JP6315480B2 - Thermal storage polymer molding - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a heat storage polymer molded article that suppresses a temperature rise due to heat generation, and effectively suppresses the temperature rise with respect to a heat source of a secondary battery such as a lithium ion battery in a battery such as an automobile. It is related with the thermal storage polymer molded object which can be relieved.

  2. Description of the Related Art In automobile parts such as electronic parts mounted on vehicles such as automobiles, the amount of generated heat is increasing with downsizing and high performance. If the amount of heat generated by a component increases, the temperature inside the housing containing the component may increase, and the function of the component or device may be reduced, malfunction, or damage may occur due to the heat. . For this reason, in various automobile parts, heat countermeasure design that suppresses temperature rise due to generated heat is a very important issue.

  For example, secondary battery batteries (battery packs) such as lithium-ion batteries (LIBs), which are expanding in the market as power sources for automobiles such as hybrid vehicles (HEV) and electric vehicles (EV), are reduced in size and output. The heat generated in the secondary battery during charge / discharge during the charge / discharge, etc. stays in the enclosure, and the secondary battery use limit temperature (for example, the use limit temperature is typically 60 ° C. to 70 ° C. for lithium ion batteries). There is a problem that the continuous operation time is limited. In particular, in a lithium ion battery, when the temperature rise is high, the electrolyte becomes unstable, the power generation element deteriorates, the battery performance is reduced, the battery life is shortened, and a high temperature state exceeding the use limit temperature is observed. If the battery continues for a long time, the battery may be damaged. Therefore, it is necessary to take measures against heat so that the battery temperature does not rise excessively.

  Automobiles are also used in thermally severe environments such as under the hot summer sun, and when used in such a high temperature environment, the outside temperature of the car becomes high, so that a housing containing a secondary battery as a heat source. And the temperature difference between it and its surroundings becomes smaller. For this reason, heat dissipation by convection heat or conduction heat is inefficient and limited, and in such an environment where the temperature difference from the surrounding environment is small, the temperature rises quickly and the time for continuous operation for a long time is reduced. It is difficult to secure. Therefore, it is important to be able to effectively suppress the temperature rise due to environmental changes.

  Here, as a heat countermeasure member of the heat source, Patent Document 1 discloses a heat storage silicone material in which silicone rubber is filled with heat conductive particles and microencapsulated heat storage material particles. A heat countermeasure member made of a silicone elastomer filled with a conductive filler and paraffin wax powder is disclosed.

  Patent Document 3 discloses a heat storage member that includes a honeycomb structure made of a resin having a large number of cells, and each cell is filled with a capsule containing a heat storage material and a thermally conductive filler. Has been. According to Patent Document 3, by filling a honeycomb structure with a capsule containing a heat storage material and a thermally conductive filler, even if the heat storage member is thick, the thermal conductivity is good, and the spacecraft has an internal structure. It is described that the present invention can also be applied to a set electronic device.

  Further, regarding a battery of a secondary battery, Patent Document 4 discloses a heat absorption made of a phase change material such as paraffin so that a heat sink connected to an electrical connection between a battery module and a cell can easily dissipate heat. It is described that a heat sink is composed of a material and a sheet member including a fiber-shaped member having a high thermal conductivity such as a metal yarn or a graphite yarn.

JP 2014-208728 A JP 2012-102264 A JP 2011-178867 A Special table 2012-523085 gazette

Here, as a heat countermeasure for a heat source (hereinafter also referred to as a heat dissipation object), in a design that suppresses the temperature rise of the heat dissipation object by contacting a heat countermeasure member, the heat of the heat dissipation object is contained in the heat dissipation object. It is necessary to quickly transfer heat from the object of heat dissipation so as not to stay. The quicker the heat transfer, the better the adhesiveness with the object to be radiated, and the better the adhesiveness, the lower the hardness of the heat countermeasure member.
In particular, in the case of a design in which a thermal countermeasure member is brought into contact with a secondary battery such as a lithium ion battery, when the secondary battery itself thermally expands, the thermal expansion is hindered by the thermal countermeasure member, and the secondary battery has a thermal countermeasure. There is a possibility that a situation may occur in which stress due to the member is applied and the secondary battery is damaged. In order to prevent this, it is necessary to absorb the stress and prevent the internal pressure from being applied to the housing that houses the secondary battery. In addition, in a secondary battery module in which a plurality of cells such as lithium ion batteries are connected in order to increase the capacity, it is necessary to absorb the dimensional tolerance of each cell and prevent temperature variation between the cells. Also from these things, it is desirable that the heat countermeasure member brought into contact with the heat dissipation object such as the secondary battery has low hardness.

  However, in the inventions of Patent Document 1 and Patent Document 2, the heat conductive filler is added in a large amount, and the heat conductivity performance as a material is good. As a result, the molded body is less likely to achieve the desired temperature rise suppression performance due to the loss of rapid movement of heat.

  Further, the invention of Patent Document 3 is a structure in which a capsule in which a heat storage material is encapsulated and a thermal conductive filler are filled in a cell of a honeycomb structure formed of metal or the like. Since shape retention for holding the filler is necessary, it is difficult to reduce the hardness. Although there is a description that the shape can be changed with a simple tool, the degree of freedom of forming is basically low and the application range is limited.

Furthermore, in the structure in which the heat-absorbing material or the fiber-based member is disposed on the heat sink of Patent Document 4, the heat sink has a structure connected by inserting an electrical connection portion into a slit provided in the heat sink. For this reason, shape retention is important as in Patent Document 3, and it is difficult to reduce the hardness.
Therefore, in the inventions of Patent Document 3 and Patent Document 4, it is difficult to obtain a desired temperature rise suppression performance as in the inventions of Patent Document 1 and Patent Document 2.

  Therefore, the present invention can increase the adhesion to the object to be radiated, can absorb the stress when the object to be radiated expands, and increase the temperature of the object to be radiated even in an environment where the temperature difference from the surroundings is small. An object of the present invention is to provide a heat storage polymer molded body having a high effect of suppressing and relaxing.

The heat storage polymer molded article of claim 1 comprises a thermoplastic base polymer, a heat conductive filler, and a latent heat storage material made of paraffins or fatty acids that absorb heat when the phase changes from a solid phase to a liquid phase. The molded polymer composition is molded, and the molded product obtained by molding the polymer composition has a Shore A hardness of 30 or more and a Shore D hardness of 60 or less.
Here, the Shore A hardness is a measured value of a durometer type A (JIS A hardness meter) according to JIS K6253 at normal temperature (25 ° C.), and the Shore D hardness is a durometer type D (JIS D hardness according to JIS K6253). The measured value at room temperature (25 ° C.).
In the heat storage polymer molded body of claim 1, the heat conductive filler is blended in the range of 20 parts by weight to 1060 parts by weight with respect to 100 parts by weight of the thermoplastic base polymer, and the heat storage material is 560 parts by weight to 1100 parts. It is blended within the range of parts by weight.

The heat storage polymer molded body of claim 2 comprises a thermoplastic base polymer made of polyvinyl chloride resin , a thermally conductive filler , and paraffins or fatty acids that absorb heat when the phase changes from a solid phase to a liquid phase. A polymer composition containing the latent heat storage material is molded, and the molded product obtained by molding the polymer composition has a Shore A hardness of 30 or more and a Shore D hardness of 60 or less.
Here, the Shore A hardness is a measured value of a durometer type A (JIS A hardness meter) according to JIS K6253 at normal temperature (25 ° C.), and the Shore D hardness is a durometer type D (JIS D hardness according to JIS K6253). The measured value at room temperature (25 ° C.).

