CN110739223B - Method for producing thermally conductive sheet - Google Patents
Method for producing thermally conductive sheet Download PDFInfo
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- CN110739223B CN110739223B CN201910625010.7A CN201910625010A CN110739223B CN 110739223 B CN110739223 B CN 110739223B CN 201910625010 A CN201910625010 A CN 201910625010A CN 110739223 B CN110739223 B CN 110739223B
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- sheet
- thermally conductive
- molded body
- component
- silicone
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the groups H01L21/18 - H01L21/326 or H10D48/04 - H10D48/07
- H01L21/4814—Conductive parts
- H01L21/4871—Bases, plates or heatsinks
- H01L21/4882—Assembly of heatsink parts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/367—Cooling facilitated by shape of device
- H01L23/3672—Foil-like cooling fins or heat sinks
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/40—Mountings or securing means for detachable cooling or heating arrangements ; fixed by friction, plugs or springs
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/40—Mountings or securing means for detachable cooling or heating arrangements ; fixed by friction, plugs or springs
- H01L23/4006—Mountings or securing means for detachable cooling or heating arrangements ; fixed by friction, plugs or springs with bolts or screws
- H01L2023/4037—Mountings or securing means for detachable cooling or heating arrangements ; fixed by friction, plugs or springs with bolts or screws characterised by thermal path or place of attachment of heatsink
- H01L2023/4043—Mountings or securing means for detachable cooling or heating arrangements ; fixed by friction, plugs or springs with bolts or screws characterised by thermal path or place of attachment of heatsink heatsink to have chip
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
- H01L2224/161—Disposition
- H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73251—Location after the connecting process on different surfaces
- H01L2224/73253—Bump and layer connectors
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
Abstract
The present application relates to a method for producing a thermally conductive sheet. The application provides a method for manufacturing a heat conductive sheet, which can enable uncured components of a binder resin to efficiently seep out to the surface of a molded body sheet and improve adhesion. The method for producing a thermally conductive sheet comprises a step of forming a thermally conductive resin composition containing a thermally conductive filler in a binder resin into a predetermined shape and curing the composition to form a thermally conductive molded body, a step of cutting the thermally conductive molded body into a sheet shape to form a molded body sheet, and a step of pressing the molded body sheet under a reduced pressure atmosphere to coat the surface of the molded body sheet with an uncured component of the binder resin oozing out from the sheet body of the molded body sheet.
Description
Technical Field
The present invention relates to a method for manufacturing a heat conductive sheet that is adhered to an electronic component or the like to improve heat dissipation.
Background
Conventionally, various cooling methods have been used for semiconductor devices mounted on various electrical devices such as personal computers and other devices, because heat is generated by operation and if the generated heat is accumulated, the operation of the semiconductor devices and peripheral devices are adversely affected. As a method for cooling electronic components such as semiconductor devices, a method of mounting a fan in the device to cool air in a device case, a method of mounting a heat sink such as a heat sink or a heat spreader in the semiconductor device to be cooled, and the like are known.
In the case of mounting a heat sink on a semiconductor element for cooling, a heat conductive sheet is provided between the semiconductor element and the heat sink in order to efficiently release heat from the semiconductor element. As the heat conductive sheet, a heat conductive sheet in which a filler such as a heat conductive filler including carbon fiber is dispersed in a silicone resin is widely used (see patent document 1). These thermally conductive fillers have thermal conductivity anisotropy, and for example, it is known that when carbon fibers are used as the thermally conductive filler, the thermally conductive filler has a thermal conductivity of about 600W/mK to 1200W/mK in the fiber direction, and when boron nitride is used, the thermally conductive filler has a thermal conductivity of about 110W/mK in the plane direction, and has a thermal conductivity of about 2W/mK in the direction perpendicular to the plane direction.
Prior art literature
Patent literature
Patent document 1 Japanese patent application laid-open No. 2012-023235
Patent document 2 Japanese patent application laid-open No. 2015-029076
Patent document 3 Japanese patent application laid-open No. 2015-029075
Disclosure of Invention
Problems to be solved by the invention
Here, as electronic components such as a CPU of a personal computer are increased in speed and performance, the heat dissipation amount tends to increase year by year. However, on the contrary, the chip size of a processor or the like has been the same size or smaller than the conventional one due to the progress of the fine silicon circuit technology, and the heat flow rate per unit area has been high. Therefore, in order to avoid such a problem caused by the temperature rise, it is required to efficiently dissipate heat and cool electronic components such as a CPU.
In order to improve the heat radiation characteristics of the heat conductive sheet, it is required to reduce the thermal resistance, which is an index indicating the difficulty of heat conduction. In order to reduce the thermal resistance, it is effective to reduce the thermal resistance by thinning the heat conductive sheet so as to improve the adhesion to the heat sink such as the heat sink or the electronic component as the heat generating body.
When the thermally conductive molded article is cut into thin sheets to form a thermally conductive sheet, the cut sheet surface has irregularities and lacks adhesion. If the adhesion is poor, there is a problem that the heat dissipation member is not sufficiently lowered in thermal resistance because air is contained due to poor adhesion to the heat sink, the electronic component, which is a heating element, and the heat sink.
