WO2015129291A1 - Method for producing piezoelectric polymer - Google Patents
Method for producing piezoelectric polymer Download PDFInfo
- Publication number
- WO2015129291A1 WO2015129291A1 PCT/JP2015/050179 JP2015050179W WO2015129291A1 WO 2015129291 A1 WO2015129291 A1 WO 2015129291A1 JP 2015050179 W JP2015050179 W JP 2015050179W WO 2015129291 A1 WO2015129291 A1 WO 2015129291A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- modeling
- piezoelectric
- piezoelectric polymer
- nozzle
- polymer
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 82
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 239000000463 material Substances 0.000 claims abstract description 65
- 238000000034 method Methods 0.000 claims abstract description 54
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- 238000007599 discharging Methods 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 16
- 239000004626 polylactic acid Substances 0.000 claims description 16
- 239000004902 Softening Agent Substances 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- 229920001400 block copolymer Polymers 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 abstract description 8
- 239000010409 thin film Substances 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920001184 polypeptide Polymers 0.000 description 3
- 102000004196 processed proteins & peptides Human genes 0.000 description 3
- 108090000765 processed proteins & peptides Proteins 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920000331 Polyhydroxybutyrate Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- -1 and the like Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 239000005015 poly(hydroxybutyrate) Substances 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000110 selective laser sintering Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/16—Measuring force or stress, in general using properties of piezoelectric devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/098—Forming organic materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/857—Macromolecular compositions
Definitions
- the present invention relates to a piezoelectric polymer modeling method and a structure obtained by the modeling method.
- piezoelectric ceramics such as lead zirconate titanate (PZT) have been widely used as piezoelectric materials, but in recent years they have excellent workability, flexibility, transparency, lightness, etc.
- piezoelectric polymers such as vinylidene, polypeptides and polylactic acid.
- polylactic acid having a helical chirality as disclosed in Patent Document 1 does not require a poling process, expresses a relatively high piezoelectricity only by a stretching process, and can maintain a piezoelectric constant for a long period of time, It is attracting attention as an ideal piezoelectric polymer material.
- a technique called rapid prototyping is known as a technique for modeling a polymer such as a resin into a three-dimensional structure.
- Known modeling methods using this rapid prototyping technology include melt deposition (Fused (Deposition Molding), inkjet method, inkjet binder method, stereolithography (Stereo ⁇ Lithography), and powder sintering method (Selective Laser Sintering). ing.
- a polymer piezoelectric material formed from a piezoelectric polymer having helical chirality is usually obtained by orienting a piezoelectric polymer molecule by uniaxially stretching a film formed from a piezoelectric polymer. It is done.
- the polymeric piezoelectric material obtained by the uniaxial stretching process is a flat film, and its use is limited to that obtained by processing the film.
- rapid prototyping technology for example, modeling by a melt deposition method
- a three-dimensional modeling apparatus also called a 3D printer. Even if the polymer is shaped, the piezoelectric polymer cannot be oriented, and the resulting structure does not exhibit piezoelectricity.
- an object of the present invention is to form a piezoelectric polymer into a structure having a desired three-dimensional structure using a three-dimensional modeling apparatus and to cause the obtained structure to exhibit piezoelectricity. It is to provide a modeling method.
- a piezoelectric polymer has a desired three-dimensional structure by using a three-dimensional modeling apparatus for modeling by ejecting a modeling material containing the piezoelectric polymer from a nozzle. It was found that a structure having good piezoelectric characteristics can be produced.
- a three-dimensional modeling apparatus for modeling by discharging a modeling material containing a piezoelectric polymer from a nozzle it is characterized in that it is modeled into a structure having a piezoelectric part.
- a method for forming a piezoelectric polymer is provided.
- the piezoelectric polymer can be modeled into structures of various shapes, and at the same time, excellent piezoelectric characteristics can be expressed.
- FIG. 1 is a schematic perspective view of a pressure-sensitive sensor according to one embodiment of the present invention.
- FIG. 2 is a graph showing the voltages measured in the examples.
- piezoelectric polymer refers to a polymer that can exhibit piezoelectricity when the molecule is uniaxially oriented and has helical chirality.
- modeling of the piezoelectric polymer is performed using a three-dimensional modeling apparatus that models by modeling a modeling material containing the piezoelectric polymer from a nozzle.
- the “three-dimensional modeling apparatus” means an apparatus that models a three-dimensional structure based on input information related to the three-dimensional solid information of the structure, and is generally melted from a nozzle. Alternatively, the softened modeling material is discharged, and the structure is modeled by sequentially stacking the modeling material in a predetermined pattern on the modeling table. Such a three-dimensional modeling apparatus is not particularly limited, and examples thereof include a stacked 3D printer.
- a modeling material is formed by discharging a modeling material containing a piezoelectric polymer from a nozzle of a three-dimensional modeling apparatus and sequentially laminating layers corresponding to the cross-sectional shape of the structure to be modeled. To do.
- the modeling material is stacked, the modeling material is stretched by pulling the modeling material with a nozzle, and the molecules of the piezoelectric polymer are oriented along the stretching direction, that is, along the moving direction of the nozzle. Sex is expressed.
- a material containing a piezoelectric polymer is used as the modeling material.
- piezoelectric polymer examples include polymers having a chirality such as polylactic acid, polypeptide, polymethylglutamate, polybenzylglutamate and the like in which the main chain draws a helix, and polylactic acid or a copolymer containing lactic acid as a structural unit.
- polylactic acid is more preferable.
- the polylactic acid may be either L-form or D-form, but polylactic acid composed of L-form which is easily available is preferable.
- the modeling material including the piezoelectric polymer applied to the modeling method of the present invention is a material mainly composed of the piezoelectric polymer.
- the content of the piezoelectric polymer is 50% by mass or more and 60% by mass or more. 70% by mass or more, or a material containing 80% by mass or more, or a material substantially composed of a piezoelectric polymer, for example, a material having a piezoelectric polymer content of 99 to 100% by mass.
- the weight average molecular weight of the piezoelectric polymer is not particularly limited.
- polylactic acid it is preferably about 10,000 to 1,000,000, more preferably about 15,000 to 400,000, and still more preferably. Is about 20,000-250,000.
- the weight average molecular weight is about 10,000 or more, the mechanical strength and elasticity of the resulting structure can be ensured. Further, when the weight average molecular weight is about 1,000,000 or less, it can be more oriented.
- the modeling material containing the piezoelectric polymer may contain a softening agent.
- the flexibility of the material formed from the piezoelectric polymer is increased, and the discharge from the nozzle becomes easy.
- the softening agent is not particularly limited, but when the piezoelectric polymer is polylactic acid, an elastomer having affinity or reactivity with a carboxylic acid group or a hydroxyl group at the polymer terminal is preferable.
- elastomers include styrene-based elastomers (for example, SBS (styrene-butadiene-styrene block copolymer), etc., to which functional groups having excellent affinity for carboxylic acid groups or hydroxyl groups, such as amines, epoxies, and carboxylic anhydrides, are added.
- SEBS Styrene / Ethylene / Butadiene / Styrene Block Copolymer obtained by hydrogenation of this, an olefin-based elastomer with the same functional group added, and a polyhydroxybutyrate-based soft copolymer (a styrene-based elastomer having an amine terminal) ) And the like.
- a block copolymer of polyalkyl methacrylate and polyalkyl acrylate for example, PMMA-PnBA-PMMA (polymethyl methacrylate-poly (n-butyl acrylate) -polymethyl methacrylate) block copolymer may be mentioned.
- the block copolymer can be obtained, for example, as LA2250 (trade name), LA2140 (trade name), LA4285 (trade name), etc., manufactured by Kuraray Co., Ltd.
- the amount of the softening agent added is about 0.1 to 50% by mass, preferably about 1 to 30% by mass, based on the total amount of the piezoelectric polymer and the softening agent.
- the modeling material containing the piezoelectric polymer used in the modeling method of the present invention may further contain another additive, such as a colorant or a plasticizer.
- the shape of the modeling material including the piezoelectric polymer used in the modeling method of the present invention is not particularly limited as long as it is generally a shape that can be used in a three-dimensional modeling apparatus, and may be, for example, a pellet shape.
- the temperature of the nozzle for discharging the modeling material of the three-dimensional modeling apparatus may be a temperature equal to or higher than the crystallization temperature of the piezoelectric polymer and lower than the melting point.
- the temperature is, for example, about 110 ° C. to 175 ° C., preferably Is about 130-170 ° C, more preferably about 150-165 ° C.
- the viscosity of modeling material can be reduced and discharge from a nozzle can be made easy.
- the piezoelectric polymer can be more oriented and the piezoelectricity of the resulting structure can be improved.
- the nozzle temperature approaches the melting point, the viscosity of the modeling material increases and it becomes difficult to discharge from the nozzle.
- pressure is applied so as to extrude the modeling material from the nozzle. Thus, discharge can be assisted.
- crystalstallization temperature and melting point can be measured by differential scanning calorimetry—DSC (Differential scanning calorimetry).
- a modeling part from which the modeling material is discharged (for example, in the case of using a laminated three-dimensional modeling apparatus, a part where the modeling material discharged from the nozzle is stacked, that is, in the case of the first layer, three-dimensional modeling.
- the temperature of the molding table of the device, the lower layer in the case of the second and subsequent layers can be about 10 ° C. to 50 ° C., for example about 20 ° C. to 30 ° C. lower than the melting point of the piezoelectric polymer.
