Coating method using a metal cartridge

Abstract

To provide a cartridge container for applying a moisture-curable thermally conductive resin composition on which no ejection failure due to container deformation occurs when pressure is to be applied to dispense, and no problems such as hardening during long-term storage occur.SOLUTION: There is provided a cylindrical metal cartridge in which: a container 2 of the metal cartridge is made of metal with a thickness of 0.4 to 0.6 mm; a dispensing port 3 is provided on the bottom surface of the cylinder; a plunger 4, which is slidable toward the top surface or the bottom surface of the cylinder, is provided between the top surface and the bottom surface of the cylinder; and a moisture-curable thermal conductive resin composition 5 adjusted to 200 PaS to 800 PaS at 23°C is filled between the plunger 4 and the bottom of the cylinder.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a metal cartridge filled with a moisture-curable thermally conductive resin composition and a coating method using the same. [Background technology]

[0002] Conventionally, various discharge devices for discharging a curable resin composition have been proposed. Patent documents 1 and 2 describe an application device (discharge device) that contains a plastic container filled with a viscous liquid (curable resin composition) in a pressure tank, pressurizes the inside of the pressure tank with compressed air to crush the flexible plastic container, and discharges and applies the viscous liquid from an application nozzle.

[0003] Furthermore, Patent Document 3 describes a liquid ejection device (ejection device) that fills a moisture-curing adhesive (curable resin composition) filled in a liquid tank into a cylinder by applying pressure from a pressure-moving plunger, and ejects the moisture-curing adhesive from the cylinder through a nozzle. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2012-192343 A (Published October 11, 2012) [Patent Document 2] JP 2012-223715 A (Published on November 15, 2012) [Patent Document 3] JP 2014-217795 A (Published on November 20, 2014) Summary of the Invention [Problem to be solved by the invention]

[0005] The coating devices described in Patent Documents 1 and 2 have a problem in that a large amount of viscous liquid remains in the plastic container without being discharged, resulting in a loss of the viscous liquid.

[0006] In addition, in the application device described in Patent Document 3, no consideration is given to suppressing the hardening of the moisture-curing adhesive filled in the liquid tank. Conventionally, the moisture-curing thermally conductive resin composition has been filled in a plastic cartridge. However, when pressure is applied to the container inside the discharge device to discharge the moisture-curing thermally conductive resin composition, problems such as the container being deformed, causing discharge failure, and hardening during long-term storage have occurred.

[0007] To provide a cartridge container which is less likely to cause defective discharge due to deformation of the container when pressure is applied to discharge the content, and is less likely to cause problems such as hardening during long-term storage. [Means for solving the problem]

[0008] As a result of extensive investigations, the present inventors have found that the above problems can be solved by the following structure. The present invention has the following configuration.

[0009] 1) A cylindrical metal cartridge, The container of the metal cartridge is made of metal with a thickness of 0.4 to 0.6 mm. The bottom surface of the cylinder has a discharge port. A plunger is provided between the top and bottom surfaces of the cylinder, the plunger being slidable toward the top or bottom surface of the cylinder; A metal cartridge characterized in that a moisture-curable thermally conductive resin composition adjusted to 200 PaS to 800 PaS at 23°C is filled between the plunger and the bottom surface of the cylinder.

[0010] 2) The metal cartridge described in 1), wherein the plunger has a circular surface parallel to the bottom surface of the cylinder and a bent portion extending parallel to the side surface of the cylinder toward the top surface of the cylinder.

[0011] 3) The metal cartridge according to 1) or 2), characterized in that the metal cartridge is made of aluminum.

[0012] 4) The metal cartridge according to any one of 1) to 3), characterized in that the discharge port and the upper surface of the cylinder are sealed with a metal lid.

[0013] 5) The metal cartridge according to 4), characterized in that it has a space between the metal cover on the upper surface of the cylinder and the plunger.

[0014] 6) The metal cartridge according to 5) above, wherein the space is filled with nitrogen.

[0015] 7) A metal cartridge according to 5) or 6), characterized in that a moisture absorbent is enclosed in the space portion.

[0016] 8) The metal cartridge according to 7), wherein the moisture absorbent is at least one selected from the group consisting of silica gel, calcium chloride, calcium carbonate, and calcium oxide.

[0017] 9) The metal cartridge according to any one of 1) to 8), wherein the moisture-curable thermally conductive resin composition contains at least a moisture-curable resin and a thermally conductive filler.

