US20200141668A1 - Resin sheet having controlled thermal conductivity distribution, and method for manufacturing the same - Google Patents
Resin sheet having controlled thermal conductivity distribution, and method for manufacturing the same Download PDFInfo
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- US20200141668A1 US20200141668A1 US16/578,019 US201916578019A US2020141668A1 US 20200141668 A1 US20200141668 A1 US 20200141668A1 US 201916578019 A US201916578019 A US 201916578019A US 2020141668 A1 US2020141668 A1 US 2020141668A1
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- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/025—Electric or magnetic properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
- F28F13/14—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by endowing the walls of conduits with zones of different degrees of conduction of heat
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
- F28F13/18—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by applying coatings, e.g. radiation-absorbing, radiation-reflecting; by surface treatment, e.g. polishing
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
- F28F2013/001—Particular heat conductive materials, e.g. superconductive elements
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
- F28F2013/005—Thermal joints
- F28F2013/006—Heat conductive materials
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F2245/00—Coatings; Surface treatments
- F28F2245/06—Coatings; Surface treatments having particular radiating, reflecting or absorbing features, e.g. for improving heat transfer by radiation
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F2270/00—Thermal insulation; Thermal decoupling
Definitions
- the present invention relates to a resin sheet having a controlled thermal conductivity distribution, and a method for manufacturing the same.
- Patent Document 5 a method using the flow of resin is also known.
- This method is a method using a flow at the time of injection.
- fibers are oriented in accordance with a flow inside a mold at the time of injection molding. Therefore, it is difficult to completely control orientation in a specified shape.
- resin to be used is limited to resin having a high fluidity.
- Patent Document 1 JP-A 2004-255600
- Patent Document 2 JP-A 2006-335957
- Patent Document 3 JP-A 2000-141505
- Patent Document 4 JP-A 2016-56352
- Patent Document 5 JP-A 2014-124785
- the present invention has been made in view of the circumstances described above. It is an object of the present invention to provide a resin sheet in which thermal conductivity is controlled according to an area at an advance level, and a method for manufacturing the same.
- the inventors have conducted intensive studies in order to achieve the object described above, and have discovered that a resin sheet that freely includes a portion having a high thermal conductivity in a thickness direction can be formed by locally performing magnetic field orientation on a resin composition having magnetic anisotropy, by using a bulk superconductor magnet. Thus, the inventors have completed the present invention.
- the present invention provides a resin sheet and a method for manufacturing the same that are described below.
- a minimum unit area of the region having the thermal conductivity that is greater than the average value of the thermal conductivity of the entirety of the resin sheet by 1 W/mK or more is 0.2 cm 2 or more.
- an area of the region having the thermal conductivity that is greater than the average value of the thermal conductivity of the entirety of the resin sheet by 1 W/mK or more is from 1 to 50% of an area of the entirety of the resin sheet. 4.
- the resin sheet described in the above 1, wherein the region having the thermal conductivity that is greater than the average value of the thermal conductivity of the entirety of the resin sheet by 1 W/mK or more includes a portion having a thermal conductivity of 5 W/mK or more. 5.
- the resin sheet described in the above 1, wherein a region having a thermal conductivity of 5 W/mK or more and a region having a thermal conductivity of 2 W/mK or more are included in both.
- a resin sheet that is obtained by cutting off the one or the plurality of regions having a thermal conductivity of 5 W/mK or more and being surrounded by the closed loop, described in the above 6 9.
- the filler having the magnetic anisotropy includes at least one filler selected from the group consisting of a carbon fiber, an alumina fiber, an aluminum nitride whisker, a metal nanowire, a carbon nanotube, a boron nitride nanotube, scaly boron nitride, plate-like aggregated boron nitride, scaly graphite, graphene, and plate-like alumina.
- a resin component of the resin sheet includes a silicone resin or an epoxy resin.
- a thickness of the resin sheet is 20 mm or less. 14.
- a resin sheet that freely includes a portion having a high thermal conductivity in a thickness direction can be formed by using a magnetic field that is concentrated on a center of a bulk superconductor magnet.
- a resin sheet can be provided that has a single composition and that changes in thermal conductivity according to an area.
- this resin sheet is that this resin sheet is not formed by joining resin sheets having thermal conductivities different from each other by using an adhesive or the like and this resin sheet has a single composition.
- a resin sheet can be provided that freely includes a portion having a high thermal conductivity.
- FIG. 1 is a conceptual diagram illustrating an example for describing a method for measuring thermal conductivity, and a region below a dotted line (reference sign L) in this drawing indicates a resin sheet;
- FIGS. 2A to 2C are conceptual diagrams illustrating an example of a region having a high thermal conductivity that is located inside an outer peripheral edge of a resin sheet and is surrounded by a closed loop
- FIGS. 2D to 2F are conceptual diagrams illustrating an example of a region having a high thermal conductivity that is surrounded in a state where a portion of the region crosses or overlaps the outer peripheral edge of the resin sheet;
- FIG. 3 is a conceptual diagram illustrating a state of a magnetic flux density of a bulk superconductor magnet
- FIG. 4 is a side view of a resin molded body having a sheet shape
- FIG. 5 is a schematic side view illustrating an example of a manufacturing apparatus used in the present invention.
