JP2022187828A - Metal cart cartridge and application method using the same - Google Patents

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

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

Conventionally, various discharge devices for discharging a curable resin composition have been proposed. In Patent Documents 1 and 2, a plastic container filled with a viscous liquid (curable resin composition) is placed in a pressurized tank, and the pressure tank is pressurized with compressed air to produce a flexible plastic container. A coating device (discharging device) is disclosed that applies a viscous liquid by crushing it and discharging it from a coating nozzle.

Further, in Patent Document 3, a moisture-curable adhesive (curable resin composition) filled in a liquid tank is filled into a cylinder by pressure from a pressure-moving plunger, and moisture-curable adhesive is passed from the cylinder through a nozzle. Liquid ejection devices (ejectors) for ejecting agents are described.

Japanese Patent Application Laid-Open No. 2012-192343 (published on October 11, 2012) Japanese Patent Application Laid-Open No. 2012-223715 (published on November 15, 2012) Japanese Patent Application Laid-Open No. 2014-217795 (published on November 20, 2014)

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

Further, in the coating device described in Patent Document 3, no consideration is given to suppressing the curing of the moisture-curable adhesive filled in the liquid tank. Conventionally, a plastic cartridge is filled with a moisture-curable thermally conductive resin composition. However, in order to apply the moisture-curable thermally conductive resin composition, when pressure is applied to the container inside the discharge device to discharge the composition, the container is deformed and discharge failure occurs, or the composition hardens during long-term storage. etc. had occurred.

To provide a cartridge container in which ejection failure due to deformation of the container is unlikely to occur when an attempt is made to eject under pressure, and problems such as hardening during long-term storage are unlikely to occur.

As a result of intensive studies, the inventors of the present invention have found that the above problems can be solved by the following structure.
The present invention has the following configurations.

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

2). The metal cartridge according to 1), wherein the plunger has a circular cylindrical bottom surface and a parallel surface, and has a bent portion extending toward the cylindrical upper surface in parallel with the cylindrical side surface.

3). A metal cartridge according to 1) or 2), wherein the metal cartridge is made of aluminum.

4). The metal cartridge according to any one of 1) to 3), wherein the ejection port and the upper surface of the cylinder are sealed with a metal lid.

5). The metal cartridge according to 4), which has a space portion between the metal lid on the upper surface of the cylinder and the plunger.

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

7). A metal cartridge according to 5) or 6), wherein a moisture absorbent is sealed in the space.

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

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.

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

11). The thermally conductive filler contains one or more thermally conductive fillers selected from aluminum, aluminum hydroxide, aluminum oxide, aluminum nitride, boron nitride, silicone carbide, graphene particles, graphene oxide particles, and calcium carbonate. A metal cartridge according to any one of 1) to 10).

12). 4) A method for applying a moisture-curable thermally conductive resin composition using the metal cartridge according to any one of 4) to 11),
removing the lid on the top surface of the cylinder or making a hole in the lid on the top surface of the cylinder;
After passing through the process of making a hole in the discharge port, install the metal cartridge in the pressure holder,
A method for applying a moisture-curable thermally-conductive resin composition, comprising the step of supplying the moisture-curable thermally-conductive resin composition in a cartridge by pressurizing the pressure holder with a gas to slide a plunger. .

According to the present invention, in order to apply a moisture-curable thermally conductive resin composition, when it is attempted to be discharged under pressure, discharge failure due to deformation of the container does not occur, and it is possible to cure during long-term storage. A problem-free cartridge container can be provided.

1 is a cross-sectional view of a metal cartridge of the present invention; FIG. FIG. 4 is a diagram showing a method of filling a container of a metal cartridge with a moisture-curable thermally conductive resin composition. It is a figure which shows the unsealing method of the ejection opening of a metal cartridge. FIG. 4 is a diagram showing a method of applying a moisture-curable thermally conductive resin composition using a metal cartridge;

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, 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 scope described, and embodiments obtained by appropriately combining technical means disclosed in different embodiments are also present. included in the technical scope of In this specification, unless otherwise specified, "A to B" representing a numerical range means "A or more and B or less". Also, "mass" and "weight" are considered synonymous. Further, "pressurization" means a state in which the pressure exceeds 1 atmosphere (atmospheric pressure), and "depressurization" means a state in which the pressure is released and returned to 1 atmosphere (atmospheric pressure). Also, "pressurization" and "positive pressure" are considered synonymous.