[0018] 10) The metal cartridge according to any one of 1) to 9), wherein the moisture-curable resin is one or more resins selected from the group consisting of modified silicone resins, silicone resins, and urethane resins.

[0019] 11) The metal cartridge according to any one of 1) to 10), characterized in that the thermally conductive filler contains one or more types of thermally conductive filler selected from aluminum, aluminum hydroxide, aluminum oxide, aluminum nitride, boron nitride, silicone carbide, graphene particles, graphene oxide particles, and calcium carbonate.

[0020] 12) A method for applying a moisture-curable thermal conductive resin composition using the metal cartridge according to any one of 4) to 11), comprising the steps of: A process of removing the lid on the top of the cylinder or drilling a hole in the lid on the top of the cylinder; After the process of drilling a hole in the discharge port, the metal cartridge is placed in a pressure holder, A method for applying a moisture-curable thermally conductive resin composition, comprising the step of sliding a plunger by pressurizing the inside of a pressure holder with a gas, thereby supplying the moisture-curable thermally conductive resin composition in a cartridge. Effect of the Invention

[0021] According to the present invention, it is possible to provide a cartridge container that does not cause ejection failure due to deformation of the container when pressure is applied to eject a moisture-curable thermally conductive resin composition, and does not cause problems such as hardening during long-term storage. [Brief description of the drawings]

[0022] [Figure 1] FIG. 2 is a cross-sectional view of a metal cartridge of the present invention. [Diagram 2] 1A to 1C are diagrams showing a method for filling a moisture-curable thermally conductive resin composition into a container of a metal cartridge. [Diagram 3] 11A to 11C are diagrams showing a method for opening the discharge port of the metal cartridge. [Figure 4] FIG. 1 is a diagram showing a method for applying a moisture-curable thermally conductive resin composition using a metal cartridge. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] Hereinafter, the embodiments of the present invention will be described in detail. However, the present invention is not limited to this, and various modifications are possible within the described range, and embodiments obtained by appropriately combining the technical means disclosed in each of the different embodiments are also included in the technical scope of the present invention. In this specification, unless otherwise specified, "A to B" representing a numerical range means "A or more, B or less". In addition, "mass" and "weight" are considered to be synonymous. Furthermore, "pressurization" means a state in which the pressure is made to exceed 1 atmosphere (atmospheric pressure), and "depressurization" means a state in which the pressure is released and returned to 1 atmosphere (atmospheric pressure). In addition, "pressurization" and "positive pressure" are considered to be synonymous.

[0024] [Metal cartridge] A metal cartridge according to one embodiment of the present invention is a cylindrical metal cartridge as shown in FIG. 1. A container 2 of the metal cartridge 1 is made of metal with a thickness of 0.4 to 0.6 mm, and has a discharge outlet 3 at the bottom of the cylinder. A plunger 4 is provided between the top and bottom of the cylinder, capable of sliding toward the top or bottom of the cylinder. A moisture-curable thermally conductive resin composition 5 adjusted to 200 PaS to 800 PaS at 23° C. is filled between the plunger and the bottom of the cylinder.

[0025] The container 2 of the metal cartridge 1 is made of a metal having a thickness of 0.4 to 0.6 mm, so that it is possible to suppress the occurrence of poor discharge caused by deformation of the container when pressure is applied to discharge the moisture-curable thermally conductive resin composition in order to apply it. Although the thickness can be made to be more than 0.6 mm, the cost of the container tends to increase and the container tends to become heavy. In addition, various metals such as aluminum, aluminum alloy, steel, SUS, and iron can be used as the material of the container 2 of the metal cartridge 1, but it is preferable that it is made of aluminum. Here, the thickness means the total thickness of the metal layer.

[0026] The discharge port 3 of the metal cartridge 1 is sealed by a metal lid 7. The metal lid 7 is preferably made of the same metal as the container 2 and is molded at the same time as the metal cartridge 1, and a hole needs to be made in the metal lid 7 so that the moisture-curable thermal conductive resin composition 5 can be discharged from the discharge port 3 during application. The thickness of the metal lid 7 is preferably 0.2 mm to 0.5 mm.

[0027] [Plunger] The plunger 4 has a circular surface parallel to the bottom surface of the cylinder, seals the container, and is capable of sliding in the supply direction when pressurized. The plunger has a disk-shaped outer shape and has a bent portion 6 that extends parallel to the side surface of the cylinder toward the top surface of the cylinder so that the posture of the plunger when pressurized can be stabilized and the moisture-curable thermally conductive resin composition 5 in the container can be stably extruded.