- FIG. 6 is a schematic view illustrating a state in a case where magnetic field orientation is performed according to the present invention.
- FIG. 7 is a conceptual diagram in a case where a magnetic field is applied to a resin molded body and a plurality of regions having a high thermal conductivity is generated on a sheet;
- FIG. 8 illustrates a thermal conductivity distribution map in a thickness direction of a sheet in each position, the thermal conductivity distribution map being obtained in Example 1;
- FIG. 9 illustrates a thermal conductivity distribution map of a sheet in each position, the thermal conductivity distribution map being obtained in Example 2;
- FIG. 10 illustrates a thermal conductivity distribution map of a sheet in each position, the thermal conductivity distribution map being obtained in Example 3;
- FIG. 11 illustrates a thermal conductivity distribution map of a sheet in each position, the thermal conductivity distribution map being obtained in Example 4.
- FIG. 12 illustrates a thermal conductivity distribution map of a sheet in each position, the thermal conductivity distribution map being obtained in Example 5;
- FIG. 13 illustrates a thermal conductivity distribution map of a sheet in each position, the thermal conductivity distribution map being obtained in Example 6;
- FIG. 14 illustrates a thermal conductivity distribution map of a sheet in each position, the thermal conductivity distribution map being obtained in Example 7;
- FIG. 15 illustrates a thermal conductivity distribution map of a sheet in each position, the thermal conductivity distribution map being obtained in Example 8;
- FIG. 16 illustrates a thermal conductivity distribution map of a sheet in each position, the thermal conductivity distribution map being obtained in Example 9;
- FIG. 17 illustrates a thermal conductivity distribution map of a sheet in each position, the thermal conductivity distribution map being obtained in Example 10.
- FIG. 18 illustrates a thermal conductivity distribution map of a sheet in each position, the thermal conductivity distribution map being obtained in Comparative Example 1.
- a resin sheet according to the present invention is effectively used as a heat radiation sheet, and the resin sheet includes a region having a thermal conductivity that is higher than an average thermal conductivity of the entirety of the sheet by 1 W/mK or more.
- a variety of thermal conductivity characteristics can be imparted to the resin sheet according to the present invention in accordance with a situation of the use of a resin sheet including a region having a high thermal conductivity, as described above.
- the thermal conductivity of a resin sheet refers to a thermal conductivity in a thickness direction of the resin sheet that has been measured according to the method described below.
- a resin sheet is sectioned into square regions having a fixed area, as illustrated in FIG. 1 .
- an end portion or a curve portion that fails to be sectioned to have a square shape is not a target to be measured.
- the area of a sectioned square be within a range of from 0.1 to 4 cm 2 . From the viewpoint of easy measurement, it is preferable that the area be 1 cm 2 .
- a thermal conductivity in a thickness direction is measured for each of the square regions by using the laser flash method.
- the obtained value (W/mK) is rounded off to one decimal place.
- a average value of the thermal conductivities of the respective regions that have been measured according to the method described above is a average thermal conductivity of the entirety of the sheet.
- to “include a region having a thermal conductivity that is greater than a average value of the entirety of the sheet by 1 W/mK or more” means that at least one of the sectioned square regions has a thermal conductivity that is higher than a “average thermal conductivity of the entirety of the sheet” by 1 W/mK or more.
- the minimum unit area of the region having a thermal conductivity that is greater than the average value of the entirety of the sheet by 1 W/mK or more be 0.2 cm 2 or more.
- the minimum unit area according to the present invention means that the region described above is measured as a square region having an area of 0.2 cm 2 or more. In this case, it is more preferable that the minimum unit area be from 0.2 to 3 cm 2 , and in particular, from 0.5 to 1 cm 2 . Above all, from the viewpoint of heat radiation from only a specified portion, it is preferable that the area of a region having a thermal conductivity that is higher than the average thermal conductivity of the entirety of the sheet by 1 W/mK or more be from 1 to 50% of the area of the entirety of the sheet.
- the area be from 5 to 45%. It is further more preferable that the area be from 15 to 40%. Further, it is preferable that the region having a thermal conductivity that is greater than the average value of the entirety of the sheet by 1 W/mK or more have a portion having a thermal conductivity of 5 W/mK or more. It is more preferable that the region have a portion having a thermal conductivity of 7 W/mK or more. It is further more preferable that the region have a portion having a thermal conductivity of 10 W/mK or more.
- the resin sheet according to the present invention include one or a plurality of regions that is spaced apart from an outer peripheral edge of the resin sheet and is surrounded by a closed loop and that has a thermal conductivity of 5 W/mK or more.
- X is an arbitrary integer of 5 or more and one X is selected, it is preferable that the resin sheet include one or a plurality of regions that has a thermal conductivity of X W/mK or more with a closed loop as a boundary.
