WO2017163316A1

WO2017163316A1 - Resin member, heat switch, composition for heat switch, and temperature adjustment structure

Info

Publication number: WO2017163316A1
Application number: PCT/JP2016/059069
Authority: WO
Inventors: 森本　剛; 高橋　裕之; 晃永井
Original assignee: 日立化成株式会社
Priority date: 2016-03-22
Filing date: 2016-03-22
Publication date: 2017-09-28
Also published as: JPWO2017163316A1; JP6414364B2

Abstract

The present invention provides a resin member (heat switch) 1 provided with a matrix resin 2 and thermally expandable components 3, wherein accommodation sections 4 for accommodating the thermally expandable components 3 are formed in the matrix resin 2, the thermally expandable components 3 occupy parts of the accommodation sections 4 at a first temperature, and, at a second temperature that is higher than the first temperature, the thermally expandable components 3 occupy the accommodation sections 4 with a larger volume proportion than the volume proportion of the thermally expandable components 3 with respect to the accommodation sections 4 at the first temperature.

Description

Resin member, heat switch, heat switch composition and temperature control structure

The present invention relates to a resin member, a heat switch, a heat switch composition, and a temperature adjustment structure.

In recent years, it has been required to use thermal energy with high efficiency in various fields. As shown in the second law of thermodynamics, thermal energy is radiated from the heat source unless it has a heat insulating structure. As a mechanism for using thermal energy, for example, a heat switch is known.

For example, Patent Document 1 discloses a sealed cavity having a predetermined first wall and a second wall, the second wall being arranged with a gap with respect to the receiving structure, and a sealed cavity. A thermal actuator material that fills the portion and is adapted to change volume with temperature, and a conductive material that fills a portion of the sealed cavity and provides a highly conductive transfer structure between the first wall and the second wall; , And the thermal actuator material moves the second wall during a temperature-induced volume change so that the gap with respect to the receiving structure is filled, thereby turning off heat conduction between the heat dissipation side and the heat source side. A highly conductive heat switch that reversibly switches between a state and an on state is disclosed.

Patent Document 2 includes a first protective layer, a radiation layer on the first protective layer, and a second protective layer disposed in a state having a gap with the radiation layer, and the surface of the first protective layer is provided. A thermal switch is disclosed in which the heat emissivity of a radiation layer is reversibly changed by heat. Further, Patent Document 3 includes a first protective layer, a second protective layer arranged to be paired with the first protective layer, and a thermal expansion member on the first protective layer, and the second protective layer, There is disclosed a thermal switch that has a gap without contact with a thermal expansion member at room temperature and contacts with the thermal expansion member due to thermal expansion of the thermal expansion member at high temperature.

Special table 2009-524190 International Publication No. 2014/148585 International Publication No. 2014/156991

The present invention provides a resin member and a heat switch capable of reversibly changing heat conduction with a simple configuration, a resin composition for the heat switch, and a temperature adjustment structure including the heat switch. Objective.

The present invention provides a resin member according to [1] to [5] below, a heat switch according to [6] to [10] or [14] below, and a heat switch according to [11] to [13] below. The composition and the temperature adjustment structure described in [15] below are provided.
[1] A matrix resin and a thermally expansible component are provided, and a housing portion for housing the thermally expandable component is formed in the matrix resin, and the thermally expandable component is stored in the housing portion at the first temperature. A resin member that occupies a portion and occupies the housing portion at a volume ratio that is greater than the volume ratio of the thermally expandable component to the housing portion at the first temperature at a second temperature that is higher than the first temperature.
[2] The resin member according to [1], wherein the housing portion is formed of a capsule, and the capsule contains a thermally expandable component.
[3] The resin member according to [1] or [2], further including a thermally conductive component housed in the housing portion.
[4] A matrix resin and a thermally expansible component are provided, and a housing portion for accommodating the thermally expansible component is formed in the matrix resin, and the coefficient of thermal expansion of the thermally expansible component is that of the matrix resin. Resin member larger than the coefficient.
[5] The thermally expansible component is stored away from the wall portion of the storage portion or in contact with a part of the wall portion at the first temperature, and is a second temperature higher than the first temperature. The resin member according to [4], wherein the wall member is in contact with an area larger than a contact area between the thermally expandable component and the wall at the first temperature.
[6] A matrix resin and a thermally expansible component are provided, and a housing portion for housing the thermally expandable component is formed in the matrix resin, and the thermally expandable component is stored in the housing portion at the first temperature. A heat switch that occupies a portion and occupies the housing portion at a volume ratio that is greater than the volume ratio of the thermally expansible component to the housing portion at the first temperature at a second temperature that is higher than the first temperature.
[7] The heat switch according to [6], in which the housing portion is formed of a capsule, and the capsule contains a thermally expandable component.
[8] The heat switch according to [6] or [7], further including a heat conductive component housed in the housing portion.
[9] A matrix resin and a thermally expansible component are provided, and a housing portion for accommodating the thermally expansible component is formed in the matrix resin, and the coefficient of thermal expansion of the thermally expansible component is that of the matrix resin. Heat switch larger than the coefficient.
[10] The thermally expandable component is stored at a first temperature apart from the wall portion of the storage portion or is in contact with a part of the wall portion, and is a second temperature higher than the first temperature. The heat switch according to [9], wherein the wall portion is in contact with an area larger than the contact area between the thermally expandable component and the wall portion at the first temperature.
[11] A composition for a heat switch, comprising a matrix resin and a thermally expandable component.
[12] The composition for a heat switch according to [11], further comprising a capsule containing a thermally expandable component.
[13] The heat switch composition according to [11] or [12], further comprising a heat conductive component.
[14] A heat switch comprising a cured product of the composition for heat switch according to any one of [11] to [13].
[15] A heat source that generates heat, and the heat switch according to any one of [6] to [10] or [14] arranged so as to be able to conduct heat from the heat source, wherein the heat switch comprises: A temperature adjustment structure that adjusts a temperature caused by heat of a heat source by changing a conduction state of heat from the heat source between a first temperature and a second temperature.