In order to solve such a problem, there has been proposed a technique of improving adhesion between a thermally conductive sheet and an electronic component by pressing the surface of a thermally conductive sheet produced by cutting a thermally conductive molded body or allowing the thermally conductive sheet to stand for a long period of time to allow uncured components of a binder resin to bleed out to the surface (see patent documents 2 and 3).
However, the binder resin present in the thin thermally conductive sheet has a smaller uncured component than that in the thick thermally conductive sheet, and does not sufficiently bleed out to the sheet surface even when pressed, and the binder does not uniformly bleed out to the sheet surface, and there is a problem that the thermal resistance increases due to variation in adhesion caused by the difference in the surface position of the thermally conductive sheet.
Further, if the thermally conductive sheet after dicing is a soft sheet containing a large amount of uncured components, there is a problem that the sheet is stretched and cannot maintain its shape when being pressed between the electronic component and the heat dissipation member for a long period of time. On the other hand, if the sheet is a hard heat conductive sheet, the uncured component of the binder resin is small, and even if pressed, the adhesive resin is less likely to bleed out, and the surface of the cover sheet is not reached, thereby improving the adhesion. Such a problem is similar to the case of standing the thermally conductive sheet, and there is a problem that the adhesion becomes insufficient.
Accordingly, an object of the present invention is to provide a method for producing a thermally conductive sheet, which can efficiently bleed out an uncured component of a binder resin onto the surface of a molded sheet and improve adhesion.
Means for solving the problems
In order to solve the above problems, the method for producing a thermally conductive sheet according to the present invention comprises a step of forming a thermally conductive resin composition containing a thermally conductive filler in a binder resin into a predetermined shape and curing the composition to form a thermally conductive molded article, a step of cutting the thermally conductive molded article into a sheet shape to form a molded article sheet, and a step of pressing the molded article sheet under a reduced pressure atmosphere to coat the surface of the molded article sheet with an uncured component of the binder resin oozing out from the sheet main body of the molded article sheet.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, the heat conductive sheet is formed by pressing the molded sheet under a reduced pressure environment, whereby uncured components of the binder resin carried by the sheet main body can be efficiently exuded to cover the sheet surface.
Drawings
Fig. 1 is a cross-sectional view showing a thermally conductive sheet to which the present invention is applied.
Fig. 2 is a perspective view showing an example of a process of cutting a thermally conductive molded body.
Fig. 3 is a cross-sectional view showing a process of pressing a molded sheet to which a release film is attached under a reduced pressure atmosphere.
Fig. 4 is a cross-sectional view showing an example of the semiconductor device.
Description of symbols
1A heat conductive sheet 1,2 a sheet body, 3 a release film, 5a resin coating layer, 6a heat conductive molded body, 7a molded body sheet.
Detailed Description
Hereinafter, a method for manufacturing a thermally conductive sheet according to the present invention will be described in detail with reference to the accompanying drawings. The present invention is not limited to the following embodiments, and various modifications can be made without departing from the spirit of the present invention. The drawings are schematic, and the ratio of the dimensions and the like may be different from the actual ratio. Specific dimensions and the like should be judged with reference to the following description. It is to be noted that the drawings include portions having different dimensional relationships and ratios.
The method for producing a thermally conductive sheet to which the present invention is applied comprises a step (step A) of forming a thermally conductive resin composition containing a thermally conductive filler in a binder resin into a predetermined shape and curing the composition to form a thermally conductive molded body, a step (step B) of cutting the thermally conductive molded body into a sheet shape to form a molded body sheet, and a step (step C) of pressing the molded body sheet under a reduced pressure atmosphere to coat the surface of the molded body sheet with an uncured component of the binder resin oozing out from the sheet body of the molded body sheet.
The thermally conductive sheet produced through the above-described steps has an uncured component of the binder resin that does not contribute to the reaction supported by the sheet main body of the molded sheet, and the molded sheet is pressed under a reduced pressure environment, whereby the uncured component of the binder resin supported by the sheet main body can be efficiently oozed out to cover the sheet surface.
Thus, according to the present invention, even a sheet body which is cut thin and has no large amount of uncured component including a binder resin can be coated by bleeding the uncured component out of the entire surface of the sheet. Further, the sheet main body which is cured from the binder resin, is relatively hard and excellent in shape retention, but does not contain a large amount of uncured component of the binder resin, and can be coated by bleeding the uncured component over the entire surface of the sheet.
Therefore, according to the thermally conductive sheet manufactured by the present invention, the adhesion to the electronic component and the heat dissipation member can be improved and the thermal resistance can be reduced, regardless of the irregularities on the sheet surface. In addition, according to the thermally conductive sheet manufactured by the present invention, it is not necessary to apply an adhesive for adhering the thermally conductive sheet to the electronic component or the heat dissipation member to the surface of the sheet, and the thermal resistance of the sheet does not increase. Further, the thermally conductive sheet containing the thermally conductive filler in the binder resin can not only reduce thermal resistance from a low load region, but also be excellent in adhesive force (adhesive force) and can improve mountability and thermal characteristics.