- the resin sheet includes a region that has a thermal conductivity of X W/mK or more with a closed loop as a boundary
- each of the square regions in which thermal conductivity has been measured has a thermal conductivity of X W/mK or more and that a boundary of continuous square regions that are adjacent to each other in vertical and lateral directions does not cross or overlap an outer periphery of the sheet so as to form a closed loop ( FIGS. 2A to 2C ). In this case, as illustrated in FIG.
- not all of the continuous square regions may have a thermal conductivity of X W/mK or more, and a region having a low thermal conductivity that is less than X W/mK may exist inside the continuous square regions (this is illustrated as if a hole were opened, in the conceptual diagram of FIG. 2C illustrating a resin sheet). Namely, this means that a region having a high thermal conductivity exists as a spot inside the sheet.
- FIGS. 2D to 2F illustrate examples of a region in which a portion having a high thermal conductivity crosses or overlaps the outer peripheral edge of the resin sheet.
- a minimum thermal conductivity inside the region with a closed loop as a boundary be different from a maximum thermal conductivity outside the region by 3 W/mK or more.
- the region having a thermal conductivity of X W/mK or more described above may appropriately be cut out and used in accordance with a use situation.
- the thickness of the resin sheet is not particularly limited. However, from the viewpoint of thermal conduction, it is preferable that the thickness be not more than 20 mm, and it is more preferable that the thickness be not more than 5 mm. It is preferable that the thickness of the resin sheet be at least 0.05 mm, and particularly it is preferable that the thickness be at least 0.1 mm.
- a resin composition used for the resin sheet according to the present invention may be selected from a thermosetting resin composition, a photocurable (UV-curable) resin composition, and an electron-beam curable resin composition. These resin compositions are solidified by being cured or being converted into a B-stage due to heating or the irradiation such as a UV laser, an electron-beam laser and the like.
- the resin composition contains curable resin and a filler having magnetic anisotropy.
- the curable resin is not particularly limited.
- the illustrative examples of the curable resin include thermosetting silicone resin, thermosetting epoxy resin, UV-curable epoxy resin, UV-curable silicone resin, and electron-beam curable silicone resin. Of these resins, the use of the thermosetting silicone resin is preferable.
- the curable resin liquid resin may be used.
- the resin composition may be blended with a curing agent or an additive according to the type of curable resin. As characteristic properties of the curable resins after curing, any characteristic of a plastic state, a rubbery state, and a gel state may be adopted.
- a filler As the filler having magnetic anisotropy added to the resin composition, a filler is used that has crystal magnetic anisotropy and/or shape magnetic anisotropy and that is oriented in one direction by being applied with a magnetic field. Thermal conductivity can be controlled by controlling the orientation of the filler described above in one direction.
- Illustrative examples of a material having crystal magnetic anisotropy include a crystalline inorganic material and a crystalline organic material such as an organic single crystal.
- the filler having shape magnetic anisotropy include: a fibrous substance such as a cellulose nanofiber, a carbon fiber, an alumina fiber, an aluminum nitride whisker, or a metal nanowire; a nanotube-based substance such as a carbon nanotube or a boron nitride nanotube; and a plate-like or columnar substance such as scaly boron nitride, plate-like aggregated boron nitride, scaly graphite, graphene, or plate-like alumina. It is preferable that the filler be a fibrous substance or a plate-like or columnar substance. From the viewpoint of thermal conductivity, it is particularly preferable that the filler be a carbon fiber.
- a pitch-based carbon fiber be used that has a thermal conductivity of 500 W/mK or more in an axial direction. Also, the use of a carbon fiber having a length of 50 ⁇ m or more is preferable from the viewpoint of thermal conductivity.
- the blending amount of the filler having magnetic anisotropy is preferably from 50 to 300 parts by weight, particularly from 75 to 200 parts by weight, per 100 parts by weight of the curable resin.
- a filler without magnetic anisotropy such as spherical silica, may be simultaneously used as the filler.
- a resin sheet having thermal conductivities different from each other according to an area, as described above, is formed by partially performing magnetic field orientation on a filler having magnetic anisotropy inside the sheet, by using a bulk superconductor magnet.
- the bulk superconductor magnet is used as magnetic poles by magnetizing a superconductor under a magnetic field of a superconducting coil or the like. Once magnetized, a magnet can be obtained that semipermanently has a high magnetic flux density in a cooled state.
- Examples of a magnetizing method include pulse magnetization and magnetization using a superconducting coil magnet. From the viewpoint of the magnitude of a captured magnetic flux density, it is preferable that magnetization be performed by using the superconducting coil magnet. It is preferable that a superconducting coil magnet used in magnetization have a magnetic flux density of 6 T or more. If the magnetic flux density is less than 6 T, a bulk superconductor magnet after magnetization may have an insufficient magnetic flux density.
- the magnetic field of the bulk superconductor magnet is strong only in a center portion, and is perpendicular to a plane. Therefore, the bulk superconductor magnet is available in order to partially orient a target portion of the resin sheet and improve thermal conductivity.