[Metal cartridge]
A metal cartridge according to one embodiment of the present invention is a cylindrical metal cartridge as shown in FIG. has a discharge port 3, has a plunger 4 between the top surface and the bottom surface of the cylinder, which is slidable toward the top surface or the bottom surface of the cylinder, and 200 PaS at 23°C between the plunger and the bottom surface of the cylinder. It is filled with a moisture-curable thermal conductive resin composition 5 adjusted to ~800 PaS.

The container 2 of the metal cartridge 1 is made of metal with a thickness of 0.4 to 0.6 mm. It is possible to suppress the occurrence of ejection defects due to deformation. Thicknesses greater than 0.6 mm are possible, but tend to increase the cost and weight of the container. As the material of the container 2 of the metal cartridge 1, various metals such as aluminum, aluminum alloy, steel, SUS, and iron can be used, but aluminum is preferable. The thickness here means the total thickness of the metal layer.

The ejection port 3 of the metal cartridge 1 is sealed with a metal lid 7 . The metal lid 7 is made of the same metal as the container 2 and is preferably molded at the same time as the metal cartridge 1 is molded. As such, it is necessary to perforate the metal lid 7 . The thickness of the metal lid 7 is preferably 0.2 mm to 0.5 mm.

[Plunger]
The plunger 4 has a circular surface parallel to the bottom surface of the cylinder, seals the container, and is slidable in the supply direction when pressurized. The plunger has a disc-shaped outer shape, and is parallel to the side surface of the cylinder so that the posture during pressurization can be stabilized and the moisture-curable thermally conductive resin composition 5 in the container can be stably extruded. It has a bent portion 6 extending toward the upper surface of the cylinder.

Examples of plungers include aluminum, steel, or SUS plungers having a length of about 20 mm, an outer diameter of about 46 mm, and a thickness of about 0.4 mm.

However, the size and material of the plunger may be appropriately set in consideration of the size and material of the container, the composition of the moisture-curable thermally conductive resin composition to be filled, and the like.

(metal cartridge lid)
The lid (end) 8 of the metal cartridge has a circular surface parallel to the bottom surface of the cylinder, has a disk-like outer shape, and is curled so that the outer peripheral portion can be bent so that it can be seamed with the cylinder. After the plunger 4, the dry gas 9, and the moisture absorbent 10 are enclosed, the aluminum cartridge is seamed by a seaming machine to be joined and sealed.

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

[Moisture Absorber]
The moisture absorbent 10 is a product that contains a material selected from silica gel, calcium chloride, calcium carbonate, and calcium oxide and is wrapped in an air-permeable packaging material.

<Moisture curable thermally conductive resin composition>
The moisture-curable thermally conductive resin composition used in the present embodiment is a resin composition that is filled in a metal cartridge and forms a cured product such as a coating film after ejection, and contains a curable liquid resin. ing. The moisture-curable thermally conductive resin composition further comprises a curing catalyst for curing the curable liquid resin, an initiator, a thermal anti-aging agent, a plasticizer, an extender, a thixotropic agent, a storage stabilizer, Various additives such as a dehydrating agent, a coupling agent, an ultraviolet absorber, a flame retardant, an electromagnetic wave absorber, a filler, and a solvent may be appropriately added depending on the application.

The moisture-curable thermally conductive resin composition is suitable for use in, for example, electronic devices, substrates, and applications in which it is applied to the surface of a heating element to form a coating film, and contains a thermally conductive filler. there is 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/(mK) or more as a cured product. It is more preferable to use a resin composition having a power of 0.8 W/(m·K) or more, and particularly preferably a resin composition of 0.9 W/(m·K) or more. Further, the moisture-curable thermally conductive resin composition is more preferably a resin composition in which the thermal conductivity of the cured product is 100 W/(m·K) or less. As a result, 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, the heat generated in the electronic device or the like can be efficiently released by the coating film. can. .