According to the present invention, a resin member and a heat switch capable of reversibly changing heat conduction with a simple configuration, a resin composition for the heat switch, and a temperature adjustment structure including the heat switch are provided. be able to.

It is a model cut end view showing one embodiment (off state) of a resin member (heat switch). It is a model cutting end view showing one embodiment (ON state) of a resin member (heat switch). It is a schematic cut end view for demonstrating one Embodiment of temperature control structure, and the effect of a resin member (heat switch). It is a model cut end view which shows other embodiment of the resin member (heat switch). It is a principal part enlarged view for demonstrating the effect of the resin member (heat switch) shown in FIG. It is a model cut end view which shows other embodiment of the resin member (heat switch). It is a principal part enlarged view for demonstrating the effect of the resin member (heat switch) shown in FIG. It is a polarizing microscope photograph of the heat switch which concerns on an Example.

Hereinafter, embodiments of the present invention will be described in detail with appropriate reference to the drawings.

FIG. 1 is a schematic cut end view showing an embodiment (off state) of a resin member. As shown in FIG. 1, the resin member (off state) 1 A includes a matrix resin 2 and a thermally expandable component 3. A plurality of accommodating portions 4 are formed in the matrix resin 2, and the thermally expandable component 3 is accommodated in each accommodating portion 4. The thickness of the resin member 1A (1) may be, for example, 100 to 5000 μm.

Since the resin member 1 can change heat conduction reversibly (details will be described later), it is preferably used as a heat switch. That is, “resin member” in the following description can be read as “heat switch”.

The heat switch means a mechanism for changing the thermal conductivity actively or passively according to changes in the amount of external energy such as heat, electricity, and magnetic field. In addition, the heat switch (resin member) in the off state is a state in which the temperature in the vicinity of the thermally expandable component is the first temperature, which is relative to the on state of the heat switch (resin member) described later. This means that the thermal conductivity is low. The first temperature may be, for example, −10 to 50 ° C., −10 to 30 ° C., or 20 to 120 ° C. 1st temperature is not restricted to the said temperature range, You may change suitably according to a use. The OFF state of the heat switch (resin member) may be, for example, a state where the thermal conductivity of the heat switch (resin member) is minimized.

The matrix resin 2 is not particularly limited, and may be, for example, a thermosetting resin or a thermoplastic resin. However, the matrix resin 2 is a component (resin) different from the thermally expandable component 3. Examples of the thermosetting resin include phenol resin, amino resin, polyamide amino resin, unsaturated polyester resin, epoxy resin, polyurethane resin, silicone resin, polyimide resin, and the like. These resins are used alone or in combination of two or more. The curing temperature of the thermosetting resin is not particularly limited, but is preferably a high temperature, for example, preferably 80 to 300 ° C., more preferably 120 to 280 ° C., and still more preferably 150 to 250 ° C. A resin having a curing temperature of 80 ° C. or higher has excellent heat resistance after curing, and a resin having a curing temperature of 300 ° C. or lower can suppress thermal degradation of the resin itself or the thermal expansion component by heating during curing.

Thermoplastic resins include various rubbers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, polyptadiene resins, polycarbonate resins, thermoplastic polyimide resins, thermoplastic polyamideimide resins. And polyamide resins such as 6-nylon and 6,6-nylon, phenoxy resins, acrylic resins, saturated polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polyamideimide resins, and fluorine resins. These thermoplastic resins are used individually by 1 type or in combination of 2 or more types.