- a superconductor used for the bulk superconductor magnet is not particularly limited, but the use of a RE-Ba—Cu—O based superconductor (RE is at least one selected from Y, Sm, Nd, Yb, La, Gd, Eu, and Er), a MgB 2 based superconductor, a NbSn 3 based superconductor, an iron based superconductor, or the like are preferable.
- RE is at least one selected from Y, Sm, Nd, Yb, La, Gd, Eu, and Er
- MgB 2 based superconductor a MgB 2 based superconductor
- NbSn 3 based superconductor a MgB 2 based superconductor
- an iron based superconductor or the like are preferable.
- the use of the RE-Ba—Cu—O based superconductor is more preferable.
- the shape and size of the bulk superconductor magnet are not particularly limited, but, from the viewpoint of the strength of a magnetic field, the use of a disc-shaped bulk superconductor magnet having a diameter of 4 cm or more, particularly a diameter of from 5 to 12 cm is preferable.
- a sheet shaped resin molded body 3 made of the resin composition described above is prepared. It is also preferable that at least an upper face of the resin molded body 3 be covered with a cover material 2 . In FIG. 4 , upper and lower faces of the resin molded body 3 are covered with the cover materials 2 and 2 . If the resin composition is exposed without being covered, since it is difficult to apply ultrasonic vibration, or the surface of resin is corrugated due to supersonic vibration with resulting in a non-uniform thickness, that is not preferable.
- the member selected from a resin film or a non-ferromagnetic metal plate is preferably used as the cover material.
- the illustrative examples of the resin film include a polyethylene terephthalate (PET) film, a polyethylene film, a polytetrafluoroethylene (PTFE) film, and a polychlorotrifluoroethylene (PCTFE) film.
- the illustrative examples of the non-ferromagnetic metal plate include an aluminum plate, a nonmagnetic stainless steel plate, a copper plate, and a titanium plate. Above all, from the viewpoint of handleability or a price, the use of PET film is preferable. Processing for imparting releasability may be performed on at least one face of the cover material.
- the thickness of the cover material is preferably 2 mm or less, particularly, from 0.5 to 0.05 mm. If the thickness of the cover material is 2 mm or less, ultrasonic vibration is sufficiently transmitted to a center portion, which is preferable.
- FIG. 5 is a side view illustrating a general configuration of an apparatus used in orientation as an embodiment of the present invention.
- a bulk superconductor magnet is denoted by reference sign 1
- a magnetic field can be applied to a portion of the resin molded body 3 .
- An ultrasonic vibrator is denoted by reference sign 4 , and vibration can be applied to the resin molded body.
- a magnetic field is applied to a portion of the prepared resin molded body 3 by using the bulk superconductor magnet 1 .
- a distance between the resin molded body 3 and the bulk superconductor magnet 1 be as short as possible.
- a center portion of the magnet be spaced apart from the outer peripheral edge of the sheet inside the sheet.
- vibration such as ultrasonic vibration is applied to a predetermined portion of the resin molded body 3 above the bulk superconductor magnet 1 , by using the ultrasonic vibrator 4 .
- vibration is used to orient the filler having magnetic anisotropy in the resin composition in a narrow region and to form a high thermal conductivity resin region 5 in which the filler has been oriented.
- examples of vibration include vibration generated by hitting, vibration generated by an air vibrator, ultrasonic vibration, and air vibration.
- the use of vibration having a frequency greater than 5,000 Hz is preferable.
- the use of ultrasonic vibration having a frequency of 20 kHz or more is preferable.
- the ultrasonic vibrator may apply vibration in a state where the resin molded body is heated.
- a magnetic field orientation operation may be performed several times while a portion to be oriented is changed ( FIG. 7 ).
- a resin sheet in which thermal conductivity is controlled can be formed by reaction-curing the oriented resin molded body or converting the oriented resin molded body into a B-stage.
- liquid resin composition can be used, as described above.
- a method may be employed for forming liquid into a sheet, performing magnetic field orientation in this state or a semi-cured state, and performing curing (fully curing).
- the viscosity of a resin composition is a measurement value at 25° measured by using a rotational viscometer described in JIS K 7117-1:1999.
- a bulk superconductor magnet was prepared that has a composition of Gd—Ba—Cu—O and has a diameter of 6 cm.
- a bulk superconductor magnet was used that had been magnetized by using a superconducting coil magnet of 6.5 T in such a way that a center magnetic flux density is 4.5 T, a magnetic flux density at a radius of 1 cm from the center is 3 T, a magnetic flux density at a radius of 2 cm from the center is 2 T, a magnetic flux density at a radius of 2.5 cm from the center is 1 T, and a magnetic flux density at a radius of 3 cm from the center is not more than 0.1 T.
- As an ultrasonic vibrator used in Examples normally a diameter of its terminal was 36 mm and its frequency was 20 kHz.
- a resin composition was prepared in which 100 parts by weight of a thermosetting liquid silicone resin composition (viscosity: 0.4 Pa ⁇ s; addition-curable silicone resin containing a vinyl group-containing polyorganosiloxane and a hydrosilyl group-containing polyorganosiloxane; hereinafter, similar silicone is used) is blended with 100 parts by weight of a carbon fiber (a mean length of 100 ⁇ m) that has a thermal conductivity in an axial direction of 900 W/mK.
