CN116802796A

CN116802796A - Method for manufacturing heat conductive member and dispenser device

Info

Publication number: CN116802796A
Application number: CN202280013566.0A
Authority: CN
Inventors: 石原实步; 野中智治
Original assignee: Polymatech Japan Co Ltd
Current assignee: Sekisui Polymatech Co Ltd
Priority date: 2021-03-31
Filing date: 2022-03-25
Publication date: 2023-09-22
Also published as: TW202247380A; JPWO2022210420A1; WO2022210420A1; JP7248222B2

Abstract

The method for manufacturing the heat conductive member comprises the following steps: a step of preparing a thermally conductive composition R containing a liquid resin and an anisotropic thermally conductive filler, the thermally conductive composition R having a puncture load of 8 to 60gf, the puncture load being stress when puncturing is performed at a puncture speed of 10 mm/min by a pressure rod having a pressing surface with a diameter of 3 mm; and a step of discharging the thermally conductive composition R in a plurality of sheets in a superimposed manner using a dispenser device having a wide-width-shaped discharge port 53 to obtain a laminate.

Description

Method for manufacturing heat conductive member and dispenser device

Technical Field

The present invention relates to a method for manufacturing a heat conductive member, and a dispenser device used in the method for manufacturing a heat conductive member, for example.

Background

In electronic devices such as computers, automobile parts, and mobile phones, a radiator such as a radiator is generally used for radiating heat generated by a heat generating element such as a semiconductor element or a mechanical part. It is known that a heat conductive member such as a heat conductive sheet is disposed between a heating element and a heat radiating body for the purpose of improving heat transfer efficiency from heat to the heat radiating body.

The thermally conductive sheet generally contains a polymer matrix and a thermally conductive filler dispersed in the polymer matrix. In order to improve the thermal conductivity in a specific direction, the thermal conductive sheet often orients an anisotropic filler having an anisotropic shape in one direction.

The heat conductive sheet in which the anisotropic filler is oriented in one direction is manufactured, for example, as follows: the anisotropic filler is produced by stretching, extruding and molding to obtain 1-time sheets each having an anisotropic filler oriented in the sheet surface direction, solidifying or semi-solidifying the 1-time sheets, integrating the 1-time sheets by stacking a plurality of sheets, and vertically slicing the obtained material. This production method is also called a flow orientation method. According to the flow alignment method, a thermally conductive sheet having a plurality of stacked unit layers with a small thickness can be obtained. The anisotropic filler can be oriented in the thickness direction of the sheet (see patent document 1, for example).

In addition, as the polymer matrix of the heat conductive sheet, silicone resins are widely used from the viewpoints of heat conductivity, heat resistance, and the like. However, if a heat conductive sheet is produced by a flow orientation method using a silicone resin for a polymer matrix, the adhesiveness between the 1 st sheets may be weakened, and in the dicing step or the like, defects such as peeling between the 1 st sheets may occur. For this reason, for example, patent document 2 discloses that when a silicone resin is used for a polymer matrix, vacuum Ultraviolet (VUV) is irradiated to the surface of 1 st sheet to improve the adhesion between 1 st sheets, and then 1 st sheets are stacked.

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 2013-254880

Patent document 2: international publication No. 2020/105601

Disclosure of Invention

Problems to be solved by the invention

However, as disclosed in patent document 1, in the method of forming 1 sheet by extrusion molding and then slicing, there is a problem that a large amount of end materials and materials are wasted in each step. Further, as disclosed in patent document 2, if VUV irradiation is used, the apparatus becomes large-scale, and thus it is desired that it can be manufactured by a simple apparatus.

Accordingly, an object of the present invention is to provide a method for producing a heat conductive member, which is less wasteful of material and which can appropriately produce a heat conductive member in which an anisotropic heat conductive filler is oriented in one direction by a simple apparatus.

Means for solving the problems

The present inventors have conducted intensive studies and as a result, have found that the above problems can be solved by using a dispenser device having a wide-width-shaped discharge port to discharge a thermally conductive composition having predetermined physical properties in a sheet form and laminating the composition to form a laminate, and have completed the present invention as described below. The present invention is based on the following items [1] to [16 ].

[1] A method for manufacturing a heat conductive member, comprising the steps of:

a step of preparing a thermally conductive composition which contains a liquid resin and an anisotropic thermally conductive filler and has a puncture load of 8 to 60gf, wherein the puncture load is stress when puncturing is performed at a puncture speed of 10 mm/min by a pressure rod having a pressing surface with a diameter of 3 mm; and

and a step of obtaining a laminate by discharging the thermally conductive composition in a sheet-like manner so as to overlap the thermally conductive composition in a plurality of sheets by using a dispenser device having a wide-width-shaped discharge port.

[2] The method for producing a heat conductive member according to the above [1], wherein the liquid resin is a curable liquid resin,

the method for manufacturing a heat conductive member further comprises the steps of: and a step of curing the thermally conductive composition after the laminate is obtained.

[3] The method for producing a heat conductive member according to the above [1] or [2], further comprising the steps of: cutting the laminate in a direction intersecting the laminate surface.

[4] The method for producing a heat conductive member according to any one of [1] to [3], wherein the liquid resin contains a volatile compound.

[5] The method for producing a thermally conductive composition according to the above [4], further comprising the steps of: and volatilizing the volatile compound.

[6] The method for producing a heat conductive member according to any one of the above [1] to [5], further comprising the steps of: and compressing the laminate in the lamination direction to deform the laminate to a thickness of 75 to 97%.

[7] The method of manufacturing a heat conductive member according to any one of [1] to [6], wherein a plurality of sheets are stacked on the stacked body by stacking the sheet-like discharged heat conductive composition while cutting the composition.

[8] The method of manufacturing a heat conductive member according to item [7], wherein the sheet-like discharged heat conductive composition is cut by a cutter provided in the discharge port and moving along a longitudinal direction of the discharge port.

[9] The method for producing a heat conductive member according to any one of [1] to [6], wherein the heat conductive composition discharged in the form of a sheet is folded to obtain the laminate.

[10] The method for producing a heat conductive member according to any one of [1] to [9], wherein the heat conductive composition is discharged between a heat radiator and a heat generator so as to overlap in a plurality of sheets, and a laminate is formed between the heat radiator and the heat generator.

[11] The method for manufacturing a heat conductive member according to [10] above, wherein the heat conductive composition is discharged in a sheet form in a direction connecting the radiator and the heating element.

[12] The method for producing a heat conductive member according to any one of [1] to [11], wherein each sheet in the laminate has a thickness of 0.1 to 9.0mm.

[13] The method for producing a heat conductive member according to any one of [1] to [12], wherein the heat conductive composition is discharged at room temperature.

[14] A dispenser device includes a head and a supply path for supplying a flowable material to the head,

the head has a wide-width outlet and a connection path connecting the supply path and the outlet,

the connection path is connected to the discharge port so that an inner diameter of the connection path in one direction increases from the supply path toward the discharge port.

[15] The dispenser device according to item [14], further comprising a cutter disposed in the discharge port and movable along a longitudinal direction of the discharge port.

[16] The dispenser device according to the above [14] or [15], wherein at least one of the head and the member to be discharged from which the flowable material is discharged is movable in a direction orthogonal to a longitudinal direction of the discharge port.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, the waste of material is small, and the heat conductive member in which the anisotropic heat conductive filler is oriented in one direction can be appropriately manufactured by a simple apparatus.

Drawings

Fig. 1 is a schematic view showing a dispenser device according to an embodiment.

Fig. 2 is a front view showing the head of the dispenser device.

Fig. 3 is a schematic view for explaining step 2 in the method for manufacturing the heat conductive member according to embodiment 1.

Fig. 4 is a schematic diagram for explaining step 5 in the method for manufacturing the heat conductive member according to embodiment 1.

Fig. 5 is a schematic cross-sectional view showing an example of the heat conductive member.

Fig. 6 is a schematic diagram for explaining a method of manufacturing the heat conductive member according to embodiment 2.

Fig. 7 is a schematic view for explaining a method of manufacturing a heat conductive member according to embodiment 3.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail. First, a dispenser device used in a method for manufacturing a heat conductive member will be described.

[ Dispenser device ]

As shown in fig. 1, the dispenser device 50 includes a head 51 and a supply path 52 for supplying a flowable material to the head 51. The head 51 includes a discharge port 53 and a connection path 54. The connection path 54 connects the discharge port 53 with the supply path 52. A table 57 is provided below the head 51, and the discharge port 53 is opposed to the table 57.

In the present manufacturing method, the flowable material is a thermally conductive composition, and may have fluidity and may be kept in a certain shape (for example, a sheet shape) when discharged to the table 57 or the like. In the following description, the direction of discharging the flowable material is MD (Machine Direction) and the lateral direction is TD (Transverse Direction). MD is the direction orthogonal to TD. Note that the vertical direction perpendicular to both MD and TD will be described as ZD.

As shown in fig. 2, the head 51 has a shape extending in the Transverse Direction (TD), and a discharge port 53 is provided in a lower surface 51A thereof. The discharge port 53 has a wide shape, that is, a long and slender shape having a Transverse Direction (TD) as shown in fig. 1 and 2. In addition, the discharge port 53 is generally rectangular.

The size of the discharge port 53 is not particularly limited, but the length L1 in TD is, for example, 2 to 100cm, preferably 5 to 50cm, and the length L2 in MD is, for example, 0.1 to 9.0mm, preferably 1.0 to 5.0mm. The length ratio L1/L2 is, for example, 3 to 1000, preferably 5 to 500, and more preferably 20 to 200.