[0028] The plunger may be, for example, an aluminum, steel or SUS plunger having a length of about 20 mm, an outer diameter of about 46 mm and a thickness of about 0.4 mm.

[0029] However, the size and material of the plunger may be appropriately determined taking into consideration the size and material of the container and the composition of the moisture-curable thermally conductive resin composition to be filled.

[0030] (Metal cartridge lid) The lid (end) 8 of the metal cartridge has a circular surface parallel to the bottom surface of the cylinder, a disk-like outer shape, and a curled outer periphery that can be bent so that it can be fastened to the cylinder. After the plunger 4, dry gas 9, and moisture absorbent 10 are sealed inside, the lid (end) 8 is fastened to the aluminum cartridge by a fastener, and the cartridge is joined and sealed.

[0031] [Dry gas] The dry gas 9 is a gas having a dew point of −50° C. or less, and is preferably nitrogen, argon, helium, or air, with nitrogen and argon being particularly preferred.

[0032] [Moisture absorbent] The moisture absorbent 10 is a product containing a material selected from the group consisting of silica gel, calcium chloride, calcium carbonate, and calcium oxide, and is wrapped in a breathable packaging material.

[0033] <Moisture-curable thermally conductive resin composition> The moisture-curable thermally conductive resin composition used in this embodiment is a resin composition that is filled into a metal cartridge and forms a cured product such as a coating film after being discharged, and contains a curable liquid resin. The moisture-curable thermally conductive resin composition may further contain various additives such as a curing catalyst for curing the curable liquid resin, an initiator, a heat aging inhibitor, a plasticizer, an extender, a thixotropic agent, a storage stabilizer, a dehydrating agent, a coupling agent, an ultraviolet absorber, a flame retardant, an electromagnetic wave absorber, a filler, and a solvent, as appropriate, depending on the application.

[0034] The moisture-curable thermally conductive resin composition is suitable for applications such as application to the surface of an electronic device, a substrate, or a heat generating body to form a coating film, and contains a thermally conductive filler. The moisture-curable thermally conductive resin composition containing a thermally conductive filler is more preferably a resin composition having a thermal conductivity of 0.5 W / (m·K) or more of the cured product, more preferably a resin composition having a thermal conductivity of 0.8 W / (m·K) or more, and particularly preferably a resin composition having a thermal conductivity of 0.9 W / (m·K) or more. The moisture-curable thermally conductive resin composition is more preferably a resin composition having a thermal conductivity of 100 W / (m·K) or less of the cured product. This allows the coating film to efficiently release heat generated in the electronic device when the moisture-curable thermally conductive resin composition is applied to the surface of an electronic device or the like to form a coating film.

[0035] (curable liquid resin) The curable liquid resin is a liquid resin that has a reactive group in the molecule and can be cured by the reaction of the reactive group. Specific examples of the curable liquid resin include curable acrylic resins, curable methacrylic resins, and curable polypropylene oxide resins; curable polyolefin resins, such as curable polyisobutylene resins; and silicone resins. Specific examples of the reactive group include reactive functional groups such as epoxy groups, hydrolyzable silyl groups, vinyl groups, acryloyl groups, SiH groups, urethane groups, carbodiimide groups, or a combination of a carboxylic acid anhydride group and an amino group.

[0036] In the case of obtaining a curable liquid resin that is cured by the reaction of two types of reactive groups combined together, or by the reaction of a reactive group with the curing catalyst, the two liquids are mixed together to obtain the curable liquid resin when applied to, for example, an electronic device, a substrate, or a heating element, after preparation as a two-liquid composition. In the case of a curable liquid resin that is cured by the reaction of a hydrolyzable silyl group, it is possible to prepare a one-liquid type room temperature curable composition since it is cured by reaction with moisture (humidity) in the air. In the case of a curable liquid resin that is cured by the combination of a vinyl group, a SiH group, and a platinum catalyst (curing catalyst), a curable liquid resin that is cured by the combination of an acryloyl group and a radical initiator (initiator), etc., it is also possible to cure the one-liquid type curable composition or two-liquid type curable composition by heating to a crosslinking temperature or by applying crosslinking energy such as ultraviolet light or electron beams. In general, when it is easy to heat the entire heat dissipation structure to a certain extent, it is preferable to use a heat-curable composition, and when it is difficult to heat the heat dissipation structure, it is preferable to use a two-part curable composition or a moisture-curable composition, but this is not limited to these.

