Apparatus and method for applying or filling a heat-insulating silicone composition containing a filler.

Abstract

The present invention provides a coating and filling method for applying a heat-insulating silicone composition containing a filler, which can be stirred and coated or filled using the transport container as is. [Solution] A method for applying and filling a two-component heat-insulating silicone composition includes: a first and second liquid defoaming mixing step in which the first and second liquids packed in first and second transport containers are stirred and mixed under negative reduced pressure defoaming while still packed in the transport containers; a first and second liquid circulation step in which the first and second liquids are drawn out and returned to the first and second transport containers before being sent to a two-liquid confluence point; a first and second liquid supply step in which the first and second liquids are drawn out and sent to a two-liquid confluence point; a first and second liquid circulation / supply switching step in which the configuration of returning the first and second liquids to the first and second transport containers and the configuration of supplying the first and second liquids to a two-liquid confluence point are switched; a mixing step in which the supplied first and second liquids are mixed at the two-liquid confluence point to produce a heat-insulating silicone composition; and a potting step of the heat-insulating silicone composition onto a substrate.

Description

[Technical Field]

[0001] This disclosure relates to a coating and filling apparatus and a coating and filling method for coating or filling a thermal insulation silicone composition containing a filler. [Background technology]

[0002] Silicone rubber adhesive compositions are used as adhesive fixatives and protective agents with properties such as heat resistance, weather resistance, and electrical insulation in various electrical and electronic components, automotive parts, and various computer-related components such as PCs and mobile devices.

[0003] Patent Document 1 teeth By adding an adhesive aid to a silicone rubber composition containing hollow fillers made of organic resin, a low specific gravity and cushioning and heat insulating properties are obtained. Low-density silicone rubber adhesive composition It is disclosed.

[0004] Patent Document 2 teeth After mixing the resin molding material in a planetary-type mixer (inside the mixing tank), the resin molding material is transferred from the mixing tank to a mixing container. The document discloses a method for manufacturing thermosetting resin molding materials. The present invention discloses a configuration in which a transfer pump is connected to this mixing container to extract the resin molding material and fill it into a product container.

[0005] Patent Document 3 teeth The two liquids are supplied one at a time from the tank by a pump, mixed in a mixer, and the mixed liquid is discharged. Liquid mixing dispenser It is disclosed.

[0006] Silicone rubber compositions (two-component systems) containing hollow organic resin fillers, such as those described in Patent Document 1, are typically filled into transport containers (200L drums, 20L pails) and transported to other factories. Because the hollow fillers have a lower specific gravity than the other components, they tend to float and separate easily. Therefore, it is necessary to stir the composition immediately before application and curing. For example, using a mixer (agitator) like the one in Patent Document 2, the silicone rubber composition (two-component system) is transferred from a transport can to separate mixing containers, and the separated filler is uniformly dispersed throughout the composition liquid. After uniform mixing, each mixing container is sent to the filling process. Using a two-component mixing dispenser device like the one in Patent Document 3, each composition is taken from each mixing container by a transport pump, mixed, and then applied. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Patent No. 5115716 [Patent Document 2] Japanese Patent Application Publication No. 61-20911 [Patent Document 3] Japanese Patent Application Publication No. 05-237363 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] In the mixer described in Patent Document 2, it is necessary to transfer the silicone rubber composition from the transport can to the mixing tank, and then transfer it from the mixing tank to the mixing container. During this transfer process, there is a risk of air being trapped in the material, in which case a degassing process (vacuum degassing) is required. Also, there is a risk of contamination occurring during the transfer. Furthermore, because of the transfer process, the material cannot be applied immediately after mixing.

[0009] Another type of agitator is the gyromixer, which rotates the container itself to agitate the contents. Smaller containers, like pails, are easy to handle, but a 200L drum is too large, making it difficult to rotate.

[0010] A material receiving container is required on the coating device side, such as a two-component mixing dispenser. Furthermore, maintenance work such as cleaning the receiving container is necessary. Additionally, if cleaning is insufficient and material remains in the receiving container, it will mix with newly transferred material, resulting in a mixture of materials from different batches and reducing the traceability of each product batch.

[0011] While it is conceivable to incorporate a stirring function into the receiving container of the coating device, stirring takes time to homogenize the separated material, thus increasing the time between setting the material and actually applying it.

[0012] The first object of this disclosure is to provide a coating apparatus or filling apparatus for coating or filling a heat insulating silicone composition containing a filler that can be stirred and coated using the transport container as is, and a coating or filling method thereof. A second objective is to provide a coating apparatus or filling apparatus and a coating or filling method for a heat-insulating silicone composition containing a filler, which can be applied or filled continuously without interrupting the stirring process and the coating or filling process by batch processing. [Means for solving the problem]

[0013] (Method for manufacturing a heat-insulating cured product; method for applying or filling with a heat-insulating silicone composition) A method for producing a heat-insulating cured product obtained by curing a two-component heat-insulating silicone composition containing a filler, or a method for coating or filling such a product, is: (For example, in a state where the easily separable filler has separated upwards) The first liquid packed in the first transport container (D1) is stirred under reduced pressure or degassed pressure (for example, using the first vacuum stirrer (2a)) while still packed in the first transport container (D1), and mixed in a first liquid degassing and mixing step (S2-1) in which the first liquid is stirred (for example, stirred until the filler is evenly dispersed in the first liquid (including substantially uniform dispersion)), After the first liquid defoaming and mixing step (S2-1) (for example, within 1 to 4 hours), the first liquid is supplied (S3-3) from the state in which it remains packed in the first transport container (D1) (for example, while being stirred by defoaming under reduced pressure using the third vacuum agitator (3) (S3-1) or while stirring has stopped), by using the first liquid supply pump (51) or a vacuum pump, and sent to the two-liquid confluence point (71). After the first liquid defoaming and mixing step (S2-1) (for example, within 1 to 4 hours), the first liquid is discharged (for example, by the first liquid transfer pump (51) or a vacuum pump) (S3-2) from the state in which it remains packed in the first transport container (D1) (for example, while being stirred by defoaming under reduced pressure using the third vacuum agitator (3) (S3-1) or while stirring has stopped), and returned to the first transport container (D1) before being sent to the two-liquid confluence point (71), in a first liquid circulation step (S3-4). A first liquid circulation / supply switching step (S3-5) is performed to switch between a configuration in which the first liquid is partially or completely returned to the first transport container (D1) for the first liquid circulation step (S3-4), and a configuration in which the first liquid is partially or completely supplied to the two-liquid confluence point (71) for the first liquid supply step (S3-3), (for example, using a three-way switching valve (53) for the first liquid), (For example, in a state where the easily separable filler has separated upwards) the second liquid packed in the second transport container (D2) is stirred under reduced pressure or degassed pressure (for example, using a second vacuum stirrer (2b)) while still packed in the second transport container (D2), and mixed in a second liquid degassing and mixing step (S2-2) in which the liquid is stirred (for example, stirred until the filler is evenly dispersed in the second liquid (including substantially uniform dispersion)), After the second liquid defoaming and mixing step (S2-2) (for example, within 1 to 4 hours), the second liquid is supplied (S4-3) from the state in which it remains packed in the second transport container (D2) (for example, while being stirred by defoaming under reduced pressure using the fourth vacuum agitator (4) (S4-1) or while stirring has stopped), by using the second liquid supply pump (61) or vacuum pump, and sent to the two-liquid confluence point (7). After the second liquid defoaming and mixing step (S2-2) (for example, within 1 to 4 hours), from the state where the second transport container (D2) is filled (for example, in the state of stirring with vacuum defoaming using the fourth decompression stirrer (4) or in the state where stirring has stopped), the second liquid is derived (for example, using the second liquid feed pump (61) or a vacuum pump) (S4-2), and before sending it to the two-liquid confluence point (71), it is returned to the second transport container (D2), which is the second liquid circulation step (S4-4), A configuration for partially or completely returning the second liquid to the second transport container (D2) for the second liquid circulation step (S4-4), and a configuration for partially or completely supplying the second liquid to the two-liquid confluence point (71) for the second liquid supply step (S4-3) are switched (for example, using a three-way switching valve (63) for the second liquid), which is the second liquid circulation and supply switching step (S4-5), At the two-liquid confluence point (71), the supplied first liquid and the second liquid are mixed to produce a heat-insulating silicone composition, which is the mixing step (S5-1), The heat-insulating silicone composition is potted (filled or coated) on the substrate (100), which is the potting step (filling step or coating step (S5-2), and includes. The manufacturing method, coating or filling method further includes a curing step of curing the potted layer at a temperature of 5°C or higher and 100°C or lower, more preferably 15°C or higher and 50°C or lower, for a predetermined time.