(Curable liquid resin)
A curable liquid resin is a liquid resin that has a reactive group in its molecule and can be cured by the reaction of the reactive group. Specific examples of the curable liquid resin include curable polyether resins represented by curable acrylic resins, curable methacrylic resins, and curable polypropylene oxide resins; typified by curable polyisobutylene resins. curable polyolefin-based resins; silicone-based resins; and the like. Specific examples of reactive groups include epoxy groups, hydrolyzable silyl groups, vinyl groups, acryloyl groups, SiH groups, urethane groups, carbodiimide groups, or combinations of carboxylic anhydride groups and amino groups. Reactive functional groups are included.

Then, in the case of obtaining a curable liquid resin that is cured by the reaction of two types of combined reactive groups or by the reaction of the reactive groups and the curing catalyst, after preparing as a two-component composition, For example, two liquids are mixed to form the curable liquid resin when applied to an electronic device, a substrate, or a heating element. In the case of a curable liquid resin that cures through the reaction of hydrolyzable silyl groups, it can be made into a one-liquid room temperature curable composition because it cures through reaction with moisture (moisture) in the air. be. In the case of a curable liquid resin that is cured by a combination of a vinyl group, a SiH group and a platinum catalyst (curing catalyst), a curable liquid resin that is cured by a combination of an acryloyl group and a radical initiator (initiator), etc. After forming a one-component curable composition or a two-component curable composition, it can be cured by heating to a crosslinking temperature or applying crosslinking energy such as ultraviolet rays or electron beams. In general, when it is easy to heat the entire heat dissipating structure to some extent, it is preferable to use a heat-curable composition, and when it is difficult to heat the heat dissipating structure, a two-component composition is used. Although it is preferred to use a curable composition or to use a moisture-curable composition, it is not limited to these.

Among the curable liquid resins, silanol condensation reaction type curable liquid resins are more preferable. In addition, among curable liquid resins, curable acrylic resins or curable polypropylene oxide resins can be used because there is little problem of contamination inside electronic devices due to low molecular weight siloxane and because they are excellent in heat resistance. preferable. Various known reactive acrylic resins can be used as the curable acrylic resin. 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. Kaneka XMAP manufactured by Kaneka Corporation is known as an example of such a curable acrylic resin. Moreover, various known reactive polypropylene oxide resins can be used as the curable polypropylene oxide resin. Kaneka MS Polymer manufactured by Kaneka Corporation is known as an example of such a reactive polypropylene oxide resin. Two or more kinds of curable liquid resins can be used in combination.

(Thermal conductive filler: (conductive filler))
The thermally conductive filler used in the moisture-curable thermally conductive resin composition (and its cured product) has thermal conductivity, availability, fillability, toxicity, insulation, electromagnetic wave absorption, etc. From various viewpoints such as electrical properties, for example, carbon compounds such as graphite and diamond; metal oxides such as aluminum oxide, magnesium oxide, beryllium oxide, titanium oxide, zirconium oxide and zinc oxide; boron nitride, aluminum nitride, nitride metal nitrides such as silicon; 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 system polymer baked products, furan resin baked products, cresol resin baked products, polyvinyl chloride baked products, sugar baked products, and charcoal baked products; Composite ferrite with Zn ferrite; Fe-Al-Si system ternary alloy; metal powder such as aluminum; and the like. Among these, aluminum, aluminum hydroxide, aluminum oxide, aluminum nitride, boron nitride, silicone carbide, graphene particles, graphene oxide particles, and calcium carbonate are preferable, and boron nitride, aluminum oxide, aluminum hydroxide, and calcium carbonate. is particularly preferred.