- this temperature can be set lower than the temperature of the nozzle.
- the molding material discharged from the nozzle is set so that the temperature at which the modeling material is laminated is about 10 ° C. to 50 ° C.
- the nozzle temperature and the temperature of the modeling location do not necessarily need to be constant during modeling, and can be appropriately adjusted according to the shape of the structure to be modeled, the position of the piezoelectric portion, and the piezoelectric characteristics.
- the moving speed of the nozzle for discharging the modeling material in the three-dimensional modeling apparatus is faster than the discharging speed of the modeling material from the nozzle.
- the moving speed of the nozzle is about 1.5 times or more, preferably about 2 times or more, more preferably about 4 times or more the discharge speed of the modeling material.
- the moving speed of the nozzle is, for example, about 10 times or less, preferably about 7 times or less, the ejection speed of the modeling material.
- the discharge speed of the modeling material containing the piezoelectric polymer from the nozzle is the length of the modeling material discharged from the nozzle per unit time, and the discharge flow rate of the modeling material per unit time (unit time)
- the volume of the modeling material discharged per hit) can be calculated by dividing by the cross-sectional area of the nozzle outlet.
- the moving speed of the nozzle of the three-dimensional modeling apparatus is 0.1 to 100 mm / second, preferably 1 to 30 mm / second, preferably 5 to 15 mm / second.
- the piezoelectric polymer can be more oriented.
- a more precise three-dimensional structure can be obtained by setting the moving speed of the nozzle to 100 mm / second or less.
- the “moving speed of the nozzle” does not mean only the moving speed of the nozzle itself, but means the relative speed with respect to the modeling location (lamination location) where the modeling material is discharged.
- the moving speed of the nozzle is the moving speed of the modeling table.
- an average speed in a certain time for example, 1 second may be set as the “nozzle moving speed”.
- the moving speed of the nozzle does not necessarily have to be a constant speed during modeling, and can be appropriately adjusted according to the shape of the structure to be modeled, the position of the piezoelectric portion, and the piezoelectric characteristics.
- the movement of the nozzle may be continuous or intermittent.
- the nozzle may stop substantially until the discharged modeling material reaches substantially the same temperature as the temperature of the above-described modeling location, and then move a predetermined distance.
- the polymer material can be oriented more by moving the nozzle intermittently to perform modeling.
- At least a part of the modeling material is stretched by about 1.5 times or more, preferably about 2 times or more, more preferably about 4 times or more. That is, the draw ratio is about 1.5 times or more, preferably about 2 times or more, more preferably about 4 times or more.
- the draw ratio is preferably about 10 times or less, more preferably about 7 times or less.
- the draw ratio can be calculated, for example, by dividing the moving speed of the nozzle by the discharge speed of the modeling material from the nozzle.
- the modeling method of the present invention forms a structure having a piezoelectric portion using a three-dimensional modeling apparatus for modeling by discharging a modeling material containing a piezoelectric polymer from a nozzle;
- the temperature of the nozzle for discharging the modeling material of the three-dimensional modeling apparatus is not less than the crystallization temperature of the piezoelectric polymer and less than the melting point;
- the moving speed of the nozzle of the three-dimensional modeling apparatus is faster than the ejection speed of the modeling material containing the piezoelectric polymer; and the stretching ratio of at least a part of the laminated piezoelectric polymer is 1.5 times or more It is characterized by being.
- the method of the present invention includes cooling, preferably quenching, the resulting structure after shaping.
- cooling preferably quenching, the resulting structure after shaping.
- the piezoelectric polymer can be modeled into various shapes of structures having piezoelectric sites. Further, according to the modeling method of the present invention, the stretching ratio and orientation of the modeling material can be controlled by adjusting the speed of the nozzle and the discharge speed of the modeling material. It is possible to form a sex site and control its piezoelectric characteristics.
- the present invention also provides a structure having a piezoelectric portion obtained by the modeling method of the present invention.
- the “piezoelectric part” means a part showing piezoelectricity.
- the piezoelectricity of the piezoelectric portion is 0.5 pC / N or more, preferably 2 pC / N or more, more preferably 3 pC / N or more, and further preferably 5 pC / N or more.
- the piezoelectric portion may exist in the entire structure, or may exist in a part or a plurality of locations.
- the piezoelectric portion of the structure obtained by the modeling method of the present invention has an orientation birefringence of 0.1 ⁇ 10 ⁇ 3 or more, more preferably 1 ⁇ 10 ⁇ 3 or more, and further preferably 10 ⁇ 10 ⁇ 3 or more. .
- the molecules of the piezoelectric polymer are oriented along the moving direction of the nozzle.
- the structure of the present invention can have various shapes, it can be used as a housing of an electronic device while having a function as a piezoelectric material.
- the present invention A structure obtained by the modeling method of the present invention; There is also provided a pressure-sensitive sensor comprising at least a pair of electrodes disposed on the piezoelectric portion.
- the pressure-sensitive sensor of the present invention using the structure can have various shapes. Therefore, for example, by forming a casing of an electronic device, which has been conventionally formed of ABS (acrylonitrile-butadiene-styrene) resin, acrylic resin, or the like, using the molding method of the present invention, the casing is formed. It becomes possible to give itself a function as a pressure-sensitive sensor. Providing a single component with a plurality of functions in this way is advantageous from the viewpoint of downsizing the device.
- FIG. 1 schematically shows a pressure-sensitive sensor 1 according to this embodiment.
- the pressure-sensitive sensor 1 of this embodiment includes a structure 2 formed of a piezoelectric polymer and electrodes 6a and 6b installed on the side surface (left side surface 14 in FIG. 1).
- the electrodes are paired and provided to face each other through the structure side surface.
- the structure 2 can be obtained by modeling a modeling material containing a piezoelectric polymer using the modeling method of the present invention using a three-dimensional modeling apparatus.
- the molecules of the piezoelectric polymer are oriented along the moving direction of the nozzle of the three-dimensional modeling apparatus.
- the location where the piezoelectric polymer is oriented becomes the piezoelectric portion.
- the piezoelectric polymer described in the modeling method can be used.
- a piezoelectric polymer having helical chirality specifically, a polymer having chirality such as polylactic acid, polypeptide, polymethylglutamate, polybenzylglutamate and the like in which the main chain draws a helix.
- Polylactic acid or a copolymer containing lactic acid as a structural unit is preferable, and polylactic acid is more preferable.
- the electrodes 6a and 6b are, for example, a metal thin film having a predetermined size, which is disposed so as to be opposed to the approximate center of the left side surface 14 in the lower part (deep part) of the structure 2 via the left side as shown in FIG. Then, a lead (not shown) may be disposed thereon, and then the electrode and the lead connecting portion may be covered with a resin (for example, epoxy resin or acrylic resin). A voltage generated when force is applied to the structure 2 by these electrodes is detected.
- a resin for example, epoxy resin or acrylic resin
- the conductive material forming the electrode is not particularly limited, and examples thereof include Au, Cu, Ag, Ni, and the like, and Au is particularly preferable.
- the method for forming the electrode is not particularly limited, and in addition to the above-described method, for example, the electrode can be formed by a method such as attaching the metal thin film with a conductive adhesive.
- the pressure-sensitive sensor of the present invention can be manufactured using the above-described modeling method of the present invention, it can have any shape that can be manufactured by the modeling method of the present invention. Therefore, by the modeling method of the present invention, the piezoelectric polymer can be modeled, for example, as a casing of a mobile phone or a portable game machine or a part thereof, thereby giving a function as a pressure sensitive sensor. .
- the structure obtained by the method of the present invention can be used for an actuator. Therefore, the present invention A structure obtained by the modeling method of the present invention; There is also provided an actuator comprising at least a pair of electrodes disposed at the piezoelectric portion.
- Actuators include drive devices, piezoelectric speakers, vibration generators, haptics, and the like.
- the actuator includes a thin film formed of a piezoelectric polymer and a first electrode formed on a first main surface of the thin film as disclosed in, for example, Japanese Patent Application Laid-Open No. 2012-157235. And a second electrode formed on the second main surface of the thin film, and applying a predetermined alternating voltage between the first electrode and the second electrode, thereby at least one end of the thin film It can be an actuator that generates a driving force at the edge, for example a driving device.
- the thin film formed from the piezoelectric polymer is formed by the modeling method of the present invention.
- the thin film can be cylindrical.
- the actuator includes, for example, a piezoelectric part formed of a piezoelectric polymer, a first electrode located on the first main surface of the piezoelectric part, and a second part of the piezoelectric part.
- the vibration generating device or the speaker having the second electrode located on the main surface of the speaker.
- the piezoelectric part formed from the piezoelectric polymer is formed by the modeling method of the present invention.
- the piezoelectric portion is formed in a cylindrical shape.
- Example 1 Using a commercially available 3D printer (Cube manufactured by 3D Systems, Inc.), a box-shaped structure having dimensions of 110 mm in length, 60 mm in width, and 10 mm in height, and having a thickness of 1 mm on each surface (described below) 1 corresponding to the structure 2 in FIG.
- the movement direction of the nozzle when forming the right side surface of the structure was the direction indicated by the arrow A in FIG.
- Modeling material Polylactic acid (pellet, manufactured by Taki Chemical Co., Ltd., number average molecular weight 7000)
- Nozzle (head) speed 10 mm / sec
- Nozzle temperature 190 ° C
- Nozzle mouth cross-sectional area 0.1 mm 2
- Molding table temperature 120 ° C
- Discharge flow rate 1 ml / min
- FIG. 1 A pressure-sensitive sensor of the present invention as shown in FIG.