[0014] The method for producing the aforementioned heat-insulating cured product, or the method for applying or filling it, may further include the following steps. After the first liquid defoaming and mixing step, if the first liquid contains bubbles, a further defoaming step (for example, using a defoamer, a stirring defoamer, etc.) may be included. After the second liquid defoaming and mixing step, if the second liquid contains bubbles, a further defoaming step (for example, using a defoamer, a stirring defoamer, etc.) may be included. In the first liquid circulation step and the first liquid supply step, flow rate adjustment for adjusting the first liquid to a predetermined flow rate and / or pressure adjustment for adjusting the first liquid to a predetermined pressure may be performed. In the first liquid circulation step and the first liquid supply step, a metering process may be performed to measure the first liquid (for example, in the first metering unit (52)). In the second liquid circulation step and the second liquid supply step, flow rate adjustment to adjust the second liquid to a predetermined flow rate and / or pressure adjustment to adjust the second liquid to a predetermined pressure may be performed. In the second liquid circulation step and the second liquid supply step, a metering process may be performed to measure the second liquid (for example, in the second metering unit (62)).

[0015] First vacuum agitator (2a) used in the first liquid defoaming and mixing step as Alternatively, the process may be carried out in a batch manner using a third vacuum agitator (3) different from the one used in the first liquid circulation process and the first liquid supply process. Second vacuum agitator (2b) used in the second liquid defoaming and mixing step. as Alternatively, the process may be carried out in a batch manner using a fourth vacuum agitator (4) different from the one used in the second liquid circulation process and the second liquid supply process.

[0016] Vacuum stirrer used in the first liquid defoaming and mixing step as Alternatively, the same vacuum agitator used in the first liquid circulation process and the first liquid supply process may be used to carry out the process continuously without moving the first transport container (D1) elsewhere. Vacuum stirrer used in the second liquid defoaming and mixing step as Alternatively, the same vacuum agitator used in the second liquid circulation process and the second liquid supply process may be used to carry out the process continuously without moving the second transport container (D2) elsewhere.

[0017] In the first liquid defoaming and mixing step (S2-1), the reduced pressure and stirring conditions may be controlled according to the components of the first liquid, viscosity, filler, rotation speed and rotation time corresponding to the stirring blades. In the second liquid defoaming and mixing step (S2-2), the reduced pressure conditions and stirring conditions (S2-2) 2 The reduced pressure and stirring may be controlled according to the liquid's components, viscosity, fillers, rotation speed (depending on the stirring blades), and rotation time. Rotating too slowly results in poor work efficiency. Rotating too fast or stirring too vigorously can damage the hollow filler, potentially altering its heat dissipation and insulation properties.

[0018] In the first liquid defoaming and mixing step (S2-1) and the second liquid defoaming and mixing step (S2-2), the floating and separated portions filler To uniformly disperse (including substantially uniformly disperse) the substance in the liquid, one or two blades may be provided, and each blade may rotate (spin) around its axis of rotation while the other blades rotate around its axis of rotation (revolve) around the central axis of the transport container. Depending on the liquid components and the stirring efficiency, the revolution and spin may be performed simultaneously, the revolution may be performed as an intermittent motion (a motion that alternates between revolution and stopping) while the spin is performed continuously, or only the spin may be performed without revolution. revolution speed For example, the speed is greater than 0 rpm and up to 40 rpm, preferably 5 rpm to 40 rpm, more preferably 10 rpm to 35 rpm, and even more preferably 20 rpm to 32 rpm. rotation speed This rotational speed is, for example, 1.2 to 2.5 times the orbital speed. For example, it is between 10 rpm and 80 rpm, more preferably between 40 rpm and 64 rpm. The stirring time required for uniform dispersion from a separated state is, for example, between 1 minute and 60 minutes. A reduced pressure is, for example, below -0.1 MPa.

[0019] The method for producing the aforementioned heat-insulating cured product, or the method for applying or filling it, may further include the following steps. The process may further include a first dispersion testing step for testing the dispersibility of the filler in the first liquid after the first defoaming and mixing step. The process may further include a second dispersion testing step for testing the dispersibility of the filler in the second liquid after the second liquid defoaming and mixing step. In the first dispersion inspection step and the second dispersion inspection step, to determine whether or not uniform dispersion has occurred, the viscosity and density (or specific gravity) of the liquid sampled at two or more fractionated positions in the liquid height direction within the transport container can be determined by comparing the values ​​of the initial state immediately after manufacturing with the values ​​before mixing in the separated state and the values ​​after mixing for a predetermined time, using the initial values ​​immediately after manufacturing as reference values. The viscosity should preferably be the same as the standard value. The density (specific gravity) should be the same as the standard value. If it is lower than the standard value, it indicates insufficient mixing (insufficient dispersion), and if it is higher than the standard value, there is a possibility of filler damage.

[0020] In the first liquid supply step (S3-3) and the first liquid circulation step (S3-4), the reduced pressure and stirring may be controlled according to the reduced pressure conditions and stirring conditions (components of the first liquid, viscosity, filler, rotation speed and rotation time according to the stirring blades). In the second liquid supply step (S4-3) and the second liquid circulation step (S4-4), the reduced pressure conditions and stirring conditions (S4-3) 2 The reduced pressure and stirring may be controlled according to the liquid's components, viscosity, fillers, rotation speed (depending on the stirring blades), and rotation time. It is preferable to set the conditions for reduced pressure stirring in order to prevent the filler from separating again and to eliminate or prevent the introduction of air bubbles that have formed in the circulated liquid return.

[0021] In the first liquid supply step (S3-3) and the first liquid circulation step (S3-4), one blade may be provided to prevent the filler from being separated again, and the blade may be configured to rotate (spin) around its axis of rotation. Depending on the arrangement of the liquid outlet piping and the liquid return piping, only one blade may be used and it may not need to revolve. rotation speed For example, this is greater than 0 and less than or equal to 20 rpm, more preferably between 1 rpm and 10 rpm. A reduced pressure is, for example, below -0.1 MPa.

[0022] It is preferable to set reduced pressure conditions that prevent the introduction of air bubbles, corresponding to the compositions of the first and second liquids. When stirring under normal atmospheric pressure rather than reduced pressure, air bubbles are introduced. If curing occurs with air bubbles present, it can lead to uneven heat dissipation and insulation, affecting safety (fire resistance, chemical resistance, electrical insulation) and the protective performance of the potted area (cell) (compression modulus, flexibility, shock absorption). If air bubbles remain on the surface of a substrate such as a battery after curing, the way heat is transferred locally will change in that area.

[0023] The blades of the agitator used to disperse the filler are preferably shaped to direct the fluid from the top to the bottom, such as gate-shaped blades, twisted blades, or blade shapes with lateral blades on a twisted blade. For example, rotating a rotational or orbital type blade at a slow rotational speed under reduced pressure can reduce the damage to the hollow filler. Whether or not the hollow filler has cracked can be determined, for example, by the degree of change in density. When a blade with an upward-facing surface that is tilted upward is rotated horizontally, the liquid that hits the upward-facing surface is propelled upward. When a blade with a downward-sloping surface is rotated horizontally, the liquid that hits the downward-sloping surface is directed downwards.

[0024] (Manufacturing apparatus for heat-insulating cured products; coating / filling apparatus for coating or filling with heat-insulating silicone compositions) A coating and filling system (A1) for applying a two-component, heat-insulating silicone composition containing a filler, A first vacuum agitator (2a) mixes the first liquid packed in the first transport container (D1) (for example, when the easily separable filler has separated upwards) under reduced pressure or negative vacuum degassing conditions, while keeping the liquid packed in the first transport container (D1), by stirring (for example, stirring until the filler is evenly dispersed in the first liquid (including substantially uniform dispersion)), In the first transport container (D1) The first liquid A third vacuum agitator (3) stirs the contents while they are still packed under reduced pressure or negative vacuum degassing conditions, In the first transport container (D1) The first liquidWith the contents still packed, the third vacuum agitator (3) is used to agitate the contents under reduced pressure, or the agitation is stopped, and a first liquid supply line (L1) is provided for sending the first liquid to the two-liquid confluence point (71). Before sending the first liquid to the two-liquid confluence point (71), a first liquid circulation line (L11) is provided to return it to the first transport container (D2), From the first transport container (D1) The first liquid A first liquid supply pump (51) (provided in the first liquid supply line (L1)) for sending liquid to the two-liquid confluence point (71) or to the first circulation line (L11), A three-way switching valve (53) for the first liquid switches the flow of the first liquid in order to send the first liquid to the two-liquid confluence point (71) or to the first circulation line (L11), A second vacuum agitator (2b) mixes the second liquid packed in the second transport container (D2) while it remains packed in the second transport container (D2), under reduced pressure or negative vacuum degassing (for example, until the filler is evenly dispersed in the second liquid), and stirs it (for example, until the filler is evenly dispersed in the second liquid). In the second transport container (D2) The second liquid A fourth vacuum agitator (4) stirs the contents while they are still packed under reduced pressure or negative vacuum degassing conditions, A second liquid supply line (L2) for sending the second liquid to the two-liquid confluence point (71) while the second liquid remains packed in the second transport container (D2) and is being stirred by vacuum degassing or stopped using the fourth vacuum agitator (4), Before sending the second liquid to the two-liquid confluence point (71), a second liquid circulation line (L21) is provided to return it to the second transport container (D2), A second liquid transfer pump (61) (provided in the second liquid supply line (L2)) for transferring liquid from the second transport container (D2) to the two-liquid confluence point (7) or to the second circulation line (L21), A three-way switching valve (63) for the second liquid is used to switch the flow of the second liquid in order to send the second liquid to the two-liquid confluence point (71) or to the second circulation line (L21), At the two-liquid confluence point (71), a coating and filling device (7) is used to pot the heat-insulating silicone composition, which is a mixture of the supplied first liquid and the second liquid, onto a substrate (100). It is equipped with.