The connection path 54 is connected to the discharge port 53 from the supply path 52 toward the discharge port 53, and increases in one direction (TD) to a size corresponding to the length L1 of the discharge port. The connection path 54 is connected to the discharge port 53 such that the inner diameter in the direction (MD) orthogonal to the TD decreases from the supply path 52 toward the discharge port 53 to a size corresponding to the length L2.

In the dispenser device 50, one end of the supply path 52 is connected to the tank 56. The tank 56 is provided with a pump, not shown, by which the flowable material stored in the tank 56 can be supplied to the head 51 via the supply passage 52 in a pressurized state. The supply passage 52 is formed by a pressure-resistant pipe body so that the pressurized flowable material can be supplied.

The table 57 is movable in the MD (i.e., in a direction orthogonal to the longitudinal direction of the discharge port 53) to discharge the flowable material from the discharge port 53, and the table 57 is movable in the MD to cause the flowable material discharged from the discharge port 53 to flow in the MD to be sheet-like. The thickness of the discharged sheet-like flowable material is substantially the same as the length L2.

Further, the table 57 may be movable along the ZD, and for example, when the flowable materials are discharged in a sheet shape and further overlapped, the table is preferably movable downward.

The dispenser device 50 further includes a cutter 58 disposed at the discharge port 53. In the present embodiment, the cutter 58 is a wire cutter disposed below the lower surface 51A. Both ends of the wire cutter are attached to attachment portions 51X, 51Y provided on the head 51. The attachment portions 51X and 51Y are movable in the head 51 along TD (i.e., in the longitudinal direction of the discharge port 53), and by moving these attachment portions 51X and 51Y, the cutter 58 is also movable in the Transverse Direction (TD). Further, by moving the cutter 58 in the TD, the flowable material discharged from the discharge port 53 can be cut. In addition, as in embodiment 2 described later, the cutter 58 may be omitted in the case where the flowable material is not cut every time each layer is formed.

In addition, the dispenser device 50 may enable the head 51 to move instead of the table 57. The head 51 is particularly preferably movable in the MD, and may further be movable in the ZD. By moving the head in the MD, the flowable material can be discharged in a sheet form in the MD without moving the table 57. Further, by moving the head along ZD, it is possible to further discharge the flowable material on the flowable material discharged in a sheet-like manner without moving the table 57.

Further, the dispenser device 50 may be movable only by one of the table 57 and the head 51, but may be movable by both.

The member for discharging the fluid material (discharged member) need not be the table 57, but the table 57 may be omitted, and members other than the table 57 may be used. Further, the member may be a member disposed on the table 57. These discharged members may be movable along ZD or MD as in the table 57.

Further, the head 51 of the dispenser device 50 may be swingable about the upper end portion. If the head 51 swings around the upper end, for example, as shown in embodiment 3 described below, when the flowable material is discharged between 2 members disposed above the discharged member, the flowable material can be discharged by contacting the 2 members with each other.

In addition, although the number of tanks 56 of the dispenser device 50 is 1, in the case where the liquid resin is a two-component curing type, tanks for storing the 1 st liquid and the 2 nd liquid may be provided, respectively, and mixed immediately before being supplied to the head 51 and then supplied to the head 51.

[ embodiment 1]

Method for producing heat conductive member

Next, a method for manufacturing a heat conductive member according to embodiment 1 of the present invention will be described in detail. The heat conductive member according to embodiment 1 is manufactured by a manufacturing method including the following steps 1 to 5. In embodiment 1, it is preferable to sequentially execute steps 1 to 5.

Step 1: a step of preparing a thermally conductive composition containing a curable liquid resin and a thermally conductive filler

Step 2: a step of discharging the thermally conductive composition obtained in step 1 in a plurality of sheets overlapped by using a dispenser device to obtain a laminate

And step 3: compressing the obtained laminate in the lamination direction

And 4, step 4: a step of curing the thermally conductive composition

And step 5: cutting the laminate along a direction intersecting the laminate surface

[ procedure 1]

In step 1, a thermally conductive composition containing a curable liquid resin and a thermally conductive filler is prepared. The thermally conductive composition contains an anisotropic thermally conductive filler (hereinafter also simply referred to as "anisotropic filler") as a thermally conductive filler. The anisotropic filler is a filler having an anisotropic shape and heat conductivity, and is an orientable filler. In the present manufacturing method, since the anisotropic filler is oriented in the discharge direction in step 2, the thermal conductivity of the thermal conductive member in one direction can be improved. However, the thermally conductive composition preferably contains, as a thermally conductive filler, a non-anisotropic thermally conductive filler (hereinafter also simply referred to as "non-anisotropic filler") in addition to the anisotropic filler. Details of the thermally conductive filler material are described below.

The puncture load of the thermally conductive composition prepared in step 1 is 8 to 60gf when the puncture speed is 10 mm/min. If the puncture load is less than 8gf, if a plurality of sheet-like thermally conductive compositions discharged from the dispenser device are superimposed, the thermally conductive compositions spread due to their own weight, and thus a laminate having a thickness of not less than a certain level cannot be obtained, and defects such as alignment disorder occur. If the flow rate exceeds 60gf, a problem such as failure to discharge the thermally conductive composition from the dispenser device 50 occurs. From the viewpoint of further suppressing the expansion due to the self weight, the puncture load is preferably 10gf or more, more preferably 16gf or more. In addition, from the viewpoint of improving the discharge performance from the dispenser device 50, the puncture load is preferably 50gf or less, more preferably 35gf or less.

The puncture load at a puncture speed of 10 mm/min was the stress at which the thermally conductive composition was punctured at a puncture speed of 10 mm/min by a pressure rod having a pressing surface with a diameter of 3 mm. The puncture load is measured at a temperature (discharge temperature) at which the thermally conductive composition is discharged from the discharge port.

The puncture load can be adjusted by appropriately selecting the raw materials used for the thermally conductive composition. Specifically, the viscosity of the liquid resin, the type and amount of the anisotropic filler, the type and amount of the non-anisotropic filler, the presence or absence of the liquid component other than the liquid resin, the type and amount of the liquid component, and the like can be adjusted.

In the present invention, the thermally conductive composition is required to have a high viscosity so as to be discharged in a sheet form from the dispenser device and to be stacked to form a laminate. In general, the viscosity measured by a viscometer such as a B-type viscometer is an index showing the viscosity of the thermally conductive composition, but a high-viscosity thermally conductive composition containing an anisotropic filler may slide with respect to a sample by a rotor of the B-type viscometer, and it is difficult to accurately measure the viscosity by the viscometer.

On the other hand, the puncture load value is effective as an index indicating the viscosity of a composition containing a thermally conductive filler such as an anisotropic filler and having a high viscosity, and thus, in the present invention, the puncture load is used.

The thermally conductive composition preferably has a puncture load of 10 to 100gf when the puncture speed is 100 mm/min. When the puncture load is within the above range at a puncture speed of 100 mm/min, the expansion due to the self weight is suppressed, and the discharge performance from the dispenser device is also easily improved. From these viewpoints, the puncture load at a puncture speed of 100 mm/min is more preferably 13gf or more, further preferably 25gf or more, further preferably 75gf or less, further preferably 45gf or less.

The puncture load at a puncture speed of 100 mm/min can be measured by the same method as the puncture load at a puncture speed of 10 mm/min, except for the puncture speed.

The curable liquid resin is preferably composed of a main agent and a curing agent for curing the main agent. In this case, in step 1, it is preferable to prepare a 1 st liquid in which at least an anisotropic filler is mixed with a main agent of a curable liquid resin and a 2 nd liquid in which at least an anisotropic filler is mixed with a curing agent of a curable liquid resin. In addition to the anisotropic filler, other components such as a non-anisotropic filler and a liquid component described later may be appropriately mixed with the liquid 1 and the liquid 2. The 1 st liquid and the 2 nd liquid may be mixed and stored in the tank 61, or may be stored in different tanks in advance and mixed immediately before the step 2.

[ procedure 2]

The thermally conductive composition obtained in step 1 is preferably filled in a tank 56 (see fig. 1) of the dispenser device 50. Further, by driving a pump, not shown, the thermally conductive composition in a pressurized state is supplied to the head 51 via the supply path 52, and the thermally conductive composition R is discharged to the outside from the discharge port 53 as shown in fig. 3 (a). At this time, as shown in fig. 3 (a), the thermally conductive composition R is discharged in a sheet form on the table 57 by moving the table 57 in one direction (also referred to as "forward direction") of the MD as the thermally conductive composition R is discharged.

After the thermally conductive composition R is discharged in a predetermined length along the MD, the cutter 58 is moved along the TD (in fig. 3, in the direction perpendicular to the paper surface), and as shown in fig. 3B, the thermally conductive composition R discharged from the discharge port 53 is cut, and the 1 st sheet S1 is formed on the table 57.

Next, as shown in fig. 3 (C), the table 57 is moved downward. Then, as shown in fig. 3D, the thermally conductive composition R is discharged onto the sheet S1, and the table 57 is moved in the opposite direction (the direction opposite to the forward direction) along the MD.

After being discharged along the MD by a predetermined length, the thermally conductive composition R discharged from the discharge port 53 is cut by a cutter 58 as shown in fig. 3 (E), and the 2 nd sheet S2 is formed on the sheet S1.