In addition, since the thermally conductive filler improves the dispersibility in the curable liquid resin, it can be used with silane coupling agents (vinylsilane, epoxysilane, (meth)acrylsilane, isocyanatosilane, chlorosilane, aminosilane, etc.) and titanate cups. Ringing agents (alkoxy titanate, amino titanate, etc.) or fatty acids (saturated fatty acids such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid; sorbic acid, elaidic acid, olein acid, unsaturated fatty acids such as linoleic acid, linolenic acid, erucic acid, etc.) and resin acids (abietic acid, pimaric acid, levopimaric acid, neoapitic acid, parastric acid, dehydroabietic acid, isopimaric acid, sandaracopimaric acid, columic acid) , secodehydroabietic acid, dihydroabietic acid, etc.).

The amount of the thermally conductive filler used can increase the thermal conductivity of the cured product obtained from the moisture-curable thermally conductive resin composition. The volume ratio (% by volume) of the conductive filler is preferably 25% by volume or more. If the amount of thermally conductive filler used is less than 25% by volume, the thermal conductivity of the cured product tends to be insufficient. When a higher thermal conductivity is desired, the amount of the thermally conductive filler used is more preferably 30% by volume or more, more preferably 40% by volume or more, and more preferably 50% by volume or more. is particularly preferred. Moreover, 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.

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

Filler volume ratio (volume%) = (weight fraction of filler / specific gravity of filler) / [(weight fraction of resin / specific gravity of resin) + (weight fraction of filler / of filler specific gravity)]×100 (1).

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

Further, 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 thermally conductive fillers having different compositions. There may be.

Furthermore, by appropriately combining a thermally conductive filler having a small maximum particle size, it is possible to secure the thin film properties of the cured product. 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 narrow gaps.

[Filling Moisture Curing Thermally Conductive Resin Composition into Container of Metal Cartridge]
The moisture-curable thermally conductive resin composition can be filled into a metal cartridge container by a combination of devices such as a vertical filling machine, a horizontal filling machine, an automatic filling machine, a semi-automatic filling machine, and a manual filling machine. For example, in the case of the vertical filling machine shown in FIG. 2, the cartridge filling device 20 consists of 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.

At the time of 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 metered by the metering pump 31 is poured (Fig. 2(a)). FIG. 2(b) is a diagram schematically showing the portion of the filling nozzle 30 and the container 2 in FIG. 2(a). is filled with the resin composition, and shows a state in which the filling is almost completed. Thereafter, a plunger capping device (not shown) is used to push in the plunger 4 with a capping jig 36 to cap it (FIG. 2(c)). At the time of capping, it is desirable to insert an air release pin to remove the internal air. In the plunger plugging state, as shown in FIG. 2(d), the air is sufficiently compressed and pushed out so that no air remains between the moisture-curable tree-type thermally conductive resin composition 5 and the plunger 4. It is desirable to keep After that, it is desirable to install the moisture absorbent 10 in the space above the plunger, as shown in FIG. 2(e). In addition, as shown in FIG. 2(f), the space of the plunger portion is filled with a gas (dry gas) such as nitrogen, argon, helium, or air, and then, as shown in FIG. The metal lid 8 is preferably closed to seal the cartridge.

[Method for applying moisture-curable thermal conductive resin composition using metal cartridge]
As a method for applying the moisture-curable thermally conductive resin composition using a metal cartridge, as shown in FIG. A step of piercing a sharp conical drilling jig 41 into the discharge port 7 in a direction 42 (FIG. 3B), and a step of pulling out the pierced drilling jig 41 in a direction 44 (FIG. 3C). ) to form an opening 43 in the ejection port 7 .

A metal cartridge having an opening 43 formed in the discharge port 7 is attached to a pressurizing holder 45 for pressurizing the metal cartridge of the coating apparatus of FIG. The coating device includes, for example, a gas generator 50 for generating compressed gas for extruding the moisture-curable thermal conductive resin composition, a pressurized gas 51, a discharge valve controller 52, a metal cartridge pressurizing gas pipe 53, and a valve control gas. A pipe 54 , robot control wiring 55 , ejection control wiring 56 , ejection valve 57 , ejection nozzle 58 , application substrate 60 , substrate stage 61 , position control robot 62 , and control computer 63 are provided.