- Test example 1 The upper electrode 4, the middle electrode 6 and the lower electrode 8 of the pressure sensor obtained in Example 1 were pressed with a finger, and the resulting voltage was measured. The results are shown in FIG.
- the modeling method of the present invention can form piezoelectric material structures of various shapes having piezoelectric parts, and such structures can be used in a wide variety of applications as a housing having a pressure-sensitive function. Can be specified.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The present invention provides a method for producing a piezoelectric polymer, the method being characterized by the following: a three-dimensional shaping device is used to shape a shaping material comprising a piezoelectric polymer into a structure having a piezoelectric site; the temperature of a nozzle for discharging the shaping material in the three-dimensional shaping device is not less than the crystallization temperature but less than the melting point of the piezoelectric polymer; the moving speed of the nozzle of the three-dimensional shaping device is greater than the discharge speed of the shaping material comprising the piezoelectric polymer; and the draw ratio of at least a part of the layered piezoelectric polymer is 1.5 times or more. According to the present invention, the piezoelectric polymer can be shaped into a desired shape by using the three-dimensional shaping device, and also the resulting structure can be endowed with piezoelectricity.
Description
本発明は、圧電性高分子の造形方法および当該造形方法により得られる構造体に関する。
The present invention relates to a piezoelectric polymer modeling method and a structure obtained by the modeling method.
従来から、圧電材料として、チタン酸ジルコン酸鉛(PZT)等の圧電セラミックスが広く用いられているが、近年、加工性、柔軟性、透明性、軽量性等に優れていることから、ポリフッ化ビニリデン、ポリペプチドおよびポリ乳酸等の圧電性高分子への関心が高まっている。その中でも、特許文献1に開示されるようなヘリカルキラリティを有するポリ乳酸が、ポーリング処理を必要とせず、延伸処理のみで比較的高い圧電性を発現し、さらに長期間圧電率を維持できることから、理想的な圧電性高分子材料として注目されている。
Conventionally, piezoelectric ceramics such as lead zirconate titanate (PZT) have been widely used as piezoelectric materials, but in recent years they have excellent workability, flexibility, transparency, lightness, etc. There is a growing interest in piezoelectric polymers such as vinylidene, polypeptides and polylactic acid. Among them, polylactic acid having a helical chirality as disclosed in Patent Document 1 does not require a poling process, expresses a relatively high piezoelectricity only by a stretching process, and can maintain a piezoelectric constant for a long period of time, It is attracting attention as an ideal piezoelectric polymer material.
一方、樹脂などの高分子を、三次元の立体構造物に造形する技術として、ラピッドプロトタイピイング(Rapid Prototyping)と呼ばれる技術が知られている。このラピッドプロトタイピング技術を用いる造形法としては、溶融物堆積法(Fused Deposition Molding)、インクジェット法、インクジェットバインダ法、光造形法(Stereo Lithography)、粉末焼結法(Selective Laser Sintering)等が知られている。
On the other hand, a technique called rapid prototyping is known as a technique for modeling a polymer such as a resin into a three-dimensional structure. Known modeling methods using this rapid prototyping technology include melt deposition (Fused (Deposition Molding), inkjet method, inkjet binder method, stereolithography (Stereo 光 Lithography), and powder sintering method (Selective Laser Sintering). ing.
ヘリカルキラリティを有する圧電性高分子から形成される高分子圧電材料は、通常、圧電性高分子から形成されたフィルムを、一軸延伸処理することにより、圧電性高分子の分子を配向させることによって得られる。しかしながら、一軸延伸処理により得られる高分子圧電材料は平面状のフィルムであり、その用途はフィルムを加工して得られるものに限られる。
A polymer piezoelectric material formed from a piezoelectric polymer having helical chirality is usually obtained by orienting a piezoelectric polymer molecule by uniaxially stretching a film formed from a piezoelectric polymer. It is done. However, the polymeric piezoelectric material obtained by the uniaxial stretching process is a flat film, and its use is limited to that obtained by processing the film.
一方、ラピッドプロトタイピイング技術、例えば、溶融物堆積法での造形は、一般的には、3Dプリンタとも称される三次元造形装置を用いて行われるが、このような装置を用いて圧電性高分子を造形したとしても、圧電性高分子を配向させることはできず、得られた構造体は圧電性を示さない。
On the other hand, rapid prototyping technology, for example, modeling by a melt deposition method, is generally performed using a three-dimensional modeling apparatus also called a 3D printer. Even if the polymer is shaped, the piezoelectric polymer cannot be oriented, and the resulting structure does not exhibit piezoelectricity.
そこで、本発明の一の目的は、圧電性高分子を、三次元造形装置を用いて所望の三次元構造を有する構造体に造形すると共に、得られる構造体に圧電性を発現させることができる造形方法を提供することである。
Accordingly, an object of the present invention is to form a piezoelectric polymer into a structure having a desired three-dimensional structure using a three-dimensional modeling apparatus and to cause the obtained structure to exhibit piezoelectricity. It is to provide a modeling method.
本発明者らは、鋭意検討した結果、圧電性高分子を、ノズルから圧電性高分子を含む造形材料を吐出して造形する三次元造形装置を用いることにより、所望の三次元構造を有し、良好な圧電特性を有する構造体を製造できることを見出した。
As a result of intensive studies, the present inventors have found that a piezoelectric polymer has a desired three-dimensional structure by using a three-dimensional modeling apparatus for modeling by ejecting a modeling material containing the piezoelectric polymer from a nozzle. It was found that a structure having good piezoelectric characteristics can be produced.
即ち、本発明の要旨によれば、ノズルから圧電性高分子を含む造形材料を吐出して造形する三次元造形装置を用いて、圧電性部位を有する構造体に造形することを特徴とする、圧電性高分子の造形方法が提供される。
That is, according to the gist of the present invention, using a three-dimensional modeling apparatus for modeling by discharging a modeling material containing a piezoelectric polymer from a nozzle, it is characterized in that it is modeled into a structure having a piezoelectric part. A method for forming a piezoelectric polymer is provided.
本発明の造形方法によれば、圧電性高分子を様々な形状の構造体に造形することができ、同時に良好な圧電特性を発現させることができる。
According to the modeling method of the present invention, the piezoelectric polymer can be modeled into structures of various shapes, and at the same time, excellent piezoelectric characteristics can be expressed.
以下、本発明の圧電性高分子の造形方法について説明する。
Hereinafter, a method for forming a piezoelectric polymer of the present invention will be described.
なお、本明細書において、「圧電性高分子」とは、その分子が一軸配向した場合に、圧電性を発現し得る高分子であり、ヘリカルキラリティを有する高分子を言う。
In the present specification, “piezoelectric polymer” refers to a polymer that can exhibit piezoelectricity when the molecule is uniaxially oriented and has helical chirality.
本発明の方法において、圧電性高分子の造形は、ノズルから圧電性高分子を含む造形材料を吐出して造形する三次元造形装置を用いて行われる。
In the method of the present invention, modeling of the piezoelectric polymer is performed using a three-dimensional modeling apparatus that models by modeling a modeling material containing the piezoelectric polymer from a nozzle.
ここに、本明細書において、「三次元造形装置」とは、構造体の三次元立体情報に関する入力情報を基に三次元の構造体を造形する装置を意味し、一般的に、ノズルから溶融または軟化した造形材料を吐出し、造形テーブル上に造形材料を所定のパターンで順次積層することによって、構造体を造形する。このような三次元造形装置としては、特に限定されないが、例えば積層型の3Dプリンタが挙げられる。
Here, in this specification, the “three-dimensional modeling apparatus” means an apparatus that models a three-dimensional structure based on input information related to the three-dimensional solid information of the structure, and is generally melted from a nozzle. Alternatively, the softened modeling material is discharged, and the structure is modeled by sequentially stacking the modeling material in a predetermined pattern on the modeling table. Such a three-dimensional modeling apparatus is not particularly limited, and examples thereof include a stacked 3D printer.
本発明の造形方法においては、圧電性高分子を含む造形材料を、三次元造形装置のノズルから吐出し、造形する構造体の断面形状に対応した層を順次積層することにより、構造体を造形する。造形材料を積層する際、ノズルで造形材料を引っ張りながら積層することにより、造形材料が延伸され、圧電性高分子の分子が延伸方向に沿って、即ちノズルの移動方向に沿って配向し、圧電性が発現する。
In the modeling method of the present invention, a modeling material is formed by discharging a modeling material containing a piezoelectric polymer from a nozzle of a three-dimensional modeling apparatus and sequentially laminating layers corresponding to the cross-sectional shape of the structure to be modeled. To do. When the modeling material is stacked, the modeling material is stretched by pulling the modeling material with a nozzle, and the molecules of the piezoelectric polymer are oriented along the stretching direction, that is, along the moving direction of the nozzle. Sex is expressed.
本発明の造形方法において、造形材料としては、圧電性高分子を含む材料が用いられる。
In the modeling method of the present invention, a material containing a piezoelectric polymer is used as the modeling material.