[ Constitution of thermally conductive sheet ]
Fig. 1 shows a thermally conductive sheet 1 to which the present invention is applied. The thermally conductive sheet 1 has a sheet body 2, and the sheet body 2 is formed by curing a binder resin containing at least a polymer matrix component and a thermally conductive filler. Both sides of the sheet main body 2 are coated with an uncured component of the binder resin oozing out from the sheet main body 2, thereby forming a resin coating layer 5. The thermally conductive sheet 1 has release films 3 adhered to both surfaces of the sheet main body 2, and uncured components of the binder resin constituting the resin coating layer 5 are held between the release films 3 and the sheet main body 2.
The both sides of the sheet main body 2 of the heat conductive sheet 1 are provided with the resin coating layer 5 to have adhesiveness, and when in use, the release film 3 is peeled off to be able to be attached to a predetermined position, and even when the surface of the sheet main body 2 has irregularities, the adhesiveness to the electronic component or the heat dissipation member can be improved by the resin coating layer 5.
[ Polymer matrix component ]
The polymer matrix component constituting the sheet main body 2 is a polymer component as a base material of the heat conductive sheet 1. The type of the polymer is not particularly limited, and a known polymer matrix component may be appropriately selected. For example, one of the polymer matrix components is a thermosetting polymer.
Examples of the thermosetting polymer include crosslinked rubber, epoxy resin, polyimide resin, bismaleimide resin, benzocyclobutene resin, phenol resin, unsaturated polyester, diallyl phthalate resin, silicone resin, polyurethane, polyimide silicone, heat-curable polyphenylene ether, heat-curable modified polyphenylene ether, and the like. The number of these may be 1 alone or 2 or more.
Examples of the crosslinked rubber include natural rubber, butadiene rubber, isoprene rubber, nitrile rubber, hydrogenated nitrile rubber, chloroprene rubber, ethylene propylene rubber, chlorinated polyethylene, chlorosulfonated polyethylene, butyl rubber, halogenated butyl rubber, fluororubber, urethane rubber, acrylic rubber, polyisobutylene rubber, and silicone rubber. The number of these may be 1 alone or 2 or more.
Among these thermosetting polymers, silicone resins are preferably used in view of excellent moldability and weather resistance, and adhesion to electronic parts and followability. The silicone resin is not particularly limited, and the type of silicone resin may be appropriately selected according to the purpose.
From the viewpoint of obtaining the molding processability, weather resistance, adhesion, and the like, the silicone resin is preferably a silicone resin composed of a main agent of a liquid silicone gel and a curing agent. Examples of such silicone resins include addition reaction type liquid silicone resins, and heat-curable kneading type silicone resins using peroxides for vulcanization. Among them, the addition reaction type liquid silicone resin is particularly preferable as a heat radiating member of an electronic device because adhesion between a heat generating surface and a heat sink surface of an electronic component is required.
As the addition reaction type liquid silicone resin, a two-component addition reaction type silicone resin having a vinyl group-containing polyorganosiloxane as a main agent and a si—h group-containing polyorganosiloxane as a curing agent is preferably used.
Here, the liquid silicone component includes a silicone a liquid component as a main agent and a silicone B liquid component containing a curing agent, and the amount of the silicone a liquid component is preferably equal to or greater than the amount of the silicone B liquid component. Thus, the heat conductive sheet 1 can provide flexibility to the sheet body 2, and the uncured component of the binder resin (polymer matrix component) can be oozed out to the surfaces 2a, 2b of the sheet body 2 by the pressing step, thereby forming the resin coating layer 5.
The content of the polymer matrix component in the thermally conductive sheet of the present invention is not particularly limited, and may be appropriately selected according to the purpose, but is preferably about 15% by volume to 50% by volume, more preferably 20% by volume to 45% by volume, from the viewpoints of securing the moldability of the sheet, the adhesion of the sheet, and the like.
[ Thermally conductive filler ]
The thermally conductive filler contained in the thermally conductive sheet 1 is a component for improving the thermal conductivity of the sheet. The type of the thermally conductive filler is not particularly limited as long as it is a material having high thermal conductivity, and examples thereof include fibrous thermally conductive fillers such as carbon fibers, metals such as silver, copper, and aluminum, ceramics such as alumina, aluminum nitride, silicon carbide, and graphite. Among these fibrous thermally conductive fillers, carbon fibers are preferably used in order to obtain higher thermal conductivity.
In addition, the thermally conductive filler may be used alone or in combination of two or more. In the case of using two or more types of the thermally conductive filler, the thermally conductive filler may be a fibrous thermally conductive filler, or a mixture of a fibrous thermally conductive filler and a thermally conductive filler having another shape may be used.
The type of the carbon fiber is not particularly limited, and may be appropriately selected according to the purpose. For example, pitch-based carbon fibers, PAN-based carbon fibers, carbon fibers obtained by graphitizing PBO fibers, and carbon fibers synthesized by arc discharge method, laser evaporation method, CVD method (chemical vapor deposition method), CCVD method (catalyst chemical vapor deposition method), or the like can be used. Among them, carbon fibers obtained by graphitizing PBO fibers and pitch-based carbon fibers are more preferable in view of obtaining high thermal conductivity.