[0025] The first vacuum agitator (2a) may be used in conjunction with the third vacuum agitator (3), and the process may be carried out continuously without moving the first transport container (D1) elsewhere. The second vacuum agitator (2b) may be used in conjunction with the fourth vacuum agitator (4), and the process may be carried out continuously without moving the second transport container (D2) elsewhere.

[0026] The first liquid circulation line (L11) and / or the first liquid supply line (L1) may be provided with a flow rate adjustment unit for adjusting the first liquid to a predetermined flow rate and / or a pressure adjustment unit for adjusting the first liquid to a predetermined pressure. The first liquid supply line (L1) may also be equipped with a first liquid metering unit (52) for measuring the mass of the first liquid being supplied. The second liquid circulation line (L2) and / or the second liquid supply line (L21) may be provided with a flow rate adjustment unit for adjusting the second liquid to a predetermined flow rate and / or a pressure adjustment unit for adjusting the second liquid to a predetermined pressure. The second liquid supply line (L2) may also be equipped with a second liquid metering unit (62) for measuring the mass of the second liquid being supplied.

[0027] The aforementioned coating and filling system (A1) is A first control unit (28a) controls the depressurization and stirring of the first vacuum stirrer (2a) according to the depressurization conditions and stirring conditions (components of the first liquid, viscosity, filler, rotation speed and rotation time corresponding to the stirring blades), A second control unit (28b) controls the depressurization and stirring of the second vacuum agitator (2b) according to the depressurization conditions and stirring conditions (components, viscosity, filler of the second liquid, rotation speed and rotation time corresponding to the stirring blades), It may also be equipped with.

[0028] The aforementioned coating and filling system (A1) is A third control unit (38) controls the depressurization and stirring of the third vacuum agitator (3) according to the depressurization conditions and stirring conditions, A fourth control unit (48) controls the depressurization and stirring of the fourth vacuum agitator (4) according to the depressurization conditions and stirring conditions, It may also be equipped with. The third control unit (38) controls the first liquid transfer pump (51) and the first For liquid The three-way switching valve (53) may be controlled. The third control unit (38) controls the value measured by the first liquid measuring unit (52) The first liquid You may decide whether to send it to the two-liquid confluence point (71) or to the first circulation line (L11). The fourth control unit (48) controls the second liquid transfer pump (61) and the second For liquid The three-way switching valve (63) may also be controlled. before The fourth control unit (48) controls the value measured by the second liquid measuring unit (62) according to the value measured by the second liquid measuring unit (62). The second liquid You may decide whether to send it to the two-liquid confluence point (71) or to the second circulation line (L21).

[0029] An apparatus for producing a heat-insulating cured product obtained by curing a two-component heat-insulating silicone composition containing a filler is: The above coating / filling apparatus (7), A drying oven for curing the potted layer at a temperature of 5°C to 100°C, more preferably 15°C to 50°C, for a predetermined time. It may also be equipped with.

[0030] The insulating silicone composition containing a filler comprises an uncured first liquid and a second liquid, and the components consisting of the first liquid and the second liquid are, (A) An organopolysiloxane containing alkenyl groups bonded to at least two silicon atoms in one molecule, (B) An organohydrogenpolysiloxane containing 0.0001 mol / g or more and 0.05 mol / g or less of hydrogen atoms bonded to silicon atoms, (C) Hollow filler made of organic resin, (D) Addition reaction catalyst, Includes.

[0031] When the total amount of component (A) and component (B) is 100 parts by mass, The content of component (C) is 5 parts by mass or more and 25 parts by mass or less, The content of component (D) is 0.01 parts by mass or more and 2.0 parts by mass or less.

[0032] The aforementioned component (C) may have inorganic material attached to at least a portion of its surface. The (C) component may be an inorganic material that has been subjected to affinity surface treatment or dispersibility surface treatment. The true density of component (C) is 0.2 g / cm³. 3 The following is also acceptable. The average particle size of component (C) may be 150 μm or less, more preferably 30 μm or more and 90 μm or less.

[0033] The aforementioned heat-insulating silicone composition, (E) The material may further contain a silicone resin having at least one alkenyl group in its molecule, with a number average molecular weight of 1000 to 10000, preferably 1400 to 4000, and more preferably 1400 to 2500.

[0034] (2 liquid type) In a two-component thermal insulation silicone composition in which the first liquid and the second liquid are mixed to initiate curing, The first solution contains components (A), (C), and (D). The first solution may further contain a reaction rate regulator and a pigment. Each component (A), (C), (D), reaction rate regulator, and pigment of the first solution may be one or two or more. The second solution contains components (A), (B), (C), and (E). Each component (A), (B), (C), and (E) in the second solution may be one type or two or more types. It is preferable that both the first and second liquids do not contain silica or adhesive aids.

[0035] [1st liquid] For a total amount of 100 parts by mass of the first liquid, Component (A) is 80 parts by mass or more and 96 parts by mass or less. Component (C) is 5 parts by mass or more and 15 parts by mass or less. Component (D) is 0.01 parts by mass or more and 0.5 parts by mass or less. The reaction rate modifier (F) is 0.1 parts by mass or less. Pigment (G) is 0.2 parts by mass or less But that's fine.

[0036] [Second liquid] For a total amount of 100 parts by mass of the second liquid, Component (A) is 24 parts by mass or more and 45 parts by mass or less. Component (B) is 45 parts by mass or more and 65 parts by mass or less. Component (C) is 5 parts by mass or more and 15 parts by mass or less. Component (E) is 0 parts by mass or more and 2.5 parts by mass or less. But that's fine.

[0037] For a total amount of 100 parts by mass of the two-component heat-insulating silicone composition, The first liquid is 40 parts by mass or more and 60 parts by mass or less. The second liquid is present in amounts of 60 parts by mass or more and 40 parts by mass or less. But that's fine.

[0038] The preferred curing condition after mixing the first and second liquids is room temperature curing. Rapid curing may also be performed at a temperature higher than room temperature. However, Growth It is preferable to set the curing temperature and curing time so that the temperature (C) does not cause deformation such as shrinkage. The curing time depends on the curing temperature; a higher curing temperature will shorten the curing time.

[0039] (Effects and Benefits) (1) Decompression application with stirring function ·filling The system is designed to directly set the transport containers, so the drums delivered from the manufacturers of the first and second liquids can be used as is, eliminating the need for transfer work. (2) The transport container can be used as is, eliminating the need to prepare a filling tank on the coating / filling equipment side, thus eliminating cleaning and contamination problems. (3) By pre-mixing the materials and performing batch processing separate from the coating or filling process, the problem of taking too long to set the first and second liquid materials and apply them when stirring takes time to ensure uniform separation of the filler can be solved. (4) If the amount of coating applied per day is equivalent to the amount in transport containers (e.g., 2 x 200L cans), a vacuum agitator can be used in addition to batch processing. [Brief explanation of the drawing]

[0040] [Figure 1] This figure shows an example of a vacuum agitator and a coating / filling system with vacuum agitation function according to Embodiment 1. [Figure 2] This figure shows an example of a stirring blade. [Figure 3A] This figure shows the mixing ratio of the first and second liquids in the example. [Figure 3B] This figure shows the evaluation results of the examples. [Figure 3C] This diagram shows the results due to differences in feather shape. [Modes for carrying out the invention]

[0041] (Embodiment 1) Figure 1 shows the vacuum agitator and the coating / filling system A1 with vacuum agitation function according to Embodiment 1. First, the first and second liquids are manufactured at the material manufacturing site. The first liquid is mixed in a stirrer and then filled from the stirrer into the first transport container D1. (S1-1). The second liquid is mixed in a stirrer and transferred from the stirrer to the second transport container D2 (S1-2). The first transport container D1 and the second transport container D2 are 200L drums with removable lids. The first transport container D1 and the second transport container D2 are transported from the material manufacturing site to a site where another coating process is performed. When the transport and storage period is long, the filler floats to the top and separates, so redispersion is performed at the coating process site.