The accommodating portion 4 in the resin member (off state) 1A is configured such that the thermally expandable component 3 is accommodated in a part of a space having a predetermined volume. That is, the accommodating portion 4 in the resin member (OFF state) 1 A includes the thermally expandable component 3 and the gap portion 5. The gap 5 may be constituted by a vacuum or a gas component such as the atmosphere. Since the void portion 5 generally has a lower thermal conductivity than the resin (for example, the thermally expansible component 3), the void portion 5 is generated in the accommodating portion 4 in the resin member (off state) 1A. Becomes a resin member capable of changing the heat conduction characteristics with temperature change. That is, the reversible change in the heat conduction characteristic in the resin member 1 can be realized by adjusting the volume or the like of the gap 5.

The ratio of the matrix resin 2 in the resin member 1A may be, for example, 10 to 90% by volume, or 20 to 74% by volume. The proportion of the accommodating portion 4 in the matrix resin 2 may be, for example, 10 to 90% by volume, or 20 to 74% by volume. The volume here means the volume at room temperature (25 ° C.).

The thermally expandable component 3 is particularly limited as long as it is a component whose volume reversibly changes with a change in temperature, more specifically, a component that expands with a rise in temperature and contracts with a drop in temperature. Not. The average volume expansion coefficient of the thermally expandable component 3 at 0 to 100 ° C. is, for example, 1.8 × 10 ⁻⁴ / ° C. or higher, 3.3 × 10 ⁻⁴ / ° C. or higher, or 5.0 × 10 ⁻⁴ / ° C. It may be above. The thermally expansible component 3 may be a component whose volume reversibly changes (expands and contracts) without causing a phase transition, and a component whose volume reversibly changes by phase transition. It's okay.

Examples of the thermally expandable component that reversibly expands and contracts without phase transition include rubber and high molecular weight polymers. Specific examples of rubber include acrylonitrile butadiene rubber (NBR), styrene butadiene rubber (SBR), chlorobutyl rubber (CBR), silicone rubber, chloroprene rubber (CR), fluorine rubber (FR), and isoprene rubber (IR). Natural rubber (NR), butadiene rubber (BR), butyl rubber (IIR), chlorinated butyl rubber (CIIR), brominated butyl rubber, acrylic rubber (AR), urethane rubber (UR), ethylene-propylene-diene rubber (EPDM), Examples include epichlorohydrin rubber. The rubber is preferably acrylonitrile butadiene rubber (NBR), styrene butadiene rubber (SBR), chlorobutyl rubber (CBR), isoprene rubber (IR), butadiene rubber (BR), butyl rubber (IIR), chlorinated butyl rubber (CIIR). Or brominated butyl rubber. The high molecular weight polymer refers to, for example, a polymer having a weight average molecular weight of 100,000 or more, and polyethylene, polypropylene and the like are preferable. These thermally expandable components are used singly or in combination of two or more.

Examples of the thermally expandable component whose volume is reversibly changed by phase transition include saturated hydrocarbon compounds, and examples thereof include saturated hydrocarbon compounds having 8 to 100 carbon atoms. The saturated hydrocarbon compound is preferably a saturated hydrocarbon compound having an alkylene group having 10 to 30 carbon atoms, more specifically, n-dodecane, n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane, n A linear aliphatic saturated hydrocarbon compound such as octadecane, n-nonadecane, n-icosane or the like, or a branched aliphatic saturated hydrocarbon compound.

The above saturated hydrocarbon compounds are used singly or in combination of two or more. For example, the temperature at which the heat switch is switched between the on state and the off state can be set to a desired value by appropriately using saturated hydrocarbon compounds having different carbon numbers.

As one aspect, the saturated hydrocarbon compound may be petroleum wax. Examples of the petroleum wax include paraffin wax and microcrystalline wax. The paraffin wax is a wax that is solid at room temperature (25 ° C.), for example, obtained by separation and purification from a vacuum distillation distillate made from petroleum or natural gas. The microcrystalline wax is, for example, a solid wax obtained at room temperature (25 ° C.) obtained by separating and refining from a vacuum distillation residue oil or heavy distillate oil that uses petroleum as a raw material. As the paraffin wax, for example, a paraffin wax having 20 to 40 carbon atoms is preferably used, and as the microcrystalline wax, for example, a microcrystalline wax having 30 to 60 carbon atoms is preferably used in terms of heat of fusion and availability.

The thermal expansion coefficient of the thermal expansion component 3 described above is preferably larger than the thermal expansion coefficient of the matrix resin 2.