当該圧電性高分子としては、ポリ乳酸、ポリペプチド、ポリメチルグルタメート、ポリベンジルグルタメート等のキラリティを持ち主鎖がらせんを描く高分子が挙げられ、ポリ乳酸または乳酸を構成単位として含む共重合体が好ましく、ポリ乳酸がさらに好ましい。当該ポリ乳酸は、L体またはD体のいずれであってもよいが、入手が容易であるL体から構成されるポリ乳酸が好ましい。
Examples of the piezoelectric polymer include polymers having a chirality such as polylactic acid, polypeptide, polymethylglutamate, polybenzylglutamate and the like in which the main chain draws a helix, and polylactic acid or a copolymer containing lactic acid as a structural unit. Preferably, polylactic acid is more preferable. The polylactic acid may be either L-form or D-form, but polylactic acid composed of L-form which is easily available is preferable.
本発明の造形方法に付される圧電性高分子を含む造形材料は、圧電性高分子を主成分とする材料であり、例えば圧電性高分子の含有量が50質量%以上、60質量%以上、70質量%以上、または80質量%以上含む材料、あるいは実質的に圧電性高分子から成る材料、例えば圧電性高分子の含有量が99~100質量%である材料が挙げられる。
The modeling material including the piezoelectric polymer applied to the modeling method of the present invention is a material mainly composed of the piezoelectric polymer. For example, the content of the piezoelectric polymer is 50% by mass or more and 60% by mass or more. 70% by mass or more, or a material containing 80% by mass or more, or a material substantially composed of a piezoelectric polymer, for example, a material having a piezoelectric polymer content of 99 to 100% by mass.
上記圧電性高分子の重量平均分子量は、特に限定されないが、例えばポリ乳酸である場合、好ましくは約10,000~1,000,000、より好ましくは約15,000~400,000、さらに好ましくは約20,000~250,000である。重量平均分子量を、約10,000以上とすることにより、得られる構造体の機械的強度および弾性を確保することができる。また、重量平均分子量を、約1,000,000以下とすることにより、より配向させることができる。
The weight average molecular weight of the piezoelectric polymer is not particularly limited. For example, in the case of polylactic acid, it is preferably about 10,000 to 1,000,000, more preferably about 15,000 to 400,000, and still more preferably. Is about 20,000-250,000. By setting the weight average molecular weight to about 10,000 or more, the mechanical strength and elasticity of the resulting structure can be ensured. Further, when the weight average molecular weight is about 1,000,000 or less, it can be more oriented.
一の態様において、圧電性高分子を含む造形材料は、柔軟化剤を含んでいてもよい。当該添加剤を用いることにより、圧電性高分子から形成された材料の柔軟性が増し、ノズルからの吐出が容易になる。
In one embodiment, the modeling material containing the piezoelectric polymer may contain a softening agent. By using the additive, the flexibility of the material formed from the piezoelectric polymer is increased, and the discharge from the nozzle becomes easy.
当該柔軟化剤としては、特に限定されないが、圧電性高分子がポリ乳酸である場合、ポリマー末端のカルボン酸基または水酸基との親和性または反応性を有するエラストマーが好ましい。このようなエラストマーとしては、カルボン酸基または水酸基との親和性に優れる官能基、例えばアミン、エポキシ、無水カルボン酸などを付加したスチレン系エラストマー(例えば、SBS(スチレン・ブタジエン・スチレンブロックコポリマー)やこれを水素添加して得られるSEBS(スチレン・エチレン/ブタジエン・スチレンブロックコポリマー))、同様の官能基を付加したオレフィン系エラストマー、およびポリヒドロキシブチレート系軟質系コポリマー(アミン末端を持つスチレン系エラストマー)などが挙げられる。具体的には、ポリアルキルメタクリレートとポリアルキルアクリレートのブロック共重合体、例えばPMMA-PnBA-PMMA(ポリメタクリル酸メチル-ポリアクリル酸n-ブチル-ポリメタクリル酸メチル)ブロック共重合体が挙げられる。当該ブロック共重合体は、例えば株式会社クラレ社製のLA2250(商品名)、LA2140(商品名)、LA4285(商品名)等として入手することができる。
The softening agent is not particularly limited, but when the piezoelectric polymer is polylactic acid, an elastomer having affinity or reactivity with a carboxylic acid group or a hydroxyl group at the polymer terminal is preferable. Examples of such elastomers include styrene-based elastomers (for example, SBS (styrene-butadiene-styrene block copolymer), etc., to which functional groups having excellent affinity for carboxylic acid groups or hydroxyl groups, such as amines, epoxies, and carboxylic anhydrides, are added. SEBS (Styrene / Ethylene / Butadiene / Styrene Block Copolymer) obtained by hydrogenation of this, an olefin-based elastomer with the same functional group added, and a polyhydroxybutyrate-based soft copolymer (a styrene-based elastomer having an amine terminal) ) And the like. Specifically, a block copolymer of polyalkyl methacrylate and polyalkyl acrylate, for example, PMMA-PnBA-PMMA (polymethyl methacrylate-poly (n-butyl acrylate) -polymethyl methacrylate) block copolymer may be mentioned. The block copolymer can be obtained, for example, as LA2250 (trade name), LA2140 (trade name), LA4285 (trade name), etc., manufactured by Kuraray Co., Ltd.
上記柔軟化剤の添加量は、圧電性高分子と柔軟化剤の総量に対して、約0.1~50質量%、好ましくは約1~30質量%である。当該添加量を約1質量%以上とすることにより、ノズルからの吐出が容易になる。また、当該添加量を約40質量%以下とすることにより、得られる構造体の弾性率および圧電率の低下を抑制することができる。
The amount of the softening agent added is about 0.1 to 50% by mass, preferably about 1 to 30% by mass, based on the total amount of the piezoelectric polymer and the softening agent. By making the addition amount about 1% by mass or more, discharge from the nozzle becomes easy. Moreover, the fall of the elastic modulus and piezoelectricity of the structure obtained can be suppressed by making the said addition amount into about 40 mass% or less.
また、本発明の造形方法に用いられる圧電性高分子を含む造形材料は、さらに別の添加剤、例えば、着色剤、可塑剤等を含んでいてもよい。
Moreover, the modeling material containing the piezoelectric polymer used in the modeling method of the present invention may further contain another additive, such as a colorant or a plasticizer.
本発明の造形方法に用いられる圧電性高分子を含む造形材料の形状は、一般的に三次元造形装置で用いることができる形状であれば特に限定されず、例えばペレット状であり得る。
The shape of the modeling material including the piezoelectric polymer used in the modeling method of the present invention is not particularly limited as long as it is generally a shape that can be used in a three-dimensional modeling apparatus, and may be, for example, a pellet shape.
一の態様において、三次元造形装置の造形材料を吐出するノズルの温度、即ち、吐出される造形材料の温度は、圧電性高分子の結晶化温度以上、融点未満の温度であってもよい。例えば、造形材料として、重量平均分子量100,000のポリ乳酸(結晶化温度=約110℃;融点=約180℃)を用いる場合、当該温度は、例えば、約110℃~175℃であり、好ましくは約130~170℃、より好ましくは約150~165℃である。当該温度を結晶化温度以上とすることにより、造形材料の粘度を低下させ、ノズルからの吐出を容易にすることができる。一方、当該温度を融点未満の温度とすることにより、圧電性高分子をより配向させることが可能になり、得られる構造体の圧電率を向上させることができる。尚、ノズルの温度が融点に近づくに従って造形材料の粘度が上昇し、ノズルからの吐出が困難になっていくが、補助手段を用いることにより、例えばノズルから造形材料を押し出すように圧力を加えることにより、吐出を補助するができる。
In one aspect, the temperature of the nozzle for discharging the modeling material of the three-dimensional modeling apparatus, that is, the temperature of the discharged modeling material may be a temperature equal to or higher than the crystallization temperature of the piezoelectric polymer and lower than the melting point. For example, when polylactic acid having a weight average molecular weight of 100,000 (crystallization temperature = about 110 ° C .; melting point = about 180 ° C.) is used as the modeling material, the temperature is, for example, about 110 ° C. to 175 ° C., preferably Is about 130-170 ° C, more preferably about 150-165 ° C. By making the said temperature more than crystallization temperature, the viscosity of modeling material can be reduced and discharge from a nozzle can be made easy. On the other hand, by setting the temperature to a temperature lower than the melting point, the piezoelectric polymer can be more oriented and the piezoelectricity of the resulting structure can be improved. As the nozzle temperature approaches the melting point, the viscosity of the modeling material increases and it becomes difficult to discharge from the nozzle. By using auxiliary means, for example, pressure is applied so as to extrude the modeling material from the nozzle. Thus, discharge can be assisted.
上記「結晶化温度」および「融点」は、示差走査熱量測定 DSC(Differential scanning calorimetry)により測定することができる。
The above “crystallization temperature” and “melting point” can be measured by differential scanning calorimetry—DSC (Differential scanning calorimetry).