  The heat storage polymer molded body according to claim 3 is a latent heat storage material in which the heat storage material has a phase change temperature in a range of 20 ° C. or more and less than 50 ° C.

  In the heat storage polymer molded body according to claim 4, the total maximum blending amount of the heat conductive filler and the heat storage material in the polymer composition is 95% by weight.

  According to the heat storage polymer molding of the invention of claim 1, the heat conductive filler and the heat storage material are contained. Since a heat conduction path is secured by the contained thermal conductive filler, the heat of the heat dissipation object is easily conducted when it is brought into contact with the heat dissipation object, and the heat conducted from the heat dissipation object is a heat storage polymer molded body. Easily diffuses into. Furthermore, since the heat storage polymer molded body contains a heat storage material, the heat diffused in the heat storage polymer molded body is stored in the heat storage material and also radiated to the outside of the periphery of the object to be radiated. For this reason, even in an environment where the temperature difference between the heat radiation object and the outside of the periphery of the heat radiation object is small, the heat of the heat radiation object can be released to suppress and mitigate the temperature rise. In particular, since the heat storage polymer molded body has a Shore A hardness of 30 or more and a Shore D hardness of 60 or less, the heat storage polymer molded body can have good adhesion to the heat dissipation object and the heat dissipation object is When it expands, the stress can be absorbed efficiently, and the effect of suppressing the temperature rise of the object to be radiated can be exhibited stably.

Here, when the Shore A hardness is less than 30 at room temperature, troubles are likely to occur when the molded body is formed by injection molding or extrusion molding. On the other hand, if the Shore D hardness exceeds 60, When the heat radiation object swells, the stress cannot be absorbed and it is difficult to suppress an increase in internal pressure.
Therefore, when the Shore A hardness is 30 or more and the Shore D hardness is within the range of 60 or less, the moldability is good and good adhesion to the heat dissipation object can be secured, and when the heat dissipation object expands The stress can be absorbed efficiently.
In addition, since the base polymer is thermoplastic, it can be molded into complex shapes by taking advantage of the thermoplastic properties, and can be adapted to the shape and size of the object to be radiated. The degree of freedom (the degree of freedom of shape selection) is high, and it can be applied to a wide range of heat dissipation objects.

In the heat storage polymer molded body of the invention of claim 1, the heat conductive filler is blended in the range of 20 parts by weight to 1060 parts by weight with respect to 100 parts by weight of the thermoplastic base polymer, and the heat storage material is 560 parts by weight. It mix | blends within the range of -1100 weight part.
Here, if the blending ratio of the heat conductive filler is too small, sufficient thermal conductivity to move the heat of the heat dissipation object cannot be obtained, and even if a heat storage material is mixed, the temperature increase of the heat dissipation object is remarkably suppressed. The effect of mitigating is not obtained. On the other hand, if the blending ratio is too large, the fluidity at the time of preparing the polymer composition is lowered and the moldability is lowered, or the heat storage polymer molded body becomes too higher than the predetermined hardness so that it adheres to the object to be radiated. The sex will be reduced. As a result, the heat of the heat dissipation object cannot be effectively released, and the effect of suppressing and relaxing the temperature increase of the heat dissipation object is reduced.
Also, if the blending ratio of the heat storage material is too small, a sufficient amount of heat storage cannot be obtained, and the temperature rise of the heat dissipation object is remarkably suppressed when there is a small temperature difference from the surrounding environment surrounding the heat dissipation object. The effect of mitigating is not obtained. On the other hand, if the blending ratio is too large, the blending amount of the base polymer in the polymer composition is reduced, and the required strength cannot be obtained, and molding itself may be difficult.
The composition of the heat conductive filler is in the range of 20 to 1060 parts by weight with respect to 100 parts by weight of the base polymer, and the composition of the heat storage material is in the range of 560 to 1100 parts by weight with respect to 100 parts by weight of the base polymer. If it is inside, the shaping | molding with required intensity | strength will be attained, and coexistence with desired heat conductivity, heat storage, and low hardness is ensured. As a result, even in an environment where the temperature difference from the surroundings is small, it is possible to reliably suppress and alleviate the temperature rise of the heat dissipation object.

According to the heat storage polymer molding of the invention of claim 2 , the heat conductive filler and the heat storage material are contained. Since a heat conduction path is secured by the contained thermal conductive filler, the heat of the heat dissipation object is easily conducted when it is brought into contact with the heat dissipation object, and the heat conducted from the heat dissipation object is a heat storage polymer molded body. Easily diffuses into. Furthermore, since the heat storage polymer molded body contains a heat storage material, the heat diffused in the heat storage polymer molded body is stored in the heat storage material and also radiated to the outside of the periphery of the object to be radiated. For this reason, even in an environment where the temperature difference between the heat radiation object and the outside of the periphery of the heat radiation object is small, the heat of the heat radiation object can be released to suppress and mitigate the temperature rise. In particular, since the heat storage polymer molded body has a Shore A hardness of 30 or more and a Shore D hardness of 60 or less, the heat storage polymer molded body can have good adhesion to the heat dissipation object and the heat dissipation object is When it expands, the stress can be absorbed efficiently, and the effect of suppressing the temperature rise of the object to be radiated can be exhibited stably.

Here, when the Shore A hardness is less than 30 at room temperature, troubles are likely to occur when the molded body is formed by injection molding or extrusion molding. On the other hand, if the Shore D hardness exceeds 60, When the heat radiation object swells, the stress cannot be absorbed and it is difficult to suppress an increase in internal pressure.
Therefore, when the Shore A hardness is 30 or more and the Shore D hardness is within the range of 60 or less, the moldability is good and good adhesion to the heat dissipation object can be secured, and when the heat dissipation object expands The stress can be absorbed efficiently.
In addition, since the base polymer made of polyvinyl chloride resin is thermoplastic, it can be molded into complex shapes by taking advantage of its thermoplastic properties, and can accommodate the shape and size of heat dissipation objects. Thus, the moldability and the degree of freedom of forming (the degree of freedom of shape selection) are high, and it can be applied to a wide range of heat dissipation objects.

  According to the heat storage polymer molded body of the invention of claim 3, the heat storage material is a latent heat storage material having a phase change temperature in a range of 20 ° C or higher and lower than 50 ° C. Since the heat storage material is a latent heat storage material having a phase change temperature within a range of 20 ° C. or more and less than 50 ° C., heat from the heat radiation target can be quickly taken in, and heat from the heat radiation target can be sufficiently stored. it can. Thereby, the temperature rise of the heat dissipation object can be efficiently suppressed.

  According to the heat storage polymer molded body of the invention of claim 4, the total amount of the heat conductive filler and the heat storage material in the polymer composition is 95% by weight at the maximum. By setting the total blending amount of the heat conductive filler and the heat storage material to 95% by weight or less, it becomes possible to keep the hardness of the heat storage polymer molded body within a predetermined range.

FIG. 1 is an explanatory view of an evaluation test apparatus for the temperature rise suppression effect. FIG. 2 is a test for evaluating the temperature rise suppression effect by the heat storage polymer molded body according to Example 1 of the present invention, and the relationship between the heat dissipation object and the heat storage polymer molded body when the evaluation test is performed under temperature adjustment of 20 ° C. It is the graph which showed the time-dependent measurement result of the temperature of a boundary surface by the comparison with a comparative example. FIG. 3 is a test for evaluating the temperature rise suppression effect by the heat storage polymer molded body according to Example 1 of the present invention, and the relationship between the heat dissipation object and the heat storage polymer molded body when the evaluation test is performed under temperature adjustment of 35 ° C. It is the graph which showed the time-dependent measurement result of the temperature of a boundary surface by the comparison with a comparative example. FIG. 4 shows the boundary between the heat radiation object and the heat storage polymer molded body when the evaluation test of the temperature rise suppression effect is performed under the temperature adjustment of 35 ° C. for the heat storage polymer molded bodies according to Examples 2 to 9 of the present invention. It is the graph which showed the measurement result of the temperature of the surface with time.