[0042] (First liquid defoaming mixing step S2-1) With the easily separable filler separated upwards, the first liquid packed in the first transport container D1 is stirred and mixed using the first vacuum agitator 2a under reduced pressure or vacuum degassing until the filler is evenly dispersed (including substantially uniform dispersion) in the first liquid, while it remains packed in the first transport container D1.

[0043] The first vacuum agitator 2a comprises a vacuum chamber 20a for arranging the first transport container D1 with its lid removed, a ceiling section 21a that can be sealed and detached from the top of the vacuum chamber 20a, an air outlet section 22a provided on the ceiling section 21a for discharging air from the vacuum chamber 20a, and a vacuum pump P connected to the air outlet section 22a for drawing in air. 1 It is provided at a and includes one orbital axis and two rotational axes, stirring blades 26a and 27a provided on the rotational axes, and a motor M that serves as a driving source for the orbital axis and the rotational axis.

[0044] The first vacuum agitator 2a is equipped with a first control unit 28a, which controls the motor M and the vacuum pump P. The first control unit 28a controls each blade to rotate around its axis while rotating (revolving) around the central axis of the first transport container D1. The first control unit 28a also sets the revolving speed to, for example, 20 rpm to 32 rpm. The rotation speed to, for example, twice the revolving speed, 40 rpm to 64 rpm. The agitation time is, for example, 15 minutes to 30 minutes. The pressure is, for example, -0.1 MPa or less. The direction of rotation of the revolving and the direction of rotation may be the same or opposite to each other. The directions of rotation of the two rotations may be the same or opposite to each other. For example, it is set so that the filler is not destroyed by turbulence.

[0045] (Second liquid defoaming mixing process S2-2) With the easily separable filler separated upwards, the second liquid packed in the second transport container D2 is stirred and mixed using the second vacuum agitator 2b under reduced pressure or vacuum degassing until the filler is evenly dispersed (including substantially uniform dispersion) in the second liquid, while the liquid remains packed in the second transport container D2.

[0046] The second vacuum agitator 2b includes a vacuum chamber 20b for arranging the second transport container D2 with its lid removed, a ceiling section 21b that can be sealed and detached from the top of the vacuum chamber 20b, an air outlet section 22b provided on the ceiling section 21b for discharging air from the vacuum chamber 20b, and a vacuum pump P connected to the air outlet section 22b for drawing in air. 1 The system is provided at b and includes one orbital axis and two rotational axes, stirring blades 26b and 27b provided on the rotational axes, and a motor M that serves as the driving source for the orbital axis and the rotational axis.

[0047] The second vacuum agitator 2b is equipped with a second control unit 28b, which controls the motor M and the vacuum pump P. The second control unit 28b controls each blade to rotate around its axis while rotating (revolving) around the central axis of the second transport container D2. The second control unit 28b also sets the revolving speed to, for example, 20 rpm to 32 rpm. The rotation speed to, for example, twice the revolving speed, 40 rpm to 64 rpm. The agitation time is, for example, 15 minutes to 30 minutes. The pressure is, for example, -0.1 MPa or less. The direction of rotation of the revolving and the direction of rotation may be the same or opposite to each other. The directions of rotation of the two rotations may be the same or opposite to each other. For example, it is set so that the filler is not destroyed by turbulence.

[0048] Figure 2 shows an example of a stirring blade. Figure 2(a) shows five baffles arranged alternately at 90-degree angles. Crossing They are arranged in a straight line vertically. Note that it is not limited to 5 pieces; one or more pieces are also acceptable. 90 degrees Crossing The angle is not limited to this. The width of the baffle plates that determine the rotation diameter of the two rotating agitator blades may be less than 50% of the inner diameter of the first and second transport containers, and may be around 30-45%. The installation angle of the baffle plates is determined by the liquid but The contact surface can be facing upwards, downwards, or alternately.

[0049] Figure 2(b) is an L-shaped design. Figure 2(c) is a rectangular gate-type design. Figure 2(d) is a gate-type design with baffles arranged to be inclined. Figure 2(e) is a 90-degree twisted design. Figure 2(f) shows two rotation axis arrangements. On the left side, the uppermost blade is inclined downwards, the middle blades are inclined downwards at both ends, and the lowermost blade is inclined upwards, sending the liquid downwards overall. On the right side, the uppermost blade is inclined downwards, the middle blades are inclined upwards at both ends, and the lowermost blade is inclined upwards, sending the liquid upwards overall. In this configuration, the liquid circulates up and down between the left and right blades, resulting in high stirring efficiency.

[0050] As shown in the lower part of Figure 1, the first and second liquids are sent to separate coating processes with the filler redispersed.

[0051] (Staying agitated to degass the first liquid S3-1) In the first transport container D1 Liquid 1 The mixture is stirred under reduced pressure using the third vacuum agitator 3 while degassing. This is done to prevent or eliminate air bubbles from being introduced when the circulating fluid returns or when the fluid is being fed. Therefore, it may be done continuously, intermittently, or in response to the return of the circulating fluid.

[0052] (First liquid derivation step S3-2) While the mixture is being stirred by degassing under reduced pressure using the third vacuum agitator 3, or while stirring has stopped, the first liquid is supplied by the first liquid transfer pump 51. The tip L1a of the first liquid supply line L1 extends to the lower part of the liquid phase inside the first transport container D1.

[0053] (First liquid supply process S3-3) The first liquid delivered by the first liquid transfer pump 51 passes through the first liquid supply line L1, and the mass (or flow rate) that has passed through the first metering unit 52 is measured (or calculated). The first liquid is the first For liquid The liquid is sent to the two-liquid confluence point 71 by the three-way switching valve 53. The amount that has passed through the first metering unit 52 can be determined, so the coating / filling device 7 fart Depending on the required supply amount, the three-way switching valve 53 for the first liquid is switched to control the return of the first liquid to the first transport container D1.

[0054] (1st liquid circulation step S3-4) The first liquid is supplied from the first liquid supply line L1 to the first liquid circulation line L11 by the first liquid three-way switching valve 53. The tip L11a of the first liquid circulation line L11 extends to the lower part of the liquid phase inside the first transport container D1.

[0055] (First liquid circulation / supply switching process S3-5) The system switches between a configuration in which the first liquid is returned to the first transport container D1 for the first liquid circulation process S3-4, and a configuration in which the first liquid is supplied to the second liquid confluence point 71 for the first liquid supply process S3-3, using a three-way switching valve 53 for the first liquid. The three-way switching valve 53 for the first liquid has an operating unit and may be switched automatically by a command from the third control unit 38, or it may be configured to be switched manually.

[0056] Third Decompression The foam agitator 3 includes a mounting section 30 that can be sealed and detached directly to the upper opening of the first transport container D1 with the lid removed, an air outlet section 31 provided on the mounting section 30 for discharging air from the first transport container D1, and a vacuum pump P connected to the air outlet section 31 for drawing in air. The third vacuum agitator 3 is provided on the mounting section 30 and includes a single rotating shaft, a stirring blade 32 provided on the rotating shaft, and a motor M that serves as the driving source for the rotating shaft.

[0057] The third vacuum agitator 3 is equipped with a third control unit 38, which controls the motor M and the vacuum pump P. 8 The rotation speed is set to, for example, between 5 rpm and 10 rpm. The pressure is reduced to, for example, -0.1 MPa or less. This prevents the incorporation of air bubbles and the re-separation of the filler. The stirring blades may be the cross baffles shown in Figure 2(a).

[0058] (Second liquid degassing and stirring maintained S4-1) In the second transport container D2 Liquid 2 The mixture is stirred using the fourth vacuum agitator 4 while degassing under reduced pressure. This is done to prevent or eliminate air bubbles from being introduced when the circulating fluid returns or when the fluid is being fed. Therefore, it may be done continuously, intermittently, or in response to the return of the circulating fluid.

[0059] (Second liquid derivation step S4-2) While the mixture is being stirred by degassing under reduced pressure using the fourth vacuum agitator 4, or while stirring has stopped, the second liquid is supplied by the second liquid supply pump 61. The tip L2a of the second liquid supply line L2 extends to the lower part of the liquid phase inside the second transport container D2.

[0060] (Second liquid supply process S4-3) The second liquid delivered by the second liquid transfer pump 61 passes through the second liquid supply line L2, and the mass (or flow rate) that has passed through the second metering unit 62 is measured (or calculated). The second liquid is then... For liquid The liquid is sent to the two-liquid confluence point 71 by the three-way switching valve 63. The amount that has passed through the second metering unit 62 is known, so the coating / filling device 7 fart Depending on the required supply amount, the three-way switching valve 63 for the second liquid is switched and controlled to return the second liquid to the second transport container D2.