The carbon fiber may be partially or entirely surface-treated as needed. Examples of the surface treatment include oxidation treatment, nitridation treatment, nitration, sulfonation, and treatment for attaching or bonding a metal, a metal compound, an organic compound, or the like to the surface of the carbon fiber or the functional group introduced to the surface by these treatments. Examples of the functional group include a hydroxyl group, a carboxyl group, a carbonyl group, a nitro group, and an amino group.
Further, the average fiber length (average long axis length) of the carbon fibers may be appropriately selected without particular limitation, and is preferably in the range of 50 μm to 300 μm, more preferably in the range of 75 μm to 275 μm, and particularly preferably in the range of 90 μm to 250 μm, from the viewpoint of reliably obtaining high thermal conductivity.
Further, the average fiber diameter (average short axis length) of the carbon fibers may be appropriately selected without particular limitation, and is preferably in the range of 4 μm to 20 μm, more preferably in the range of 5 μm to 14 μm, in order to reliably obtain high thermal conductivity.
The aspect ratio (average major axis length/average minor axis length) of the carbon fiber is preferably 8 or more, more preferably 9 to 30, in view of reliably obtaining high thermal conductivity. If the aspect ratio is less than 8, the fiber length (long axis length) of the carbon fiber is short, and therefore there is a concern that the thermal conductivity may be lowered, while if it exceeds 30, the dispersibility in the thermally conductive sheet may be lowered, and therefore there is a concern that sufficient thermal conductivity may not be obtained.
Here, the average major axis length and the average minor axis length of the carbon fibers may be measured by, for example, a microscope, a Scanning Electron Microscope (SEM), or the like, and an average value may be calculated from a plurality of samples.
The content of the fibrous thermal conductive filler in the thermal conductive sheet 1 is not particularly limited, and may be appropriately selected according to the purpose, and is preferably 4% by volume to 40% by volume, more preferably 5% by volume to 35% by volume. If the content is less than 4% by volume, it may be difficult to obtain a sufficiently low thermal resistance, and if it exceeds 40% by volume, the moldability of the thermal conductive sheet 1 and the orientation of the fibrous thermal conductive filler may be affected. The content of the thermal conductive filler including the fibrous thermal conductive filler in the thermal conductive sheet 1 is preferably 15% by volume to 75% by volume.
[ Mineral filler ]
The thermally conductive sheet 1 may further contain an inorganic filler as a thermally conductive filler. By containing the inorganic filler, the thermal conductivity of the thermal conductive sheet 1 can be further improved, and the strength of the sheet can be improved. The shape, material, average particle diameter, and the like of the inorganic filler are not particularly limited, and may be appropriately selected according to the purpose. Examples of the shape include spherical, elliptic spherical, block, granular, flat, needle-like, and the like. Among them, the spherical or elliptical shape is preferable from the viewpoint of filling properties, and the spherical shape is particularly preferable.
Examples of the material of the inorganic filler include aluminum nitride (aluminum nitride: alN), silicon dioxide, aluminum oxide (aluminum oxide), boron nitride, titanium dioxide, glass, zinc oxide, silicon carbide, silicon (silicon), silicon oxide, and metal particles. One kind of them may be used alone, or two or more kinds may be used in combination. Among them, aluminum oxide, boron nitride, aluminum nitride, zinc oxide, and silicon dioxide are preferable, and aluminum oxide and aluminum nitride are particularly preferable in terms of thermal conductivity.
In addition, in the case of the optical fiber, the inorganic filler may be used and implemented surface treated inorganic filler is provided. As the surface treatment, if the inorganic filler is treated with a coupling agent, the dispersibility of the inorganic filler is improved and the flexibility of the thermally conductive sheet is improved.
The average particle diameter of the inorganic filler may be appropriately selected according to the type of inorganic material. When the inorganic filler is alumina, the average particle diameter is preferably 1 μm to 10. Mu.m, more preferably 1 μm to 5. Mu.m, particularly preferably 4 μm to 5. Mu.m. If the average particle diameter is less than 1. Mu.m, the viscosity may be increased, and the mixing may be difficult. On the other hand, if the average particle diameter exceeds 10 μm, there is a concern that the thermal resistance of the thermal conductive sheet 1 becomes large.
Further, when the inorganic filler is aluminum nitride, the average particle diameter thereof is preferably 0.3 μm to 6.0 μm, more preferably 0.3 μm to 2.0 μm, particularly preferably 0.5 μm to 1.5 μm. If the average particle diameter is less than 0.3 μm, the viscosity may be increased, and mixing may be difficult, and if it exceeds 6.0 μm, the thermal resistance of the thermal conductive sheet 1 may be increased.
The average particle diameter of the inorganic filler can be measured by, for example, a particle size distribution meter or a Scanning Electron Microscope (SEM).