Embodiments of the present invention will be described below.
The heat storage polymer molded body of the present embodiment is formed by molding a polymer composition containing a thermoplastic base polymer, a thermally conductive filler, and a heat storage material.

  As the thermoplastic base polymer, a thermoplastic resin can be used. For example, polyamide 46 (PA46) resin, polyamide (PA) resin (nylon, etc.) belonging to engineering plastic (engineering plastic), polyacetal (POM) resin, polycarbonate (PC) Resin, modified polyphenylene ether resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, glass fiber reinforced polyethylene terephthalate resin, cyclic polyolefin resin, and polytetrafluoroethylene belonging to super engineering plastics (super engineering plastics) (PTFE) resin, polysulfone (PSF) resin, polyethersulfone (PES) resin, amorphous polyarylate (PAR) resin, liquid crystal polymer (LCP) resin Polyetheretherketone (PEEK) resin, polyphenylene sulfide (PPS) resin, polyamideimide resin, etc., polyethylene (PE) resin, polypropylene (PP) resin, polyvinyl chloride (PVC) resin, polystyrene (PS) belonging to general-purpose resin Resin, polyvinyl acetate (PVAc) resin, ABS resin, acrylonitrile styrene (AS) resin, acrylic (PMMA) resin, etc. are mentioned, These 1 type can be used individually or in combination of 2 or more types.

  Thermoplastic elastomers can also be used, for example, styrene-based thermoplastic elastomer (TPS), olefin-based thermoplastic elastomer (TPO), vinyl chloride-based thermoplastic elastomer (TPVC), polyurethane-based thermoplastic elastomer (TPU), polyamide-based, for example. A thermoplastic elastomer (TBA), a polyester-type thermoplastic elastomer (TPEE), etc. are mentioned, These 1 type can be used individually or in combination of 2 or more types.

  When practicing the present invention, among these, materials having high heat resistance, mechanical properties, chemical resistance, incombustibility (low combustibility), self-extinguishing properties, etc., electrical and electronic equipment parts materials, automobile parts Styrenic, olefinic, and vinyl chloride thermoplastic resins and thermoplastic elastomers that can be widely used for materials and the like are preferable. In particular, by using a material having a relatively low melting temperature, such as a polyvinyl chloride resin, it is not necessary to use a high temperature condition at the time of molding, so the range of available heat storage materials can be widened. That is, when the melting temperature of the polymer material as the base is high, it is necessary to apply a high amount of heat at the time of molding, so when a heat storage capsule is used as a heat storage material to be described later, it will melt depending on the material of the capsule, There is a risk of the heat storage material oozing out. However, when such a polymer material having a relatively low melting temperature is used, such a problem does not occur, so the degree of freedom in selecting a heat storage material can be increased.

  The blending of the thermoplastic base polymer is preferably in the range of 5 to 40% by weight in the polymer composition. If the blending ratio is too small, it becomes brittle and the strength is insufficient. On the other hand, if the blending ratio is too large, the blending ratio of the heat conductive filler and the heat storage material in the entire polymer composition decreases. The effect of suppressing the increase cannot be obtained sufficiently and becomes impractical. If the blend of the thermoplastic base polymer is within the range of 5 wt% to 40 wt% in the entire polymer composition, stable strength can be ensured in the obtained heat storage polymer molded body, and effective for heat dissipation objects. A temperature rise suppression effect can be exhibited.

  The thermally conductive filler may be electrically insulating or conductive. Examples of the insulating thermally conductive filler include aluminum oxide, magnesium oxide, titanium oxide, zinc oxide, silicon oxide, and beryllium oxide. Metal oxides such as copper oxide, zirconium oxide, calcium oxide, metal nitrides such as boron nitride, aluminum nitride, silicon nitride, boehmite, aluminum hydroxide, magnesium hydroxide, zinc hydroxide, calcium hydroxide, water Examples thereof include metal hydroxides such as tin oxide, carbon compounds such as silicon carbide and diamond, magnesite, magnesium carbonate, titanium boride, calcium titanate, and quartz.

Examples of the conductive thermal conductive filler include carbon compounds such as graphite, carbon black, graphite, carbon fiber (especially coal pitch (Pitch) and PAN are preferred), carbon nanotube (CNT), and carbon nanofiber (CNF). Alternatively, metal compounds such as silver, copper, nickel, aluminum, stainless steel, titanium, and SUS, metal fibers such as metal fibers, tin oxide, and metal compounds such as ferrites can be used.
In addition, it is also possible to use an insulating filler in which an insulating property is imparted to the conductive filler by covering the conductive thermal conductive filler with silica or the like, and this can be used as the thermal conductive filler. The thermally conductive filler may be subjected to surface treatment such as silane coupling treatment, titanate coupling treatment, epoxy treatment, urethane treatment, oxidation treatment, and the like. By performing such surface treatment, the affinity with the resin interface is improved, and workability such as mixing and kneading is easy. Furthermore, a small amount of impurities derived from raw materials or the like may be included as long as high thermal conductivity can be achieved.

These can be used singly or in combination of two or more, but the insulating or conductive electrical characteristics are selected according to the member using the heat storage polymer molded body.
As for the insulating thermally conductive filler, a nitrogen compound such as boron nitride is preferable from the viewpoint of thermal conductivity, warpage of the molded body, and the like. Boron nitride includes c-BN (cubic structure), w-BN (wurtzite structure), h-BN (hexagonal crystal structure), r-BN (rhombohedral crystal structure), and t-BN (turbulent layer structure). The hexagonal structure type having a structure similar to graphite is preferable. By using boron nitride having a hexagonal crystal structure, it is possible to reduce wear of a molding machine and a mold used when obtaining a molded body. In addition, the boron nitride has a spherical shape and a scaly shape, and any of them can be used in the present invention. When a scaly shape is used, it has excellent insulation and good mechanical properties. Can be obtained.
The conductive thermal conductive filler is preferably a carbon compound such as carbon fiber because it is inexpensive and can effectively improve thermal conductivity and conductivity.

The shape of the heat conductive filler is, for example, fiber, plate, sphere, scale, rod, particle, powder, rod, tube, curved plate, needle, curved plate, needle However, any shape can be used.
The median diameter (≈average particle diameter) of the thermally conductive filler is preferably in the range of 1 μm to 300 μm, more preferably in the range of 2 μm to 250 μm. If the particle size of the thermally conductive filler is too small, aggregation is likely to occur during preparation of the polymer composition, resulting in poor uniform high dispersibility and poor moldability. As a result, stable heat conductivity may not be ensured in the heat storage polymer molded body. And since a moldability is inferior, adhesiveness with a heat dissipation target object falls, and there exists a possibility that the heat conductive effect by a thermal storage polymer molded object may fall. On the other hand, if the particle size is too large, the filling property is lowered, the distribution is not uniform, and sufficient thermal conductivity may not be obtained stably. Moreover, there is a possibility of adversely affecting the appearance, and further, when formed into a sheet shape, it may become brittle and easy to tear. When the median diameter (≈average particle diameter) of the thermally conductive filler is in the range of 1 μm to 300 μm, more preferably in the range of 2 μm to 250 μm, stable high thermal conductivity can be ensured. In addition, when two or more kinds having different median diameters (≈average particle diameters) are mixed, the filling property can be improved by combining the small diameter particles and the large diameter particles.