[0037] Among the curable liquid resins, silanol condensation reaction type curable liquid resins are more preferable. Among the curable liquid resins, it is preferable to use a curable acrylic resin or a curable polypropylene oxide resin because there is little problem of contamination in electronic devices due to low molecular weight siloxane and the resin has excellent heat resistance. As the curable acrylic resin, various known reactive acrylic resins can be used. Among these, it is preferable to use an acrylic oligomer having a reactive group at the molecular end. As the curable acrylic resin, a combination of a curable acrylic resin produced by living radical polymerization, particularly atom transfer radical polymerization, and a curing catalyst is most preferable. As an example of such a curable acrylic resin, Kaneka XMAP manufactured by Kaneka Corporation is known. As the curable polypropylene oxide resin, various known reactive polypropylene oxide resins can be used. As an example of such a reactive polypropylene oxide resin, Kaneka MS Polymer manufactured by Kaneka Corporation is known. Two or more types of curable liquid resins can also be used in combination.

[0038] (Thermal conductive filler: (Conductive filler)) Examples of the thermally conductive filler used in the moisture-curable thermally conductive resin composition (and its cured product) include, from the viewpoints of thermal conductivity, ease of availability, packing property, toxicity, and electrical properties such as insulation and electromagnetic wave absorption, carbon compounds such as graphite and diamond; metal oxides such as aluminum oxide, magnesium oxide, beryllium oxide, titanium oxide, zirconium oxide, and zinc oxide; metal nitrides such as boron nitride, aluminum nitride, and silicon nitride; metal carbides such as boron carbide, aluminum carbide, and silicon carbide; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; metal carbonates such as magnesium carbonate and calcium carbonate; crystalline silica; organic polymer baked products such as acrylonitrile-based polymer baked products, furan resin baked products, cresol resin baked products, polyvinyl chloride baked products, sugar baked products, and charcoal baked products; composite ferrites with Zn ferrite; Fe-Al-Si-based ternary alloys; and metal powders such as aluminum. Among these, aluminum, aluminum hydroxide, aluminum oxide, aluminum nitride, boron nitride, silicone carbide, graphene particles, graphene oxide particles, and calcium carbonate are preferred, and boron nitride, aluminum oxide, aluminum hydroxide, and calcium carbonate are particularly preferred.

[0039] In addition, since the thermally conductive filler has improved dispersibility in the curable liquid resin, it is preferable that the surface of the filler is treated with a silane coupling agent (vinyl silane, epoxy silane, (meth)acrylic silane, isocyanato silane, chlorosilane, amino silane, etc.), a titanate coupling agent (alkoxy titanate, amino titanate, etc.), or a fatty acid (saturated fatty acids such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, etc.; unsaturated fatty acids such as sorbic acid, elaidic acid, oleic acid, linoleic acid, linolenic acid, erucic acid, etc.), a resin acid (abietic acid, pimaric acid, levopimaric acid, neoapitic acid, palustric acid, dehydroabietic acid, isopimaric acid, sandaracopimaric acid, columic acid, secodehydroabietic acid, dihydroabietic acid, etc.), etc.

[0040] The amount of the thermally conductive filler used is preferably an amount such that the volume ratio (volume %) of the thermally conductive filler in the moisture-curable thermally conductive resin composition is 25% by volume or more, since the thermal conductivity of the cured product obtained from the moisture-curable thermally conductive resin composition can be increased. If the amount of the thermally conductive filler used is less than 25% by volume, the thermal conductivity of the cured product tends to be insufficient. If a higher thermal conductivity is desired, the amount of the thermally conductive filler used is more preferably 30% by volume or more, even more preferably 40% by volume or more, and particularly preferably 50% by volume or more. In addition, the amount of the thermally conductive filler used is preferably 90% by volume or less. If the amount of the thermally conductive filler used is more than 90% by volume, the viscosity of the thermally conductive curable resin composition before curing may become too high.

[0041] Here, the volume fraction (volume %) of the thermally conductive filler is a value calculated from the weight fraction and specific gravity of the curable liquid resin component (curable resin composition excluding the thermally conductive filler) and the thermally conductive filler, and is calculated by the following formula (1). In formula (1), the curable liquid resin component is simply referred to as the "resin component," and the thermally conductive filler is simply referred to as the "filler."