[0061] (Second liquid circulation process S4-4) The second liquid is supplied from the second liquid supply line L2 to the second liquid circulation line L21 via the third liquid three-way switching valve 63. 2 Liquid is supplied. The tip L21a of the second liquid circulation line L21 extends to the lower part of the liquid phase inside the second transport container D2.

[0062] (Second liquid circulation / supply switching process S4-5) The configuration for returning the second liquid to the second transport container D2 for the second liquid circulation process S4-4, and the configuration for supplying the second liquid to the two-liquid confluence point 71 for the second liquid supply process S4-3, are switched using the three-way switching valve 63 for the second liquid. The three-way switching valve 63 for the second liquid has an operating unit and may be switched automatically by a command from the fourth control unit 48, or it may be configured to be switched manually.

[0063] 4th Decompression The agitator 4 includes a mounting section 40 that can be sealed and detached directly to the upper opening of the second transport container D2 when the lid is removed, an air outlet section 41 provided on the mounting section 40 for discharging air from the second transport container D2, and a vacuum pump P connected to the air outlet section 41 for drawing in air. The fourth vacuum agitator 4 is also provided on the mounting section 40 and includes a single rotation shaft, a stirring blade 42 provided on the rotation shaft, and a motor M that serves as the driving source for the rotation shaft.

[0064] The fourth vacuum agitator 4 is equipped with a fourth control unit 48, which controls the motor M and the vacuum pump P. 8The rotation speed is set to, for example, between 5 rpm and 10 rpm. The pressure is reduced to, for example, -0.1 MPa or less. This prevents the incorporation of air bubbles and the re-separation of the filler. The stirring blades may be the cross baffles shown in Figure 2(a).

[0065] (Mixing process S5-1) At the two-liquid confluence point 71, the supplied first liquid and second liquid are mixed to produce a heat-insulating silicone composition. This mixing is performed in the mixing section 72 of the coating and filling apparatus 7.

[0066] (Coating process S5-2) The heat-insulating silicone composition 90, which is a mixture of the first and second liquids, is filled into the gaps between cells of the battery pack 100 (substrate) before curing. The filled layer 90a is cured at a temperature of 15°C to 50°C for a predetermined time to produce a cured product. filling Layer 90a is cured and adhered to fill the gaps between cells in the battery pack 100 (substrate).

[0067] (Insulating silicone composition) A thermal insulation silicone composition is a composition for forming a thermal insulation cured product. The thermal insulation silicone composition can be used as a potting agent and is applicable to specific substrates, such as substrates for electrical or electronic equipment, circuit chips, automotive components, battery components, and the like. The following describes in detail each component of the thermal insulation silicone composition when the curing method of the thermal insulation silicone composition according to the present invention is an addition reaction type.

[0068] (A: Organopolysiloxane) Component (A) is the main component of the heat-insulating silicone composition and is an organopolysiloxane containing alkenyl groups bonded to at least two silicon atoms in one molecule.

[0069] (A) The viscosity and degree of polymerization of component are not particularly limited and can be selected according to the required mixed viscosity of the thermally insulating silicone composition, for example, the viscosity at 25°C may be 10 mPa·s or more and 100,000 mPa·s or less. Organopolysiloxanes can be used individually or in appropriate combinations of two or more. They are the main component of thermally insulating silicone compositions and have an average of at least two, preferably 2 to 50, and more preferably 2 to 20 alkenyl groups bonded to silicon atoms per molecule.

[0070] The molecular structure of component (A) is not particularly limited and may be, for example, a linear structure, a partially branched linear structure, a branched linear structure, a cyclic structure, or a branched cyclic structure. Of these, component (A) is preferably a substantially linear organopolysiloxane, and more specifically, it may be a linear diorganopolysiloxane in which the molecular chain mainly consists of repeating diorganosiloxane units and both ends of the molecular chain are sealed with triorganosiloxy groups. Some or all of the ends of the molecular chain, or some of the side chains, may be silanol groups.

[0071] The position of the alkenyl group bonded to the silicon atom in component (A) is not particularly limited, and component (A) may be an organopolysiloxane having alkenyl groups bonded to silicon atoms at both ends of the molecular chain. Organopolysiloxanes that have one alkenyl group at each end of the molecular chain have the advantage of having a low content of alkenyl groups that act as reaction sites for crosslinking, thus increasing the flexibility of the gap filler obtained after curing. If the organopolysiloxane has alkenyl groups not only at both ends of the molecular chain but also in the side chains of the molecular chain, it is possible to improve the crosslinking density and increase the hardness of the gap filler. The number of alkenyl groups in one molecule of component (A) can be appropriately determined according to the required hardness of the cured product and the molecular weight of component (A). The number of alkenyl groups in one molecule should be two or more, more preferably two to five, and most preferably two (having one alkenyl group at each end of the molecular chain).

[0072] The alkenyl group may be bonded to only one of the silicon atoms at the end of the molecular chain or to a silicon atom at the non-terminus (part of the molecular chain), or it may be bonded to both. Furthermore, component (A) may be a polymer consisting of a single siloxane unit, or a copolymer consisting of two or more siloxane units.

[0073] The viscosity of component (A) at 25°C may be 10 mPa·s or more and 8,000,000 mPa·s or less, preferably 50 mPa·s or more and 50,000 mPa·s or less, and more preferably 100 mPa·s or more and 10,000 mPa·s or less.

[0074] To adjust the viscosity (mixed viscosity) of the thermal insulation silicone composition before curing, organopolysiloxanes having two or more alkenyl groups with different viscosities can also be used.

[0075] Specifically, the average empirical formula of component (A) is represented by the following general formula (1). R 1 a SiO (4-a) / 2 (1) (However, in equation (1), R 1 These are unsubstituted or substituted monovalent hydrocarbon groups having 1 to 18 carbon atoms, either identical or different from each other. a is 1.7 to 2.1. Furthermore, a is preferably 1.8 to 2.5, and more preferably 1.95 to 2.05.

[0076] In one embodiment, the above R 1Among the monovalent hydrocarbon groups represented by, at least two or more are selected from alkenyl groups such as vinyl group, aryl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, hexenyl group, cyclohexenyl group, and the other groups are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 18 carbon atoms. Specifically, they are alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, aryl groups such as phenyl group, tolyl group, xylyl group, biphenyl group, naphthyl group, aralkyl groups such as benzyl group, phenylethyl group, phenylpropyl group, methylbenzyl group, and halogen-substituted alkyl groups and cyano-substituted alkyl groups such as chloromethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, 3-chloropropyl group, cyanoethyl group in which some or all of the hydrogen atoms in these hydrocarbon groups are substituted by halogen atoms, cyano groups, etc.

[0077] R 1 In the selection of, as the alkenyl groups required to be two or more, vinyl group, aryl group, propenyl group, isopropenyl group, 2-methyl-1-propenyl group, 2-methylallyl group, 2-butenyl group are preferred, and vinyl group is particularly preferred. R other than alkenyl group 1 is preferably a methyl group and a phenyl group, and particularly preferably a methyl group. Also, it is preferable that 70 mol% or more of all R 1 is a methyl group in terms of physical properties and economic efficiency of the cured product, and usually those with 80 mol% or more of methyl group are used.

[0078] The molecular structure of component (A) is as follows: dimethylpolysiloxane with dimethylvinylsiloxy groups sealed at both ends of the molecular chain; dimethylsiloxane-methylphenylsiloxane copolymer with dimethylvinylsiloxy groups sealed at both ends of the molecular chain; dimethylsiloxane-methylvinylsiloxane copolymer with dimethylvinylsiloxy groups sealed at both ends of the molecular chain; dimethylsiloxane-methylvinylsiloxane copolymer with dimethylvinylsiloxy groups sealed at both ends of the molecular chain; dimethylsiloxane-methylvinylsiloxane copolymer with trimethylsiloxy groups sealed at both ends of the molecular chain; formula: (CH3)2ViSiO 1 / 2 The siloxane unit shown is (CH3)3SiO 1 / 2 Siloxane units represented by formula: SiO 4 / 2 Examples include organopolysiloxanes consisting of siloxane units represented by (wherein Vi represents a vinyl group), organopolysiloxanes in which some or all of the methyl groups of these organopolysiloxanes are replaced with alkyl groups such as ethyl groups and propyl groups; aryl groups such as phenyl groups and tolyl groups; halogenated alkyl groups such as 3,3,3-trifluoropropyl groups; and mixtures of two or more of these organopolysiloxanes. However, from the viewpoint of increasing the elongation of the cured product when cleaved by increasing the molecular chain length, linear diorganopolysiloxanes having vinyl groups at both ends of the molecular chain are preferred.

[0079] These organopolysiloxanes may be commercially available or manufactured by methods known to those skilled in the art.