- the resin composition was applied onto a PET film having releasability and a thickness of 100 ⁇ m within a range of 5 cm ⁇ 5 cm at a thickness of 1 mm.
- the resin composition was covered with a PET film having a thickness of 100 ⁇ m, and a periphery was blocked by a double-sided tape in order to prevent resin from leaking out, so that a resin molded body was prepared.
- the resin molded body was disposed in such a way that a position of a length of 2.5 cm and a width of 2.5 cm of the resin molded body is located above a center portion of the bulk superconductor magnet. Ultrasonic vibration was applied to the center portion of the magnet from above the film having a thickness of 100 ⁇ m. Then, the resin molded body was cured, and a resin sheet was obtained.
- the resin sheet was sectioned into squares of 1 cm 2 , and thermal conductivity was measured in each of the sections, the results of which is illustrated in FIG. 8 .
- the average thermal conductivity of the resin sheet was 3.7 W/mK.
- each square has a size of 1 cm ⁇ 1 cm, and a numerical value in each of the squares indicates thermal conductivity (unit: W/mK) (hereinafter, the similar is applied to respective Examples and a Comparative Example).
- a resin composition was prepared in which 100 parts by weight of a thermosetting liquid silicone resin composition (viscosity: 0.4 Pa ⁇ s) is blended with 100 parts by weight of a carbon fiber (a mean length of 100 ⁇ m) that has a thermal conductivity in the axial direction of 900 W/mK.
- the resin composition was applied onto a PET film having releasability and a thickness of 100 ⁇ m within a range of 9 cm ⁇ 9 cm at a thickness of 1 mm. After application, the resin composition was covered with a PET film having a thickness of 100 ⁇ m, and a periphery was blocked by a double-sided tape in order to prevent resin from leaking out, so that a resin molded body was prepared.
- the resin molded body was disposed in such a way that a position of a length of 4.5 cm and a width of 4.5 cm of the resin molded body is located above a center portion of the bulk superconductor magnet. Ultrasonic vibration was applied to the center portion of the magnet from above the film having a thickness of 100 ⁇ m. Then, the resin molded body was cured, and a resin sheet was obtained. The resin sheet was sectioned into squares of 1 cm 2 , and thermal conductivity was measured in each of the sections, the result of which is illustrated in FIG. 9 . The average thermal conductivity of the resin sheet was 1.8 W/mK.
- a resin composition was prepared in which 100 parts by weight of a thermosetting liquid silicone resin composition (viscosity: 0.4 Pa ⁇ s) is blended with 100 parts by weight of a carbon fiber (a mean length of 200 ⁇ m) that has a thermal conductivity in the axial direction of 900 W/mK.
- the resin composition was applied onto a PET film having releasability and a thickness of 100 ⁇ m within a range of 5 cm ⁇ 5 cm at a thickness of 1 mm. After application, the resin composition was covered with a PET film having a thickness of 100 ⁇ m, and a periphery was blocked by a double-sided tape in order to prevent resin from leaking out, so that a resin molded body was prepared.
- the resin molded body was disposed in such a way that a position of a length of 2.5 cm and a width of 2.5 cm of the resin molded body is located above a center portion of the bulk superconductor magnet. Ultrasonic vibration was applied to the center portion of the magnet from above the film having a thickness of 100 ⁇ m. Then, the resin molded body was cured, and a resin sheet was obtained. The resin sheet was sectioned into squares of 1 cm 2 , and thermal conductivity was measured in each of the sections, the result of which is illustrated in FIG. 10 . The average thermal conductivity of the resin sheet was 6.2 W/mK.
- a resin composition was prepared in which 100 parts by weight of a thermosetting liquid silicone resin composition (viscosity: 0.4 Pa ⁇ s) is blended with 100 parts by weight of a carbon fiber (a mean length of 200 ⁇ m) that has a thermal conductivity in the axial direction of 900 W/mK.
- the resin composition was applied onto a PET film having releasability and a thickness of 100 rpm within a range of 9 cm ⁇ 9 cm at a thickness of 1 mm. After application, the resin composition was covered with a PET film having a thickness of 100 ⁇ m, and a periphery was blocked by a double-sided tape in order to prevent resin from leaking out, so that a resin molded body was prepared.
- the resin molded body was disposed in such a way that a position of a length of 4.5 cm and a width of 4.5 cm of the resin molded body is located above a center portion of the bulk superconductor magnet. Ultrasonic vibration was applied to the center portion of the magnet from above the film having a thickness of 100 ⁇ m. Then, the resin molded body was cured, and a resin sheet was obtained. The resin sheet was sectioned into squares of 1 cm 2 , and thermal conductivity was measured in each of the sections, the result of which is illustrated in FIG. 11 . The average thermal conductivity of the resin sheet was 2.6 W/mK.