[ Other Components ]
The thermally conductive sheet 1 may contain other components as appropriate according to the purpose, in addition to the polymer matrix component and the thermally conductive filler. Examples of the other components include magnetic metal powder, thixotropic agent, dispersant, curing accelerator, retarder, micro tackifier, plasticizer, flame retardant, antioxidant, stabilizer, colorant, and the like. Further, electromagnetic wave absorption performance may be imparted to the heat conductive sheet 1 by adjusting the content of the magnetic metal powder.
[ Process for producing thermally conductive sheet ]
[ Procedure A ]
Next, a process for manufacturing the thermally conductive sheet 1 will be described. As described above, the process for producing the thermally conductive sheet 1 to which the present invention is applied includes the step a of forming the thermally conductive resin composition containing the thermally conductive filler in the binder resin into a predetermined shape and curing the composition to form the thermally conductive molded body.
In this step a, the polymer base component, the thermally conductive filler, and other components appropriately contained therein are blended to prepare a thermally conductive resin composition. The steps of blending and preparing the components are not particularly limited, and for example, the thermally conductive resin composition is prepared by adding a thermally conductive filler, an appropriate inorganic filler, a magnetic metal powder, and other components to the polymer matrix component and mixing them.
Next, a fibrous thermally conductive filler such as carbon fiber is oriented in one direction. The method of orientation of the filler is not particularly limited as long as it can be oriented in one direction. For example, by extruding or pressing the thermally conductive resin composition into a hollow mold under a high shear force, the fibrous thermally conductive filler can be relatively easily oriented in one direction, and the orientation of the fibrous thermally conductive filler can be made the same (within ±10°).
The method of extruding or pressing the thermally conductive resin composition into a hollow mold under high shear force is specifically an extrusion molding method or a mold molding method. When the thermally conductive resin composition is extruded from a die in the extrusion molding method or when the thermally conductive resin composition is pressed into a die in the die molding method, the thermally conductive resin composition flows, and the fibrous thermally conductive filler is oriented in the flow direction. At this time, if a slit is installed at the front end of the die, it is easier to orient the fibrous thermally conductive filler.
The heat conductive resin composition extruded or pressed into a hollow mold is molded into a block (shape) corresponding to the shape and size of the mold, and the polymer matrix component is cured while maintaining the oriented state of the fibrous heat conductive filler, thereby forming a heat conductive molded body. The thermally conductive molded article is a sheet cutting base material (molded article) that is a raw material of the thermally conductive sheet 1 obtained by cutting into a predetermined size.
The size and shape of the hollow mold and the thermally conductive molded body can be determined according to the size and shape of the thermally conductive sheet 1 required, and examples thereof include rectangular parallelepiped having a cross section of 0.5cm to 15cm in the longitudinal direction and 0.5cm to 15cm in the lateral direction. The length of the cuboid is determined according to the requirement.
The method and conditions for curing the polymer matrix component may be changed depending on the type of the polymer matrix component. For example, when the polymer matrix component is a thermosetting resin, the curing temperature at the time of thermosetting may be adjusted. Further, when the thermosetting resin contains a main agent of a liquid silicone gel and a curing agent, it is preferable to cure at a curing temperature of 80 ℃ to 120 ℃. The curing time during the heat curing is not particularly limited, and may be 1 to 10 hours.
In step a, the uncured component is supported instead of the entire amount of the polymer matrix component being cured. The uncured component penetrates the surface of the sheet in a step of pressing the molded sheet in a reduced pressure atmosphere, which will be described later, to form a resin coating layer having tackiness.
[ Procedure B ]
As shown in fig. 2, the process for producing the thermally conductive sheet 1 to which the present invention is applied includes a step B of cutting the thermally conductive molded body 6 into a sheet shape to form a molded body sheet 7. In this step B, the thermally conductive resin molded body 6 is cut into a sheet shape so as to form an angle of 0 ° to 90 ° with respect to the longitudinal direction of the fibrous thermally conductive filler after orientation.
The thermally conductive molded body 6 is cut by a cutting device. The cutting device is not particularly limited as long as it can cut off the thermally conductive molded body 6, and a known cutting device can be suitably used. For example, an ultrasonic cutter, a planer (planing), or the like may be used.
The thickness of the molded sheet 7 is set appropriately according to the use of the thermally conductive sheet 1, and is, for example, 0.2mm to 1.0mm.
In step B, the plurality of molded body pieces 7 may be reduced in size by applying a cutting mark to the molded body pieces 7 cut out from the thermally conductive molded body 6.
[ Procedure C ]
The process for producing the thermally conductive sheet 1 to which the present invention is applied includes a step C of covering the surface of the molded body sheet 7 with an uncured component of the binder resin oozing out from the sheet main body of the molded body sheet 7 by pressing the molded body sheet 7 under a reduced pressure environment.