[0080] (B: Organohydrogenpolysiloxane) Component (B) is an organohydrogenpolysiloxane containing 0.0001 mol / g or more and 0.05 mol / g or less of hydrogen atoms bonded to silicon atoms. Component (B) is an organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to silicon atoms in one molecule, and is a crosslinking component for forming a cured product by an addition curing reaction between SiH groups and alkenyl groups.

[0081] The organohydrogenpolysiloxane, which is component (B), is represented by the following average composition formula (2). [ka] (In formula (2), R 2 These are, independently of each other, a hydrogen atom, a hydroxyl group, or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. However, each molecule contains two or more hydrogen atoms bonded to a silicon atom, where a is an integer of 2 or more, b is an integer of 1 or more, c is an integer of 0 or more, and d is an integer of 0 or more. (The values ​​of a+b+c+d are not particularly limited as long as they satisfy the viscosity range described later; they can be between 5 and 600, or between 10 and 400.)

[0082] The viscosity of component (B) at 25°C may be between 1 mPa·s and 10,000 mPa·s, and preferably between 10 mPa·s and 2,000 mPa·s.

[0083] (B) R bonded to the silicon atom in component 2 If the monovalent hydrocarbon group is another monovalent hydrocarbon group, then the monovalent hydrocarbon group is specifically an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, neopentyl, hexyl, 2-ethylhexyl, heptyl, octyl, nonyl, decyl, dodecyl; a cycloalkyl group such as cyclopentyl, cyclohexyl, cycloheptyl; an aryl group such as phenyl, tolyl, xylyl, biphenyl, naphthyl; or a benzyl Examples include aralkyl groups such as chloromethyl, 2-bromoethyl, 3,3,3-trifluoropropyl, 3-chloropropyl, chlorophenyl, dibromophenyl, tetrachlorophenyl, difluorophenyl, β-cyanoethyl, γ-cyanopropyl, and β-cyanopropyl groups, in which some or all of the hydrogen atoms in these hydrocarbon groups are substituted with halogen atoms, cyano groups, etc. Particularly preferred monovalent hydrocarbon groups are methyl and phenyl groups.

[0084] Component (B) may further include those having an -SiOH group at one end of the molecular chain. In this case, the total organo in component (B) Hydrogen The ratio of silicon atoms having OH groups to the total number of terminal silicon atoms in the polysiloxane is less than 5%, preferably less than 2%. If this ratio satisfies the above conditions, addition polymerization will proceed sufficiently, and a sufficiently cured film can be obtained.

[0085] The hydrogen content (H content) of component (B) is 0.0001 mol / g or more and 0.05 mol / g or less, preferably 0.0002 mol / g or more and 0.01 mol / g or less, more preferably 0.0003 mol / g or more and 0.005 mol / g or less, and even more preferably 0.0004 mol / g or more and 0.005 mol / g or less.

[0086] Component (B) may function as a crosslinking agent. Preferably, the crosslinking agent is an organohydrogenpolysiloxane having two or more hydrosilyl groups, and may have 10 to 50 hydrosilyl groups. The organohydrogenpolysiloxane that acts as a crosslinking agent has at least two hydrosilyl groups in its side chain. The number of hydrosilyl groups at the end of the molecular chain can be 0 to 2, but 2 is economically preferable. The molecular structure of the organohydrogenpolysiloxane may be linear, cyclic, branched, or a three-dimensional network structure. There are no particular restrictions on the position of the silicon atom to which the hydrogen atom is bonded; it may be at the end of the molecular chain, at the non-end, or in the side chain. Other conditions, such as organic groups other than hydrosilyl groups, bond positions, degree of polymerization, and structure, are not particularly limited, and two or more organohydrogenpolysiloxanes may be used.

[0087] The content of component (B) is, for example, 25 parts by mass or more and 40 parts by mass or less, based on the total of component (A) and component (B) per 100 parts by mass.

[0088] The hydrosilyl group in component (B) may be located at the end of the molecular chain, at the side chain, or at both the end of the molecular chain and the side chain. An organohydrogenpolysiloxane having a hydrosilyl group only at the end of the molecular chain and an organohydrogenpolysiloxane having a hydrosilyl group only at the side chain may be used in combination.

[0089] Component (B) may also contain an organohydrogenpolysiloxane having at least one aromatic group in its molecule, from the viewpoint of improving heat resistance. For economic reasons, a phenyl group is more preferable as the aromatic group. An aromatic group-containing organohydrogenpolysiloxane and an organohydrogenpolysiloxane without an aromatic group can also be used in mixture form.

[0090] (C: Hollow filler made of organic resin) Component (C) is a hollow filler made of organic resin. The hollow filler made of organic resin may be, for example, a polymer of vinylidene chloride, acrylonitrile, methacrylonitrile, acrylic acid ester, methacrylic acid ester, or a copolymer of two or more of these.

[0091] The average particle size of the hollow filler made of organic resin may be 15 μm or more and 150 μm or less, preferably 20 μm or more and 120 μm or less, and more preferably 30 μm or more and 90 μm or less. The average particle size is the value measured as the cumulative weight average (D50) or median diameter using a particle size distribution analyzer by laser diffraction.

[0092] (C) Component or (C) component to which inorganic matter is attached has a true specific gravity of 0.1 to 0.3, preferably 0.11 to 0.25, more preferably 0.12 to 0.20. The specific gravity of the filler is controlled in the composition. 1st liquid, 2nd liquid This can suppress the separation (floating) of the filler in the )

[0093] Component (C) is such that, when the total amount of components (A) and (B) is 100 parts by mass, the content of component (C) is 5 parts by mass or more and 25 parts by mass or 6 parts by mass or more and 22 parts by mass or less, preferably 7 parts by mass or more and 20 parts by mass or less, more preferably 7 parts by mass or more and 15 parts by mass or less.

[0094] (C) Component may have inorganic material attached to at least a portion of its surface. Examples of such inorganic material include calcium carbonate, silica, zinc oxide, hydroxyapatite, hydrated magnesium silicate, and titanium dioxide.

[0095] Component (C) may be an inorganic material that has been subjected to affinity surface treatment or dispersive surface treatment. Affinity surface treatment or dispersive surface treatment to For example, organic substances such as fatty acids and resin acids. is used .

[0096] By coating hollow organic resin fillers with inorganic materials, in the heat insulating silicone composition (1st liquid, 2nd liquid) This can suppress the separation (lifting) of the filler in the low viscosity thermal insulating silicone composition. (1st liquid, 2nd liquid) Since the filler tends to float during storage, the specific gravity of the filler is adjusted and surface treatment is applied to suppress filler floating.

[0097] (D: Addition reaction catalyst) The addition reaction catalyst of component (D) is an addition reaction catalyst that promotes the addition hardening reaction between the alkenyl group bonded to the silicon atom in component (A) described above and the hydrogen atom bonded to the silicon atom in component (B) described above, and is a catalyst known to those skilled in the art. Examples of component (D) include platinum group metals such as platinum, rhodium, palladium, osmium, iridium, and ruthenium, or these fixed to a particulate support material (e.g., activated carbon, aluminum oxide, silicon oxide). Furthermore, component (D) includes platinum compounds such as platinum halides, platinum-olefin complexes, platinum-alcohol complexes, platinum-alkoxide complexes, platinum-vinylsiloxane complexes, dicyclopentadiene-platinum dichloride, cyclooctadiene-platinum dichloride, and cyclopentadiene-platinum dichloride.

[0098] Furthermore, from an economic standpoint, metal compound catalysts other than the platinum group metals mentioned above may be used as component (D). For example, examples of hydrosilylated iron catalysts include iron-carbonyl complex catalysts, iron catalysts having a cyclopentadienyl group as a ligand, iron catalysts having a terpyridine ligand or a terpyridine ligand and a bistrimethylsilylmethyl group, iron catalysts having a bisiminopyridine ligand, iron catalysts having a bisiminoquinoline ligand, iron catalysts having an aryl group as a ligand, iron catalysts having a cyclic or acyclic olefin group with an unsaturated group, and iron catalysts having a cyclic or acyclic olefinyl group with an unsaturated group. Other examples include hydrosilylated cobalt catalysts, vanadium catalysts, ruthenium catalysts, iridium catalysts, samarium catalysts, nickel catalysts, and manganese catalysts.

[0099] The amount of component (D) used depends on the desired curing temperature and curing time for the application, but the concentration of the catalyst metal element relative to the total mass of the thermal insulating silicone composition is preferably in the range of 0.5 ppm to 1,000 ppm, more preferably 1 ppm to 500 ppm, and even more preferably 1 ppm to 100 ppm. If the amount is less than 0.5 ppm, the addition reaction becomes significantly slower, while if the amount exceeds 1,000 ppm, the cost increases, making it economically undesirable.

[0100] The content of component (D) may be 0.001 parts by mass or more and 2.0 parts by mass or less, preferably 0.08 parts by mass or more and 1.6 parts by mass or less, when the total amount of component (A) and component (B) is 100 parts by mass.