[0042] Volume fraction of filler (volume %) = (weight fraction of filler / specific gravity of filler) ÷ [(weight fraction of resin content / specific gravity of resin content) + (weight fraction of filler / specific gravity of filler)] × 100 ... (1).

[0043] As a method for increasing the volume ratio of the thermally conductive filler in the moisture-curable thermally conductive resin composition, it is preferable to use two or more types of thermally conductive fillers with different particle sizes. In this case, it is preferable to use a thermally conductive filler with a particle size of more than 10 μm as the thermally conductive filler with a larger particle size, and a thermally conductive filler with a particle size of 10 μm or less as the thermally conductive filler with a smaller particle size.

[0044] Furthermore, when two or more types of thermally conductive fillers are used in combination, these thermally conductive fillers may be thermally conductive fillers having the same composition, or may be thermally conductive fillers having different compositions.

[0045] Furthermore, by appropriately combining a thermally conductive filler having a small maximum particle size, the thin film property of the cured product can be ensured. The maximum particle size is preferably 200 μm or less, more preferably 100 μm or less, and even more preferably 50 μm or less. By using a thermally conductive filler having a small maximum particle size, the moisture-curable thermally conductive resin composition can be poured into a narrow gap.

[0046] [Filling of moisture-curable thermally conductive resin composition into metal cartridge container] The moisture-curable thermally conductive resin composition can be filled into a metal cartridge container by a combination of devices such as a vertical filler, a horizontal filler, an automatic filler, a semi-automatic filler, a manual filler, etc. For example, in the case of the vertical filler shown in Fig. 2, the cartridge filling device 20 comprises a filling nozzle 30, a metering pump 31, a flexible hose 32, a raw material drum 33, a discharge pressure piston 34, and a compression plate 35.

[0047] When filling, the filling nozzle 30 of the cartridge filling device 20 is inserted into the container 2 of the metal cartridge 1, and the moisture-curable thermally conductive resin composition 5 measured by the metering pump 31 is poured in (FIG. 2(a)). FIG. 2(b) is a schematic diagram of the filling nozzle 30 and the container 2 in FIG. 2(a), and shows the state in which the moisture-curable thermally conductive resin composition is discharged from the filling nozzle and filled into the cartridge with the resin composition, and the filling is almost completed. Thereafter, the plunger 4 is pushed in with a plugging tool 36 using a plunger plugging device (not shown) to plug the cartridge (FIG. 2(c)). When plugging the cartridge, it is preferable to insert an air vent pin to remove the air inside the cartridge. In the plunger plugging state, it is preferable to compress the cartridge sufficiently to push out the air so that no air remains between the moisture-curable resin-type thermally conductive resin composition 5 and the plunger 4, as shown in FIG. 2(d). It is then preferable to place a moisture absorbent 10 in the space above the plunger as shown in Fig. 2(e). It is also preferable to fill the space in the plunger with a gas (dry gas) such as nitrogen, argon, helium, or air as shown in Fig. 2(f), and then close the metal lid 8 on the top of the cylinder to seal the cartridge as shown in Fig. 2(g).

[0048] [Method of applying moisture-curable thermally conductive resin composition using a metal cartridge] As shown in Figure 3, the method of applying the moisture-curing thermally conductive resin composition using a metal cartridge involves removing the cover 8 and moisture absorbent 10 from the cylindrical top of the metal cartridge, inserting a conical drilling jig 41 with a sharp tip into the discharge outlet 7 in direction 42 (Figure 3(b)), and then pulling out the drilling jig 41 in direction 44 (Figure 3(c)), to form an opening 43 at the discharge outlet 7.

[0049] The metal cartridge having the opening 43 formed at the discharge port 7 is attached to a pressure holder 45 for pressurizing the metal cartridge of the coating device shown in Fig. 4. The coating device includes a gas generator 50 for generating compressed gas for extruding the moisture-curable thermally conductive resin composition, a pressurized gas 51, a discharge valve controller 52, gas piping for pressurizing the metal cartridge 53, gas piping for valve control 54, wiring for robot control 55, wiring for discharge control 56, a discharge valve 57, a discharge nozzle 58, a substrate to be coated 60, a stage 61 for the substrate, a robot for position control 62, and a control computer 63.