FIG. 2 is a schematic cut end view showing an embodiment (ON state) of a resin member (heat switch). As shown in FIG. 2, the resin member (ON state) 1 B includes a matrix resin 2 and a thermally expandable component 3, similarly to the resin member (OFF state) 1 A. A plurality of accommodating portions 4 are formed in the matrix resin 2, and the thermally expandable component 3 is accommodated in each accommodating portion 4.

The on state of the resin member (heat switch) is a state in which the temperature in the vicinity of the thermally expandable component 3 is the second temperature, and is relatively compared to the above-described off state of the resin member (heat switch). It means a state with high thermal conductivity. The second temperature may be higher than the first temperature, and may be, for example, 0 to 120 ° C., or 30 to 120 ° C. The on state of the resin member (heat switch) may be, for example, a state where the thermal conductivity of the resin member (heat switch) is maximized.

The accommodating portion 4 in the resin member (on state) 1B accommodates the thermally expandable component 3 that is expanded as compared with the thermally expandable component 3 in the resin member (off state) 1A. That is, the volume ratio of the thermally expandable component 3 occupying the housing part 4 in the resin member (ON state) 1B is larger than the volume ratio of the thermally expandable component 3 occupying the housing part 4 in the resin member (OFF state) 1A. It has become. The accommodating part 4 in the resin member (ON state) 1B may be filled with the thermally expansible component 3, and may contain the thermally expansible component 3 and the space | gap part.

FIG. 3 is a schematic cut end view for explaining the effect of the embodiment of the temperature adjustment structure and the resin member (heat switch). As shown in FIG. 3A, the resin member (OFF state) 1A is used, for example, disposed between a heat source (high temperature part) 6 that generates heat and a low temperature part 7. The temperature of the heat source (high temperature part) 6 is higher than the temperature of the low temperature part 7. In addition, the low temperature part 7 does not need to be provided, and the opposite side to the heat source 6 of the resin member 1A may be open | released, for example to air | atmosphere. That is, the temperature adjustment structure 8 includes at least the heat source 6 and the resin member 1 A arranged so as to be able to conduct heat from the heat source 6.

At this time, the temperature in the vicinity of the heat-expandable component 3 is the first temperature, and the volume ratio of the heat-expandable component 3 occupying the housing part 4 may be, for example, 5 to 90% by volume. That is, the thermally expandable component 3 is in contact with a part of the wall portion 4 a of the housing portion 4.

Next, as shown in FIG. 3B, as heat is conducted from the heat source (high temperature part) 6 to the resin member 1C, the temperature in the vicinity of the thermally expandable component 3 rises from the first temperature, and the accommodating part The thermally expandable component 3 expands within 4 (the volume ratio of the thermally expandable component 3 occupying the housing part 4 increases).

And as shown in FIG.3 (c), the temperature of the thermal expansible component 3 vicinity reaches 2nd temperature, and the thermal expansible component 3 expand | swells until it becomes the volume substantially the same as the accommodating part 4, for example. . At this time, the volume ratio of the thermally expansible component 3 to the accommodating part 4 may be 95 volume% or more, 98 volume% or more, for example, and may be 100 volume%.

As a result, the accommodating portion 4 has a higher thermal conductivity than the accommodating portion 4 in the resin member (OFF state) 1A. Therefore, the resin member 1B is turned on, and the heat conducted from the heat source (high temperature part) 6 to the resin member 1B is further conducted to the low temperature part 7 through the thermally expandable component 3 housed in the housing part 4. .

On the other hand, when the temperature in the vicinity of the thermally expandable component 3 decreases from the ON state of the resin member 1B as shown in FIG. 3C, the thermally expandable component 3 contracts accordingly (the heat occupied in the housing portion 4). The volume ratio of the expandable component 3 decreases). And the thermal conductivity of the accommodating part 4 falls, As a result, the resin member 1 returns to an OFF state as shown to Fig.3 (a).

As described above, in the resin member (heat switch) 1 according to the present embodiment, the thermally expandable component 3 is a component that thermally expands, and therefore occupies a part of the housing portion 4 at the first temperature. In the 2nd temperature, the accommodating part 4 is occupied by the volume ratio larger than the volume ratio of the thermally expansible component 3 with respect to the accommodating part 4 in 1st temperature. In other words, the contact area between the wall 4a and the thermally expandable component 3 constituting the housing part 4 at the second temperature is such that the wall 4a of the housing 4 at the first temperature and the thermally expandable component 3 are in contact with each other. It is larger than the contact area. Therefore, the thermally expandable component 3 is thermally expanded (its volume is increased as the temperature rises), thereby increasing the thermal conductivity of the housing portion 4 (conversely, the thermally expandable component 3 is accompanied by a decrease in temperature. The thermal conductivity of the accommodating part 4 is reduced by reducing the volume).