[0101] (E: Silicone resin) Component E has a number-average molecular weight of 10 This is a silicone resin having at least one alkenyl group in its molecule, with a molecular weight of 00 or greater. The silicone resin may be a mixture of resin (E) and an organopolysiloxane containing an alkenyl group.

[0102] Examples of silicone resins include methyl silicone resin and methylphenyl silicone resin. Examples of modified silicone resins include alkyd-modified, epoxy-modified, acrylic-modified, and polyester-modified silicone resins.

[0103] The heat-insulating silicone composition of the present invention may, to the extent that it does not impair the objective of the present invention, further optional components other than the above components (A) to (E) may be used, which are conventionally known additives to silicone rubber and gels. Examples of such additives include crosslinking agents, organic silicon compounds or organosiloxanes (also called silane coupling agents) that produce silanols by hydrolysis, reaction rate modifiers, condensation catalysts, pigments, dyes, curing inhibitors, heat-resistance modifiers, flame retardants, antistatic agents, conductivity modifiers, airtightness improvers, radiation shielding agents, electromagnetic shielding agents, preservatives, stabilizers, organic solvents, plasticizers, antifungal agents, and organopolysiloxanes containing one silicon-bonded hydrogen atom or alkenyl group per molecule and not containing other functional groups, or non-functional organopolysiloxanes that do not contain silicon-bonded hydrogen atoms or alkenyl groups. These further optional components may be used individually or in combination of two or more.

[0104] (Reaction rate modifier: F) antiReaction rate regulators are, for example, those that have the ability to adjust the curing rate of an addition reaction. Examples include acetylene compounds, hydrazines, triazoles, phosphines, and mercaptans. As compounds that have a curing inhibitory effect, all conventionally known curing inhibitors in the art can be used. Examples of such compounds include phosphorus-containing compounds such as triphenylphosphine, nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole, sulfur-containing compounds, acetylene compounds, compounds containing two or more alkenyl groups, hydroperoxy compounds, and maleic acid derivatives. Silanes and silicone compounds having amino groups may also be used. In particular for this application, it is preferable that the effect on fluidity is small and that curing proceeds at room temperature. In this case, low viscosity (e.g., viscosity of 100 mPa·s or less) is preferred, and examples include various "en-yine" systems such as 3-methyl-3-penten-1-yine and 3,5-dimethyl-3-hexen-1-yine; acetylene alcohols such as 3,5-dimethyl-1-hexyn-3-ol, 1-ethynyl-1-cyclohexanol, and 2-phenyl-3-butyne-2-ol; well-known dialkyl, dialkenyl, and dialkoxyalkyl fumarates and maleates; and cyclovinylsiloxanes.

[0105] (Pigment: G) Examples of pigments include titanium dioxide, aluminasilic acid, iron oxide, zinc oxide, calcium carbonate, carbon black, rare earth oxides, chromium oxide, cobalt pigments, ultramarine, cerium silanolate, aluminum oxide, aluminum hydroxide, titanium yellow, barium sulfate, precipitated barium sulfate, and mixtures thereof. The amount of pigment used depends on the desired curing temperature and curing time for the application, but generally, the amount of pigment component relative to the total mass of the heat-insulating silicone composition is preferably in the range of 0.001% to 5%. Preferably, it is in the range of 0.01% to 2%, and more preferably 0.05% to 1%. If the amount is less than 0.001%, the coloring will be insufficient, and it will be difficult to visually distinguish between the first and second liquids. On the other hand, if the amount exceeds 5%, the cost will increase, which is economically undesirable.

[0106] Furthermore, the heat-insulating silicone composition of the present invention may contain one or more selected from the group consisting of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), and hexadecamethylcyclooctasiloxane (D8). The total content of (D4), (D5), (D6), (D7), and (D8) above may be less than 0.1 parts by mass (i.e., less than 1,000 ppm) when the total amount of component (A) and component (B) is 100 parts by mass. If the total content of (D4) to (D8) in the heat-insulating silicone composition is within the above range, the flash point of the composition as a whole will be increased, improving safety during storage. Furthermore, it will be possible to provide a cured product obtained by curing the composition that is less likely to cause contact failures to electronic components, etc. A heat insulating silicone composition in which the total content of (D4) to (D8) is less than 0.1 parts by mass when the total amount of component (A) and component (B) is 100 parts by mass can be manufactured by using component (A) in which the total content xA of (D4) to (D8) is less than 0.1 parts by mass, and component (B) in which the total content xB of (D4) to (D8) is less than 0.1 parts by mass, such that xA + xB < 0.1 parts by mass. The content of (D4) to (D8) is measured by gas chromatography. The measurement conditions for gas chromatography should be appropriately selected according to conventionally known methods.

[0107] (base material) The base material includes, for example, various electrical and electronic components, automotive parts, electric vehicle battery units, various computer-related components such as PCs and mobile devices, battery units, electrical equipment, and electronic equipment. Substrate used in These are some examples. Electrical and electronic equipment are not particularly limited and include, for example, mobile phones, smartphones, tablets, smartwatches, computers, semiconductor package substrates, electronic circuit boards, LED package substrates, sensor substrates, image sensor substrates, liquid crystal substrates, organic EL substrates, etc.

[0108] A heat-insulating silicone composition can be potted into the gaps between multiple substrates and cured. A heat-insulating silicone composition can be potted into the gaps between components of the substrates and cured.

[0109] The viscosity of the uncured thermal insulation silicone composition at 25°C may be 100,000 mPa·s or less, more preferably 1,000 mPa·s to 8,000 mPa·s. If the thermal insulation silicone composition is a two-component mixture type, the viscosity of each of the first and second liquids at 25°C may be 100,000 mPa·s or less, more preferably 1,000 mPa·s to 8,000 mPa·s. The viscosity of the first and second liquids mixed at 25°C before curing begins or in the early stages of curing may be 100,000 mPa·s or less, more preferably 1,000 mPa·s to 8,000 mPa·s. (Measurement method) The viscosity of the thermal insulating silicone composition at 25°C is measured according to JIS K 7117-2. For example, the uncured thermal insulating silicone composition is placed between a cone with a diameter of 25 mm and an angle of rotation of 1° or 2° and a fixed plate, and the viscosity is measured using a viscometer at a shear rate of 10 (1 / s) and a gap of 0.106 mm.

[0110] The aforementioned heat-insulating silicone composition, The ease with which component (C) floats relative to other components may be 40% to 70%, preferably 40% to 65%. (Measurement method) The ease with which the filler floats is determined from the interface position between the liquid phase (silicone phase) and the filler phase (component C phase) after an uncured thermal insulation silicone composition has been left to stand for a certain period of time. For example, in a 50 mL container with a diameter of 35 mm and a height of 78 mm, the material is filled to a depth of 55 mm from the bottom. (1st liquid, 2nd liquid) After pouring in the mixture and storing it at a high temperature for a predetermined time (for example, 50°C for one week), the interface position between the silicone phase and the filler phase is measured with a ruler or similar tool, and the ease with which the filler floats is determined from the interface position and the amount of filler filled. Determine the volume fraction of component C and other components in the heat-insulating silicone composition. For example, the ratio of C component to other components in the liquid phase is 4:6. Theoretical liquid phase height H0 = volume fraction of the liquid phase (6) × 55 mm (filling height) Measure the height H1 of the liquid phase with a ruler after storage at a high temperature for a predetermined time. For example, the ratio of component C to other components in the liquid phase is 7:3. The buoyancy is calculated as H1 / H0.

[0111] The strength of the suspended matter in component (C) may be 2N or less. (Measurement method) The hardness of the filler component (component C) suspended on the surface of the sample after the buoyancy evaluation is measured. For example, the maximum load value when a spherical compression jig with a diameter of φ12.7 mm is pressed and penetrated at a compression speed of 240 mm / min is measured using a compression testing machine.

[0112] <Examples> The following describes examples of two-component mixtures. However, the present invention is not limited to these examples. Figure 3A shows the mixing ratios of the first and second liquid components in formulation examples 1 to 4. Figure 3B shows the evaluation results for formulation examples 1 to 4. The mixing ratio values ​​are in parts by mass. Figure 3C shows the results after re-stirring. Hollow fillers made of organic resin are polymers whose main components are acrylonitrile, methyl methacrylate, and methacrylonitrile.