Incidentally, according to the definition of terms in the text and explanation of JIS Z 8901 “Test Powder and Test Particles”, the median diameter is the number (or mass) larger than a certain particle diameter in the particle size distribution of the powder. ) is the particle diameter when occupying 50% of its Zenkonatai (diameter), i.e., a particle size of oversized 50%, usually expressed as the median diameter or 50% particle size and good D _50. By definition, the size of the particle group is expressed by the average particle diameter and the median diameter, but here, it is a value measured by the display of the product description and the laser diffraction / scattering method.
The “median diameter measured by the laser diffraction / scattering method” is a particle whose cumulative weight part is 50% in the particle size distribution obtained by the laser diffraction / scattering method using a laser diffraction particle size distribution measuring apparatus. This refers to the diameter (D ₅₀ ).
The above numerical values are not strict, but are approximate, and are naturally approximate values including errors due to measurement and the like, and do not deny errors of several percent. From the viewpoint of this error, the difference from the average particle diameter is also very small, the average particle diameter is approximately the median diameter, and the average particle diameter can be regarded as the median diameter.

  In addition, it is preferable that the thermal conductive filler has a thermal conductivity in the range of 0.2 W / (m · K) to 200 W / (m · K). When the thermal conductivity is small, it is necessary to add a large amount in order to ensure sufficient thermal conductivity, and it becomes difficult to achieve low hardness of the heat storage polymer molded body. On the other hand, those with high thermal conductivity are expensive and difficult to obtain. By using a thermally conductive filler having a thermal conductivity in the range of 0.2 W / (m · K) to 200 W / (m · K), both high thermal conductivity and low hardness are ensured, and Cost reduction can be achieved.

Here, the blend of the heat conductive filler is set so as to satisfy both the desired hardness and heat conductivity in the heat storage polymer molded body, and is used alone or in combination. If the blending ratio of the thermal conductive filler is too small, sufficient thermal conductivity to move the heat of the object to be radiated cannot be obtained, and even if a heat storage material is blended, the temperature rise of the object to be radiated is remarkably suppressed and mitigated. The effect is not obtained. On the other hand, if the blending ratio is too large, the fluidity at the time of preparing the polymer composition is lowered and the moldability is lowered, or the hardness of the heat storage polymer molded body is increased, so that the adhesion to the heat dissipation object is increased. It reduces, and the effect which suppresses and eases the temperature rise of a thermal radiation target object falls. Further, when the hardness of the heat conductive filler alone cannot be set to a desired range, the desired range is obtained by combining with another heat conductive filler.
Therefore, the blend of the thermally conductive filler is preferably in the range of 20 parts by weight to 1060 parts by weight with respect to 100 parts by weight of the thermoplastic base polymer. Within this range, both high thermal conductivity and low hardness are ensured in the heat dissipation object, and the temperature of the heat dissipation object can be increased even in an environment where the temperature difference from the surroundings (the outside of the periphery of the heat dissipation object) is small. It can be effectively suppressed and relaxed.

As heat storage materials, latent heat storage materials, sensible heat storage materials, chemical heat storage materials can be mentioned due to differences in heat storage methods, but from the viewpoint of heat storage (heat storage density, etc.), stability, safety, cost, durability, etc. A latent heat storage material composed of a phase change material having latent heat when the phase of the material changes at a specific temperature is optimal.
Here, examples of the latent heat storage material include a solid-liquid phase transition type latent heat storage material, an electronic phase transition type latent heat storage material, and a solid-solid phase transition type latent heat storage material.

Specifically, examples of the electronic phase transition type latent heat storage material include vanadium oxide, LiMn ₂ O ₄ , LiVS ₂ , LiVO ₂ , NaNiO ₂ , REBaFe ₂ O ₅ , REBaCo ₂ O _5.5 (where RE is Y , Sm, Pr, Eu, Gd, Dy, Ho, Tb and other rare earth elements).
Solid-solid phase transition type latent heat storage materials include, for example, materials that cause martensite transformation (shape memory alloys such as NiTi, CuZnAl, CuAlNi), thermochromic materials (N, N-diethylethylenediamine copper complex, etc.), plastic viscosity Crystals (trimethylolethane, pentaerythritol, neopentyl glycol, etc.), magnetic phase transition materials (Mn—Zn ferrite, NiFe alloy, etc.), paraelectric-ferroelectric transition materials (BaTiO _3, etc.) can be mentioned.

  Solid-liquid phase transition type latent heat storage materials include n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, n-eicosane, n-nonadecane, n-icosane, n-henicosane, n- Docosan, n-tricosane, n-tetracosane, n-pentacosane, n-hexacosan, n-heptacosane, n-octacosane, n-nonacosane, n-triacontane, n-hentriacontane, n-dotriacontane, n-triacon Paraffins such as triacontane and paraffin wax, capric acid, caproic acid, caprylic acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, Henicosylic acid, behenic acid, lignocelli Fatty acids (including fatty acid esters) such as acid, triacontanoic acid, hydroxystearic acid, sebacic acid, crotonic acid, elaidic acid, erucic acid and nervonic acid, and aromatic hydrocarbon compounds such as naphthalene, benzene and p-xylene And alcohols such as cetyl alcohol, stearyl alcohol, tetradecanol, dodecanol, xylitol, erythritol, pentaerythritol, mannitol, sorbitol, galactitol, threitol, polyethylene glycol, amides such as propionamide, acetamide, Polyethylene, calcium chloride hydrate, sodium acetate hydrate, potassium acetate hydrate, sodium hydroxide hydrate, potassium hydroxide hydrate, strontium hydroxide hydrate, barium hydroxide hydrate, chloride Sodium water Japanese hydrate, Magnesium chloride hydrate, Zinc chloride hydrate, Lithium nitrate hydrate, Magnesium nitrate hydrate, Calcium nitrate hydrate, Aluminum nitrate hydrate, Cadmium nitrate, Iron nitrate hydrate, Zinc nitrate Hydrate, manganese nitrate hydrate, lithium sulfate hydrate, sodium sulfate hydrate, sodium thiosulfate hydrate, magnesium sulfate hydrate, calcium sulfate hydrate, potassium aluminum sulfate hydrate, aluminum sulfate Ammonium hydrate, sodium thiosulfate hydrate, potassium phosphate hydrate, sodium phosphate hydrate, potassium hydrogen phosphate hydrate, sodium hydrogen phosphate hydrate, sodium borate hydrate, odor Calcium hydrate, potassium fluoride hydrate, sodium carbonate hydrate, calcium chloride hexahydrate, potassium bicarbonate aqueous solution, sodium sulfate decahydrate And the like of the inorganic hydrate-inorganic eutectic material is.

Among these, as the latent heat storage material, it is preferable to use a solid-liquid phase transition type latent heat storage material.
This solid-liquid phase change type latent heat storage material is a phase change type that changes phase from solid phase to liquid phase when absorbing heat, and stores (absorbs) heat by the latent heat of the phase change (melting). It is a heat storage material (phase change material). Among solid-liquid phase transition type latent heat storage materials, especially organic compounds such as paraffins and fatty acids (including fatty acid esters) have a relatively large latent heat and a large amount of heat storage per unit volume. Even if it repeats, stable heat dissipation and heat storage action are obtained. In addition, it is difficult to corrode, is inexpensive, and the phase change temperature (melting point) can be easily adjusted according to the molecular weight, etc., so there are many material types with different phase change temperatures (melting points), and there is a wide selection of materials. wide. For this reason, it is preferably used.