And with the change of the thermal conductivity of the accommodating part 4 by the change of the volume ratio of the thermally expansible component 3 which occupies for the accommodating part 4, the thermal conductivity of the resin member (heat switch) 1 whole also changes, and thereby the resin member (Heat switch) 1 is switched between an off state and an on state. Therefore, in the resin member (heat switch) 1 according to the present embodiment, the heat conduction is in an off state and an on state with a simple configuration as compared with, for example, a conventional heat switch as described in Patent Document 1 described above. Can be switched reversibly. Further, the temperature adjustment structure 8 is caused by the heat of the heat source 6 by the resin member (heat switch) 1 changing the conduction state of the heat from the heat source 6 between the first temperature and the second temperature. It is possible to adjust the temperature of the heat source 6 and the vicinity thereof.

The resin member (heat switch) 1 according to the present embodiment can be provided in various shapes such as a sheet shape, a film shape, or a liquid shape, and thus can be reduced in thickness and weight. Thereby, for example, it can be applied to a narrow pitch structure such as an electronic material. Even when the resin member (heat switch) 1 is applied to such a narrow pitch structure, the heat conductivity (heat resistance value) is reversibly changed according to the ambient temperature, and the conduction of the heat energy generated from the heat source is performed. Can be controlled.

The ratio (on / off) of the thermal conductivity of the resin member (heat switch) 1B in the on state to the thermal conductivity of the resin member (heat switch) 1A in the off state only needs to exceed 1, preferably 2 or more. More preferably, it is 10 or more, More preferably, it is 50 or more.

FIG. 4 is a schematic cut end view showing another embodiment of a resin member (heat switch). As shown in FIG. 4, the resin member (heat switch) 11 has an irregular shape in the housing portion 14 as compared to the resin member (heat switch) 1 according to the embodiment described above, and a plurality of housings. In this embodiment, the portion 14 is formed in the matrix resin 2 in a denser state.

Also in this embodiment, similarly to the above-described embodiment, in the resin member (OFF state) 11A, the housing portion 14 includes the thermally expandable component 13 and the gap portion 15 at the first temperature (see FIG. 4 (a)). Then, in the resin member (ON state) 11B, the temperature in the vicinity of the thermally expandable component 13 reaches the second temperature, and the thermally expandable component 13 expands, for example, to have substantially the same volume as the accommodating portion 14 ( FIG. 4 (b)).

FIG. 5 is an enlarged view of a main part in which the housing part 14 of the resin member (heat switch) 11 shown in FIG. 4 is enlarged. As shown in FIG. 5A, when the resin member 11 is in the off state, the thermally expandable component 13 may exist away from the wall portion 14a of the accommodating portion 14 (that is, the thermally expandable component). 13 may be surrounded by the gap 15). Then, as shown in FIG. 5B, when the resin member 11 is in the ON state, the thermally expandable component 13 is inflated, for example, until it has substantially the same volume as the accommodating portion 14, and the accommodating portion 14 is configured. The contact area between the wall portion 14a and the thermally expandable component 13 is larger than the contact area between the wall portion 14a of the housing portion 14 and the thermally expandable component 13 at the first temperature. Thereby, the resin member (heat switch) 11 can change heat conduction reversibly similarly to the above-mentioned embodiment.

FIG. 6 is a schematic cut end view showing another embodiment of the resin member (heat switch). In the resin members (heat switches) 1 and 11 according to the above-described embodiment, one thermally

expandable component

3 and 13 integrated into one

accommodating portion

4 and 14 is accommodated, but according to the present embodiment. In the resin member (heat switch) 21, as shown in FIG. 6, a plurality of thermally expandable components 23 integrated into one housing portion 24 are housed.

Also in this embodiment, similarly to the above-described embodiment, in the resin member (OFF state) 21A, the housing portion 24 includes the thermally expandable component 23 and the void portion 25 at the first temperature (FIG. 4 (a)). Then, in the resin member (ON state) 21B, the temperature in the vicinity of the thermally expandable component 23 reaches the second temperature, and the thermally expandable component 23 expands, for example, to have substantially the same volume as the accommodating portion 24 ( FIG. 4 (b)).

FIG. 7 is an enlarged view of a main part in which the housing part in which a plurality of integrated thermal expansion components 23 are housed among the housing parts 24 of the resin member (heat switch) 21 shown in FIG. 6 is enlarged. As shown in FIG. 7A, when the resin member 21 is in the off state, a plurality of the thermally expandable components 23 that are integrated are accommodated in one accommodating portion 24.