Then, the table 57 is again moved downward, and the above operation is repeated, thereby obtaining a plurality of sheets S1, S2 laminate 22 (see fig. 4 a) in which Sn (n is an arbitrary integer) is superimposed. In fig. 4, a form in which a plurality of sheets are stacked is shown, but the number of sheets stacked (the number of layers) is not particularly limited as long as it is 2 or more, and for example, it may be 10 or more, or it may be about 1000 or less, or it may be about 100 or less.

In step 2, the temperature at which the thermally conductive composition R is discharged from the discharge port 53 (discharge temperature) is preferably room temperature. In step 2, since the discharge temperature is set to room temperature, it is not necessary to provide a heating device or the like in the dispenser device 50, and the device can be simplified.

Here, the room temperature means substantially the same as the ambient temperature at which the dispenser device is installed. Accordingly, in the dispenser device 50, the heat conductive composition R is discharged without being heated by the heating device, and the discharge temperature is also set to room temperature. The specific discharge temperature is, for example, about 0 to 40 ℃, preferably about 10 to 30 ℃.

In step 2, the thermally conductive composition R is discharged in the MD, and the anisotropic filler mixed in the thermally conductive composition R is oriented in the discharge direction (MD). Thereby the processing time of the product is reduced, each sheet S1, S2 in the case of Sn, the anisotropic filler material is oriented in one direction (MD) along the planar direction of the sheet. Further, as described later, the anisotropic filler is oriented in one direction along the plane direction even in the unit layer of the thermal conductive member, and thus can be oriented in the thickness direction of the thermal conductive member.

More specifically, when the anisotropic filler is a fibrous filler as described later, the orientation of the anisotropic filler is more specifically described, that is, when the anisotropic filler is in a state in which the ratio of the number of anisotropic fillers having an angle smaller than 30 ° formed by the long axis of the fibrous filler to the total amount of the anisotropic filler exceeds 50% with respect to one direction along the plane direction (MD, in the case of a heat conductive member described later, the thickness direction), the ratio is preferably more than 80%.

When the anisotropic filler is a scale-like filler, the ratio of the number of anisotropic fillers having an angle smaller than 30 ° formed by the scale-like surfaces of the scale-like filler to the total amount of the anisotropic filler may be more than 50%, and may preferably be more than 80%, with respect to one direction along the plane direction (MD, in the case of a thickness direction of a heat conductive member described later).

In addition, in the anisotropic filler, from the viewpoint of improving the thermal conductivity, the angle formed by the major axis or the angle formed by the scale surface with respect to one direction along the plane direction (MD, in the case of a thermal conductive member described later, the thickness direction) is preferably set to 0 ° or more and less than 10 °, more preferably 0 ° or more and less than 5 °. These angles are average values of orientation angles of the anisotropic filler of a predetermined number (for example, 50 arbitrary anisotropic fillers).

Further, when the anisotropic filler is not in any of a fibrous shape and a scaly shape, it means a state in which the ratio of the number of anisotropic fillers having an angle smaller than 30 ° formed by the long axis of the anisotropic filler to the total amount of the anisotropic filler exceeds 50% with respect to one direction along the plane direction (i.e., MD, thickness direction in the heat conductive member), and the ratio is preferably more than 80%.

In the case where the anisotropic filler is a scaly material, the anisotropic filler is more preferably oriented in a predetermined direction, specifically, in the thickness direction of each sheet (ZD, the direction of stacking a plurality of unit layers 13 described later). By orienting the normal direction in the lamination direction in this way, the thermal conductivity in one direction (in the thermal conductive member, the thickness direction) is improved. In addition, the thermal conductivity in the direction along the surface of the sheet-like thermal conductive member and the direction orthogonal to the lamination direction is also improved.

The normal direction of the fin surface is directed in the thickness direction (i.e., stacking direction) of the fin body, and means a state in which the proportion of the number of scale-like materials forming an angle smaller than 30 ° in the normal direction is more than 50%, and the proportion is preferably more than 80% with respect to the thickness direction (stacking direction).

In the laminate obtained in step 2, each sheet S1, S2 the thickness of Sn is not particularly limited, but is preferably 0.1 to 9.0mm. By setting the thickness of the sheet to 0.1mm or more, the thermally conductive composition R can be discharged without increasing the discharge pressure, and even if a thermally conductive composition containing a large amount of thermally conductive filler is mixed, the thermally conductive composition can be easily discharged. In addition, the orientation of the anisotropic filler is easily improved by 9.0mm or less. From these points of view, each sheet S1, S2 the thickness of Sn is more preferably 0.5 to 7mm. The thickness of each sheet in the laminate may be reduced by compression due to the weight of the thermally conductive composition itself to be laminated, with respect to the discharge thickness of the sheet (the thickness of the sheet that is not laminated), and as a result, the thickness of each sheet is, for example, 80% to 100% of the discharge thickness, and preferably 90% to 100%.

[ procedure 3]

In step 3, the laminate 22 obtained in step 2 is preferably compressed by pressing in the lamination direction. In step 3, the laminate 22 is compressed by pressurization, so that the sheets S1, S2, & Sn can be closely adhered to each other, preventing peeling between sheets, etc. Further, since the plurality of sheets are not cured, even in the case of using a silicone resin as a liquid resin, the sheets can be firmly bonded to each other by compression with pressure.

The laminate 22 is preferably compressed to a thickness of 75 to 97% by compression, assuming that the original thickness is 100%. By deforming the laminate 22 by compression in the above range, the sheets are easily and firmly bonded to each other without excessively deforming the laminate. Further, the laminate 22 is more preferably compressed and deformed to a thickness of 85 to 95%.

Further, since the laminate 22 is plastically deformed by being compressed, the thickness of the laminate 22 is maintained within the above range even when the compressed laminate is released from the pressing.

Compression of the laminate can be performed by, for example, pressing with a roller or a press. The pressure at the time of pressurization is not particularly limited, and when a roller is used, the pressure is preferably set to 0.3 to 3kgf/50mm, for example.

[ procedure 4]

Next, in step 4, the laminate compressed and deformed in step 3 is cured. The curing method is preferably set appropriately according to the kind of the curable liquid resin. For example, if the curable liquid resin is photocurable, the laminate (thermally conductive composition) may be cured by irradiation of ultraviolet rays or the like to the laminate. In addition, if the curable liquid resin is thermosetting, the laminate (thermally conductive composition) may be cured by heating.

The curable liquid resin is preferably thermosetting. Therefore, the heat conductive composition in step 4 is preferably cured by heating. Specifically, for example, the reaction is preferably carried out at a temperature of about 50 to 150 ℃. The heating time is, for example, about 10 minutes to 10 hours.

In addition, in the case of blending a volatile compound into the thermally conductive composition as described below, the volatile compound may be volatilized at any timing. Specifically, the resin may be volatilized by heating during curing. In more detail, during the heating at the time of curing, the heat conductive composition is initially cured, and the heating may be continued further or the temperature may be raised to heat the composition, thereby volatilizing the volatile compound.

However, it is preferable that the step 5 is further followed by a step of heating to volatilize the volatile components. Since the sheet-like product is formed in step 5, the volatile compound can be volatilized more efficiently than in the case of a laminate. In addition, a part of the volatile compound may be volatilized by heating during curing, and the volatile compound may be volatilized further after step 5 described later.

In the case of heating after the step 5 described later, the heating is preferably performed at, for example, 70 to 170 ℃, preferably 100 to 160 ℃, and the heating time is, for example, about 30 minutes to 24 hours.

[ procedure 5]

Then, as shown in FIG. 4B, the cured laminate 22 is cut by the blade 18 along the lamination direction of the sheets S1, S2, & gtSn, a sheet-like heat conductive member 10 (heat conductive sheet) was obtained. In this case, the laminate 22 is preferably cut in a direction perpendicular to the orientation direction of the anisotropic filler. As the cutting tool 18, for example, a double-edged razor blade, a cutter, a single-edged razor blade, a round blade, a wire blade, a saw blade, or the like can be used. The stacked body 22 is cut by using a cutter 18, for example, by pressing, shearing, rotating, sliding, or the like.

The cutting direction in step 5 is preferably a direction aligned with the stacking direction, but may deviate from the direction aligned with the stacking direction as long as the cutting direction intersects the stacking surface of the stacked body 22.

According to the manufacturing method of the present embodiment described above, it is possible to manufacture a heat conductive member in which the anisotropic filler is oriented in one direction without using a large-scale apparatus and without generating an end material or the like much. Therefore, the waste of material is small, and the heat conductive member having excellent heat conductivity can be manufactured by a simple apparatus.

Further, according to the manufacturing method of the present embodiment, since each layer of the thermally conductive composition R is cut off when the laminate 22 is obtained, the thickness is easily uniform at the end portion of the laminate 22, and the orientation is also less likely to be disturbed, so that the occurrence of edge material can be more suppressed.

[ Heat conductive Member ]

Fig. 5 shows an example of the heat conductive member obtained by the above-described manufacturing method. The heat conductive member 10 has a sheet shape, and includes a plurality of unit layers 13 each including a matrix resin 11 and a heat conductive filler. The plurality of unit layers 13 are stacked along one direction x, and adjacent unit layers 13 are bonded to each other. In each unit layer 13, the matrix resin 11 is a matrix resin that holds a thermally conductive filler, and the thermally conductive filler is mixed in a dispersed manner in the matrix resin 11. The base resin 11 is a cured material of the curable liquid resin, and is preferably a silicone resin. The direction x of the laminated unit layers 13 is a direction perpendicular to the thickness direction z of the heat conductive member.