[0050] The resin composition can be applied onto a substrate, for example, by the following method. Pressurized gas 51 generated from a gas generator 50 is sent to the pressurized holder 45 and the discharge valve controller roller 52. Pressurization of the pressurized holder 45 causes the plunger 4 of the internal metal cartridge to slide. The sliding of the plunger 4 causes the moisture-curable thermally conductive resin composition 5 inside to be pushed out from the discharge port 7.

[0051] The moisture-curable thermally conductive resin composition 5 extruded from the discharge port 7 is sent to the discharge valve 57 through a pipe. The discharge valve 57 is controlled to open and close by the pressurized gas discharged and controlled by the discharge valve controller 52. When the discharge valve 57 is open, the moisture-curable thermally conductive resin composition 5 is applied to the substrate 60 through the discharge nozzle 58. When the valve is closed, the discharge from the discharge nozzle 58 is stopped. The control of the application pattern shape of the moisture-curable thermally conductive resin composition 59 after discharge is performed by the control computer 63, which controls the position of the discharge valve 57 through the robot control wiring 55. The robot is moved left and right 64, and the substrate stage 61 is moved forward and backward to adjust the position. The discharge valve controller 52 is controlled by the discharge controller wiring 56, which controls the opening and closing of the discharge valve 57 to control the amount of application and the timing of application. All controls such as the movement of the robot and the amount of resin discharged can be controlled by the control computer 63. EXAMPLES

[0052] [Synthesis Example 1] CuBr (1.09 kg), acetonitrile (11.4 kg), butyl acrylate (26.0 kg), and diethyl 2,5-dibromoadipate (2.28 kg) were added to a 250 L reactor under a nitrogen gas atmosphere, and the mixture was stirred at 70 to 80 ° C for about 30 minutes. Pentamethyldiethylenetriamine was added to the resulting mixture to start the reaction. Thirty minutes after the reaction started, butyl acrylate (104 kg) was continuously added over 2 hours. In addition, pentamethyldiethylenetriamine was appropriately added during the reaction so that the internal temperature (temperature of the reaction liquid) was 70 ° C to 90 ° C. The total amount of pentamethyldiethylenetriamine used in the reaction was 220 g. After 4 hours had passed since the start of the reaction, the volatile matter was removed by heating and stirring under reduced pressure at 80 ° C. Acetonitrile (45.7 kg), 1,7-octadiene (14.0 kg), and pentamethyldiethylenetriamine (439 g) were added to the residue and stirred for 8 hours, after which the mixture was heated and stirred under reduced pressure at 80° C. to remove volatiles.

[0053] Toluene was added to the concentrate obtained to dissolve the polymer contained in the concentrate, and then diatomaceous earth as a filter aid and aluminum silicate and hydrotalcite as adsorbents were added, followed by heating and stirring in an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6%) at an internal temperature (solution temperature) of 100° C. The solid content in the solution was removed by filtration, and the filtrate was heated and stirred under reduced pressure at an internal temperature of 100° C. to remove the volatile content.

[0054] Further, aluminum silicate and hydrotalcite as adsorbents, and a thermal deterioration inhibitor were added to the obtained concentrate, and the mixture was heated and stirred under reduced pressure (average temperature about 175°C, reduced pressure of 10 Torr or less). Thereafter, aluminum silicate and hydrotalcite as adsorbents were further added, an antioxidant was added, and the mixture was heated and stirred at an internal temperature of 150°C in an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6%).

[0055] Toluene was added to the concentrate to dissolve the polymer contained in the concentrate, and the solid content in the solution was removed by filtration, and the filtrate was heated and stirred under reduced pressure to remove the volatile content, thereby obtaining a polymer having an alkenyl group.

[0056] This polymer having alkenyl groups was mixed with dimethoxymethylsilane (2.0 molar equivalents relative to the alkenyl groups), methyl orthoformate (1.0 molar equivalent relative to the alkenyl groups), and a xylene solution of platinum complex catalyst bis(1,3-divinyl-1,1,3,3-tetramethyldisiloxane) (amount equivalent to 10 mg of platinum per 1 kg of polymer), and reacted under nitrogen gas atmosphere with heating and stirring at 100°C. After confirming that the alkenyl groups had disappeared, the reaction mixture was concentrated to obtain a resin (I-1) consisting of poly(n-butyl acrylate) having dimethoxysilyl groups at the ends. The number average molecular weight of the obtained polymer was about 26,000, and the molecular weight distribution was 1.3. The number of silyl groups introduced per polymer molecule was determined by 1H-NMR analysis to be about 1.8.