Next, as shown in FIG. 7B, when the resin member 21 is in the ON state, the plurality of thermally

expandable components

23, 23 are expanded, and they are in contact with each other to form an integral thermally expandable component 23. Form. Then, the thermally expandable component 23 formed by integrating the plurality of thermally

expandable components

23, 23 expands, for example, until it has substantially the same volume as the accommodating portion 14. Thereby, like the above-mentioned embodiment, the resin member (heat switch) 21 can change heat conduction reversibly.

Resin member (heat switch) may further contain other components in addition to the components described above. From the viewpoint of further improving the thermal conductivity of the resin member in the on state and further increasing the ratio of the thermal conductivity of the resin member in the on state to the thermal conductivity of the resin member in the off state, the resin member is preferably thermally conductive. It further contains a sex component. In this case, the accommodating part further accommodates the thermally conductive component in addition to the thermally expandable component.

The thermal conductive component is not particularly limited as long as the thermal conductivity at 25 ° C. is 0.1 W / m · K or more, and is appropriately selected according to the purpose of use. The thermally conductive component may contain a metal, a ceramic, a carbon material, a crystalline polymer, a conductive polymer, and the like.

The metal may be, for example, a pure metal or an alloy containing at least one selected from alkali metals, alkaline earth metals, amphoteric metals, transition metals, and rare earths. More specifically, the metal is a pure metal containing at least one selected from Mg, Al, Ti, Fe, Co, Ni, Cu, Zn, Ag, In, Sn, Ru, Au, Pt and Pb, or It may be an alloy. The metal may be in the form of a powder, for example, a powder having a particle size of 5 to 10,000 nm, 10 to 5000 nm, or 50 to 1000 nm.

The ceramic is not particularly limited as long as it is an inorganic solid component, and the above metal is oxidized metal oxide, carbonized metal carbide, nitrided metal nitride, borated metal boride, sulfided Metal sulfides, sulfated metal sulfates, nitrated metal nitrates, phosphorylated metal phosphorous oxides, titanium oxidized metal titanium oxides, semiconductors doped with trace amounts of different elements, etc. It's okay. More specifically, the ceramic includes SiO ₂ , Al ₂ O ₃ , TiO ₂ , ZnO, FeO, Fe ₂ O ₃ , Fe ₃ O ₄ , MgO, CuO, Cu ₂ O, ZrO ₂ , SnO ₂ , ZrO, CaSO ₄ , BaSO ₄ or the like may be used. The ceramic may be in the form of a powder, for example, a powder having a particle size of 5 to 10,000 nm, 10 to 5000 nm, or 50 to 1000 nm.

The carbon material may be diamond, graphite, graphene, carbon nanotube, fullerene, carbon black, graphite, hydrocarbon, a compound obtained by carbonizing a hydrocarbon derivative, or the like. The carbon material may be in the form of a powder, for example, a powder having a particle size of 5 to 10,000 nm, 10 to 5000 nm, or 50 to 1000 nm.

The particle size of the heat conductive component can be measured by a laser diffraction method using a laser diffraction particle size distribution meter.

The content of the thermally conductive component may be, for example, 20 to 50 parts by volume with respect to 100 parts by volume of the thermally expandable component. The volume here means the volume at room temperature (25 ° C.).

The accommodating portion described above can be in various modes other than the above. The accommodating part may be formed with the capsule in one aspect. In this case, the capsule contains a thermally expandable component (and a thermally conductive component used as necessary). The average particle size of the capsules may be, for example, 0.1-100 μm, or 1-30 μm. When the accommodating part is formed with the capsule, it becomes easy to adjust the size of the gap part 5 of the accommodating part 4 in the resin member (OFF state) 1A.

The capsule may be made of a film forming material such as polystyrene, polyacrylonitrile, polyamide, polyacrylamide, ethyl cellulose, polyurethane, melamine resin, aminoplast resin, or the like. These film forming materials can be obtained by a method such as an interfacial polymerization method or an in situ method. The film forming material may be, for example, a synthetic resin or natural resin of gelatin and carboxymethyl cellulose or gum arabic. This synthetic resin is obtained, for example, by a coacervation method.

When the accommodating part is formed of a capsule, the resin member (heat switch) is obtained by the following method in one aspect. That is, for example, a varnish prepared by mixing a matrix resin and a capsule containing a heat-expandable component (and a heat-conductive component used as necessary) with an organic solvent so as to obtain a desired concentration. The switch composition is formed on the base material by coating the base material with a comma coater, bar coater, etc., placing the heat switch composition layer, and then removing the organic solvent by heat drying. A sheet-like heat switch (sheet-like molding material) is obtained.