The thermal conductive member 10 shown in fig. 5 contains an anisotropic filler 14 and a non-anisotropic filler 15 as thermal conductive fillers. The anisotropic filler 14 is oriented in the thickness direction z of the sheet-like heat conductive member 10. That is, the anisotropic filler 14 is oriented in one direction along the plane direction of each unit layer 13. The heat conductive member 10 contains the anisotropic filler 14 oriented in the thickness direction z, thereby improving the heat conductivity in the thickness direction. Further, the thermal conductive member 10 further contains the non-anisotropic filler 15, thereby further improving thermal conductivity.

However, the heat conductive member 10 may not contain the non-anisotropic filler material 15.

In the thermal conductive member 10, the filling ratio of the matrix resin 11, expressed as volume%, is preferably 15 to 60 volume%, more preferably 20 to 45 volume%, with respect to the entire thermal conductive member.

In the heat conductive member 10, the filling rate of the anisotropic filling material 14 is preferably 2 to 45% by volume, more preferably 8 to 35% by volume, based on the entire heat conductive member. If the filling ratio of the anisotropic filling material 14 is within the above range, high thermal conductivity can be imparted to the heat conductive member 10, and can be suitably manufactured by a dispenser device.

In the case of containing the non-anisotropic filler 15, the filling rate of the non-anisotropic filler 15 is preferably 10 to 75% by volume, more preferably 30 to 60% by volume, relative to the heat conductive member, if expressed on a volume basis.

The anisotropic filler 14 is exposed on both surfaces 10A and 10B of the heat conductive member 10 in the thickness direction z. The exposed anisotropic filler 14 may protrude from each of the two surfaces 10A and 10B. The anisotropic filler 14 is exposed on both surfaces 10A and 10B of the heat conductive member 10, whereby both surfaces 10A and 10B become non-adhesive surfaces. Further, since the heat conductive member is cut by the blade, the both surfaces 10A and 10B become cut surfaces, and the anisotropic filler 14 is exposed on the both surfaces 10A and 10B. However, either or both of the two surfaces 10A, 10B may be adhesive surfaces without exposing the anisotropic filler.

The thickness of the thermal conductive member 10 is appropriately changed according to the shape and application of the electronic device on which the thermal conductive member is mounted. The thickness of the heat conductive member is not particularly limited, but is preferably in the range of 0.1 to 5 mm.

The thickness of each unit layer 13 is not particularly limited, but is preferably 0.1 to 8.5mm, more preferably 0.5 to 6mm. The thickness of the unit layer 13 is the length of the unit layer 13 along the lamination direction z of the unit layer 13.

The heat conductive member is used in an electronic device or the like. Specifically, the heat conductive member is interposed between the heat generating body and the heat radiating body, and transfers heat generated by the heat generating body to the heat radiating body, thereby radiating heat from the heat radiating body. Here, examples of the heating element include various electronic components such as a CPU, a power amplifier, and a power supply, which are used in the electronic device. Examples of the radiator include a radiator, a heat pump, and a metal case of an electronic device. The heat conductive member 10 is preferably used with both surfaces 10A and 10B thereof being in close contact with the heating element and the heat sink, respectively, and compressed.

[ thermally conductive composition ]

The components used in the thermally conductive composition will be described in detail below.

(liquid resin)

In this embodiment, the thermally conductive composition contains a curable liquid resin as described above. By using a curable liquid resin, the thermally conductive composition can be appropriately discharged in a sheet form from the dispenser device, and by curing, appropriate mechanical strength can be imparted to the thermally conductive member. In the present specification, the term "liquid" means a liquid at 25℃under 1 atmosphere. The curable liquid resin may be photocurable or thermosetting, but is preferably thermosetting.

As the curable liquid resin, specifically, epoxy resin, polyurethane resin, silicone resin, acrylic resin, polyisobutylene resin, and the like can be cited.

The curable liquid resin is not limited to the above, and may be acrylic rubber, nitrile rubber, isoprene rubber, urethane rubber, ethylene propylene rubber, styrene butadiene rubber, fluororubber, butyl rubber, or the like. In the case of using these rubbers, an uncrosslinked rubber may be used, and a crosslinking agent may be further blended into the thermally conductive composition.

Among the above curable liquid resins, silicone resins are preferred. The silicone resin is not particularly limited as long as it is a thermosetting curable silicone resin, but addition reaction type is preferably used. In the case of the addition reaction type, the curable silicone resin is preferably composed of an organosilicon compound (organopolysiloxane) as a main agent and a curing agent for curing the main agent.

The organosilicon compound used as the main agent is preferably an organopolysiloxane containing an alkenyl group, and specifically, examples thereof include vinyl-terminated organopolysiloxanes such as vinyl-terminated polydimethylsiloxane, vinyl-terminated polyphenylmethylsiloxane, vinyl-terminated dimethylsiloxane-diphenylsiloxane copolymer, vinyl-terminated dimethylsiloxane-phenylmethylsiloxane copolymer, and vinyl-terminated dimethylsiloxane-diethylsiloxane copolymer.

The curing agent is not particularly limited as long as it is a substance capable of curing the organosilicon compound as the main agent, but is preferably an organohydrogen polysiloxane as an organopolysiloxane having 2 or more hydrosilyl groups (SiH).

The liquid resin is not particularly limited, but the viscosity is, for example, about 30 to 2000 mPas, preferably about 100 to 500 mPas. By setting the viscosity to the above range, the puncture load can be easily adjusted to be within the above-described predetermined range. The viscosity referred to herein is a viscosity measured at a rotational speed of 10rpm using a rotary viscometer (Brookfield viscometer DV-E, rotor SC 4-14), and the measurement temperature is a temperature at which the thermally conductive composition is discharged.

In addition, in the case of a silicone resin comprising a main agent and a curing agent as described above, the viscosity of the liquid resin is a viscosity obtained by mixing them.

(Anisotropic filler material)

The anisotropic filler is a filler having an anisotropic shape and heat conductivity, and is an orientable filler. Examples of the anisotropic filler include fibrous materials and scaly materials. The anisotropic filler is generally high in aspect ratio, and the aspect ratio is more than 2, more preferably 5 or more. By making the aspect ratio larger than 2, it is easy to orient the anisotropic filler in the discharge direction, and it is easy to improve the thermal conductivity of the thermal conductive member.

The upper limit of the aspect ratio is not particularly limited, but practically 100.

The aspect ratio is a ratio of a length in a major axis direction to a length in a minor axis direction of the anisotropic filler, and refers to a fiber length/a fiber diameter in the fibrous material and a length/a thickness in the major axis direction in the scaly material.

The content of the anisotropic filler in the thermally conductive composition is preferably 10 to 500 parts by mass, more preferably 50 to 350 parts by mass, relative to 100 parts by mass of the liquid resin. By setting the content of the anisotropic filler to 10 parts by mass or more, the thermal conductivity of the thermal conductive member can be easily improved. Further, when the amount is within the above range, the puncture load of the thermally conductive composition tends to be appropriate.

In the case where the anisotropic filler is a fibrous material, the average fiber length thereof is preferably 10 to 500. Mu.m, more preferably 20 to 350. Mu.m. When the average fiber length is 10 μm or more, the anisotropic filler is properly brought into contact with each other in each of the heat conductive members, and a heat transfer path is ensured, so that the heat conductivity of the heat conductive members is improved.

On the other hand, if the average fiber length is 500 μm or less, the volume of the anisotropic filler becomes low, and the filler can be highly filled in the liquid resin.

The average fiber length can be calculated by observing the anisotropic filler with a microscope. More specifically, the fiber lengths of 50 arbitrary anisotropic fillers can be measured using an electron microscope or an optical microscope, and the average value (arithmetic average value) thereof is set as the average fiber length.

For example, the anisotropic filler to be mixed with the heat conductive member may have an average fiber length measured in the same manner as in the case of the anisotropic filler in which the matrix resin is dissolved and separated. At this time, large shearing is not applied in order not to crush the fibers. In addition, when it is difficult to separate the anisotropic filler from the heat conductive member, the fiber length of the anisotropic filler may be measured using an X-ray CT apparatus, and the average fiber length may be calculated. In the present invention, the term "arbitrary substance" means a randomly selected substance.

In the case where the anisotropic filler is a scaly material, the average particle diameter thereof is preferably 5 to 400 μm, more preferably 10 to 300 μm. In addition, it is particularly preferably 20 to 200. Mu.m. By setting the average particle diameter to 5 μm or more, the anisotropic filler is easily contacted with each other in the heat conductive member, the heat transfer path is ensured, and the heat conductivity of the heat conductive member is improved. On the other hand, if the average particle diameter is 400 μm or less, the volume of the anisotropic filler becomes low, and the anisotropic filler in the liquid resin can be highly filled.

The average particle diameter of the scale-like material can be calculated by observing the anisotropic filler with a microscope and taking the long diameter as the diameter. More specifically, the long diameter of 50 anisotropic fillers can be measured using an electron microscope, an optical microscope, or an X-ray CT apparatus in the same manner as the average fiber length, and the average value (arithmetic average value) thereof is set as the average particle diameter. The thickness of the anisotropic filler can be measured by using an electron microscope, an optical microscope, or an X-ray CT apparatus in the same manner.