Application of the resin composition onto the substrate can be performed, for example, by the following method.
A pressurized gas 51 generated from a gas generator 50 is sent to a pressurizing holder 45 and a discharge valve controller 52 . When the pressure holder 45 is pressurized, the plunger 4 of the metal cartridge inside slides. As the plunger 4 slides, the moisture-curable thermally conductive resin composition 5 inside is pushed out from the ejection port 7 .

The moisture-curable thermally conductive resin composition 5 extruded from the discharge port 7 is sent to the discharge valve 57 through the pipe. The discharge valve 57 is controlled to be opened or closed by the pressurized gas controlled by the discharge valve controller 52. When the valve of the discharge valve 57 is open, moisture curing heat is conducted to the coating substrate 60 through the discharge nozzle 58. A flexible resin composition 5 is applied. When the valve is closed, ejection from the ejection nozzle 58 is stopped. Control of the application pattern shape of the moisture-curable thermally conductive resin composition 59 after ejection is performed by controlling the position of the ejection valve 57 with the wiring 55 for robot control by the control computer 63 . By moving the robot left and right 64 and moving the substrate stage 61, the substrate stage 61 is moved forward and backward to adjust the position. The ejection valve controller 52 is controlled by the ejection controller wiring 56 to control the ejection opening/closing of the ejection valve 57 to control the application amount and the timing of application. All controls such as the movement of the robot and the amount of resin to be discharged can be controlled by the control computer 63 .

[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 placed in a 250 L reactor under a nitrogen gas atmosphere. was added and stirred at 70 to 80° C. for about 30 minutes. Pentamethyldiethylenetriamine was added to the resulting mixture to initiate the reaction. After 30 minutes had passed since the start of the reaction, butyl acrylate (104 kg) was continuously added over 2 hours. In addition, during the reaction, pentamethyldiethylenetriamine was appropriately added so that the internal temperature (the temperature of the reaction solution) was 70°C to 90°C. The total amount of pentamethyldiethylenetriamine used in the reaction was 220 g. After 4 hours from the initiation of the reaction, the volatile matter was removed by heating and stirring at 80° C. under reduced pressure. Acetonitrile (45.7 kg), 1,7-octadiene (14.0 kg), and pentamethyldiethylenetriamine (439 g) were added to the resulting residue and stirring was continued for 8 hours. Thereafter, the obtained mixture was heated and stirred at 80° C. under reduced pressure to remove volatile matter.

After adding toluene to the obtained concentrate and dissolving the polymer contained in the concentrate, diatomaceous earth as a filter aid, aluminum silicate and hydrotalcite as adsorbents are added, and an oxygen-nitrogen mixed gas atmosphere is added. (oxygen concentration 6%) and the internal temperature (solution temperature) of 100°C. The solid content in the solution was removed by filtration, and the filtrate was heated and stirred at an internal temperature of 100° C. under reduced pressure to remove volatile content.

Further, aluminum silicate and hydrotalcite as adsorbents and a heat deterioration inhibitor were added to the obtained concentrate, and the mixture was heated and stirred under reduced pressure (average temperature: about 175°C, degree of reduced pressure: 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%).

Toluene was added to the resulting concentrate to dissolve the polymer contained in the concentrate, solids in the solution were removed by filtration, and the filtrate was heated and stirred under reduced pressure to remove volatiles. . Thus, a polymer having alkenyl groups was obtained.

To this alkenyl group-containing polymer, dimethoxymethylsilane (2.0 molar equivalents relative to the alkenyl groups), methyl orthoformate (1.0 molar equivalents relative to the alkenyl groups), and a platinum complex catalyst bis(1 ,3-divinyl-1,1,3,3-tetramethyldisiloxane) in xylene (an amount to give 10 mg of platinum per 1 kg of polymer) is mixed, and the mixture is heated and stirred at 100° C. in a nitrogen gas atmosphere. reacted. After confirming that the alkenyl group disappeared, the reaction mixture was concentrated to obtain a resin (I-1) composed of poly(n-butyl acrylate) having a dimethoxysilyl group at its end. The resulting polymer had a number average molecular weight of about 26,000 and a molecular weight distribution of 1.3. When the number of silyl groups introduced per polymer molecule was determined by 1H-NMR analysis, it was about 1.8.