好ましい態様において、造形材料が吐出される造形箇所(例えば、積層型の三次元造形装置を用いる場合は、ノズルから吐出された造形材料を積層する箇所、即ち、第1層の場合は三次元造形装置の造形テーブル、2層目以降の場合は下層)の温度は、圧電性高分子の融点よりも、約10℃~50℃、例えば約20℃~30℃低い温度であり得る。好ましくは、この温度は、ノズルの温度よりも低く設定され得る。このように造形材料を積層する箇所の温度を、圧電性高分子の融点よりも約10℃~50℃低く、好ましくはノズルの温度よりも低い温度とすることにより、ノズルから吐出された造形材料は、積層箇所に触れた際の、積層箇所への付着性が向上する。その結果、その付着箇所を基点にして、ノズルの移動により積層しながら造形材料を延伸することが容易になる。
In a preferred embodiment, a modeling part from which the modeling material is discharged (for example, in the case of using a laminated three-dimensional modeling apparatus, a part where the modeling material discharged from the nozzle is stacked, that is, in the case of the first layer, three-dimensional modeling. The temperature of the molding table of the device, the lower layer in the case of the second and subsequent layers, can be about 10 ° C. to 50 ° C., for example about 20 ° C. to 30 ° C. lower than the melting point of the piezoelectric polymer. Preferably, this temperature can be set lower than the temperature of the nozzle. Thus, the molding material discharged from the nozzle is set so that the temperature at which the modeling material is laminated is about 10 ° C. to 50 ° C. lower than the melting point of the piezoelectric polymer, preferably lower than the temperature of the nozzle. Is improved in adhesion to the laminated part when the laminated part is touched. As a result, it becomes easy to stretch the modeling material while laminating by the movement of the nozzle, with the adhesion site as a base point.
尚、ノズル温度および造形箇所の温度は、造形中、必ずしも一定の温度である必要はなく、造形する構造体の形状、圧電性部位の位置および圧電特性に応じて適宜調整することができる。
In addition, the nozzle temperature and the temperature of the modeling location do not necessarily need to be constant during modeling, and can be appropriately adjusted according to the shape of the structure to be modeled, the position of the piezoelectric portion, and the piezoelectric characteristics.
一の態様において、三次元造形装置における造形材料を吐出するノズルの移動速度は、ノズルからの造形材料の吐出速度よりも速い。例えば、ノズルの移動速度は、造形材料の吐出速度の約1.5倍以上、好ましくは約2倍以上、より好ましくは約4倍以上である。ノズルの移動速度を造形材料の吐出速度よりも速くすることにより、吐出された造形材料は、ノズルに引っ張られて延伸する。その結果、圧電性高分子をより配向させることができる。また、造形の精度を高める観点からは、ノズルの移動速度は、例えば、造形材料の吐出速度の約10倍以下、好ましくは約7倍以下である。
In one aspect, the moving speed of the nozzle for discharging the modeling material in the three-dimensional modeling apparatus is faster than the discharging speed of the modeling material from the nozzle. For example, the moving speed of the nozzle is about 1.5 times or more, preferably about 2 times or more, more preferably about 4 times or more the discharge speed of the modeling material. By making the moving speed of the nozzle faster than the discharge speed of the modeling material, the discharged modeling material is pulled by the nozzle and stretched. As a result, the piezoelectric polymer can be more oriented. Further, from the viewpoint of increasing the accuracy of modeling, the moving speed of the nozzle is, for example, about 10 times or less, preferably about 7 times or less, the ejection speed of the modeling material.
ここに、ノズルからの圧電性高分子を含む造形材料の吐出速度とは、単位時間当たりに、ノズルから吐出される造形材料の長さであり、単位時間当たりの造形材料の吐出流量(単位時間当たりに吐出される造形材料の体積)を、ノズルの吐出口の断面積で除することにより算出することができる。
Here, the discharge speed of the modeling material containing the piezoelectric polymer from the nozzle is the length of the modeling material discharged from the nozzle per unit time, and the discharge flow rate of the modeling material per unit time (unit time) The volume of the modeling material discharged per hit) can be calculated by dividing by the cross-sectional area of the nozzle outlet.
好ましい態様において、三次元造形装置のノズルの移動速度は、0.1~100mm/秒、好ましくは1~30mm/秒、好ましくは5~15mm/秒である。ノズルの移動速度を、0.1mm/秒以上とすることにより、圧電性高分子をより配向させることができる。一方、ノズルの移動速度を、100mm/秒以下とすることにより、より精密な立体構造体を得ることができる。
In a preferred embodiment, the moving speed of the nozzle of the three-dimensional modeling apparatus is 0.1 to 100 mm / second, preferably 1 to 30 mm / second, preferably 5 to 15 mm / second. By setting the moving speed of the nozzle to 0.1 mm / second or more, the piezoelectric polymer can be more oriented. On the other hand, a more precise three-dimensional structure can be obtained by setting the moving speed of the nozzle to 100 mm / second or less.
ここに、本明細書において、「ノズルの移動速度」とは、ノズル自体の移動速度のみを意味するものではなく、造形材料が吐出される造形箇所(積層箇所)との相対速度を意味する。例えば、ノズルが固定されており、造形テーブルが移動することにより造形を行う三次元造形装置においては、ノズルの移動速度とは、造形テーブルの移動速度となる。また、ノズルが断続的に移動する場合は、ある一定の時間(例えば、1秒)における平均の速度を、「ノズルの移動速度」としてもよい。
Here, in this specification, the “moving speed of the nozzle” does not mean only the moving speed of the nozzle itself, but means the relative speed with respect to the modeling location (lamination location) where the modeling material is discharged. For example, in a three-dimensional modeling apparatus in which the nozzle is fixed and modeling is performed by moving the modeling table, the moving speed of the nozzle is the moving speed of the modeling table. When the nozzle moves intermittently, an average speed in a certain time (for example, 1 second) may be set as the “nozzle moving speed”.
尚、ノズルの移動速度は、造形中、必ずしも一定の速度である必要はなく、造形する構造体の形状、圧電性部位の位置および圧電特性に応じて適宜調整することができる。
In addition, the moving speed of the nozzle does not necessarily have to be a constant speed during modeling, and can be appropriately adjusted according to the shape of the structure to be modeled, the position of the piezoelectric portion, and the piezoelectric characteristics.
また、ノズルの移動は、連続的であっても、断続的であってもよい。好ましい態様において、ノズルは、吐出した造形材料が上記した造形箇所の温度と実質的に同じ温度になるまで実質的に停止し、その後、所定の距離を移動してもよい。このようにノズルを断続的に移動させて造形を行うことにより、高分子材料をより配向させることができる。
Further, the movement of the nozzle may be continuous or intermittent. In a preferred embodiment, the nozzle may stop substantially until the discharged modeling material reaches substantially the same temperature as the temperature of the above-described modeling location, and then move a predetermined distance. Thus, the polymer material can be oriented more by moving the nozzle intermittently to perform modeling.
一の態様において、造形材料は、少なくともその一部が約1.5倍以上、好ましくは約2倍以上、より好ましくは約4倍以上に延伸される。即ち、延伸倍率が、約1.5倍以上、好ましくは約2倍以上、より好ましくは約4倍以上である。延伸倍率を約1.5倍以上とすることにより、特に4倍以上とすることにより、圧電性高分子の分子をより良好に配向させることができ、より高い圧電率を得ることができる。また、得られる構造体の強度を確保する観点から、延伸倍率は、好ましくは約10倍以下であり、より好ましくは約7倍以下である。
In one embodiment, at least a part of the modeling material is stretched by about 1.5 times or more, preferably about 2 times or more, more preferably about 4 times or more. That is, the draw ratio is about 1.5 times or more, preferably about 2 times or more, more preferably about 4 times or more. By setting the draw ratio to about 1.5 times or more, and particularly to 4 times or more, the molecules of the piezoelectric polymer can be more favorably oriented, and a higher piezoelectric rate can be obtained. Further, from the viewpoint of securing the strength of the resulting structure, the draw ratio is preferably about 10 times or less, more preferably about 7 times or less.
延伸倍率は、例えば、ノズルの移動速度を、ノズルからの造形材料の吐出速度で除することにより算出することができる。
The draw ratio can be calculated, for example, by dividing the moving speed of the nozzle by the discharge speed of the modeling material from the nozzle.
好ましい態様において、本発明の造形方法は、ノズルから圧電性高分子を含む造形材料を吐出して造形する三次元造形装置を用いて、圧電性部位を有する構造体に造形すること;
上記三次元造形装置の造形材料を吐出するノズルの温度が、圧電性高分子の結晶化温度以上、融点未満の温度であること;
上記三次元造形装置のノズルの移動速度が、圧電性高分子を含む造形材料の吐出速度よりも速いこと;および
積層された圧電性高分子の少なくとも一部の延伸倍率が、1.5倍以上であること
を特徴とする。 In a preferred embodiment, the modeling method of the present invention forms a structure having a piezoelectric portion using a three-dimensional modeling apparatus for modeling by discharging a modeling material containing a piezoelectric polymer from a nozzle;
The temperature of the nozzle for discharging the modeling material of the three-dimensional modeling apparatus is not less than the crystallization temperature of the piezoelectric polymer and less than the melting point;
The moving speed of the nozzle of the three-dimensional modeling apparatus is faster than the ejection speed of the modeling material containing the piezoelectric polymer; and the stretching ratio of at least a part of the laminated piezoelectric polymer is 1.5 times or more It is characterized by being.
上記三次元造形装置の造形材料を吐出するノズルの温度が、圧電性高分子の結晶化温度以上、融点未満の温度であること;
上記三次元造形装置のノズルの移動速度が、圧電性高分子を含む造形材料の吐出速度よりも速いこと;および
積層された圧電性高分子の少なくとも一部の延伸倍率が、1.5倍以上であること
を特徴とする。 In a preferred embodiment, the modeling method of the present invention forms a structure having a piezoelectric portion using a three-dimensional modeling apparatus for modeling by discharging a modeling material containing a piezoelectric polymer from a nozzle;
The temperature of the nozzle for discharging the modeling material of the three-dimensional modeling apparatus is not less than the crystallization temperature of the piezoelectric polymer and less than the melting point;
The moving speed of the nozzle of the three-dimensional modeling apparatus is faster than the ejection speed of the modeling material containing the piezoelectric polymer; and the stretching ratio of at least a part of the laminated piezoelectric polymer is 1.5 times or more It is characterized by being.