The anisotropic filler material is of a type having thermal conductivity The known materials may be used. The anisotropic filler may have conductivity or insulation. If the anisotropic filler has insulation properties, the insulation properties in the direction in which the anisotropic filler of the heat conductive member is oriented can be improved, and thus the anisotropic filler can be suitably used in electrical equipment. In the present invention, the term "conductive" means, for example, a volume resistivity of 1×10 ⁹ Omega cm or less. The term insulating means that the volume resistivity exceeds 1×10, for example ⁹ Omega cm.

Specific examples of the anisotropic filler include carbon-based materials represented by carbon fibers and scaly carbon powders, metal materials represented by metal fibers, metal oxides, boron nitride, metal nitrides, metal carbides, metal hydroxides, and poly-p-phenylene benzobisonAzole fiber, and the like. Among them, a carbon-based material is preferable because of its small specific gravity and good dispersibility into a liquid resin, and among them, a graphitized carbon material having high thermal conductivity is more preferable. In addition, boron nitride and poly-p-phenylene benzohouse->The azole fiber is preferable from the viewpoint of having insulation properties, and among them, boron nitride is more preferable. Boron nitride is not particularly limited, but is preferably used as a scale-like material. The scale-like boron nitride may or may not be aggregated, but preferably some or all of the scale-like boron nitride is not aggregated.

The anisotropic filler may be used alone or in combination of 2 or more.

The anisotropic filler is not particularly limited, but the thermal conductivity along the direction having anisotropy (i.e., the long axis direction) is generally 30W/m·k or more, preferably 100W/m·k or more. The upper limit of the thermal conductivity of the anisotropic filler is not particularly limited, but is, for example, 2000W/mK or less. The thermal conductivity was measured by a laser flash method.

The anisotropic filler may be used alone or in combination of 2 or more. For example, as the anisotropic filler material, an anisotropic filler material having at least 2 average particle diameters or average fiber lengths different from each other may be used. It is considered that if anisotropic filler materials of different sizes are used, the anisotropic filler materials can be filled in a liquid resin at a high density and heat conduction efficiency can be improved by adding a small anisotropic filler material between relatively large anisotropic filler materials.

The carbon fiber used as the anisotropic filler is preferably graphitized carbon fiber. Further, as the scaly carbon powder, scaly graphite powder is preferable. Among them, the anisotropic filler material is more preferably graphitized carbon fiber.

The crystalline planes of the graphite of the graphitized carbon fibers are connected along the fiber axis direction, and the fiber axis direction has high thermal conductivity. Therefore, by matching the fiber axis direction with a predetermined direction, the thermal conductivity in a specific direction can be improved. The crystal planes of graphite of the flake graphite powder are connected in the in-plane direction of the flake plane, and have high thermal conductivity in the in-plane direction. Therefore, by matching the scale surface with a predetermined direction, the thermal conductivity in a specific direction can be improved. Graphitized carbon fibers and flake graphite powders preferably have a high graphitization degree.

As the graphitized carbon material such as graphitized carbon fiber, graphitized materials of the following raw materials may be used. Examples thereof include fused polycyclic hydrocarbon compounds such as naphthalene, and fused heterocyclic compounds such as PAN (polyacrylonitrile) and pitch, and graphitized mesophase pitch, polyimide and polybenzazole which have a high graphitization degree are particularly preferable. By using, for example, mesophase pitch, in the spinning step described later, pitch is oriented in the fiber axis direction by its anisotropy, and graphitized carbon fibers having excellent thermal conductivity in the fiber axis direction can be obtained.

The form of use of the mesophase pitch in the graphitized carbon fiber is not particularly limited as long as it can be spun, and the mesophase pitch may be used alone or in combination with other raw materials. However, the use of mesophase pitch alone, that is, graphitized carbon fibers having a mesophase pitch content of 100% is most preferable in terms of high heat conduction, spinnability, and stability of quality.

The graphitized carbon fiber may be produced by sequentially spinning, non-melting, and carbonizing, and graphitizing the fiber after pulverization or cutting into a predetermined particle size, or graphitizing the fiber after carbonization. In the case of pulverization or cutting before graphitization, the polycondensation reaction and cyclization reaction are easily performed at the time of graphitization treatment in the surface newly exposed to the surface by pulverization, and therefore graphitized carbon fibers having an improved graphitization degree and further improved thermal conductivity can be obtained. On the other hand, in the case of graphitizing and pulverizing the spun carbon fiber, the graphitized carbon fiber is rigid, and therefore, the graphitized carbon fiber is easily pulverized, and the carbon fiber powder having a narrow fiber length distribution can be obtained by pulverizing in a short period of time.

The graphitized carbon fibers preferably have an average fiber length of 50 to 500. Mu.m, more preferably 70 to 350. Mu.m. The aspect ratio of the graphitized carbon fiber is more than 2, preferably 5 or more, as described above. The thermal conductivity of the graphitized carbon fiber is not particularly limited, but the thermal conductivity in the fiber axis direction is preferably 400W/m·k or more, more preferably 800W/m·k or more.

(non-Anisotropic filler Material)

As described above, the thermally conductive composition may further contain a non-anisotropic filler material. The non-anisotropic filler is a material that imparts thermal conductivity to the heat conductive member together with the anisotropic filler. In this embodiment, by containing the non-anisotropic filler, the filler is interposed in the gap between the aligned anisotropic fillers, and thus a thermal conductive member having high thermal conductivity can be obtained.

The non-anisotropic filler is a filler having a shape substantially free of anisotropy, and is not oriented in a predetermined direction even in an environment where the anisotropic filler is oriented in the predetermined direction, for example, when the thermally conductive composition is discharged from the discharge port in one direction, as described later.

The aspect ratio of the non-anisotropic filler is 2 or less, more preferably 1.5 or less. By containing such a non-anisotropic filler having a low aspect ratio, the filler having thermal conductivity is properly interposed between the gaps of the anisotropic filler, and a thermal conductive member having high thermal conductivity can be obtained. Further, by setting the aspect ratio to 2 or less, the puncture load of the thermally conductive composition can be prevented from rising, and high filling can be performed.

The non-anisotropic filler may have electrical conductivity, but preferably has insulation, and in the thermal conductive member, it is preferable that both the anisotropic filler and the non-anisotropic filler have insulation. In this way, if both the anisotropic filler and the non-anisotropic filler are insulating, it is easy to further improve the insulating property in the direction in which the anisotropic filler of the heat conductive member is oriented.

Specific examples of the non-anisotropic filler include metals, metal oxides, metal nitrides, metal hydroxides, carbon materials, oxides other than metals, nitrides, and carbides. Examples of the shape of the non-anisotropic filler include spherical and amorphous powders.

In the non-anisotropic filler, aluminum, copper, nickel, and the like are exemplified as the metal, aluminum oxide, magnesium oxide, zinc oxide, and the like typified by aluminum oxide are exemplified as the metal oxide, and aluminum nitride and the like are exemplified as the metal nitride. As the metal hydroxide, aluminum hydroxide is exemplified. Further, as the carbon material, spherical graphite and the like are exemplified. Examples of the oxides, nitrides, and carbides other than metals include quartz, boron nitride, and silicon carbide.

Among them, aluminum oxide and aluminum are preferable in terms of high thermal conductivity and easy availability of spherical matters, and aluminum hydroxide is preferable in terms of easy availability and improvement of flame retardancy of the thermal conductive member.

Among the above, examples of the non-anisotropic filler having insulation properties include metal oxides, metal nitrides, metal hydroxides, and metal carbides, but aluminum oxide and aluminum hydroxide are particularly preferable.

The non-anisotropic filler may be used alone or in combination of at least 1 kind of the above substances, or at least 2 kinds of the above substances may be used.

The average particle diameter of the non-anisotropic filler is preferably 0.1 to 100. Mu.m, more preferably 0.3 to 50. Mu.m. In addition, 0.5 to 15 μm is particularly preferable. By setting the average particle diameter to 50 μm or less, defects such as disturbance of the orientation of the anisotropic filler are less likely to occur. Further, by setting the average particle diameter to 0.1 μm or more, the specific surface area of the non-anisotropic filler is not excessively increased, and the non-anisotropic filler is not easily increased even when the puncture load is large in blending, and is easily filled with a high level.

The average particle diameter of the non-anisotropic filler can be measured by observation with an electron microscope or the like. More specifically, as in the measurement of the anisotropic filler, 50 particle diameters of any of the non-anisotropic fillers can be measured using an electron microscope, an optical microscope, and an X-ray CT apparatus, and the average value (arithmetic average value) thereof is set as the average particle diameter.

The content of the non-anisotropic filler in the thermally conductive composition is preferably in the range of 50 to 1500 parts by mass, more preferably in the range of 200 to 800 parts by mass, relative to 100 parts by mass of the liquid resin. By setting the amount to 50 parts by mass or more, the amount of the non-anisotropic filler interposed between the gaps between the anisotropic fillers becomes a certain amount or more, and the thermal conductivity becomes good. On the other hand, when the content is 1500 parts by mass or less, the effect of improving the thermal conductivity corresponding to the content can be obtained, and the thermal conductivity due to the anisotropic filler is not hindered by the non-anisotropic filler. Further, when the amount is within the above range, the puncture load of the thermally conductive composition tends to be appropriate. Further, the thermal conductive member has excellent thermal conductivity and a puncture load is also suitable in the range of 200 to 800 parts by mass.

(liquid component)

The thermally conductive composition may contain a liquid component in addition to the liquid resin. By containing the liquid component, even if the content of the thermally conductive filler is large, the puncture load can be easily adjusted to be within a predetermined range. As the liquid component, as described later, volatile compounds and silicone oils are mentioned. Either or both of the volatile compound and the silicone oil may be used.