[Synthesis Example 2]
Propylene oxide was polymerized using a polyoxypropylene diol having a number average molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to obtain a hydroxyl group-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 HLC-8120GPC manufactured by Tosoh Corporation as a liquid feeding system, using TSK-GEL H type manufactured by Tosoh Corporation as a column, and using THF as a solvent. It is a polystyrene conversion value of the measured value.

Subsequently, after adding a methanol solution of 1.2 equivalents of methoxysodium to the hydroxyl groups of this hydroxyl-terminated polypropylene oxide, the methanol was distilled off, and allyl chloride was added to convert the terminal hydroxyl groups to allyl groups. Converted. Unreacted allyl chloride was then removed by vacuum devolatilization.

300 parts by weight of n-hexane and 300 parts by weight of water were mixed with 100 parts by weight of the obtained unpurified allyl group-terminated polypropylene oxide, and the mixture was stirred, and the water was removed by centrifugation. After 300 parts by weight of water was further mixed with the obtained hexane solution and stirred, the water was again removed by centrifugation. Hexane was then removed by vacuum devolatilization. As a result, a bifunctional polypropylene oxide having a number average molecular weight of about 25,500 and an allyl terminal was obtained.

To 100 parts by weight of the purified allyl group-terminated polypropylene oxide obtained, 150 ppm of a platinum-vinylsiloxane complex isopropanol solution (platinum content: 3% by weight) and 0.95 parts by weight of trimethoxysilane were added as a catalyst. and reacted at 90° C. for 5 hours. As a result, a resin (I-2) composed of trimethoxysilyl group-terminated polypropylene oxide was obtained. When the number of trimethoxysilyl groups introduced per polymer molecule was determined by 1H-NMR analysis, it was about 1.3.

[Preparation of thermally conductive curable liquid resin]
50 parts by weight of the resin (I-1) obtained in Synthesis Example 1, 50 parts by weight of the resin (I-2) obtained in Synthesis Example 2, and di-isononyl-cyclohexane-dicarboxylate (DINCH) as a plasticizer (manufactured by BASF) 100 parts by weight, antioxidant (Irganox 1010) 1 part by weight, and alumina (DENKA Corporation) 1,500 parts by weight as a thermally conductive filler are sufficiently mixed by hand. Stir and knead. After that, the kneaded product was dehydrated by drawing a vacuum while heating and kneading the kneaded product using a 5 L butterfly mixer. After the dehydration was completed, the kneaded material was cooled, and 5 parts by weight of a dehydrating agent (A171) and 4 parts by weight of tin neodecanoate as a curing catalyst were mixed. Thus, a moisture-curable thermally conductive resin composition was prepared.

(Example 1)
Aluminum with a thickness of 0.5 mm was used for the material of the container, and a metal cartridge with a capacity of 330 ml having a discharge port with a thickness of 0.4 mm was used on the bottom surface of the cylinder.
800 g of the moisture-curable thermally conductive resin composition was filled in a metal cartridge using the vertical filling machine shown in FIG. After filling, a plunger was driven in, and after sealing with nitrogen, silica gel was placed as a desiccant and the lid was sealed. After the filling, a discharge test was performed by applying pressure to 0.3 MPa with a pressurized gas (dry air) generated from a gas generator using a discharge nozzle of 1 mmΦ using the discharge test apparatus FIG. Discharge was performed by opening the discharge valve and continuously discharging the moisture-curable thermally conductive resin composition.
Discharge rate (%) = Y/X x 100 Formula 1
In this example, the ejection ratio after ejection was 95%, and no deformation or the like was observed in the cartridge after ejection.