The organic solvent may be an organic solvent that dissolves the matrix resin, and may be, for example, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, methanol, ethanol, 1-propanol, toluene, xylene, or the like. The substrate is not particularly limited, and may be, for example, a polyethylene terephthalate (PET) sheet, an aluminum foil, a copper foil, or the like. The thickness of the base material is not particularly limited, but may be, for example, 25 μm to 100 μm. In general usage, the base material is peeled and removed after the resin member (heat switch) is attached to the adherend.

From the viewpoint of suppressing streaking during coating, it is preferable to apply the heat switch composition onto the substrate so that the thickness of the heat switch composition layer is equal to or larger than the maximum diameter of the capsule. For example, when a capsule having a particle size (volume average particle size) of 1 to 30 μm is used, the heat switch composition is applied onto the substrate so that the thickness of the heat switch composition layer is 50 to 300 μm. It is preferable. When the thickness of the composition layer for heat switch is 300 μm or less, the organic solvent can be easily removed during heat drying. When the thickness of the heat switch composition layer is larger than 300 μm, for example, a heat switch composition layer having a thickness of 300 μm or less is formed on the base material, and this is separately formed on the base material. It can be obtained by laminating with a laminator or the like on the composition layer.

When the container is formed of a capsule, in another embodiment, for example, the heat switch composition is made into a desired composition, and then the composition is molded by heating and pressurizing using a mold or the like. A heat switch (block-shaped molding material) may be obtained.

In another embodiment, the accommodating portion may be formed by phase separation between the matrix resin and the thermally expandable component. In this case, the resin member (heat switch) is obtained by the following method, for example. That is, first, as a combination of the matrix resin and the thermally expandable component, a combination in which the melting point of the matrix resin is higher than the melting point of the thermally expandable component and is incompatible with each other is selected. Next, for example, the thermally expandable component, the dispersant, and the thermally conductive component are kneaded (primary kneading). Further, the primary kneaded product and the matrix resin are kneaded (secondary kneading). The dispersant is a dispersant for dispersing the thermally conductive component with respect to the thermally expandable component, and is incompatible with the matrix resin.

According to this method, pores (accommodating portions) are formed in a dispersed manner in a matrix phase mainly composed of a matrix resin. And the thermally expansible component containing a heat conductive component is accommodated in the said hole (accommodating part). The thermally conductive component may be unevenly distributed in the thermally expandable component.

As described above, the composition containing the matrix resin and the thermally expandable component is suitable as a composition (heat switch composition) used in the heat switch according to this embodiment. That is, the heat switch according to the present embodiment may be formed of a cured product of the above-described composition (heat switch composition). The composition for heat switches may further contain a heat conductive component.

The content of the matrix resin may be, for example, 10 to 90% by volume, or 20 to 74% by volume based on the total amount of the heat switch composition. The content of the heat-expandable component may be, for example, 10 to 90% by volume, or 20 to 74% by volume, based on the total amount of the heat switch composition. The content of the thermally conductive component may be, for example, 20 to 50 parts by volume with respect to 100 parts by volume of the thermally expandable component. The volume here means a volume at room temperature (25 ° C.) (hereinafter the same).

When the accommodating part in a heat switch (resin member) is formed with a capsule, the composition for heat switch contains the capsule which includes a thermally expansible component (and the heat conductive component used as needed). It may well contain an organic solvent. The capsule content may be, for example, 10 to 90% by volume, or 20 to 74% by volume, based on the total amount of the heat switch composition. The content of the organic solvent may be, for example, 10 to 80% by mass, or 20 to 50% by mass based on the total amount of the heat switch composition.

When the accommodating part in the heat switch (resin member) is formed by phase separation between the matrix resin and the thermally expandable component, the heat switch composition may further contain a dispersant. The content of the dispersant may be, for example, 10 to 80 parts by mass, or 20 to 50 parts by mass with respect to 100 parts by mass of the thermally expandable component.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the following examples.

(Example 1, Comparative Example 1)
Each component was weighed so that the mixing ratio (parts by mass) shown in Table 1 was obtained. Components (1) to (4) in Table 1 are as follows.
(1) 1,3-bis (4,5-dihydro-2-oxazolyl) benzene (manufactured by Mikuni Pharmaceutical Co., Ltd.)
(2) 4,4′-Diaminodiphenylmethane (manufactured by Tokyo Chemical Industry Co., Ltd.)
(3) 1-bromooctane (manufactured by Tokyo Chemical Industry Co., Ltd.)
(4) Hi-Z Million 240M (Mitsui Chemicals)

Next, the components (1) to (3) were mixed and further melt-mixed on a hot plate set at 130 ° C. For Example 1, component (4) was further added here. After the mixture was stirred, both Example 1 and Comparative Example 1 were heat cured on a hot plate set at 180 ° C. for 1 hour. The cured composition was cooled and processed into a size of 10 mm × 10 mm × 0.5 mm to obtain a sample.