好ましい態様において、本発明の方法は、造形後、得られた構造体を冷却、好ましくは急冷することを含む。急冷することにより、圧電性に悪影響を及ぼす球晶の生成を抑制することができ、圧電性高分子の配向をより安定化することができる。
In a preferred embodiment, the method of the present invention includes cooling, preferably quenching, the resulting structure after shaping. By rapidly cooling, the formation of spherulites that adversely affect the piezoelectricity can be suppressed, and the orientation of the piezoelectric polymer can be further stabilized.
上記のような本発明の造形方法によれば、圧電性高分子を、圧電性部位を有する様々な形状の構造体に造形することが可能になる。また、本発明の造形方法によれば、ノズルの速度および造形材料の吐出速度を調整することにより、造形材料の延伸倍率および配向性を制御することができるので、構造体の任意の箇所に圧電性部位を形成することができ、また、その圧電特性も制御することが可能になる。
According to the modeling method of the present invention as described above, the piezoelectric polymer can be modeled into various shapes of structures having piezoelectric sites. Further, according to the modeling method of the present invention, the stretching ratio and orientation of the modeling material can be controlled by adjusting the speed of the nozzle and the discharge speed of the modeling material. It is possible to form a sex site and control its piezoelectric characteristics.
従って、本発明は、上記本発明の造形方法により得られる、圧電性部位を有する構造体をも提供する。
Therefore, the present invention also provides a structure having a piezoelectric portion obtained by the modeling method of the present invention.
ここに、「圧電性部位」とは、圧電性を示す部位を意味する。圧電性部位の圧電率は、0.5pC/N以上であり、好ましくは2pC/N以上であり、より好ましくは3pC/N以上であり、さらに好ましくは5pC/N以上である。本発明の構造体において、圧電性部位は、構造体全体に存在してもよく、一部または複数箇所に存在してもよい。
Here, the “piezoelectric part” means a part showing piezoelectricity. The piezoelectricity of the piezoelectric portion is 0.5 pC / N or more, preferably 2 pC / N or more, more preferably 3 pC / N or more, and further preferably 5 pC / N or more. In the structure of the present invention, the piezoelectric portion may exist in the entire structure, or may exist in a part or a plurality of locations.
本発明の造形方法により得られる構造体の圧電性部位は、0.1×10-3以上、より好ましくは1×10-3以上、さらに好ましくは10×10-3以上の配向複屈折を有する。
The piezoelectric portion of the structure obtained by the modeling method of the present invention has an orientation birefringence of 0.1 × 10 −3 or more, more preferably 1 × 10 −3 or more, and further preferably 10 × 10 −3 or more. .
本発明の造形方法により得られる構造体の圧電性部位において、圧電性高分子の分子は、ノズルの移動方向に沿って配向している。
In the piezoelectric portion of the structure obtained by the modeling method of the present invention, the molecules of the piezoelectric polymer are oriented along the moving direction of the nozzle.
本発明の構造体は、様々な形状を有し得るので、圧電性材料としての機能を有しつつ、電子機器の筐体等としても用いることができる。
Since the structure of the present invention can have various shapes, it can be used as a housing of an electronic device while having a function as a piezoelectric material.
本発明の造形方法により得られる構造体は、圧電性を有するので、感圧センサーとして機能し得る。したがって、本発明は、
本発明の造形方法により得られる構造体と、
その圧電性部位に設置された少なくとも一対の電極と
を有して成る、感圧センサーをも提供する。 Since the structure obtained by the modeling method of the present invention has piezoelectricity, it can function as a pressure-sensitive sensor. Therefore, the present invention
A structure obtained by the modeling method of the present invention;
There is also provided a pressure-sensitive sensor comprising at least a pair of electrodes disposed on the piezoelectric portion.
本発明の造形方法により得られる構造体と、
その圧電性部位に設置された少なくとも一対の電極と
を有して成る、感圧センサーをも提供する。 Since the structure obtained by the modeling method of the present invention has piezoelectricity, it can function as a pressure-sensitive sensor. Therefore, the present invention
A structure obtained by the modeling method of the present invention;
There is also provided a pressure-sensitive sensor comprising at least a pair of electrodes disposed on the piezoelectric portion.
上記したように本発明の構造体は、様々な形状を有し得るので、これを用いる本発明の感圧センサーは、様々な形状とすることができる。したがって、例えば、従来ABS(アクリロニトリル-ブタジエン-スチレン)樹脂、アクリル樹脂等で形成されていた電子機器の筐体を、本発明の造形方法を用いて圧電性高分子で形成することにより、筐体自体に感圧センサーとしての機能を持たせることが可能になる。このように1つの部品に複数の機能を持たせることは、機器の小型化の点からも有利である。
As described above, since the structure of the present invention can have various shapes, the pressure-sensitive sensor of the present invention using the structure can have various shapes. Therefore, for example, by forming a casing of an electronic device, which has been conventionally formed of ABS (acrylonitrile-butadiene-styrene) resin, acrylic resin, or the like, using the molding method of the present invention, the casing is formed. It becomes possible to give itself a function as a pressure-sensitive sensor. Providing a single component with a plurality of functions in this way is advantageous from the viewpoint of downsizing the device.
以下、本発明の感圧センサーについて、図面を参照しながら、詳細に説明する。
Hereinafter, the pressure sensor of the present invention will be described in detail with reference to the drawings.
本実施形態の感圧センサー1を図1に模式的に示す。本実施形態の感圧センサー1は、圧電性高分子から形成された構造体2と、その側面(図1においては左側面14)に設置された電極6a、6bを有する。電極は対になっており、構造体側面を介して対向して設けられている。
FIG. 1 schematically shows a pressure-sensitive sensor 1 according to this embodiment. The pressure-sensitive sensor 1 of this embodiment includes a structure 2 formed of a piezoelectric polymer and electrodes 6a and 6b installed on the side surface (left side surface 14 in FIG. 1). The electrodes are paired and provided to face each other through the structure side surface.
構造体2は、圧電性高分子を含む造形材料を、三次元造形装置を用いる本発明の造形方法を用いて造形することにより得ることができる。本発明の造形方法を用いて得られた構造体2は、三次元造形装置のノズルの移動方向に沿って、圧電性高分子の分子が配向している。このように圧電性高分子が配向した箇所が、圧電性部位となる。
The structure 2 can be obtained by modeling a modeling material containing a piezoelectric polymer using the modeling method of the present invention using a three-dimensional modeling apparatus. In the structure 2 obtained using the modeling method of the present invention, the molecules of the piezoelectric polymer are oriented along the moving direction of the nozzle of the three-dimensional modeling apparatus. Thus, the location where the piezoelectric polymer is oriented becomes the piezoelectric portion.
構造体2を構成する圧電性高分子は、上記造形方法において記載した圧電性高分子を用いることができる。例えば、ヘリカルキラリティを有する圧電性高分子、具体的には、ポリ乳酸、ポリペプチド、ポリメチルグルタメート、ポリベンジルグルタメート等のキラリティを持ち主鎖がらせんを描く高分子が挙げられる。ポリ乳酸または乳酸を構成単位として含む共重合体が好ましく、ポリ乳酸がさらに好ましい。
As the piezoelectric polymer constituting the structure 2, the piezoelectric polymer described in the modeling method can be used. For example, a piezoelectric polymer having helical chirality, specifically, a polymer having chirality such as polylactic acid, polypeptide, polymethylglutamate, polybenzylglutamate and the like in which the main chain draws a helix. Polylactic acid or a copolymer containing lactic acid as a structural unit is preferable, and polylactic acid is more preferable.
電極6a、6bは、例えば、所定の大きさの金属の薄膜を、図1に示すように構造体2の下段部(深部)における左側面14の略中央に左側面を介して対向して配置し、その上にリード(図示していない)を配置し、次いで、電極およびリードとの接続部を樹脂(例えば、エポキシ樹脂、アクリル樹脂)で覆うことにより設置することができる。これらの電極により構造体2に力が作用した際に生じる電圧を検出する。
The electrodes 6a and 6b are, for example, a metal thin film having a predetermined size, which is disposed so as to be opposed to the approximate center of the left side surface 14 in the lower part (deep part) of the structure 2 via the left side as shown in FIG. Then, a lead (not shown) may be disposed thereon, and then the electrode and the lead connecting portion may be covered with a resin (for example, epoxy resin or acrylic resin). A voltage generated when force is applied to the structure 2 by these electrodes is detected.
上記電極を形成する導電性材料は、特に限定されるものではないが、例えばAu、Cu、Ag、Ni等が挙げられ、特にAuが好ましい。電極の形成方法としては、特に限定されず、上記した方法の他に、例えば上記金属の薄膜を導電性接着材で貼り付けるなどの方法によっても形成することができる。
The conductive material forming the electrode is not particularly limited, and examples thereof include Au, Cu, Ag, Ni, and the like, and Au is particularly preferable. The method for forming the electrode is not particularly limited, and in addition to the above-described method, for example, the electrode can be formed by a method such as attaching the metal thin film with a conductive adhesive.