- a resin composition was prepared in which 100 parts by weight of a thermosetting liquid silicone resin composition (viscosity: 0.4 Pa ⁇ s) is blended with 100 parts by weight of a carbon fiber (a mean length of 200 ⁇ m) that has a thermal conductivity in the axial direction of 900 W/mK.
- the resin composition was applied onto a PET film having releasability and a thickness of 100 ⁇ m within a range of 9 cm ⁇ 9 cm at a thickness of 1 mm. After application, the resin composition was covered with a PET film having a thickness of 100 ⁇ m, and a periphery was blocked by a double-sided tape in order to prevent resin from leaking out, so that a resin molded body was prepared.
- the resin molded body was disposed in such a way that a position of a length of 2.5 cm and a width of 2.5 cm of the resin molded body is located above a center portion of the bulk superconductor magnet. Ultrasonic vibration was applied to the center portion of the magnet from above the film having a thickness of 100 ⁇ m.
- the resin molded body was disposed in such a way that a position of a length of 6.5 cm and a width of 6.5 cm of the resin molded body is located above the center portion of the bulk superconductor magnet. Ultrasonic vibration was applied to the center portion of the magnet from above the film having a thickness of 100 ⁇ m.
- the resin molded body was cured, and a resin sheet was obtained.
- the resin sheet was sectioned into squares of 1 cm 2 , and thermal conductivity was measured in each of the sections, the result of which is illustrated in FIG. 12 .
- the average thermal conductivity of the resin sheet was 4.2 W/mK.
- a resin composition was prepared in which 100 parts by weight of a thermosetting liquid silicone resin composition (viscosity: 0.4 Pa ⁇ s) is blended with 100 parts by weight of a carbon fiber (a mean length of 400 ⁇ m) that has a thermal conductivity in the axial direction of 900 W/mK.
- the resin composition was applied onto a PET film having releasability and a thickness of 100 ⁇ m within a range of 9 cm ⁇ 9 cm at a thickness of 1 mm. After application, the resin composition was covered with a PET film having a thickness of 100 ⁇ m, and a periphery was blocked by a double-sided tape in order to prevent resin from leaking out, so that a resin molded body was prepared.
- the resin molded body was disposed in such a way that a position of a length of 2.5 cm and a width of 2.5 cm of the resin molded body is located above a center portion of the bulk superconductor magnet. Ultrasonic vibration was applied to the center portion of the magnet from above the film having a thickness of 100 ⁇ m.
- the resin molded body was disposed in such a way that a position of a length of 6.5 cm and a width of 6.5 cm of the resin molded body is located above the center portion of the bulk superconductor magnet. Ultrasonic vibration was applied to the center portion of the magnet from above the film having a thickness of 100 ⁇ m.
- the resin molded body was cured, and a resin sheet was obtained.
- the resin sheet was sectioned into squares of 1 cm 2 , and thermal conductivity was measured in each of the sections, the result of which is illustrated in FIG. 13 .
- the average thermal conductivity of the resin sheet was 4.2 W/mK.
- a resin composition was prepared in which 100 parts by weight of a thermosetting liquid silicone resin composition (viscosity: 0.4 Pa ⁇ s) is blended with 100 parts by weight of a carbon fiber (a mean length of 200 ⁇ m) that has a thermal conductivity in the axial direction of 900 W/mK.
- the resin composition was applied onto a PET film having releasability and a thickness of 100 ⁇ m within a range of 9 cm ⁇ 9 cm at a thickness of 1 mm. After application, the resin composition was covered with a PET film having a thickness of 100 ⁇ m, and a periphery was blocked by a double-sided tape in order to prevent resin from leaking out, so that a resin molded body was prepared.
- the resin molded body was disposed in such a way that a position of a length of 3.5 cm and a width of 3.5 cm width of the resin molded body is located above a center portion of the bulk superconductor magnet. Ultrasonic vibration was applied to the center portion of the magnet from above the film having a thickness of 100 ⁇ m.
- the resin molded body was disposed in such a way that a position of a length of 5.5 cm and a width of 5.5 cm of the resin molded body is located above the center portion of the bulk superconductor magnet. Ultrasonic vibration was applied to the center portion of the magnet from above the film having a thickness of 100 ⁇ m.
- the resin molded body was cured, and a resin sheet was obtained.
- the resin sheet was sectioned into squares of 1 cm 2 , and thermal conductivity was measured in each of the sections, the result of which is illustrated in FIG. 14 .
- the average thermal conductivity of the resin sheet was 3.7 W/mK.
- a resin composition was prepared in which 100 parts by weight of a thermosetting liquid silicone resin composition (viscosity: 0.4 Pa ⁇ s) is blended with 100 parts by weight of a carbon fiber (a mean length of 100 ⁇ m) that has a thermal conductivity in the axial direction of 900 W/mK.
- the resin composition was applied onto a PET film having releasability and a thickness of 100 ⁇ m within a range of 5 cm ⁇ 5 cm at a thickness of 1 mm. After application, the resin composition was covered with a PET film having a thickness of 100 ⁇ m, and a periphery was blocked by a double-sided tape in order to prevent resin from leaking out, so that a resin molded body was prepared.