  In addition, these latent heat storage materials may be used individually by 1 type, and may use the mixture and eutectic of 2 or more types of materials, and also other subcomponent ( You may use the mixture which added benzoic acid, urea, water, etc.).

In particular, when using a phase change material such as a solid-liquid phase transition type as the latent heat storage material, a material corresponding to the required phase change temperature (corresponding to the melting point in the case of a solid-liquid phase change type phase change material) That is, a material having a phase change temperature (melting point) in a target temperature range is selected. For example, when the heat storage polymer molded body of the present embodiment is applied to a battery of a lithium ion electric ground mounted on an automobile, the phase change is within the operating temperature range (temperature change range) of the battery (heat dissipation object). By using a solid-liquid phase transition type latent heat storage material having a temperature (melting point), when the temperature of the battery is about to rise, the heat of fusion of the phase change is caused by the phase change of the latent heat storage material from solid to liquid. Therefore, it is possible to suppress an increase in battery temperature. Specifically, those having a phase change temperature in the range of 20 ° C. or more and less than 50 ° C. are preferable from the viewpoints of performance and durability. When the phase change temperature is less than 20 ° C., the heat storage capacity immediately exceeds the limit at a high temperature, and the temperature rise of the battery cannot be effectively suppressed. Further, even when the battery is not operating, the phase change is likely to be repeated due to the temperature change around the battery, so that the performance is deteriorated and the speed of deterioration is high and the durability is insufficient. On the other hand, since the use limit temperature of the lithium ion electric field is usually 60 ° C. to 70 ° C., the phase change temperature of 50 ° C. or more can hardly use the latent heat of the phase change, until the phase change and the heat storage. In addition, the heat generation temperature of the battery becomes too high, and the operation time of the lithium ion electric field cannot be extended. By using a latent heat storage material having a phase change temperature in the range of 20 ° C. or more and less than 50 ° C., heat from the object to be radiated can be quickly taken in, and heat from the object to be radiated can be sufficiently stored. It is possible to efficiently suppress the temperature rise of the heat dissipation object.
Two or more materials having different phase change temperatures (melting points) can be mixed and used.

Incidentally, the solid-liquid phase transition type latent heat storage material changes into a liquid at the melting point or higher. It may be used as a heat storage capsule (microcapsule). Since the latent heat storage material is encapsulated in the capsule, the shape is stabilized, so that the handling becomes easy and the dispersion stability is high. For this reason, the heat storage property of the heat storage material can be fully utilized, and a high heat storage effect can be obtained even with a small amount.
In addition, as a membrane material (capsule membrane material) constituting the outer shell of the heat storage capsule, polystyrene, acrylic, polyacrylonitrile, polyamide, polyacrylamide obtained by a technique such as an interfacial polymerization method or an in-situ method, Examples thereof include resins such as ethyl cellulose, polyurethanes, aminos, and melamine, and resins using a coacervation method of carboxymethyl cellulose or gum arabic and gelatin. Among these, a film material that forms a thermosetting resin film that is physically and chemically stable, thermally strong, and has good workability is preferable. For example, a melamine resin film or urea resin film formed by an in situ method is preferable. The heat storage capsule used is preferred.

The heat storage capsule containing the heat storage material has a volume average particle diameter of 50% by the laser diffraction particle size distribution (the cumulative volume part is 50% in the particle size distribution obtained by the laser diffraction / scattering method using the laser diffraction particle size distribution measuring device). It is preferable to use a particle having a particle diameter (D ₅₀ ) of 1 μm to 100 μm. If the volume average particle size is too small, the polymer composition may be broken by physical pressure (external force such as mechanical shearing force or impact) at the time of preparation or molding of the polymer composition. In addition, the viscosity increases during the preparation of the polymer composition, the uniform high dispersibility decreases, and the moldability also deteriorates. As a result, there is a possibility that stable and sufficient heat storage property may not be exhibited in the heat storage polymer molded body. Furthermore, since the formability is inferior, the adhesiveness with the heat radiating object may be reduced, and the temperature rise suppressing effect of the heat radiating object may be reduced. On the other hand, when the volume average particle diameter is too large, the filling property is lowered, the uniform distribution is lacking, and it is difficult to ensure a stable and high heat storage property. By using a heat storage capsule having a volume average particle diameter in the range of 1 μm to 100 μm, a stable and sufficient heat storage property can be obtained. A more preferable volume average particle diameter is in the range of 5 μm to 50 μm.
Further, the shape of the heat storage material or the heat storage microcapsule including the heat storage material is not particularly limited, and for example, a spherical shape, an elliptical shape, a daruma shape, a weight shape, a box shape, a rod shape, or the like is used. The heat storage capsule may be blended in any form such as a sheet, pellet, gel, particle (powder), granule, or liquid. In addition, when implementing this invention, the thing etc. which packed the heat storage material with resin etc. other than the heat storage capsule which included the heat storage material are also possible, for example.

  Here, the blending of the latent heat storage material is preferably in the range of 40 to 1100 parts by weight with respect to 100 parts by weight of the thermoplastic base polymer. If the blending ratio is too small, a sufficient amount of heat storage cannot be obtained, and when the temperature difference between the object to be radiated and the surroundings of the object to be radiated is small, an effect of remarkably suppressing and relaxing the temperature rise of the object to be radiated is obtained. I can't. On the other hand, when there are too many compounding ratios, the compounding quantity of the thermoplastic base polymer in a polymer composition will decrease, and required intensity | strength will not be obtained, and shaping | molding itself will become impossible depending on the case. If the composition of the heat storage capsule is in the range of 40 to 1100 parts by weight with respect to 100 parts by weight of the thermoplastic base polymer, the heat storage polymer molded body can be molded with the required strength, and the hardness is reduced. In addition, it is possible to ensure both high heat storage properties. Thereby, even in an environment where the temperature difference from the surroundings is small, it is possible to effectively suppress and mitigate the temperature rise of the heat dissipation object.

Further, the heat storage material preferably has a heat storage amount in the range of 10 KJ / m ² (KJ / Kg ) to 250 KJ / m ² (KJ / Kg ). When the amount of heat storage is small, especially when the temperature difference between the object to be radiated and the surroundings of the object to be radiated is small, the amount of heat of the object to be radiated cannot be stored so that the temperature rise of the object to be radiated can be significantly suppressed I do not get. Although it is conceivable to add a large amount of the heat storage material in order to ensure sufficient heat storage properties, it is difficult to achieve low hardness in the heat storage polymer molded body when a large amount of the heat storage material is mixed. On the other hand, those having a heat storage amount of 250 KJ / m ² (KJ / Kg ) are expensive. An environment where high heat storage is ensured and the temperature difference from the surroundings is small by using a heat storage material having a heat storage amount in the range of 10 KJ / m ² (KJ / Kg ) to 250 KJ / m ² (KJ / Kg ). Even underneath, the temperature rise of the heat dissipation object can be effectively suppressed and mitigated.

  The heat storage polymer molded body of the present embodiment is formed from a polymer composition containing at least a thermoplastic base polymer, a heat conductive filler, and a heat storage material. The reinforcing filler for improving the strength and rigidity can be blended into the polymer composition as long as the hardness of the heat storage polymer molded body is within a predetermined hardness range.

  As the reinforcing filler appropriately blended in the polymer composition of the present embodiment, for example, silica, talc, mica, kaolin, bentonite, pyroferrite, wollastonite, calcium carbonate, barium sulfate, potassium titanate, zonotrite, Various fiber systems such as gypsum fiber, aluminum borate, MOS, aramid fiber, carbon fiber (carbon fiber), glass fiber (glass fiber, chopped fiber, milled fiber), glass flake, polyoxybenzoyl whisker, etc. Species can be used alone or in combination of two or more.