The reduced pressure environment is a vacuum pressure lower than that in an ordinary pressure (atmospheric pressure) environment in which no reduced pressure treatment is performed, and is set so as to be capable of bleeding the uncured component of the binder resin over the entire surface of the sheet, and may be appropriately set depending on the thickness of the molded article sheet, the blending ratio of the silicone a liquid component as a main component of the liquid silicone component constituting the binder resin and the silicone B liquid component containing the curing agent, and the like. For example, a gauge pressure gauge in which the atmospheric pressure is set to zero in a reduced pressure environment may be set to-0.2 kPa. If the vacuum pressure x (kPa) in the pressing step is too low, the uncured component of the binder resin volatilizes to impair the tackiness of the sheet surface, and if too high, bleeding of the uncured component cannot be promoted, and for example, the range of-5.0 kPa.ltoreq.x.ltoreq.0.1 kPa may be appropriately set.
As for the above-mentioned pressing, for example, a pair of pressing devices formed of a flat plate and a pressing head having a flat surface may be used. In addition, nip rolls may be used for pressing.
The pressure during the pressing is not particularly limited, and may be appropriately selected depending on the purpose, but if too low, the specific thermal resistance tends to be unchanged from that when the pressing is not performed, and if too high, the sheet tends to be stretched, so that the pressure is preferably in the range of 0.1mpa to 100mpa, more preferably in the range of 0.5mpa to 95 mpa.
Here, as described above, in the thermally conductive molded body, not the entire amount of the polymer matrix component is cured, but the molded body sheet has an uncured component of the binder resin (polymer matrix component) supported on the sheet main body, and a part of the uncured component is efficiently oozed out to the sheet surface by the pressing step in a reduced pressure environment. This can form the thermally conductive sheet 1 having the resin coating layer formed on the sheet surface. The thermally conductive sheet 1 has adhesiveness due to the resin coating layer 5 formed on the sheet surface.
Further, by performing the pressing step, the surface of the molded sheet is smoothed, so that the adhesion of the thermally conductive sheet 1 is enhanced, and the interface contact resistance at the time of load reduction can be reduced.
Thus, according to the present invention, even a sheet body which is cut thin and has no large amount of uncured component including a binder resin can be coated by bleeding the uncured component out over the entire surface of the sheet. Further, the sheet main body which is cured from the binder resin, is relatively hard and excellent in shape retention, but does not contain a large amount of uncured component of the binder resin, and can be coated by bleeding the uncured component over the entire surface of the sheet.
Therefore, according to the thermally conductive sheet manufactured by the present invention, the adhesion to the electronic component and the heat dissipation member can be improved and the thermal resistance can be reduced, regardless of the irregularities on the sheet surface. In addition, according to the thermally conductive sheet manufactured by the present invention, it is not necessary to apply an adhesive for adhering the thermally conductive sheet to the electronic component or the heat dissipation member to the surface of the sheet, and the thermal resistance of the sheet does not increase. Further, the thermally conductive sheet containing the thermally conductive filler in the binder resin can reduce the thermal resistance from the low load region, is excellent in the adhesive force (adhesive force), and can improve the mountability and thermal characteristics.
[ Release film ]
In the step C, as shown in fig. 3, it is preferable to press the molded sheet 7 in a state where the release film 3 is attached to at least one surface, preferably both surfaces. As the release film 3, for example, a PET film is used. The release film 3 may be subjected to a release treatment on the surface of the molded body sheet 7 to be adhered.
By adhering the release film 3 to the surface of the sheet body of the molded sheet 7, uncured components that ooze out to the sheet surface in the pressing step under a reduced pressure environment are held on the sheet surface by the tension acting between the release film 3, and the resin coating layer 5 that uniformly covers the entire surface of the sheet surface can be formed with a uniform thickness. This eliminates variation in adhesion and reduces thermal resistance of the thermally conductive sheet 1.
By going through the above steps, the thermally conductive sheet 1 is formed. In addition, the thermal conductive sheet 1 is used to release the release film 3 in actual use, thereby exposing the adhesive resin coating layer 5 for mounting on electronic components and the like.
[ Use form example ]
In actual use, the release film 3 of the thermally conductive sheet 1 is peeled off and mounted in electronic parts such as semiconductor devices and various electronic devices.
As shown in fig. 4, for example, the heat conductive sheet 1 is mounted on a semiconductor device 50 incorporated in various electronic devices, and is sandwiched between a heat source and a heat radiation member. The semiconductor device 50 shown in fig. 4 includes at least an electronic component 51, a heat spreader (HEAT SPREADER) 52, and a heat conductive sheet 1, and the heat conductive sheet 1 is sandwiched between the heat spreader 52 and the electronic component 51. By using the heat conductive sheet 1, the semiconductor device 50 has high heat dissipation properties, and also has excellent electromagnetic wave suppression effects depending on the content of the magnetic metal powder in the binder resin.
The electronic component 51 is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include various semiconductor elements such as a CPU, an MPU, a graphics processing element, and an image sensor, an antenna element, and a battery. The soaking sheet 52 is not particularly limited as long as it is a member for radiating heat generated from the electronic component 51, and may be appropriately selected according to the purpose. The heat conductive sheet 1 is sandwiched between the heat spreader 52 and the electronic component 51. The heat conductive sheet 1 is sandwiched between the heat spreader 52 and the heat sink 53, and thus constitutes a heat dissipation member that dissipates heat of the electronic component 51 together with the heat spreader 52.