- the resin molded body was disposed in such a way that a position of a length of 5 cm and a width of 5 cm of the resin molded body is located above a center portion of the bulk superconductor magnet. Ultrasonic vibration was applied to the center portion of the magnet from above the film having a thickness of 100 ⁇ m. Then, the resin molded body was cured, and a resin sheet was obtained. The resin sheet was sectioned into squares of 1 cm 2 , and thermal conductivity was measured in each of the sections, the result of which is illustrated in FIG. 15 . The average thermal conductivity of the resin sheet was 2.2 W/mK.
- a resin composition was prepared in which 100 parts by weight of a thermosetting liquid silicone resin composition (viscosity: 0.4 Pa ⁇ s) is blended with 100 parts by weight of a carbon fiber (a mean length of 150 ⁇ m) that has a thermal conductivity in the axial direction of 900 W/mK.
- the resin composition was applied onto a PET film having releasability and a thickness of 100 rpm within a range of 5 cm ⁇ 5 cm at a thickness of 1 mm. After application, the resin composition was covered with a PET film having a thickness of 100 ⁇ m, and a periphery was blocked by a double-sided tape in order to prevent resin from leaking out, so that a resin molded body was prepared.
- the resin molded body was disposed in such a way that a position of a length of 2.5 cm and a width of 2.5 cm of the resin molded body is located above a center portion of the bulk superconductor magnet. Ultrasonic vibration was applied to the center portion of the magnet from above the film having a thickness of 100 ⁇ m. Then, the resin molded body was cured, and a resin sheet was obtained. The resin sheet was sectioned into squares of 1 cm 2 , and thermal conductivity was measured in each of the sections, the result of which is illustrated in FIG. 16 . The average thermal conductivity of the resin sheet was 6 W/mK.
- a resin composition was prepared in which 100 parts by weight of a thermosetting liquid silicone resin composition (viscosity: 0.4 Pa ⁇ s) is blended with 100 parts by weight of a carbon fiber (a mean length of 200 ⁇ m) that has a thermal conductivity in the axial direction of 900 W/mK.
- the resin composition was applied onto a PET film having releasability and a thickness of 100 ⁇ m within a range of 5 cm ⁇ 5 cm at a thickness of 2 mm. After application, the resin composition was covered with a PET film having a thickness of 100 ⁇ m, and a periphery was blocked by a double-sided tape in order to prevent resin from leaking out, so that a resin molded body was formed.
- the resin molded body was disposed in such a way that a position of a length of 2.5 cm and a width of 2.5 cm of the resin molded body is located above a center portion of the bulk superconductor magnet. Ultrasonic vibration was applied to the center portion of the magnet from above the film having a thickness of 100 ⁇ m. Then, the resin molded body was cured, and a resin sheet was obtained. The resin sheet was sectioned into squares of 1 cm 2 , and thermal conductivity was measured in each of the sections, the result of which is illustrated in FIG. 17 . The average thermal conductivity of the resin sheet was 6.3 W/mK.
- a resin composition was prepared in which 100 parts by weight of a thermosetting liquid silicone resin composition (viscosity: 0.4 Pa ⁇ s) is blended with 100 parts by weight of a carbon fiber (a mean length of 200 ⁇ m) that has a thermal conductivity in the axial direction of 900 W/mK.
- the resin composition was applied onto a PET film having releasability and a thickness of 100 ⁇ m within a range of 5 cm ⁇ 5 cm at a thickness of 1 mm. After application, the resin composition was covered with a PET film having a thickness of 100 ⁇ m, and a periphery was blocked by a double-sided tape in order to prevent resin from leaking out, so that a resin molded body was formed.
- the resin molded body was disposed inside a superconducting coil magnet of 6 T having a diameter of 10 cm, and ultrasonic vibration was applied from above the film having a thickness of 100 ⁇ m. Then, the resin molded body was cured, and a resin sheet was obtained. The resin sheet was sectioned into squares of 1 cm 2 , and thermal conductivity was measured in each of the sections, the result of which is illustrated in FIG. 18 . The average thermal conductivity of the resin sheet was 12.5 W/mK.
- Table 1 described below indicates the respective items “length of carbon fiber”, “size and thickness of resin sheet”, “center position of bulk superconductor magnet in orientation”, “average thermal conductivity of curable resin sheet after magnetic field orientation”, “thermal conductivity distribution”, “ratio of area having thermal conductivity higher than average thermal conductivity of sheet by 1 W/mK or more”, “value of integer X of 5 or more by which boundary of region having thermal conductivity of X W/mK or more forms closed loop”, and “value of integer X of 5 or more by which boundary of region having thermal conductivity of X W/mK or more forms closed loop and minimum thermal conductivity inside region with closed loop as boundary is different from thermal conductivity outside region by 3 W/mK or more”.