Further, when the present invention is carried out, in order to improve flexibility, workability, etc., polybutene, polyisobutylene, process oil (paraffinic process oil, etc.), phthalate ester, epoxy ester, nitrile -Based and chlorinated softeners, especially when a thermoplastic resin is used for the base polymer, the plasticizer is used to plasticize the thermoplastic resin as necessary, to improve dispersibility and to improve workability and flexibility. Is blended. The plasticizer is not particularly limited as long as it can impart plasticity to the polymer composition. Examples of the plasticizer for the vinyl chloride resin-based thermoplastic resin include dibutyl phthalate (DBP), dihexyl phthalate (DHP), Di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate (DnOP), diisooctyl phthalate (DIOP), didecyl phthalate (DDP), dinonyl phthalate (DNP), diisononyl phthalate (DINP), dimethyl phthalate (DMP), diethyl phthalate (DEP), bis-2-ethylhexyl phthalate (DEHP), diisodecyl phthalate (DIDP), C ₆ ~C ₁₀ mixed higher alcohols phthalate, butyl benzyl phthalate (BBP), octyl benzyl phthalate, Noniruben Rufutareto, esters such as dimethyl cyclohexyl phthalate (DMCHP) or, polyester of adipic acid, polyesters such as phthalic acid-based polyester is used. These can be used singly or in appropriate combination of two or more. Among them, phthalate esters are the most common plasticizers that are easily available and low in cost. Especially, considering the point that they do not cause environmental impact, ease of handling, solubility, storage stability, etc., among phthalate esters, Most commonly used are diisononyl phthalate (DINP) and dioctyl phthalate (DOP).

  These raw materials constituting the polymer composition of the present embodiment are usually disperse, planetary mixer, bead mill, Henschel mixer, V-type blender, mechanochemical apparatus, static mixer, dynamic mixer, tumbler, super mixer, plast mill. , Banbury mixer, kneader, roll, feeder ruder, brabender, extruder, etc., mixed and kneaded, defoamed as necessary, then molded into a desired shape by a known molding process to store heat It is a polymer molded body.

  As the molding method, molding methods generally used for polymer compositions, for example, compression molding (press molding), injection molding, extrusion molding, blow molding, hollow molding such as gas assist, vacuum molding, calender molding, atypical Molding, rotational molding, transfer molding, film molding, foam molding (including supercritical fluid), thermoforming, laminate molding, and the like can be used.

As a shaping | molding form, according to the structure of a heat dissipation object, the application form to a heat dissipation object, etc., it can shape | mold into a sheet form, a film form, a molded article, etc.
For example, when applied to a secondary battery pack such as a lithium ion battery, the polymer composition is formed into a sheet or secondary battery pack housing, and the heat storage polymer molded body thus formed is used as a lithium ion battery or the like. It is possible to effectively suppress and mitigate the temperature rise of a lithium ion battery or the like that is a heat dissipation object.

  More specifically, when a sheet-like heat storage polymer molded body is interposed between individual lithium batteries of a battery pack in which a plurality of lithium ion batteries are arranged as heat dissipation objects, or a housing having a partition is made of a heat storage polymer composition. It is assumed that each lithium ion battery is molded and accommodated in this casing. In such a state, the individual lithium batteries are in close contact with the sheet-shaped heat storage polymer molded body or the heat storage polymer molded housing to efficiently transfer heat, and the temperature rise of each lithium battery is suppressed during use. . At this time, even if the temperature of some of the plurality of lithium batteries becomes high, the heat storage polymer molded body has heat storage properties, so that heat is not transferred to the adjacent lithium battery, and the adjacent lithium battery is the original one. It is possible to prevent the temperature from rising beyond the temperature rise.

  In addition, even if a part of the lithium battery generates abnormal heat and the lithium battery that has generated abnormal heat expands, the heat storage polymer molded body is set to a predetermined low hardness as will be described later. The rise in the expansion pressure (internal pressure) due to can be absorbed. As a result, the adjacent lithium battery is not affected by the increase in expansion pressure.

Thus, since the heat storage polymer molded body of the present invention has predetermined hardness and heat storage properties to be described later, the temperature rise of the heat dissipation object can be efficiently suppressed, and the heat dissipation object is accommodated. It is possible to efficiently suppress an increase in the expansion pressure of the housing storage container and avoid a situation in which the storage container and the heat dissipation object are damaged.
In addition, since the heat storage polymer molded body has thermal conductivity, the heat transferred to the heat storage polymer molded body is dissipated from the housing container to the outside, which also increases the temperature of the lithium battery. It is suppressed.

  Here, examples of the method for forming into a sheet include compression molding (press molding), extrusion molding, calendar molding, and the like. Examples of molding into a housing include injection molding. In addition, the thickness of the sheet at this time is preferably within a range of 0.3 mm to 10 mm. By setting the sheet thickness to 0.3 mm or more, sufficient thermal conductivity and heat storage property can be secured in the heat storage polymer molded body, and by making the sheet thickness 10 mm or less, the contact thermal resistance is lowered. It is possible to suppress the heat of the object to be radiated efficiently and to effectively suppress and mitigate the temperature rise of the object to be radiated. The thickness of the casing is preferably at least 1.0 mm for holding the casing. The maximum thickness of the housing is preferably 10 mm or less for the same reason as the sheet.

According to the heat storage polymer molded body of the present embodiment formed as described above, the heat conductive filler and the heat storage material are contained, whereby the heat conductive path is secured by the heat conductive filler, and the heat dissipation object. The heat of the object to be radiated is easily conducted when it is brought into contact with the heat, and the heat conducted from the object to be radiated is diffused in the heat conduction path, absorbed by the heat storage material and stored, and the outside of the object to be radiated Also dissipated.
In particular, in an environment where the temperature difference between the object to be radiated and the surrounding area outside the object to be radiated is small, the heat storage material that absorbs and stores heat from the object to be radiated effectively functions to reduce the temperature difference from the surroundings. However, the temperature rise of the heat dissipation object is effectively suppressed and alleviated.

  Here, when only the heat storage material is contained without containing the heat conductive filler, the thermoplastic resin or thermoplastic elastomer used as the base polymer used in the present invention is generally low in heat conductivity. It is difficult for heat to be efficiently conducted to the heat storage material, and the heat storage property of the heat storage material cannot be fully utilized, and heat is not easily radiated to the outside. For this reason, the effect of suppressing and mitigating the temperature rise of the object to be radiated is small.In particular, it is difficult to dissipate heat to the outside, so it is quick to exceed the limit of the heat storage capacity of the heat storage material, and the limit of the heat storage capacity of the heat storage material is reduced. When it exceeds, the temperature of the heat storage polymer molded body becomes high, and the temperature increase rate of the heat dissipation object increases. Therefore, in the combination of heat storage materials only, there is a limit to the effect of suppressing and mitigating the temperature rise for the object to be radiated, and it is effective in an environment where the temperature difference between the object to be radiated and the outside of the object to be radiated is small. It cannot suppress and mitigate the temperature rise of the heat dissipation object.

  However, in the present invention, since not only the heat storage material but also the heat conductive filler is contained, a heat conduction path is secured by the heat conductive filler, so that the heat of the heat dissipation object is efficiently conducted to the heat storage material. The heat storage property of the heat storage material can be fully utilized, and the heat can be easily radiated to the outside. That is, the heat of the heat dissipation object can be efficiently transferred and released by the heat conductive filler, and the heat of the heat dissipation object can be stored by the heat storage material. For this reason, even in an environment where the temperature difference from the surroundings is small, it is possible to effectively suppress and mitigate the temperature increase of the heat dissipation object.