[0113] (Manufacturing method) The first and second solutions shown in the examples and comparative examples were mixed to prepare the products. For example, put 40 wt% of the liquid material (first liquid or second liquid) in the composition and the entire amount of filler into a rotary-orbit mixer and mix for 2 minutes at an orbital speed of 660 rpm and a rotational speed of 220 rpm. Then, add the remaining liquid material (60 wt%) and mix for 2 minutes at the same speed as above. Next, it was stored in a static state for three weeks. Next, the first and second liquids were mixed in a mass ratio of 1:1. Next, various evaluations were performed on the states of the first and second liquids, and after mixing in the uncured state. The evaluation methods (measurement methods) for each evaluation are shown below. For mixing conditions, an L-shaped single-shaft and double-shaft agitator, and a gantry-type single-shaft agitator with an inclined baffle plate were used. The orbital speed and rotational speed were set in Figure 3C. The reduced pressure was set to -0.1 MPa or less. The baseline was set to 100, representing the initial values ​​immediately after production of the first and second liquids. The judgment criteria were based on meeting all criteria of appearance, viscosity, and specific gravity.

[0114] (Theoretical specific gravity) Theoretical specific gravity can be determined from the specific gravity of each component and their mixing ratio.

[0115] (Specific gravity: density) Measure the specific gravity (density) of the first and second liquids. Use the density immediately after manufacturing, when the filler has not separated, as a baseline, and measure the density before and after mixing.

[0116] (viscosity) The viscosity of the thermal insulating silicone composition at 25°C was measured according to JIS K 7117-2. The uncured thermal insulating silicone composition was placed between a cone with a diameter of 25 mm and an angle of rotation of 1° or 2° and a fixed plate, and the viscosity was measured using a Physica MR 301 viscometer (Anton Paar) at a shear rate of 10¹ / s and a gap of 0.106 mm. In Figure 3B, "Liquid 1 (D=10)" shows the viscosity of Liquid 1 at a shear rate of 10¹ / s, "Liquid 2 (D=10)" shows the viscosity of Liquid 2 at a shear rate of 10¹ / s, and "Mixed (D=10)" shows the viscosity of Liquid 1 and Liquid 2 when mixed at a shear rate of 10¹ / s. Figure 3C shows only "Mixed (D=10)".

[0117] (Ease of floating) Add 40 wt% of the liquid material (either liquid 1 or liquid 2) from the composition and the entire amount of filler to a rotating / revolving mixer and mix for 2 minutes at a rotational speed of 660 rpm and a rotational speed of 220 rpm. Then, add the remaining liquid material (60 wt%) and mix for 2 minutes at the same speed as above. Subsequently, the ease with which the filler floated was determined from the interface position between the liquid phase (silicone phase) and the filler phase (component C phase) after the uncured thermal insulation silicone composition had been left to stand for a certain period of time. The material was then filled to a depth of 55 mm from the bottom of a 50 mL container with a diameter of 35 mm and a height of 78 mm. (1st liquid, 2nd liquid) The mixture was poured in and stored at a high temperature for a predetermined time (for example, 50°C for one week). The interface between the silicone phase and the filler phase was then measured using a ruler or similar tool, and the ease with which the filler would float was determined from the interface position and the amount of filler added. The volume fractions of component C and other components in the heat-insulating silicone composition (first liquid or second liquid) were determined. Theoretical liquid phase height H0 = volume fraction of the liquid phase (6) × 55 mm (filling height) The height H1 of the liquid phase after storage at a high temperature for a predetermined time was measured with a ruler. Easy to float Sa It can be calculated using H1 / H0. In Figure 3B, "Liquid Phase Height A" and "Difference from Theoretical Value of Liquid Phase Height A" represent the evaluation results for the first liquid, while "Liquid Phase Height B" and "Difference from Theoretical Value of Liquid Phase Height B" represent the evaluation results for the second liquid.

[0118] (Strength of floating objects) The hardness of the filler component (component C) suspended on the surface of the sample after evaluation of its buoyancy was measured. The maximum load value (N) was measured using a compression tester (Shimadzu Autograph AGS-X) when a spherical compression jig with a diameter of φ12.7 mm was pressed and penetrated at a compression speed of 240 mm / min. In Figure 3B, "Test Force A" shows the strength result for the first liquid, and "Test Force B" shows the strength result for the second liquid.

[0119] Let's examine the results of re-stirring as shown in Figure 3C. Examples 1 to 4 were re-stirred using the composition of Formulation Example 1, Example 5 using the composition of Formulation Example 2, Example 6 using the composition of Formulation Example 3, and Example 7 using the composition of Formulation Example 4. In Example 1, with one L-shaped blade, the rotation speed was 40 rpm, the revolution speed was 20 rpm, and the process took 30 minutes. i We were able to disperse Ra without destroying it. In Example 2, with a single L-shaped blade, the filler could be dispersed without being destroyed in 20 minutes at a rotational speed of 64 rpm and an orbital speed of 32 rpm. In Example 3, the L-shaped blade with two axes was able to disperse the filler without damaging it in 15 minutes at a rotational speed of 64 rpm and an orbital speed of 32 rpm. In the single-axis gate-type vane with inclined baffles of Example 4, the filler could be dispersed without being destroyed at a rotational speed of 64 rpm, an orbital speed of 32 rpm, and 15 minutes. In Example 5, with a single L-shaped blade, the filler could be dispersed without being destroyed in 20 minutes at a rotational speed of 64 rpm and an orbital speed of 32 rpm. In Example 6, with a single L-shaped blade, the filler could be dispersed without being destroyed in 15 minutes at a rotational speed of 64 rpm and an orbital speed of 32 rpm. In Example 7, with a single L-shaped blade, the filler could be dispersed without being destroyed in 15 minutes at a rotational speed of 64 rpm and an orbital speed of 32 rpm.

Claims

1. A first liquid defoaming and mixing step is performed in which the first liquid, which is packed in the first transport container, is stirred and mixed under reduced pressure or negative reduced pressure defoaming while still packed in the first transport container. A first liquid circulation step involves drawing out the first liquid from the state in which it remains packed in the first transport container and returning it to the first transport container before sending it to the two-liquid confluence point. A first liquid supply step involves drawing out the first liquid from the state in which it remains packed in the first transport container and sending it to the two-liquid confluence point, A first liquid circulation / supply switching step that switches between a configuration in which the first liquid is returned to the first transport container and a configuration in which the first liquid is supplied to the two liquids confluence point, The second liquid, which is packed in the second transport container, is stirred and mixed under reduced pressure or negative reduced pressure degassing while still packed in the second transport container; A second liquid circulation process involves drawing out the second liquid from the state in which it remains packed in the second transport container, returning it to the second transport container before sending it to the two-liquid confluence point, A second liquid supply step involves drawing out the second liquid from the state in which it remains packed in the second transport container and sending it to the two-liquid confluence point, A second liquid circulation / supply switching step that switches between a configuration in which the second liquid is returned to the second transport container and a configuration in which the second liquid is supplied to the two-liquid confluence point, A mixing step is performed at the two-liquid confluence point to mix the supplied first liquid and second liquid to produce a heat insulating silicone composition. The process includes a potting step of potting the aforementioned heat-insulating silicone composition onto a substrate, A method for applying and filling a two-component, heat-insulating silicone composition containing a filler.

2. The vacuum agitator used in the first liquid defoaming and mixing step is different from the vacuum agitator used in the first liquid circulation step and the first liquid supply step, and / or The vacuum agitator used in the second liquid defoaming and mixing step is different from the vacuum agitator used in the second liquid circulation step and the second liquid supply step. The coating and filling method according to claim 1.

3. A first vacuum agitator stirs and mixes the first liquid, which is packed in the first transport container, under reduced pressure or negative vacuum degassing, while it remains packed in the first transport container. A third vacuum agitator is used to agitate the contents while they remain packed in the first transport container under reduced pressure or negative vacuum degassing conditions. A first liquid supply line for sending the first liquid to the two-liquid confluence point, while the first liquid remains packed in the first transport container and is being stirred by vacuum degassing or stopped using the third vacuum agitator, Before sending the first liquid to the two-liquid merging point, a first liquid circulation line is provided to return it to the first transport container, A three-way switching valve for the first liquid switches the flow of the first liquid in order to send the first liquid to the two-liquid merging point or to the first circulation line, A second vacuum agitator stirs and mixes the second liquid, which is packed in the second transport container, under reduced pressure or negative vacuum degassing conditions, while it remains packed in the second transport container. A fourth vacuum agitator is used to agitate the contents while they remain packed in the second transport container under reduced pressure or negative vacuum degassing conditions. A second liquid supply line for sending the second liquid to the two-liquid confluence point while the second liquid is still packed in the second transport container and being stirred by vacuum degassing or stopped using the fourth vacuum agitator, Before sending the second liquid to the two-liquid confluence point, a second liquid circulation line is provided to return it to the second transport container, A three-way switching valve for the second liquid is provided to switch the flow of the second liquid in order to send the second liquid to the two-liquid merging point or to the second circulation line, At the two-liquid confluence point, a coating and filling apparatus is used to pot the heat-insulating silicone composition, which is a mixture of the supplied first liquid and second liquid, onto a substrate. Equipped with, A coating and filling system for coating or filling with a two-component, heat-insulating silicone composition containing a filler.

Images