- FIG. FIG. FIG. FIG. FIG. FIG. FIG. FIG. FIG. FIG. FIG. FIG. FIG. FIG. FIG. distribution of sheet 8 9 10 11 12 13 14 15 16 17 18 Ratio of area having 36 16 36 16 31 23 28 24 36 36 0 thermal conductivity higher than average thermal conductivity of sheet by 1 W/mK or more (%) Value of integer X of 5.6 5.6 6-12 5-12 6-12 6-15 5-12 None 7-10 5-12 None 5 or more by which boundary of region having thermal conductivity of X W/mK or more forms closed loop Value of integer X of None None 6-10 6-11 6-11 6-12 6-11 None 7-9 5-11 None 5 or more by which boundary of region having thermal conductivity of X W/mK or more forms closed loop and minimum thermal conductivity inside region with closed loop as boundary is different from thermal conductivity outside region by 3 W/mK or more
- a region having a high thermal conductivity can be freely generated without joining resin by using an adhesive or the like. If a fiber length increases, as in Examples 3 and 9, thermal conductivity can significantly change by 3 W/mK or more between the inside of a region having a high thermal conductivity and the outside of the region. By performing magnetic field orientation several times, as in Examples 5 to 7, the region having a high thermal conductivity can be widened, or can be deformed. As described above, by employing the technique of the present invention, a resin molded body can be formed that has a variety of thermal conductivity distributions in a single resin molded body. In contrast, in a case where a superconducting coil magnet is used, as in Comparative Example 1, it is difficult to improve a thermal conductivity in only a portion of a sheet.
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JP2018188049A JP2020055961A (ja) | 2018-10-03 | 2018-10-03 | 制御された熱伝導率分布を有する樹脂シート及びその製造方法 |
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CN114426691B (zh) * | 2022-02-11 | 2023-04-07 | 电子科技大学 | 一种石墨烯电磁屏蔽复合材料及其制备方法 |
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JP2000141505A (ja) * | 1998-11-09 | 2000-05-23 | Polymatech Co Ltd | 高分子複合材料の成形方法および磁場配向プレス成形装置 |
JP2001172398A (ja) * | 1999-12-17 | 2001-06-26 | Polymatech Co Ltd | 熱伝導性成形体およびその製造方法 |
DE10102991C2 (de) * | 2000-02-19 | 2003-11-20 | Ald Vacuum Techn Ag | Einrichtung zum Aufheizen eines Werkstücks aus Metall |
JP2001291431A (ja) * | 2000-04-10 | 2001-10-19 | Jsr Corp | 異方導電性シート用組成物、異方導電性シート、その製造方法および異方導電性シートを用いた接点構造 |
KR20010090778A (ko) * | 2000-04-10 | 2001-10-19 | 마쯔모또 에이찌 | 복합시이트 및 그의 제조 방법 |
JP2001351445A (ja) * | 2000-06-09 | 2001-12-21 | Jsr Corp | 複合シートの製造方法および複合シート |
JP4345958B2 (ja) | 2003-02-24 | 2009-10-14 | 独立行政法人物質・材料研究機構 | 異方性成形体の製造装置および異方性成形体の製造方法 |
JP4657816B2 (ja) * | 2005-06-03 | 2011-03-23 | ポリマテック株式会社 | 熱伝導性成形体の製造方法及び熱伝導性成形体 |
JP5011786B2 (ja) * | 2006-03-30 | 2012-08-29 | 豊田合成株式会社 | 高熱伝導絶縁体とその製造方法 |
JP5788760B2 (ja) * | 2011-10-19 | 2015-10-07 | 日東電工株式会社 | 熱伝導性シート、led実装用基板およびledモジュール |
JP5761111B2 (ja) * | 2012-04-17 | 2015-08-12 | 信越化学工業株式会社 | 絶縁放熱シート及び窒化ホウ素の造粒方法 |
JP5244256B1 (ja) | 2012-12-25 | 2013-07-24 | 日進工業株式会社 | 射出成形方法及び射出成形品 |
US9731456B2 (en) * | 2013-03-14 | 2017-08-15 | Sabic Global Technologies B.V. | Method of manufacturing a functionally graded article |
US20160326419A1 (en) * | 2013-12-31 | 2016-11-10 | The Regents Of The University Of California | Thermal interface materials with alligned fillers |
JP6626647B2 (ja) | 2014-09-05 | 2019-12-25 | Toyo Tire株式会社 | 熱伝導率可変材料、当該熱伝導率可変材料を用いた熱制御装置、及び当該熱伝導率可変材料を用いた熱制御方法 |
JP2017098485A (ja) * | 2015-11-27 | 2017-06-01 | 住友理工株式会社 | 放熱性成形体 |
EP3428221B1 (en) * | 2016-04-28 | 2022-01-26 | Sekisui Polymatech Co., Ltd. | Method for producing thermally-conductive sheet |
CN108328938B (zh) * | 2017-01-20 | 2020-10-30 | 株洲晨昕中高频设备有限公司 | 一种导热石墨片及其生产方法 |
CN107953628B (zh) * | 2017-11-16 | 2020-07-21 | 东莞市弗勒特电子科技有限公司 | 一种三维高导热垫片及其制备方法 |
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