  As described above, according to the heat storage polymer molded body of the present embodiment, even if a material having poor heat conduction is used for the thermoplastic base polymer, a heat conduction path is ensured by the heat conductive filler and is brought into contact with the object to be radiated. Sometimes the heat of the object to be radiated is efficiently conducted to the heat storage polymer molded body, and the heat from the object to be radiated can be stored by the heat storage material, while the heat radiating to the outside of the object is also ensured. It is possible to efficiently release the heat of the object and suppress the temperature increase of the heat dissipating object to mitigate it. Of course, if a material having excellent thermal conductivity is used for the thermoplastic base polymer, a further temperature rise suppressing effect can be expected.

  Further, according to the heat storage polymer molded body of the present embodiment, a thermal conductive filler and a heat storage material are blended with the thermoplastic base polymer, and the polymer as the base is thermoplastic, so a polymer composition is prepared. It sometimes exhibits appropriate fluidity and viscosity, and the thermally conductive filler and the heat storage material are easily and uniformly dispersed, and the moldability is also good. Since the heat conductive filler and the heat storage material are uniformly and highly dispersed, the heat conductivity by the heat conductive filler and the heat storage property by the heat storage material can be effectively exhibited.

  At this time, the blending amount of the heat conductive filler and the heat storage material is appropriately determined according to the required specifications in a range where the hardness of the heat storage polymer molded body is within a predetermined low hardness range. By setting the hardness of the heat storage polymer molded body within a predetermined low hardness range, even when the heat dissipation object has an uneven shape, it sufficiently follows, and the contact area with the heat dissipation object is large and high adhesion is obtained. It is possible. As a result, the heat insulation generated in the gap between the contact thermal resistance and the object to be radiated is reduced, and the heat of the object to be radiated is easily conducted, so that the heat is stored by the heat storage material, and the heat of the object to be radiated efficiently. Can be missed. Therefore, the effect of suppressing and mitigating the temperature rise of the heat dissipation object can be sufficiently exhibited.

Here, the predetermined low hardness range is within a range of hardness that can ensure good adhesion to the heat dissipation object and can absorb expansion of the heat dissipation object. For example, when used in a secondary battery such as a lithium ion battery, it is optimal that the Shore A hardness is 30 or more and the Shore D hardness is 60 or less (measured at room temperature).
When the heat storage polymer molded body is brought into contact with a heat radiation target object of a secondary battery such as a lithium ion battery to suppress the temperature rise of the heat radiation target object, if the Shore D hardness of the heat storage polymer molded body exceeds 60, the heat radiation target object When the object to be radiated swells, the stress cannot be absorbed and it is difficult to suppress the increase in internal pressure. When the Shore D hardness of the heat storage polymer molded body is 60 or less, it is possible to ensure high adhesion with the battery that is the object of heat dissipation, and even when the battery itself swells due to deterioration, the stress is absorbed and internal pressure is applied. Can be prevented and damage can be prevented. It is also effective for vibration countermeasures such as vibration and soundproofing. Furthermore, in the secondary battery module in which a plurality of cells of the secondary battery are connected to increase the capacity, the dimensional tolerance of each cell is absorbed to prevent the temperature variation between the cells, and the overall is high. A temperature suppression effect can be obtained.
However, those having a Shore A hardness of less than 30 are unsuitable because problems may occur during molding when molding methods such as injection molding and extrusion molding are employed, making molding impossible.
Therefore, if the Shore A hardness of the heat storage polymer molded body is within the range of 30 or more and the Shore D hardness is 60 or less, the moldability is good and good adhesion to the heat radiation object can be secured, and the heat radiation object expands. In that case, the stress can be absorbed efficiently.

  And according to the experimental study of the present inventors, the Shore A hardness of the heat storage polymer molded body is 30 or more by setting the total blending amount of the heat conductive filler and the heat storage material in the polymer composition to 95% by weight at the maximum. It has been confirmed that the Shore D hardness can fall within the range of 60 or less. That is, a predetermined low hardness can be secured by setting the total blending amount of the heat conductive filler and the heat storage material to 95% by weight or less.

When a solid-liquid phase transition type latent heat storage material is used as the heat storage material, it absorbs latent heat by phase change from solid to liquid as the temperature rises due to the operation of the heat dissipation target, As the temperature decreases due to the stoppage of the operation of the object, latent heat is released by phase change from liquid to solid. In particular, the solid-liquid phase transition type latent heat storage material has a property that the state change is slow, and when the amount of heat is not supplied from the outside, the stored latent heat is gradually released to the outside.
Due to such properties, when a relatively low latent heat storage material having a phase change temperature (melting point) of less than 50 ° C. is used in a heat storage polymer molded body used in a secondary battery such as a lithium ion battery mounted on an automobile. When the difference between the environmental temperature outside the vehicle and the temperature of the secondary battery such as a battery becomes large, such as in a low temperature environment in winter, after the operation of the secondary battery such as a lithium ion battery stops, it is absorbed by the heat storage polymer molding. The release of the latent heat promotes the heat retention of secondary batteries such as lithium ion batteries, and the temperature drop of the batteries is mitigated, preventing the drop in electromotive force due to low temperature, and the battery at startup and charging Good performance can be maintained.

  As described above, according to the heat storage polymer molded body of the present embodiment, while ensuring the heat conduction path by the heat conductive filler, by absorbing the heat of the heat radiation object to the heat storage material, In an environment where the temperature difference between the object to be radiated and the outside of the object to be radiated is small, it is possible to effectively suppress and mitigate the temperature rise of the object to be radiated. Make it possible. And the compounding quantity of a heat conductive filler and a thermal storage material can ensure the favorable adhesiveness with respect to the heat radiation target object, and can ensure the low hardness which can aim at suppression of the internal pressure increase in a housing | casing when a heat radiation target object expand | swells. Within range.

In addition, it can be molded into complex shapes by taking advantage of the thermoplastic properties of the base polymer, and can be adapted to the shape and size of the object to be dissipated. It can be applied to a wide range of heat dissipation objects. Further, since the base polymer is thermoplastic, it can be integrally molded with other resin materials and metal materials.
For this reason, it is applicable to a wide part etc. as a heat countermeasure member which suppresses the temperature rise by the heat of a heat generating source.

  Therefore, the heat storage polymer molded body of the present embodiment is subjected to thermally severe environmental conditions such as, for example, a large amount of heat generated by the heat source and a high temperature of the surrounding environment of the heat dissipation object when the heat dissipation object is used. Suitable for automotive parts, specifically, secondary battery batteries such as lithium-ion batteries where the temperature difference between the heat dissipation object and the surrounding environment of the heat dissipation object is small and the heat of the heat dissipation object is difficult to dissipate, capacitors, etc. Can be used for

