Method for producing laminate substrate and laminate substrate | |
JP6786930B2 (en) | Manufacturing method of thermoplastic resin film | |
TW201219181A (en) | Optical sheet with laminated double-sided light guide plate | |
TW200824882A (en) | Method for manufacturing a sheet having transferred minute shape and apparatus for manufacturing the same | |
Melentiev et al. | Large-scale hot embossing of 1 µm high-aspect-ratio textures on ABS polymer | |
TW201223742A (en) | Optical sheet manufactured with micro-patterned carrier | |
JP4135769B2 (en) | Intermittent film forming apparatus and forming method | |
JP5104228B2 (en) | Fine shape transfer sheet manufacturing apparatus and fine shape transfer sheet manufacturing method | |
WO2009084615A1 (en) | Die member, method for manufacturing the die member and method for forming light controlling member by using the die member | |
JP5167583B2 (en) | Pattern forming method and pattern forming sheet | |
JP5469364B2 (en) | Embossed transfer thermoplastic resin sheet, thermoplastic resin embossed sheet, and thermoplastic resin embossed sheet manufacturing method | |
JP2010030192A (en) | Minute shape transfer sheet and method of manufacturing minute shape transfer sheet | |
JP5328040B2 (en) | Laminated body having fine structure and method for producing the same | |
JP2019084744A (en) | Mold, method of producing thermoplastic resin film using the same, and thermoplastic film | |
JP2015188576A (en) | Method for manufacturing flake | |
WO2019159792A1 (en) | Resin structure and method for manufacturing resin structure | |
JP2017164906A (en) | Laminate having projection and method for producing the same | |
JP2008120073A (en) | Manufacturing process and apparatus of detailed configuration transfer sheet | |
JP6095447B2 (en) | Hollow structure plate manufacturing method and hollow structure plate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201480021206.0 Country of ref document: CN |
|
ENP | Entry into the national phase |
Ref document number: 2014523119 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14786003 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 14786003 Country of ref document: EP Kind code of ref document: A1 |