In the heat conductive composition, the liquid component other than the liquid resin is preferably 5 to 120 parts by mass, more preferably 10 to 80 parts by mass, and still more preferably 15 to 50 parts by mass. By setting the amount of the thermally conductive filler within the above range, the puncture load can be adjusted to be within a predetermined range even when the amount of the thermally conductive filler is large.

(volatile Compounds)

In the present specification, the volatile compound means a compound having at least one of a temperature T1 in a range of 70 to 300 ℃ and a boiling point (1 atm) in a range of 60 to 200 ℃ which is 90% in weight reduction when heated up under a condition of 2 ℃/min by thermogravimetric analysis. Here, the temperature T1 at which the weight reduction is 90% is a temperature at which the weight of the sample before thermogravimetric analysis is 100% and 90% of the weight is reduced (that is, a temperature at which the weight before measurement is 10%).

The thermally conductive composition contains a volatile compound, so that even if the content of the thermally conductive filler is large, the puncture load can be kept low, and the discharge property can be improved when the composition is discharged from the dispenser device. On the other hand, by volatilizing the thermally conductive member during the production process, the filling rate of the thermally conductive filler in the thermally conductive member can be improved. Therefore, the thermal conductive composition contains the volatile compound, thereby improving the thermal conductivity of the thermal conductive member and improving the discharge property.

Examples of the volatile compound include a volatile silane compound and a volatile solvent, and among these, a volatile silane compound is preferable.

Examples of the volatile silane compound include alkoxysilane compounds. The alkoxysilane compound has a structure in which 1 to 3 bonds among 4 bonds of a silicon atom (Si) are bonded to an alkoxy group, and the remaining bonds are bonded to an organic substituent. Examples of the alkoxy group contained in the alkoxysilane compound include methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexoxy groups. The alkoxysilane compound may be contained as a dimer.

Among the alkoxysilane compounds, from the viewpoint of ease of obtaining, an alkoxysilane compound having a methoxy group or an ethoxy group is preferable. The number of alkoxy groups in the alkoxysilane compound is preferably 3 from the viewpoint of improving affinity with the thermally conductive filler which is an inorganic material. More preferably, the alkoxysilane compound is at least one selected from trimethoxysilane compounds and triethoxysilane compounds.

Examples of the functional group contained in the organic substituent of the alkoxysilane compound include an acryl group, an alkyl group, a carboxyl group, a vinyl group, a methacryl group, an aromatic group, an amino group, an isocyanate group, an isocyanurate group, an epoxy group, a hydroxyl group, and a mercapto group. Here, when an addition reaction type curable silicone resin is used as the liquid resin and a platinum catalyst is used, an alkoxysilane compound which is less likely to affect the curing reaction of the organopolysiloxane is preferably selected and used. Specifically, in the case of using an addition reaction type organopolysiloxane containing a platinum catalyst, the organic substituent of the alkoxysilane compound preferably does not contain an amino group, an isocyanate group, an isocyanurate group, a hydroxyl group, or a mercapto group.

The alkoxysilane compound is preferably an alkylalkoxysilane compound having an alkyl group bonded to a silicon atom, that is, an alkoxysilane compound having an alkyl group as an organic substituent, because it is easy to highly fill the thermally conductive filler by improving the dispersibility of the thermally conductive filler. The number of carbon atoms of the alkyl group bonded to the silicon atom is preferably 4 or more. In addition, from the viewpoint of the viscosity of the alkoxysilane compound itself being low and the viscosity of the thermally conductive composition being suppressed to be low, the number of carbon atoms of the alkyl group bonded to the silicon atom is preferably 16 or less.

One or more alkoxysilane compounds may be used. Specific examples of the alkoxysilane compound include an alkyl group-containing alkoxysilane compound, a vinyl group-containing alkoxysilane compound, an acryl group-containing alkoxysilane compound, a methacryl group-containing alkoxysilane compound, an aromatic group-containing alkoxysilane compound, an amino group-containing alkoxysilane compound, an isocyanate group-containing alkoxysilane compound, an isocyanurate group-containing alkoxysilane compound, an epoxy group-containing alkoxysilane compound, and a mercapto group-containing alkoxysilane compound. Among them, an alkoxysilane compound containing an alkyl group is preferable.

Examples of the alkoxysilane compound containing an alkyl group include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, and n-decyltrimethoxysilane. Among the alkoxysilane compounds containing an alkyl group, at least one selected from the group consisting of isobutyl trimethoxysilane, isobutyl triethoxysilane, n-hexyl trimethoxysilane, n-hexyl triethoxysilane, cyclohexyl methyl dimethoxy silane, n-octyl triethoxysilane, and n-decyl trimethoxysilane is preferable, at least one selected from the group consisting of n-octyl triethoxysilane and n-decyl trimethoxysilane is more preferable, and n-decyl trimethoxysilane is particularly preferable.

As the volatile solvent, a solvent having a boiling point (1 atm) of 60 to 200℃and preferably a boiling point of 100 to 130℃can be used. Further, the volatile solvent preferably has a boiling point 10 ℃ or higher, more preferably 20 ℃ or higher, than the curing temperature of the organopolysiloxane.

The type of the volatile solvent may be appropriately selected to satisfy the above requirements, but an aromatic compound such as toluene is preferably used.

The volatile compounds may be used alone or in combination of 2 or more.

The content of the volatile compound in the heat conductive composition is preferably 5 to 100 parts by mass, more preferably 10 to 70 parts by mass, and even more preferably 12 to 45 parts by mass, relative to 100 parts by mass of the liquid resin.

(Silicone oil)

As described above, the thermally conductive composition may contain silicone oil. By adding silicone oil, the volatile compound is mixed with the thermally conductive composition, and thus the puncture load can be adjusted to be within a predetermined range even when the content of the thermally conductive filler is large. Therefore, the thermal conductivity of the thermal conductive member can be made high, and the discharge property of the thermal conductive composition can be made good.

Examples of the silicone oil include linear silicone oil and modified silicone oil. Examples of the linear silicone oil include dimethyl silicone oil (dimethylpolysiloxane) and methylphenyl silicone oil (methylphenyl polysiloxane).

Examples of the modified silicone oil include polyether modified silicone oil, aralkyl modified silicone oil, fluoroalkyl modified silicone oil, long-chain alkyl modified silicone oil, higher fatty acid ester modified silicone oil, higher fatty acid amide modified silicone oil, and phenyl modified silicone oil.

Among the silicone oils, linear silicone oils are preferred.

The silicone oil may be used alone or in combination of 1 kind or 2 or more kinds.

From the viewpoint of improving the discharge property of the heat conductive composition, the kinematic viscosity (reduced viscosity) of the silicone oil is preferably 10 to 10,000mm at 25 ℃ ² And/s or less, more preferably 50 to 1,000mm ² And/s or less.

The content of the silicone oil is preferably in the range of 1 to 70 parts by mass, more preferably 2 to 50 parts by mass, and even more preferably 3 to 20 parts by mass, relative to 100 parts by mass of the liquid resin.

(additive component)

The heat conductive composition may further contain various additives within a range that does not impair the function as a heat conductive member. Examples of the additive include at least 1 or more selected from dispersants, coupling agents, adhesives, flame retardants, antioxidants, colorants, and anti-settling agents.

In addition, a curing catalyst or the like that promotes the curing of the curable liquid resin may be compounded. When the liquid resin is a curable silicone resin, a platinum-based catalyst is used as the curing catalyst. In the case of using an uncrosslinked rubber as the curable liquid resin, a crosslinking agent such as a sulfur compound or a peroxide may be contained.

[ embodiment 2 ]

Next, a method for manufacturing the heat conductive member according to embodiment 2 will be described in detail.

In embodiment 1, by cutting and overlapping the discharged heat conductive composition R, thereby, a plurality of sheets S1, S2, & gtSn are stacked in the laminate. In contrast, in the present embodiment, each layer is formed without being cut by the cutter 58, and the thermally conductive composition (sheet S) discharged in a sheet form is folded to form a laminate.

Regarding embodiment 2, only the differences from embodiment 1 will be described in detail below. Hereinafter, the description is the same as embodiment 1.

In the present embodiment, as shown in fig. 6 (a), as in embodiment 1, the thermally conductive composition R is discharged in a sheet form on the table 57 by moving the table 57 in one direction (positive direction) of the MD as the thermally conductive composition R is discharged.

Next, in the present embodiment, after the predetermined length is discharged as described above, the table 57 is moved downward as shown in fig. 6 (B) without cutting the thermally conductive composition R by a cutter.

Then, as shown in fig. 6 (C), the thermally conductive composition R discharged onto the stage 57 is discharged, and the stage 57 is moved by a predetermined distance in the reverse direction (the direction opposite to the forward direction) of the MD. By repeating such an operation, as shown in fig. 6 (D), the sheet S made of the thermally conductive composition R is folded in a plurality of layers on the table 57, thereby obtaining the laminate 22B. The number of layers of the laminate 22B is not particularly limited, as described in embodiment 1. Then, the obtained laminate 22B is molded into a heat conductive member by the same process as in embodiment 1. The details of the obtained heat conductive member are the same as those of embodiment 1.

In this embodiment, a heat conductive member containing an anisotropic filler and having the anisotropic filler oriented in one direction can be manufactured without using a large-scale device and without generating an end material or the like. Therefore, the waste of the material is small, and the heat conductive member having excellent heat conductivity can be manufactured by a simple apparatus.