[0057] [Synthesis Example 2] Propylene oxide was polymerized using a zinc hexacyanocobaltate glyme complex catalyst and a polyoxypropylene diol having a number average molecular weight of about 2,000 as an initiator, to obtain a hydroxyl-terminated polypropylene oxide having a number average molecular weight of 25,500. The number average molecular weight of the hydroxyl-terminated polypropylene oxide was measured using a Tosoh Corporation HLC-8120GPC as a liquid delivery system, a Tosoh Corporation TSK-GEL H type column, and THF as a solvent, in terms of polystyrene.

[0058] Next, a methanol solution of 1.2 times the equivalent of methoxysodium relative to the hydroxyl groups of this hydroxyl-terminated polypropylene oxide was added, and then the methanol was distilled off, and allyl chloride was added to convert the terminal hydroxyl groups to allyl groups. Next, the unreacted allyl chloride was removed by volatilization under reduced pressure.

[0059] 100 parts by weight of the obtained unpurified allyl-terminated polypropylene oxide were mixed with 300 parts by weight of n-hexane and 300 parts by weight of water, and the mixture was stirred, and then the water was removed by centrifugation. 300 parts by weight of water was further mixed with the obtained hexane solution, and the mixture was stirred, and then the water was removed again by centrifugation. Then, the hexane was removed by devolatilization under reduced pressure. This resulted in a bifunctional polypropylene oxide having an allyl group at the end and a number average molecular weight of about 25,500.

[0060] To 100 parts by weight of the purified allyl-terminated polypropylene oxide obtained, 150 ppm of a platinum vinylsiloxane complex isopropanol solution (platinum content 3% by weight) as a catalyst and 0.95 parts by weight of trimethoxysilane were added and reacted at 90°C for 5 hours. This resulted in a resin (I-2) consisting of trimethoxysilyl-terminated polypropylene oxide. The number of trimethoxysilyl groups introduced per polymer molecule was determined by 1H-NMR analysis to be about 1.3.

[0061] [Preparation of Thermally Conductive Curable Liquid Resin] 50 parts by weight of resin (I-1) obtained in Synthesis Example 1, 50 parts by weight of resin (I-2) obtained in Synthesis Example 2, 100 parts by weight of di-isononyl-cyclohexane-dicarboxylate (DINCH) (manufactured by BASF) as a plasticizer, 1 part by weight of antioxidant (Irganox 1010), and 1,500 parts by weight of alumina (manufactured by DENKA Co., Ltd.) as a thermally conductive filler were thoroughly stirred and kneaded by manual stirring. Then, the kneaded mixture was dehydrated by vacuuming while being heated and kneaded using a 5L butterfly mixer. After completion of dehydration, the kneaded mixture was cooled and mixed with 5 parts by weight of dehydrating agent (A171) and 4 parts by weight of tin neodecanoate as a curing catalyst. This prepared a moisture-curable thermally conductive resin composition.

[0062] Example 1 The container was made of aluminum having a thickness of 0.5 mm, and a metal cartridge having a capacity of 330 ml and a discharge port having a thickness of 0.4 mm was used at the bottom of the cylinder. The moisture-curable thermally conductive resin composition was filled into a metal cartridge at 800 g using the vertical filling machine shown in FIG. 2. After filling, the plunger was driven in, nitrogen was charged, silica gel was placed as a desiccant, and the lid was sealed. After filling, a discharge test was performed using the discharge test device shown in FIG. 4, pressurized to 0.3 MPa using a pressurized gas (dry air) generated from a gas generator using a 1 mmΦ discharge nozzle. The discharge valve was opened to continuously discharge the moisture-curable thermally conductive resin composition, and the discharge ratio was calculated from Equation 1, with the weight at the time of filling being Xg and the weight after discharge being Yg. Discharge ratio (%) = Y ÷ X × 100 Formula 1 In this embodiment, the ejection rate after ejection was 95%, and no deformation or the like was observed in the cartridge after ejection.

[0063] Comparative Example 1 The experiment was carried out in the same manner as in Example 1, except that the material of the container was a laminate of high-density polyethylene layer / aluminum sheet (thickness 0.1 μm) / craft paper / printed aluminum foil (total metal thickness 0.1 μm) on the outermost layer. The discharge rate after continuous coating was 52%, and the side surface of the container was deformed during coating, resulting in 40% of the moisture-curable thermally conductive resin composition remaining and not being able to be coated.