本発明の感圧センサーは、上記した本発明の造形方法を利用して製造できるので、本発明の造形方法で製造可能なあらゆる形状とすることができる。したがって、本発明の造形方法により、圧電性高分子を、例えば、携帯電話または携帯ゲーム機の筐体あるいはそれらの一部として造形することによって、それに感圧センサーとしての機能を付与することができる。
Since the pressure-sensitive sensor of the present invention can be manufactured using the above-described modeling method of the present invention, it can have any shape that can be manufactured by the modeling method of the present invention. Therefore, by the modeling method of the present invention, the piezoelectric polymer can be modeled, for example, as a casing of a mobile phone or a portable game machine or a part thereof, thereby giving a function as a pressure sensitive sensor. .
以上、本発明の一の実施形態により本発明の感圧センサーを説明したが、本発明はこれに限定されるものではない。
As mentioned above, although the pressure-sensitive sensor of this invention was demonstrated by one Embodiment of this invention, this invention is not limited to this.
また、本発明に用いられるポリ乳酸のような圧電性高分子は圧電性、特にずり圧電性を有し得るので、本発明の方法により得られる構造体は、アクチュエータに用いることができる。したがって、本発明は、
本発明の造形方法により得られる構造体と、
その圧電性部位に設置された少なくとも一対の電極と
を有して成る、アクチュエータをも提供する。 In addition, since a piezoelectric polymer such as polylactic acid used in the present invention can have piezoelectricity, particularly shear piezoelectricity, the structure obtained by the method of the present invention can be used for an actuator. Therefore, the present invention
A structure obtained by the modeling method of the present invention;
There is also provided an actuator comprising at least a pair of electrodes disposed at the piezoelectric portion.
本発明の造形方法により得られる構造体と、
その圧電性部位に設置された少なくとも一対の電極と
を有して成る、アクチュエータをも提供する。 In addition, since a piezoelectric polymer such as polylactic acid used in the present invention can have piezoelectricity, particularly shear piezoelectricity, the structure obtained by the method of the present invention can be used for an actuator. Therefore, the present invention
A structure obtained by the modeling method of the present invention;
There is also provided an actuator comprising at least a pair of electrodes disposed at the piezoelectric portion.
アクチュエータとしては、駆動装置、圧電スピーカー、振動発生装置、ハプティクス等が挙げられる。
Actuators include drive devices, piezoelectric speakers, vibration generators, haptics, and the like.
一の態様において、アクチュエータは、例えば、特開2012-157235号に開示されるような、圧電性高分子から形成された薄膜と、該薄膜の第1の主面に形成された第1の電極と、該薄膜の第2の主面に形成された第2の電極を備え、該第1の電極と該第2の電極間に所定の交流電圧を印加することで該薄膜の少なくとも一の端縁部において駆動力を発生させるアクチュエータ、例えば駆動装置であり得る。この態様においては、圧電性高分子から形成された薄膜は、本発明の造形方法により形成される。好ましくは、該薄膜は、円筒状であり得る。
In one aspect, the actuator includes a thin film formed of a piezoelectric polymer and a first electrode formed on a first main surface of the thin film as disclosed in, for example, Japanese Patent Application Laid-Open No. 2012-157235. And a second electrode formed on the second main surface of the thin film, and applying a predetermined alternating voltage between the first electrode and the second electrode, thereby at least one end of the thin film It can be an actuator that generates a driving force at the edge, for example a driving device. In this aspect, the thin film formed from the piezoelectric polymer is formed by the modeling method of the present invention. Preferably, the thin film can be cylindrical.
また、別の態様において、アクチュエータは、例えば、圧電性高分子から形成された圧電性部位と、該圧電性部位の第1の主面に位置する第1電極と、該圧電性部位の第2の主面に位置する第2電極とを有する振動発生装置またはスピーカーであり得る。この態様においては、圧電性高分子から形成された圧電性部位は、本発明の造形方法により形成される。好ましくは、該圧電性部位は、円筒状に形成される。
In another aspect, the actuator includes, for example, a piezoelectric part formed of a piezoelectric polymer, a first electrode located on the first main surface of the piezoelectric part, and a second part of the piezoelectric part. The vibration generating device or the speaker having the second electrode located on the main surface of the speaker. In this aspect, the piezoelectric part formed from the piezoelectric polymer is formed by the modeling method of the present invention. Preferably, the piezoelectric portion is formed in a cylindrical shape.
尚、本発明のアクチュエータは、上記の態様に限定されるものではない。
Note that the actuator of the present invention is not limited to the above embodiment.
以下の実施例において、本発明についてより具体的に説明するが、本発明はこれら実施例に限定されるものではない。
In the following examples, the present invention will be described more specifically, but the present invention is not limited to these examples.
実施例1
市販の3Dプリンタ(3Dシステムズ社製、Cube)を用いて、下記する条件で、縦110mm×横60mm×高さ10mmの寸法を有し、各面の厚みが1mmである箱形の構造体(図1の構造体2に対応する)を造形した。構造体の右側面(図1の右側面14に対応する)を形成する際のノズルの移動方向は、図1の矢印Aで示される方向であった。
造形材料:ポリ乳酸(ペレット状、多木化学社製、数平均分子量7000)
ノズル(ヘッド)スピード:10mm/秒
ノズル温度:190℃
ノズル口断面積:0.1mm2
造形テーブル温度:120℃
吐出流量:1ml/分
Example 1
Using a commercially available 3D printer (Cube manufactured by 3D Systems, Inc.), a box-shaped structure having dimensions of 110 mm in length, 60 mm in width, and 10 mm in height, and having a thickness of 1 mm on each surface (described below) 1 corresponding to thestructure 2 in FIG. The movement direction of the nozzle when forming the right side surface of the structure (corresponding to the right side surface 14 in FIG. 1) was the direction indicated by the arrow A in FIG.
Modeling material: Polylactic acid (pellet, manufactured by Taki Chemical Co., Ltd., number average molecular weight 7000)
Nozzle (head) speed: 10 mm / sec Nozzle temperature: 190 ° C
Nozzle mouth cross-sectional area: 0.1 mm 2
Molding table temperature: 120 ° C
Discharge flow rate: 1 ml / min
市販の3Dプリンタ(3Dシステムズ社製、Cube)を用いて、下記する条件で、縦110mm×横60mm×高さ10mmの寸法を有し、各面の厚みが1mmである箱形の構造体(図1の構造体2に対応する)を造形した。構造体の右側面(図1の右側面14に対応する)を形成する際のノズルの移動方向は、図1の矢印Aで示される方向であった。
造形材料:ポリ乳酸(ペレット状、多木化学社製、数平均分子量7000)
ノズル(ヘッド)スピード:10mm/秒
ノズル温度:190℃
ノズル口断面積:0.1mm2
造形テーブル温度:120℃
吐出流量:1ml/分
Example 1
Using a commercially available 3D printer (Cube manufactured by 3D Systems, Inc.), a box-shaped structure having dimensions of 110 mm in length, 60 mm in width, and 10 mm in height, and having a thickness of 1 mm on each surface (described below) 1 corresponding to the
Modeling material: Polylactic acid (pellet, manufactured by Taki Chemical Co., Ltd., number average molecular weight 7000)
Nozzle (head) speed: 10 mm / sec Nozzle temperature: 190 ° C
Nozzle mouth cross-sectional area: 0.1 mm 2
Molding table temperature: 120 ° C
Discharge flow rate: 1 ml / min
上記のようにして得られた構造体の右側面に1対の金箔(縦6mm×横12mm)を、各対の金箔が構造体の側面を介して対向するように3対貼り付け(図1の電極上部電極4a,b、中部電極6a,b、下部電極8a,bに対応する)、さらにその上に配線用のリードを配置して、これらの上からエポキシ樹脂でコーティングを施し、図1に示すような本発明の感圧センサーを作製した。
A pair of gold foils (length 6 mm × width 12 mm) is attached to the right side of the structure obtained as described above, and three pairs are attached so that each pair of gold foils faces each other through the side surface of the structure (FIG. 1). 1 corresponding to the upper electrode electrodes 4a and 4b, the middle electrodes 6a and b, and the lower electrodes 8a and b), and leads for wiring are arranged thereon, and coating with epoxy resin is performed on these, FIG. A pressure-sensitive sensor of the present invention as shown in FIG.
試験例1
実施例1で得られた感圧センサーの上部電極4、中部電極6および下部電極8を指で押し、生じる電圧を測定した。結果を、図2に示す。 Test example 1
The upper electrode 4, the middle electrode 6 and the lower electrode 8 of the pressure sensor obtained in Example 1 were pressed with a finger, and the resulting voltage was measured. The results are shown in FIG.
実施例1で得られた感圧センサーの上部電極4、中部電極6および下部電極8を指で押し、生じる電圧を測定した。結果を、図2に示す。 Test example 1
The upper electrode 4, the middle electrode 6 and the lower electrode 8 of the pressure sensor obtained in Example 1 were pressed with a finger, and the resulting voltage was measured. The results are shown in FIG.
図2から明らかなように、側面部の電極に力を加えた場合、電圧が検出され、センサーとして機能することが確認された。
As is clear from FIG. 2, when a force is applied to the electrode on the side surface, a voltage is detected and it is confirmed that the device functions as a sensor.
本発明の造形方法は、圧電性部位を有する、種々の形状の圧電性材料の構造体を形成することができ、このような構造体は、感圧機能を有する筐体等として幅広く様々な用途に仕様され得る。
The modeling method of the present invention can form piezoelectric material structures of various shapes having piezoelectric parts, and such structures can be used in a wide variety of applications as a housing having a pressure-sensitive function. Can be specified.