In addition, according to the manufacturing method of the present embodiment, when the laminate 22B is obtained, the thermally conductive composition R is not cut at each layer, and the folded-back portion 23B is provided in the end portion of the laminate 22B. The folded-back portion 23B may have a thickness different from that of the portion other than the end portion due to easy variation in thickness or may have disorder in the orientation of the anisotropic filler. Therefore, in such a case, the folded-back portion 23B may be cut off appropriately. The cut-out folded portion 23B becomes an end material that cannot be used as a heat conductive member, but if compared with the case of manufacturing a heat conductive member by extrusion molding or the like, the amount of end material generation can be suppressed to be small.

Modification of embodiment 1 and 2

The above embodiments 1 and 2 show an embodiment of the present invention, and the present invention is not limited to the above configuration, and various modifications are possible. Specifically, any of the steps 3 to 5 may be omitted as appropriate.

For example, if step 3 is omitted, the adhesion between unit layers in the heat conductive member tends to be low, but it can be used for applications where high mechanical strength is not considered to be required. In the case where step 3 is omitted, the laminate that has not been compressively deformed in step 4 is cured. Other configurations are the same as those of embodiment 1 and embodiment 2.

If step 5 is omitted, the laminate is used as it is as a heat conductive member, instead of a sheet-like heat conductive member.

Further, for example, if step 4 (i.e., curing) is omitted, the mechanical strength of the heat conductive member becomes low, and therefore the heat conductive member is preferably used in applications where high mechanical strength is not considered to be required, and the like. In addition, if step 4 is omitted, it is difficult to cut the laminate, for example, to mass-produce the heat conductive member, and therefore, when step 4 is omitted, step 5 is preferably also omitted.

In the case where step 4 is omitted, the liquid resin contained in the thermally conductive composition is not necessarily a curable liquid resin, and may be a liquid resin which does not cure even when heated or irradiated with light. Specifically, for example, the above-described uncrosslinked rubber may be used as the liquid resin, and a crosslinking agent may not be compounded in the thermally conductive composition.

In addition to the steps 4 and 5, 2 or more steps among the steps 3 to 5 may be omitted. For example, step 3 and step 4 may be omitted, or step 3 and step 5 may be omitted. Further, all of steps 3 to 5 may be omitted. When step 4 and step 5 are omitted or all of steps 3 to 5 are omitted, the uncured liquid resin is directly used as the base resin, and the laminate is preferably used as the heat conductive member.

Further, in each of the above embodiments, the stage 57 is moved in the MD and ZD, but the head 51 may be moved in the MD and ZD instead of the stage 57, or both the stage 57 and the head 51 may be moved.

[ embodiment 3 ]

Next, embodiment 3 of the present invention will be described. In embodiments 1 and 2, the thermally conductive composition is discharged onto the table 57 to form a laminate, but the thermally conductive composition may be discharged outside the table 57, for example, onto a member to be actually used, and may be used as a thermally conductive member. Specifically, the thermally conductive composition is discharged so as to overlap in a plurality of sheets between the heat generating element and the heat generating element, and preferably a laminate is formed between the heat generating element and the heat generating element.

A method for manufacturing the heat conductive member according to embodiment 3 will be described in detail below with reference to fig. 7. In the following description, only the differences from embodiments 1 and 2 will be described in detail, and the description will be omitted in the same manner as embodiments 1 and 2.

In the present embodiment, steps 1 and 2 are preferably performed in this order as in the above embodiments. That is, the thermally conductive composition prepared in step 1 is discharged from the head 51 of the dispenser device in step 2, and the laminate 22C is formed. In the present embodiment, the laminate 22C is preferably formed as follows.

In the following description, the heat radiator 61 is provided with the base portion 61B and the side portion 61A connected to the base portion 61B, and the thermally conductive composition is discharged on the base portion 61B (discharged member) between the side portion 61A and the heating element 62. Specific examples of the heat radiator 61 and the heat generator 62 are as described above.

First, as shown in fig. 7, a radiator 61 and a heating element 62 are placed on a table 57. Further, the heat conductive composition R is discharged on the base 61B between the side portion 61A of the heat radiator 61 and the heat generator 62. At this time, as in embodiment 2, the stacked body 22C in which the sheet S is folded is formed while the table 57 (i.e., the radiator 61 and the heating element 62) is moved in the MD and the downward direction. When the thermally conductive composition R is discharged during formation of the laminate 22C, the head 51 of the dispenser device is typically disposed between the radiator 61 and the heating element 62, as shown in fig. 7.

Here, in the formation of the laminate 22C, the discharge direction (MD) of the thermally conductive composition R is a direction connecting the heat radiator 61 (side portion 61A) and the heat generator 62, and in the laminate 22C, the anisotropic filler is oriented in a direction connecting the heat radiator 61 (side portion 61A) and the heat generator 62. Therefore, the heat generated by the heat generating element 62 can be efficiently transferred to the heat radiating body 61 (the side portion 61A) and radiated from the heat radiating body 61.

As described above, in the present embodiment, a heat conductive member containing an anisotropic filler and having the anisotropic filler oriented in one direction can be manufactured without using a large-scale apparatus and without producing an end material. Further, since a large-scale device is not used, for example, the dispenser device can be introduced at a site where the electronic device is used, and the heat conductive member can be formed between the heating element and the heat radiator at the site.

Further, in the present embodiment, the laminate 22C formed of the thermally conductive composition R is preferably formed so as to be in contact with each of the side portion 61A of the radiator 61 and the heating element 62. The laminate 22C is in contact with each of the side portion 61A of the radiator 61 and the heating element 62, so that heat generated by the heating element 62 can be efficiently radiated from the side portion 61A of the radiator 61.

In order to bring the laminate 22C into contact with the side portion 61A of the radiator 61 and the heating element 62, it is preferable to discharge the thermally conductive composition R while swinging around the upper end portion of the head 51 as shown in fig. 7 when both end portions (i.e., the folded portion 23C and the vicinity thereof) of the laminate 22C are formed.

In the present embodiment, as shown in fig. 7, the laminate 22C formed between the side portion 61A and the heating element 62 is preferably used as a heat conductive member. However, as in embodiment 1 and embodiment 2, either one or both of the steps 3 and 4 may be performed, but at least the step 4 is preferably performed. Details of steps 3 and 4 are as described above.

In the case of performing step 4, as described in embodiment 1, the heat conductive composition may be prepared as the 1 st liquid and the 2 nd liquid, and may be mixed immediately before step 2 and then subjected to step 2.

If step 3 is performed to compressively deform the laminate 22C, the laminate 22C expands a certain amount in the planar direction. Therefore, in the case of performing step 3, the head 51 may not be swung at the time of forming both end portions of the laminate 22C.

By forming the laminate 22C without swinging the head 51 in step 2, even if both ends of the laminate 22C in the MD are not in contact with the side portion 61A of the radiator 61 and the heating element 62, the laminate 22C can be expanded in the MD by the implementation of step 3, and the laminate 22C can be brought into contact with the side portion 61A of the radiator 61 and the heating element 62.

In the description of embodiment 3, the laminate 22C is formed by folding the sheet S without cutting each layer by the cutter 58 in the production of the laminate 22C, as in embodiment 2. As shown in embodiment 1, however, each layer may be cut by a cutter every time it is formed, the plurality of sheets S1, S2 Sn formed by cutting are overlapped, a laminate 22C was obtained.

In the present embodiment, the heat radiator 61 and the heat generator 62 are arranged on the table 57 and moved in the MD and the downward direction, and the laminate 22C is obtained, but the heat radiator 61 and the heat generator 62 do not need to be arranged on the table 57, and the table 57 may be omitted as long as the heat radiator 61 and the heat generator 62 can be moved in the MD and the downward direction. Further, as described in embodiment 1 and embodiment 2, the head 51 of the dispenser device can be moved in MD and the downward direction.

In the present embodiment, the laminate 22C is formed by being laminated on a part (the base 61B) of the radiator 61, but the laminate 22C need not be formed on a part of the radiator 61, and may be laminated on a member different from the radiator 61.

Examples

The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.

The raw materials used in this example and comparative example are as follows.

[ curable liquid resin ]

Cured silicone resin: a main agent formed from an alkenyl-containing organopolysiloxane, a curing agent formed from a hydrogen organopolysiloxane, and the viscosity of a mixture thereof at 25 ℃): 300 mPas

[ liquid component ]

Methyl phenyl polysiloxane: kinematic viscosity at 25℃of 125mm ² S, refractive index 1.496

N-decyl trimethoxysilane: the temperature T1 at which the weight reduction upon heating up at 2℃per minute by thermogravimetric analysis became 90% was 187 ℃

[ Anisotropic filler ]

Boron nitride (1): scaly, with aspect ratio of 4-8, average particle diameter of 40 μm

Boron nitride (2): scaly, with aspect ratio of 2-3, average particle size of 10 μm

[ non-Anisotropic filler Material ]

Alumina (1): spherical, with an average particle diameter of 0.5 μm

Alumina (2): spherical, with an average particle diameter of 4. Mu.m

Alumina (3): spherical, with an average particle diameter of 71. Mu.m

Aluminum hydroxide: amorphous, average particle diameter of 1 μm

Example 1

(Process 1)

An alkenyl group-containing organopolysiloxane (main agent) as a curable silicone resin was mixed with hydrogen organopolysiloxane (curing agent) (total 100 parts by mass), methylphenyl polysiloxane 3 parts by mass, n-decyl trimethoxysilane 12 parts by mass, boron nitride (1) 168 parts by mass, alumina (1) 274 parts by mass, and alumina (2) 239 parts by mass, to obtain a thermally conductive composition. The puncture load of the obtained thermally conductive composition is shown in table 1.