[0064] Comparative Example 2 Except for using aluminum having a thickness of 0.3 mm as the material of the container, the same procedure as in Example 1 was carried out. The discharge rate after continuous application was 60%, and the side surface of the container was deformed during application, resulting in 40% of the moisture-curable thermally conductive resin composition remaining and unable to be applied. [Explanation of symbols]

[0065] 1. Metal cartridge 2. Container 3.Discharge port 4. Plunger 5. Moisture-curable thermally conductive resin composition 6. (Plunger) bent part 7. Metal cover for the outlet 8. Metal lid on top of cylinder 9. Space section 10. Moisture absorbent 20. Cartridge filling device 30.Filling nozzle 31. Metering pump 32. Flexible hose 33. Raw material drum 34. Discharge pressure adding piston 35. Compression plate 36. Stoppering tool 37.Dry Gas 38. Blower nozzle 41.Drilling jig 42. Piercing direction 43. Opening 44. Pulling direction 45. Pressure holder 50. Gas generator 51. Pressurized Gas 52.Discharge valve controller 53. Gas piping for pressurizing metal cartridges 54.Gas piping for valve control 55. Robot control wiring 56. Wiring for discharge control 57.Discharge valve 58. Discharge nozzle 59. Moisture-curable thermally conductive resin composition after extrusion 60. Coated substrate 61. Substrate stage 62. Position control robot 63. Control computer 64. Robot left and right movement

Claims

1. A method for applying a moisture-curable thermal conductive resin composition using a cylindrical metal cartridge, comprising the steps of: the container of the metal cartridge is made of aluminum having a thickness of 0.4 to 0.6 mm, has a discharge port on the bottom surface of the cylinder, has a plunger between the top surface and the bottom surface of the cylinder that can slide toward the top surface or the bottom surface of the cylinder, and is filled between the plunger and the bottom surface of the cylinder with a moisture-curable thermally conductive resin composition adjusted to 200 PaS to 800 PaS at 23°C, and the discharge port and the top surface of the cylinder are sealed with a metal lid; A process of removing the lid on the top of the cylinder or drilling a hole in the lid on the top of the cylinder; After the step of drilling a hole in the discharge port, the metal cartridge is placed in a pressure holder of a coating device, A method for applying a moisture-curable thermally conductive resin composition, comprising the steps of: applying pressure to a pressure holder with gas to slide a plunger, extruding the moisture-curable thermally conductive resin composition in a cartridge and feeding the composition through a pipe to a discharge valve, and applying the composition to a substrate through a discharge nozzle connected to the discharge valve.

2. 2. The method for applying a moisture-curable thermal conductive resin composition according to claim 1, wherein the plunger has a circular surface parallel to the bottom surface of the cylinder and a bent portion extending parallel to the side surface of the cylinder toward the top surface of the cylinder.

3. A method for applying a moisture-curing thermally conductive resin composition as described in claim 1, characterized in that the metal cartridge has a space between the metal lid on the upper surface of the cylinder and the plunger.

4. A method for applying a moisture-curing thermally conductive resin composition as described in claim 3, characterized in that the space portion is filled with nitrogen.

5. A method for applying a moisture-curing thermally conductive resin composition as described in claim 3 or 4, characterized in that a moisture absorbent is enclosed in the space portion.

6. 6. The method for applying a moisture-curable thermally conductive resin composition according to claim 5, wherein the moisture absorbent is at least one selected from the group consisting of silica gel, calcium chloride, calcium carbonate, and calcium oxide.

7. The method for applying a moisture-curable thermally conductive resin composition according to any one of claims 1 to 6, wherein the moisture-curable thermally conductive resin composition contains at least a moisture-curable resin and a thermally conductive filler.

8. The method for applying the moisture-curable thermal conductive resin composition according to any one of claims 1 to 7, characterized in that the moisture-curable resin is one or more resins selected from the group consisting of modified silicone resins, silicone resins, and urethane resins.

9. 9. The method for applying the moisture-curable thermal conductive resin composition according to any one of claims 1 to 8, characterized in that the thermal conductive filler contains one or more thermal conductive fillers selected from aluminum, aluminum hydroxide, aluminum oxide, aluminum nitride, boron nitride, silicone carbide, graphene particles, graphene oxide particles, and calcium carbonate.

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