1…感圧センサー
2…成形体
4a…上部電極
4b…上部電極
6a…中部電極
6b…中部電極
8a…下部電極
8b…下部電極
14…右側面 DESCRIPTION OFSYMBOLS 1 ... Pressure sensor 2 ... Molded object 4a ... Upper electrode 4b ... Upper electrode 6a ... Middle electrode 6b ... Middle electrode 8a ... Lower electrode 8b ... Lower electrode 14 ... Right side
2…成形体
4a…上部電極
4b…上部電極
6a…中部電極
6b…中部電極
8a…下部電極
8b…下部電極
14…右側面 DESCRIPTION OF
Claims (11)
- ノズルから圧電性高分子を含む造形材料を吐出して造形する三次元造形装置を用いて、圧電性部位を有する構造体に造形すること;
上記三次元造形装置の造形材料を吐出するノズルの温度が、圧電性高分子の結晶化温度以上、融点未満の温度であること;
上記三次元造形装置のノズルの移動速度が、圧電性高分子を含む造形材料の吐出速度よりも速いこと;および
積層された圧電性高分子の少なくとも一部の延伸倍率が、1.5倍以上であること
を特徴とする圧電性高分子の造形方法。 Modeling a structure having a piezoelectric portion using a three-dimensional modeling apparatus that models by ejecting a modeling material containing a piezoelectric polymer from a nozzle;
The temperature of the nozzle for discharging the modeling material of the three-dimensional modeling apparatus is not less than the crystallization temperature of the piezoelectric polymer and less than the melting point;
The moving speed of the nozzle of the three-dimensional modeling apparatus is faster than the ejection speed of the modeling material containing the piezoelectric polymer; and the stretching ratio of at least a part of the laminated piezoelectric polymer is 1.5 times or more A method for forming a piezoelectric polymer, characterized in that: - 造形材料が吐出される造形箇所の温度が、ノズルの温度よりも低いことを特徴とする、請求項1に記載の造形方法。 The modeling method according to claim 1, wherein the temperature of the modeling location where the modeling material is discharged is lower than the temperature of the nozzle.
- 三次元造形装置のノズルの移動速度が、0.01~100mm/秒であることを特徴とする、請求項1または2に記載の造形方法。 3. The modeling method according to claim 1, wherein the moving speed of the nozzle of the three-dimensional modeling apparatus is 0.01 to 100 mm / second.
- 積層された圧電性高分子の少なくとも一部の延伸倍率が、4倍以上であることを特徴とする、請求項1~3のいずれかに記載の造形方法。 The modeling method according to any one of claims 1 to 3, wherein the stretch ratio of at least a part of the laminated piezoelectric polymer is 4 times or more.
- 圧電性高分子がポリ乳酸または乳酸を構成単位として含む共重合体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造形方法。 The modeling method according to any one of claims 1 to 4, wherein the piezoelectric polymer is polylactic acid or a copolymer containing lactic acid as a structural unit.
- 圧電性高分子を含む造形材料が柔軟化剤を含む、請求項1~5のいずれかに記載の造形方法。 The modeling method according to any one of claims 1 to 5, wherein the modeling material containing the piezoelectric polymer contains a softening agent.
- 柔軟化剤が、PMMA-PnBA-PMMAブロック共重合体である、請求項6に記載の造形方法。 The modeling method according to claim 6, wherein the softening agent is a PMMA-PnBA-PMMA block copolymer.
- 請求項1~7のいずれかに記載の造形方法により得られる、圧電性部位を有する構造体。 A structure having a piezoelectric part, obtained by the molding method according to any one of claims 1 to 7.
- 圧電性部位の圧電率が、0.5pC/N以上であることを特徴とする、請求項8に記載の構造体。 The structure according to claim 8, wherein the piezoelectric part has a piezoelectricity of 0.5 pC / N or more.
- 請求項8または9に記載の構造体と、
その圧電性部位に設置された少なくとも一対の電極と
を有して成る、感圧センサー。 A structure according to claim 8 or 9, and
A pressure-sensitive sensor comprising at least a pair of electrodes installed at the piezoelectric portion. - 請求項8または9に記載の構造体と、
その圧電性部位に設置された少なくとも一対の電極と
を有して成る、アクチュエータ。 A structure according to claim 8 or 9, and
An actuator comprising at least a pair of electrodes installed at the piezoelectric portion.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016505084A JP6592780B2 (en) | 2014-02-26 | 2015-01-06 | Method for forming piezoelectric polymer |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014-035278 | 2014-02-26 | ||
JP2014035278 | 2014-02-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015129291A1 true WO2015129291A1 (en) | 2015-09-03 |
Family
ID=54008621
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/050179 WO2015129291A1 (en) | 2014-02-26 | 2015-01-06 | Method for producing piezoelectric polymer |
Country Status (2)
Country | Link |
---|---|
JP (1) | JP6592780B2 (en) |
WO (1) | WO2015129291A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017065154A (en) * | 2015-09-30 | 2017-04-06 | ニチアス株式会社 | Three-dimensional shaped object and shaping method thereof |
WO2018025161A1 (en) * | 2016-08-04 | 2018-02-08 | Colliselli Stefano | Sample element |
EP4036995A2 (en) | 2021-01-29 | 2022-08-03 | Seiko Epson Corporation | Injection-molded article of polymer piezoelectric material, apparatus and method for manufacturing the same, and piezoelectric element |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008194968A (en) * | 2007-02-14 | 2008-08-28 | Imoto Seisakusho:Kk | Direct molding method and direct molding device of polymer material |
WO2010104196A1 (en) * | 2009-03-13 | 2010-09-16 | 三井化学株式会社 | Piezoelectric polymer material, process for producing same, and piezoelectric element |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4445277B2 (en) * | 2004-01-29 | 2010-04-07 | 三井化学株式会社 | Polymer piezoelectric material comprising polylactic acid resin and inorganic compound |
-
2015
- 2015-01-06 WO PCT/JP2015/050179 patent/WO2015129291A1/en active Application Filing
- 2015-01-06 JP JP2016505084A patent/JP6592780B2/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008194968A (en) * | 2007-02-14 | 2008-08-28 | Imoto Seisakusho:Kk | Direct molding method and direct molding device of polymer material |
WO2010104196A1 (en) * | 2009-03-13 | 2010-09-16 | 三井化学株式会社 | Piezoelectric polymer material, process for producing same, and piezoelectric element |
Non-Patent Citations (1)
Title |
---|
DAICHI AOKI ET AL.: "Poly L-gata Nyusan no Atsuden Haiko Shori Seikeiho ni Kansuru Kento", THE ACOUSTICAL SOCIETY OF JAPAN (ASJ) KOEN RONBUNSHU, vol. 2014, 3 March 2014 (2014-03-03), pages 875 - 876 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017065154A (en) * | 2015-09-30 | 2017-04-06 | ニチアス株式会社 | Three-dimensional shaped object and shaping method thereof |
WO2018025161A1 (en) * | 2016-08-04 | 2018-02-08 | Colliselli Stefano | Sample element |
EP4036995A2 (en) | 2021-01-29 | 2022-08-03 | Seiko Epson Corporation | Injection-molded article of polymer piezoelectric material, apparatus and method for manufacturing the same, and piezoelectric element |
Also Published As
Publication number | Publication date |
---|---|
JPWO2015129291A1 (en) | 2017-03-30 |
JP6592780B2 (en) | 2019-10-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6592780B2 (en) | Method for forming piezoelectric polymer | |
CN105706029B (en) | Tactile prompt device | |
JP5671192B2 (en) | Piezoelectric vibrator | |
TWI610881B (en) | Method for manufacturing an electromechanical structure and an arrangement for carrying out the method | |
JP2009006538A (en) | Three-dimensional shaping apparatus and method for three-dimenshional shaping | |
CN108269911A (en) | Inertial haptic actuator with cantilever beam and intellectual material | |
KR102180850B1 (en) | Microelectromechanical apparatus for generating a physical effect | |
JP2014513510A (en) | Deformable polymer device and automated manufacturing process for making deformable polymer film | |
Li et al. | Printed strain sensors for on‐skin electronics | |
CN103282865B (en) | Piezoelectric vibrating device and touch-panel device | |
US10384402B2 (en) | Methods and apparatuses for additive manufacturing | |
KR101765431B1 (en) | Polymer piezoelectric material, laminate body, method for producing polymer piezoelectric material, and method for producing laminate body | |
CN114026708A (en) | Polymer composite piezoelectric body and piezoelectric thin film | |
JP5964947B2 (en) | Piezoelectric actuator, inkjet head, and method of manufacturing piezoelectric actuator | |
JP6550454B2 (en) | Three-dimensional modeling apparatus, filler feeder, and method of manufacturing shaped article | |
JP2016226175A5 (en) | ||
US20240206341A1 (en) | Laminated piezoelectric element and electroacoustic transducer | |
CN115066760A (en) | Piezoelectric film | |
CN107873120A (en) | Piezo vibration module | |
JP2011150467A (en) | Touch panel assembly and driving method therefor | |
JP6582370B2 (en) | Piezoelectric manufacturing method, ultrasonic transducer, and ultrasonic imaging apparatus | |
WO2014087914A1 (en) | Method for molding piezoelectric polymer and molded body | |
JP5151995B2 (en) | Drive device | |
JP6318970B2 (en) | Vibrating body and tactile presentation device | |
JP6337685B2 (en) | Tactile presentation device |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15755666 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016505084 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 15755666 Country of ref document: EP Kind code of ref document: A1 |