(Process 2)

The obtained thermally conductive composition was filled in a tank of the dispenser device shown in fig. 1, supplied to the head at a pressure of 0.5MPa, and discharged from a rectangular discharge port having a length l1=50 mm and a length l2=3 mm at 25 ℃. At this time, the table was moved at a speed of 100 mm/min in the MD positive direction, and 50mm portions of the sheet-like thermally conductive composition were discharged at a thickness of 3 mm. After the discharge length was 50mm, the sheet-like heat conductive composition was cut by a cutter, and the 1 st sheet was formed on a table. Then, the table was moved downward, and then the table was moved at a speed of 100 mm/min in the opposite direction to the MD, and after the thermally conductive composition was discharged at the same thickness and the same length, the thermally conductive composition was cut by a cutter, and the 2 nd sheet was stacked on the 1 st sheet. This operation was repeated until 20 sheets were stacked, to obtain a laminate.

(Process 3 to 5)

Then, the laminate was obtained by pressing with a roller at a pressure of 1.5kgf/50mm in an environment of 25℃to obtain a compression-deformed laminate, and then heated at 80℃for 480 minutes to cure the laminate. Then, the sheet was cut parallel to the lamination direction and perpendicular to the orientation direction of the anisotropic filler, and the sheet was heated at 150 ℃ for 300 minutes to volatilize the n-decyltrimethoxysilane, thereby obtaining a sheet-like heat conductive member having a thickness of 2mm and a thickness of 2mm for each unit layer.

Examples 2 to 5 and comparative examples 1 and 2

The procedure of example 1 was repeated except that the blending of the thermally conductive composition was changed as shown in table 1.

[ puncture load ]

The puncture load of the thermally conductive composition was measured by the following method.

The heat conductive composition was defoamed, and 30g of the defoamed heat conductive composition was introduced into a cylindrical container having a diameter of 25 mm. Then, a puncture rod (rod diameter 1 mm) having a disk-shaped member having a diameter of 3mm and a thickness of 1mm at the tip was pressed at a speed of 10 mm/min (puncture speed) against the thermally conductive composition introduced into the container from the tip side of the puncture rod, and the load (gf) at which the tip of the puncture rod reached a depth of 12mm from the liquid surface was measured. The puncture rod is made of stainless steel. The measurement was performed at 25 ℃.

The puncture load was measured in the same manner as in the case where the puncture speed of the puncture rod was set to 100 mm/min.

Each example and comparative example were evaluated based on the following evaluation criteria.

(1) Evacuative properties of dispenser device

In step 2, whether the thermally conductive composition can be discharged through the dispenser device or not was visually confirmed, and if it can be discharged, whether the discharged thermally conductive composition maintains a shape in a single layer state was visually confirmed, and evaluated according to the following evaluation criteria.

A: can be discharged without spreading in the plane direction in the single-layer state, and can maintain the discharged shape.

B: can be discharged, and the expansion in the planar direction is extremely small, less than 10%, in the single-layer state, and the discharged shape can be basically maintained.

C: although the discharge is possible, the expansion in the plane direction is large, 10% or more in the single-layer state, and the discharged shape cannot be maintained.

D: cannot be discharged.

(2) Lamination of

In step 2, the shape retention of the laminate obtained by stacking a plurality of sheets was evaluated according to the following evaluation criteria.

A: a laminate having a thickness as designed was obtained without expanding due to the dead weight.

B: although the expansion is due to the dead weight, the expansion is less than 25%, and a laminate having a thickness substantially as designed is obtained.

C: the laminate was greatly expanded by its own weight to 25% or more, and thus a laminate having a thickness as designed was not obtained.

(3) Compression test of laminate

The compression ratio (thickness change) when the laminate obtained in step 2 was pressurized at a pressure of 1kPa for 10 seconds was shown.

(4) Amount of end material produced

The amount of the end material generated in the step until the heat conductive member was obtained was evaluated according to the following evaluation criteria.

A: most of the discharged heat conductive composition can be used for formation of the heat conductive member.

C: most of the discharged heat conductive composition cannot be used for formation of the heat conductive member.

(5) Orientation of anisotropic filler material

The obtained heat conductive member was evaluated by the orientation of the anisotropic filler based on the following evaluation criteria.

A: the anisotropic filler is oriented in the thickness direction of the heat conductive member.

B: although the anisotropic filler is oriented in the thickness direction of the heat conductive member, the orientation is slightly disturbed.

C: the anisotropic filler material is not oriented in the thickness direction of the thermal conductive member.

TABLE 1

The filling ratio is calculated from the specific gravity and the mass parts of each component as a value obtained by volatilizing the total amount of n-decyl trimethoxysilane.

As described in the above examples, by discharging the thermally conductive composition, which is a predetermined puncture load, in a sheet form and laminating the thermally conductive composition using the dispenser device, it is possible to manufacture a thermally conductive member in which the anisotropic filler is oriented in one direction with a thickness as designed, with good discharge properties, without substantially expanding due to self weight during discharge and lamination, and without causing disturbance of orientation. Further, the thermal conductive member can be manufactured without using a large-scale manufacturing apparatus, and an end material is not substantially generated in the manufacturing process thereof. Therefore, it can be said that the waste of the material is small, and the heat conductive member having excellent heat conductivity can be manufactured by a simple apparatus.

In contrast, in the comparative example, since the puncture load is low, if the thermally conductive composition is discharged in a sheet form and stacked using the dispenser device, the thermally conductive composition expands due to its own weight at the time of discharge and at the time of stacking, and the thermally conductive member cannot be manufactured to a thickness as designed.

Description of symbols

10. Heat conductive member

11. Matrix resin

13. Unit layer

14. Anisotropic filler material

15. Non-anisotropic filler material

18. Cutting tool

22. 22B, 22C laminate

23B, 23C folded back portion

50. Distributor device

51. Head

52. Supply path

53. Discharge outlet

54. Connecting path

57. Working table

58. Cutting device

61. Radiator body

62. Heating element

R heat conductive composition

S, S1, S2, & gtSn sheet.

Claims

1. A method for manufacturing a heat conductive member, comprising the steps of:

a step of preparing a thermally conductive composition which contains a liquid resin and an anisotropic thermally conductive filler and has a puncture load of 8 to 60gf, wherein the puncture load is stress when puncturing is performed at a puncture speed of 10 mm/min with a pressure lever having a pressing surface with a diameter of 3 mm; and

and a step of obtaining a laminate by discharging the thermally conductive composition in a sheet-like manner so as to overlap a plurality of the thermally conductive compositions by using a dispenser device having a wide-width-shaped discharge port.

2. The method for manufacturing a heat conductive member according to claim 1, wherein the liquid resin is a curable liquid resin,

the method for manufacturing a heat conductive member further comprises the following steps: and a step of curing the thermally conductive composition after the laminate is obtained.

3. The method for manufacturing a heat conductive member according to claim 1 or 2, further comprising the steps of: and cutting the laminate in a direction intersecting the laminate surface.

4. The method for manufacturing a heat conductive member according to any one of claims 1 to 3, wherein the liquid resin contains a volatile compound.

5. The method for producing a thermally conductive composition according to claim 4, further comprising the steps of: and volatilizing the volatile compound.

6. The method for manufacturing a heat conductive member according to any one of claims 1 to 5, further comprising the steps of: and compressing the laminate in the lamination direction to deform the laminate to a thickness of 75 to 97%.

7. The method for manufacturing a heat conductive member according to any one of claims 1 to 6, wherein a plurality of sheets are stacked on the stacked body by stacking the sheet-like discharged heat conductive composition while cutting it.

8. The method for manufacturing a thermally conductive member according to claim 7, wherein the thermally conductive composition discharged in the form of a sheet is cut by a cutter provided at the discharge port and moving along a longitudinal direction of the discharge port.

9. The method for manufacturing a heat conductive member according to any one of claims 1 to 6, wherein the heat conductive composition discharged in the form of a sheet is folded to obtain the laminate.

10. The method for manufacturing a heat conductive member according to any one of claims 1 to 9, wherein the heat conductive composition is discharged between a heat radiator and a heat generator so as to overlap in a plurality of sheets, and a laminate is formed between the heat radiator and the heat generator.

11. The method for manufacturing a heat conductive member according to claim 10, wherein the heat conductive composition is discharged in a sheet shape in a direction connecting the heat radiator and the heat generating body.

12. The method for producing a heat conductive member according to any one of claims 1 to 11, wherein each sheet in the laminate has a thickness of 0.1 to 9.0mm.

13. The method for manufacturing a heat conductive member according to any one of claims 1 to 12, wherein the heat conductive composition is discharged at room temperature.

14. A dispenser device includes a head and a supply path for supplying a flowable material to the head,

the head has a wide-width discharge port and a connection path connecting the supply path and the discharge port,

the connection path is connected to the discharge port such that an inner diameter in one direction from the supply path toward the discharge port becomes larger.

15. The dispenser device according to claim 14, further comprising a cutter disposed at the discharge port and movable along a longitudinal direction of the discharge port.

16. The dispenser device according to claim 14 or 15, at least any one of the head and the discharged member from which the flowable material is discharged is movable in a direction orthogonal to a longitudinal direction of the discharge port.