The mounting position of the heat conductive sheet 1 is not limited to between the heat spreader 52 and the electronic component 51 and between the heat spreader 52 and the heat sink 53, and may be appropriately selected depending on the configuration of the electronic device and the semiconductor device. The heat dissipation member may be any heat dissipation member that conducts heat generated from a heat source and dissipates the heat to the outside, other than the heat spreader 52 and the heat sink 53, and examples thereof include a radiator, a cooler, a chip carrier, a printed circuit board, a cooling fan, a peltier element, a heat pipe, a metal cover (metal cover), and a case.
Examples
Hereinafter, examples of the present invention will be described. In examples and comparative examples, samples of the thermally conductive sheet were formed by changing the component ratio of the binder component to the curing agent component of the thermally conductive resin composition, and the tackiness and the thermal resistance value were measured for each sample.
[ Measurement of tackiness ]
The tackiness (gf) of the sheet surface of each sample before and immediately after pressing was measured using an tackiness tester (TACKINESS TESTER MODEL TACII, force world Co.). The tackiness was measured 3 times at 5 points in four corners and a center of a rectangular sample, and an average value of the measured values was used. The measurement conditions are as follows.
Pressing speed (im speed) 30mm/min
The stretching speed (TEST SPEED) is 120mm/min
Initial load (Pre speed): 196g
Pressing time (PRESS TIME) 5sec
Distance of elongation (Distance) 5mm
And (3) a die head:
[ measurement of thermal impedance value ]
The thermal resistance value (K.cm 2/W) of each sample was measured under a load of 1.0kgf/cm 2 by the method according to ASTM-D5470.
Example 1
As shown in table 1, in a two-component addition reaction type liquid silicone, 42 vol% of alumina particles having an average particle diameter of 4 μm, which were subjected to a coupling treatment with a silane coupling agent, and 23 vol% of pitch-based carbon fibers having an average fiber length of 150 μm, which were fibrous fillers, were mixed to prepare a silicone composition (heat conductive resin composition). The two-component addition reaction type liquid silicone resin was prepared by using a silicone resin containing an organopolysiloxane as a main component, and blending the silicone agent a and the agent B in a ratio of 57:43.
The obtained silicone composition was extrusion-molded in a hollow quadrangular mold (50 mm. Times.50 mm) to form a 50mm square silicone molded body. The silicone molded body was heated at 100 ℃ for 6 hours by an oven to prepare a silicone cured product (thermally conductive molded body). The cured silicone was cut by a microtome to a thickness of 0.5mm to obtain a molded sheet. The obtained molded sheet was sandwiched between PET films subjected to a peeling treatment, and then vacuum-pressed under a reduced pressure atmosphere having a gauge pressure of-2.0 kPa under conditions of a pressure of 2MPa, a temperature of 100℃and a pressing time of 3 minutes, whereby a sample of a thermally conductive sheet was obtained. The tackiness of the sample was 20gf before pressing and 178gf after pressing. The thermal resistance value was 0.3 K.cm 2/W.
Example 2
As shown in table 1, 20% by volume of alumina particles having an average particle diameter of 4 μm, which were subjected to coupling treatment with a silane coupling agent, 24% by volume of aluminum nitride particles, and 23% by volume of pitch-based carbon fibers having an average fiber length of 150 μm as a fibrous filler were mixed with a two-component addition reaction type liquid silicone to prepare a silicone composition (thermally conductive resin composition). The two-component addition reaction type liquid silicone resin is prepared by mixing a silicone resin containing an organopolysiloxane as a main component such that the mixing ratio of the silicone agent a to the silicone agent B is 50:50.
The obtained silicone composition was extrusion-molded in a hollow quadrangular mold (50 mm. Times.50 mm) to form a 50mm square silicone molded body. The silicone molded body was heated at 100 ℃ for 6 hours by an oven to prepare a silicone cured product (thermally conductive molded body). The cured silicone was cut by a microtome to a thickness of 0.5mm to obtain a molded sheet. The obtained molded sheet was sandwiched between PET films subjected to peeling treatment, and then vacuum-pressed under a reduced pressure atmosphere having a gauge pressure of-2.0 kPa under conditions of a pressure of 2MPa, a temperature of 100℃and a pressing time of 3 minutes, whereby a sample of a thermally conductive sheet was obtained. The tackiness of the sample was 19gf before pressing and 124gf after pressing. The thermal resistance value was 0.25 K.cm 2/W.
Example 3
As shown in table 1, the same silicone composition (thermally conductive resin composition) as in example 2 was extrusion molded in a hollow quadrangular mold (50 mm×50 mm) to form a 50mm square silicone molded body. The silicone molded body was heated at 100 ℃ for 6 hours by an oven to prepare a silicone cured product (thermally conductive molded body). The cured silicone was cut by a microtome to a thickness of 1.0mm, whereby a molded sheet was obtained. The obtained molded sheet was sandwiched between PET films subjected to peeling treatment, and then vacuum-pressed under a reduced pressure atmosphere having a gauge pressure of-2.0 kPa under conditions of a pressure of 2MPa, a temperature of 100℃and a pressing time of 3 minutes, whereby a sample of a thermally conductive sheet was obtained. The tackiness of the sample was 18gf before pressing and 152gf after pressing. The thermal resistance value was 0.40 K.cm 2/W.