(Evaluation)
Regarding the samples obtained in Example 1 and Comparative Example 1, structural changes due to heat were observed. For the observation, a polarizing microscope (ECLIPSE LV10N POL, manufactured by Nikon Corporation) was used. The sample was heated using a hot stage (FP82, manufactured by METTLER TOLEDO), heated from 30 ° C. to 180 ° C. at a heating rate of 20 ° C./min, and then lowered to 30 ° C.

FIG. 8 shows a polarizing microscope photograph of the heat switch before heating (30 ° C., FIG. 8 (a)) and after heating (180 ° C., FIG. 8 (b)) for the sample (heat switch) of Example 1. Indicates. In the photomicrograph, the black portion indicates a void portion (region in which no thermally expandable component exists) in the housing portion. Thereby, in the heat switch (resin member) obtained using the composition for heat switches of the present invention, the volume of the thermally expansible component occupying the accommodating portion is increased by heat (the volume of the void portion occupying the accommodating portion is Reduced). After that, when the temperature was lowered to 30 ° C., it was confirmed that the volume of the thermally expansible component occupying the accommodating portion decreased (the volume of the void portion occupying the accommodating portion) decreased as in FIG. 8A. It was done. On the other hand, in Comparative Example 1 containing no thermally expandable component, no structural change was observed before and after heating.

DESCRIPTION OF

SYMBOLS

1,11,21 ... Resin member (heat switch), 2 ... Matrix resin, 3, 13, 23 ... Thermal expansion component, 4, 14, 24 ... Accommodating part, 6 ... Heat source, 8 ... Temperature control structure.

Claims

Comprising a matrix resin and a thermally expandable component;
In the matrix resin, an accommodating portion for accommodating the thermally expandable component is formed,
The thermally expansible component occupies a part of the accommodating portion at a first temperature, and at a second temperature higher than the first temperature, the thermally expansible component with respect to the accommodating portion at the first temperature. The resin member which occupies the said accommodating part with the volume ratio larger than a volume ratio.
The resin member according to claim 1, wherein the housing portion is formed of a capsule, and the thermally expandable component is included in the capsule.
The resin member according to claim 1 or 2, further comprising a thermally conductive component housed in the housing portion.
Comprising a matrix resin and a thermally expandable component;
In the matrix resin, an accommodating portion for accommodating the thermally expandable component is formed,
A resin member, wherein a thermal expansion coefficient of the thermal expansion component is larger than a thermal expansion coefficient of the matrix resin.
The thermally expansible component is stored away from the wall portion of the storage portion or in contact with a part of the wall portion at the first temperature, and the second temperature is higher than the first temperature. 5. The resin member according to claim 4, wherein the resin is in contact with the wall at an area larger than a contact area between the thermally expandable component and the wall at the first temperature.
Comprising a matrix resin and a thermally expandable component;
In the matrix resin, an accommodating portion for accommodating the thermally expandable component is formed,
The thermally expansible component occupies a part of the accommodating portion at a first temperature, and at a second temperature higher than the first temperature, the thermally expansible component with respect to the accommodating portion at the first temperature. The heat switch which occupies the said accommodating part with the volume ratio larger than a volume ratio.
The heat switch according to claim 6, wherein the accommodating portion is formed of a capsule, and the thermally expandable component is included in the capsule.
The heat switch according to claim 6 or 7, further comprising a heat conductive component housed in the housing portion.
Comprising a matrix resin and a thermally expandable component;
In the matrix resin, an accommodating portion for accommodating the thermally expandable component is formed,
A heat switch, wherein a thermal expansion coefficient of the thermal expansion component is larger than a thermal expansion coefficient of the matrix resin.
The thermally expansible component is stored away from the wall portion of the storage portion or in contact with a part of the wall portion at the first temperature, and the second temperature is higher than the first temperature. 10. The heat switch according to claim 9, wherein the heat switch is in contact with the wall portion at an area larger than a contact area between the thermally expandable component and the wall portion at the first temperature.
A heat switch composition containing a matrix resin and a thermally expandable component.
The composition for a heat switch according to claim 11, further comprising a capsule containing the thermally expandable component.
The composition for heat switches according to claim 11 or 12, further comprising a heat conductive component.
A heat switch comprising a cured product of the composition for a heat switch according to any one of claims 11 to 13.
A heat source for generating heat, and the heat switch according to any one of claims 6 to 10 or 14 arranged so as to be able to conduct heat from the heat source,
The temperature adjustment structure, wherein the heat switch adjusts a temperature caused by heat of the heat source by changing a conduction state of heat from the heat source between a first temperature and a second temperature.