(Comparative example 1)
Same as Example 1, except that the material of the container was a laminate of high-density polyethylene layer/aluminum sheet (thickness 0.1 μm)/kraft paper/printed aluminum foil (total metal thickness 0.1 μm) as the outermost layer. went. The discharge ratio after continuous application was 52%, and the side surface of the container was deformed during application, resulting in 40% of the moisture-curable thermally conductive resin composition remaining, and application could not be performed.

(Comparative example 2)
The material of the container was the same as in Example 1, except that aluminum with a thickness of 0.3 mm was used as the material of the container. The discharge ratio 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 application could not be performed.

1. Metal cartridge 2 . container 3 . discharge port 4 . plunger 5 . 5. Moisture curable thermally conductive resin composition; Bend (of plunger) 7 . 8. Metal cover for outlet. 9. Metal lid on top of cylinder. space section 10 . Moisture absorbents20. 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 . Plugging jig 37 . dry gas 38 . blower nozzle 41 . Drilling jig 42 . stabbing direction 43 . opening 44 . Pulling direction 45 . pressure holder 50 . gas generator 51 . pressurized gas 52 . discharge valve controller 53 . Gas pipe for pressurizing metal cartridge 54 . Gas piping for valve control 55 . Wiring for robot control 56 . Discharge control wiring 57 . Discharge valve 58 . discharge nozzle 59 . Moisture-curable thermally conductive resin composition after ejection60. Application substrate 61 . Substrate stage 62 . Position control robot 63 . control computer 64 . Robot left/right movement

Claims (12)

A cylindrical metal cartridge,
The metal cartridge container is made of metal with a thickness of 0.4 to 0.6 mm,
The bottom surface of the cylinder has a discharge port,
having a plunger between the top and bottom surfaces of the cylinder and slidable toward the top or bottom surface of the cylinder;
A metal cartridge characterized by being filled with a moisture-curable thermal conductive resin composition adjusted to 200 PaS to 800 PaS at 23°C between a plunger and a bottom surface of a cylinder.
2. The metal cartridge according to claim 1, wherein the plunger has a circular cylindrical bottom surface and a parallel surface, and has a bent portion extending toward the cylindrical upper surface in parallel with the cylindrical side surface.
3. The metal cartridge according to claim 1, wherein the metal cartridge is made of aluminum.
4. The metal cartridge according to any one of claims 1 to 3, wherein the ejection port and the upper surface of the cylinder are sealed with a metal lid.
5. The metal cartridge according to claim 4, wherein a space is provided between the metal lid on the upper surface of the cylinder and the plunger.
6. A metal cartridge according to claim 5, wherein the space is filled with nitrogen.
7. A metal cartridge according to claim 5, wherein a moisture absorbent is enclosed in the space.
8. A metal cartridge according to claim 7, wherein said moisture absorbent is at least one selected from silica gel, calcium chloride, calcium carbonate and calcium oxide.
9. The metal cartridge according to any one of claims 1 to 8, wherein the moisture-curable thermally conductive resin composition contains at least a moisture-curable resin and a thermally conductive filler.
10. The metal cartridge according to any one of claims 1 to 9, wherein the moisture-curable resin is one or more resins selected from modified silicone resins, silicone resins and urethane resins.
The thermally conductive filler contains one or more thermally conductive fillers selected from aluminum, aluminum hydroxide, aluminum oxide, aluminum nitride, boron nitride, silicone carbide, graphene particles, graphene oxide particles, and calcium carbonate. The metal cartridge according to any one of claims 1 to 10.
A method for applying a moisture-curable thermally conductive resin composition using the metal cartridge according to any one of claims 4 to 11,
removing the lid on the top surface of the cylinder or making a hole in the lid on the top surface of the cylinder;
After passing through the process of making a hole in the discharge port, install the metal cartridge in the pressure holder,
A method for applying a moisture-curable thermally-conductive resin composition, comprising the step of supplying the moisture-curable thermally-conductive resin composition in a cartridge by pressurizing the pressure holder with a gas to slide a plunger. .

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