Comparative example 1
As shown in table 1, the same silicone composition (thermally conductive resin composition) as in example 1 was extrusion molded in a hollow quadrangular mold (50 mm×50 mm) to form a 50mm square silicone molded body. The silicone molded body was heated at 100 ℃ for 6 hours by an oven to prepare a silicone cured product (thermally conductive molded body). The cured silicone was cut by a microtome to a thickness of 0.5mm to obtain a molded sheet. After the obtained molded sheet was sandwiched by the PET film subjected to the peeling treatment, the molded sheet was pressed under an atmospheric pressure atmosphere under conditions of a pressure of 2MPa, a temperature of 100℃and a pressing time of 3 minutes, whereby a sample of a thermally conductive sheet was obtained. The tackiness of the sample was 12gf before pressing and 38gf after pressing. The thermal resistance value was 0.40 K.cm 2/W.
Comparative example 2
As shown in table 1, the same silicone composition (thermally conductive resin composition) as in example 2 was extrusion molded in a hollow quadrangular mold (50 mm×50 mm) to form a 50mm square silicone molded body. The silicone molded body was heated at 100 ℃ for 6 hours by an oven to prepare a silicone cured product (thermally conductive molded body). The cured silicone was cut by a microtome to a thickness of 0.5mm to obtain a molded sheet. After the obtained molded sheet was sandwiched by the PET film subjected to the peeling treatment, the molded sheet was pressed under an atmospheric pressure atmosphere under conditions of a pressure of 2MPa, a temperature of 100℃and a pressing time of 3 minutes, whereby a sample of a thermally conductive sheet was obtained. The tackiness of the sample was 14gf before pressing and 19gf after pressing. The thermal resistance value was 0.35 K.cm 2/W.
Comparative example 3
As shown in table 1, the same silicone composition (thermally conductive resin composition) as in example 2 was extrusion molded in a hollow quadrangular mold (50 mm×50 mm) to form a 50mm square silicone molded body. The silicone molded body was heated at 100 ℃ for 6 hours by an oven to prepare a silicone cured product (thermally conductive molded body). The cured silicone was cut by a microtome to a thickness of 1.0mm, whereby a molded sheet was obtained. After the obtained molded sheet was sandwiched by the PET film subjected to the peeling treatment, the molded sheet was pressed under an atmospheric pressure atmosphere under conditions of a pressure of 2MPa, a temperature of 100℃and a pressing time of 3 minutes, whereby a sample of a thermally conductive sheet was obtained. The tackiness of the sample was 13gf before pressing and 15gf after pressing. The thermal resistance was 0.48 K.cm 2/W.
TABLE 1
As in examples 1 to 3, when the molded sheet was sandwiched between the PET films subjected to the peeling treatment and then vacuum-pressed, the adhesiveness was increased, and the uncured component of the binder resin was efficiently oozed out to the surface of the molded sheet.
When comparing example 1 with comparative example 1, it was found that even when the sheet thickness was as small as 0.5mm, the uncured component carried in the sheet main body was small, and the bleeding of the uncured component was promoted under a reduced pressure atmosphere under the condition that the bleeding of the uncured component was not easily generated under normal pressure, the tackiness was also high, and the tackiness was obtained over the entire surface of the sheet.
In examples 2 and 3 and comparative examples 2 and 3, the silicone a agent and the B agent were blended so that the blending ratio of the silicone a agent and the B agent was 50:50, whereby the uncured component carried in the sheet main body was small, the hardness was also high, and the bleeding of the uncured component was not likely to occur, but the bleeding of the uncured component was promoted under a reduced pressure atmosphere, and in example 2, the adhesive properties were exhibited on the surface by the bleeding of the uncured component even under the condition that the bleeding of the uncured component was not likely to occur even when the sheet thickness was 0.5 mm.
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| JP6986648B2 (en) * | 2020-05-28 | 2021-12-22 | デクセリアルズ株式会社 | Heat conduction sheet and its manufacturing method, heat dissipation structure and electronic equipment |
| US20220240411A1 (en) * | 2020-05-28 | 2022-07-28 | Dexerials Corporation | Thermal conductive sheet and method for producing the same, and heat dissipation structure and electronic device |
| JP6987941B1 (en) * | 2020-09-11 | 2022-01-05 | デクセリアルズ株式会社 | Method for manufacturing a heat conductive sheet and a heat conductive sheet |
| JP2022125691A (en) * | 2021-02-17 | 2022-08-29 | デクセリアルズ株式会社 | Method for manufacturing thermal conductive sheet, thermal conductive sheet package, and method for manufacturing thermal conductive sheet package |
| WO2022176748A1 (en) * | 2021-02-19 | 2022-08-25 | デクセリアルズ株式会社 | Heat conductive sheet and method for manufacturing heat conductive sheet |
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| JP7096723B2 (en) | 2022-07-06 |
| JP2020013872A (en) | 2020-01-23 |
| CN110739223A (en) | 2020-01-31 |
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