In addition, various parts such as electronic materials, magnetic materials, catalyst materials, structural materials, optical materials, medical materials, automotive materials, building materials, such as home appliances, OA equipment parts, AV equipment parts, precision equipment, automobiles, etc. Heat sources such as interior and exterior parts (for example, computer CPU, liquid crystal backlight, plasma display panel, LED element, organic EL element, Peltier element, thermoelectric conversion element, temperature sensor, converter, transformer, inverter, (high) power It can also be used as a heat radiating material for radiating heat from a heat source such as a transistor. Specific product parts include personal computers, game machines, VTRs, televisions, irons, air conditioners, air cleaners, negative ion generators, vacuum cleaners, refrigerators, irons, hair dryers, and other beauty equipment, lighting equipment, rice cookers, electronics Home appliance parts such as microwave ovens, microwave cooking pots, cooking utensils such as heat-resistant dishes, personal digital assistants (so-called PDAs), electronic dictionaries, electronic books, portable TVs, compact discs, laser discs (registered trademarks), Drives / readers for recording media (CDs, MDs, DVDs, next-generation high-density disks, hard disks, IC cards, smart media, memory sticks, etc.), ferrules for optical cables, coils, sealing elements such as semiconductor elements and resistors, terminal blocks , Printed circuit board, circuit board, chip, thermal head, sensor, connector, socket, Electrical components such as a laser component, coil bobbin, optical pickup, oscillator, LSI, CPU, computer-related components, lighting fixture components such as LED lighting, lamp socket, lamp reflector, lamp housing, CRT, liquid crystal, plasma, projector , Display devices such as organic EL and audio back panels, audio product parts such as stereos and speakers, copier / printer related parts such as printers, copiers, scanners, fax machines, separation nails and heater holders, pachinko, Game machine related parts such as slot machines, impellers, fan gears, gears, bearings, motor parts and case parts, power distribution parts such as breakers, automotive mechanism parts, engine parts, engine room parts, lamp reflectors, Instrumental panel Center console panels, deflectors, lamps, car stereos, car navigation, car audio visuals, car parts such as automobiles such as electrical equipment and interior parts such as auto mobile computer parts, parts for aircraft and spacecraft, and parts for sensors And communication equipment parts such as telephones (mobile phones, landline phones, etc.), modems, image display / recording equipment such as optical cameras, digital cameras, typewriters, and product parts such as parabolic antennas and power tools. .
For example, when used in a CPU of a computer, it is optimal that the phase change temperature of the heat storage material is in the range of 70 ° C to 90 ° C. Moreover, when using with a silicon semiconductor, it is optimal although the phase change temperature of a thermal storage material shall be in the range of 50 to 70 degreeC. When used in a canister in a vehicle component, it is optimal that the phase change temperature of the heat storage material is in the range of 30 ° C. to 50 ° C.

Next, examples of the heat storage polymer molded body according to the embodiment of the present invention will be specifically described with reference to FIGS. 1 to 4.
First, the thermal storage polymer molded object which concerns on Example 1 is demonstrated.
In the heat storage polymer molded body of Example 1, polyvinyl chloride (PVC) resin (“PCH-72” manufactured by Kaneka Corporation) is used as the base polymer, and boron nitride (Momentive Materials, Inc.) is used as the thermally conductive filler. “PT110” manufactured by Performance Japan GK was used. In addition, a heat storage capsule (Mitsubishi Paper Co., Ltd.) encapsulating myristyl myristate with a melting point of 39 ° C in a capsule made of melamine resin, assuming use in a lithium-ion battery installed in an automobile. “FP-39” (average particle size: 50 μm)) was blended. Furthermore, diisononyl phthalate (DINP: J Plus Co., Ltd.) was used as a plasticizer.

  In Example 1, 13% by weight of a PVC resin as a base polymer, 10% by weight of boron nitride as a thermally conductive filler, 40% by weight of a heat storage capsule containing myristyl myristate as a heat storage material, and as a plasticizer By blending 37% by weight of DINP, the total polymer composition is 100% by weight. In the blending of Example 1, the blending amount of the heat conductive filler is 77 parts by weight and the blending amount of the heat storage capsule is 308 parts by weight with respect to 100 parts by weight of the base polymer.

In producing the heat storage polymer molded body of this example, the polymer composition blended in the blending amounts shown in Table 1 is put into a stirring vessel, stirred and mixed with a disper, and the mixed material is defoamed. It was prepared by.
Next, the polymer composition thus prepared is poured into a mold having a concave cross section (lower mold), and then the convex mold (upper mold) engaged with the concave shape of the lower mold is used as the lower mold. Inserted and fixed to the lower mold so that the upper mold does not move. At this time, the lower mold and the upper mold are designed to form a molded product in which the polymer composition has a sheet shape of 50 mm in length, 100 mm in width, and 5 mm in thickness. And in this state, after putting in a 150 degreeC oven and heating for 30 minutes, it took out and naturally cooled to normal temperature, and the sheet-like heat storage polymer molded object for evaluation was obtained. The sheet-like heat storage polymer molded body thus obtained was subjected to measurement of hardness and thermal conductivity and an evaluation test of a temperature rise suppression effect (temperature rise suppression / relaxation effect of a heat dissipation object).

  The hardness was measured within 1 second using a durometer type A (JIS A hardness meter, manufactured by Kobunshi Keiki Co., Ltd.) in accordance with JIS K6253.

About thermal conductivity, it measured by the laser flash method (JIS-R1611) using the thermal conductivity measuring apparatus ("TC-7000H" by ULVAC-RIKO Co., Ltd.).
In the laser flash method, the surface of a sample (polymer molded body) having a disk shape (10 mmφ, thickness 2 mm) is irradiated with laser light from a laser light source, and the temperature of the back surface of the sample is measured with a thermocouple.

Here, for comparison, in the same production procedure as in Example 1, as Comparative Example 1, a heat storage material was not blended, and a thermally conductive filler (boron nitride), a thermoplastic resin (PVC resin), and a plasticizer (DINP) ) Was used as a raw material in the blending amounts shown in Table 1, and Comparative Example 1 was formed into a sheet shape.
And also about this comparative example 1, the same evaluation as Example 1 was performed.

  The upper part of Table 1 shows the blending contents of Example 1 and Comparative Example 1, and the lower part of Table 1 collectively shows the measurement results of their hardness and thermal conductivity. In addition, the numerical value shown in the upper part of Table 1 shows each compounding component by weight part and weight%.

As shown in Table 1, in the heat storage polymer molded body according to Example 1, compared to Comparative Example 1, the Shore A hardness at room temperature is as low as 32 °, but the thermal conductivity is low. The thermal conductivity is about 1/5 of 0.3 W / (m · k), which is 1.6 W / (m · k) of Comparative Example 1.
Using Example 1 and Comparative Example 1 having such characteristics, an evaluation test for suppressing temperature rise was performed.
Hereinafter, the evaluation test for temperature rise suppression will be described.

As for the evaluation test of the temperature rise suppression effect, the evaluation tester 11 shown in FIG. 1 is prepared and the evaluation tester 11 is used on the assumption that it is used in a lithium ion battery mounted on an automobile. The temperature rise suppression effect was evaluated.
As shown in FIG. 1, the evaluation testing machine 11 has a sponge-like heat insulating material 14 that encloses a heater H (corresponding to a heat dissipation object) disposed in a recess of a base 13 having a recess on the upper surface. At this time, the heater H is included in the heat insulating material 14 so that the upper surfaces of the heater H and the heat insulating material 14 coincide with each other. For this reason, only the upper surface of the heater H is not covered with the heat insulating material 14. Then, the evaluation polymer molded body A is placed in contact with the upper surface of the heater H not covered with the heat insulating material 14, and the temperature is measured between the upper surface of the heater H and the evaluation polymer molded body A. A pair T is arranged. With this thermocouple T, the temperature at the boundary surface between the heater H and the polymer molded body A can be measured.

Further, a PP resin plate 15 is disposed on the upper surface of the polymer molded body A, and the PP resin plate 15 is configured to exert a force that pushes the polymer molded body A downward by a weight setting table 16 and a weight 17 of 500 g. . Therefore, the polymer molded body A comes into close contact with the heater H by the PP resin plate 15, the installation table 16, and the weight 17. The heat insulating material 14, the polymer molded body A, the PP resin plate 15, the installation base 16, and the weight 17 that contain these heaters H arranged on the base 13 are acrylic resins provided in contact with the inner walls of the recesses of the base 13. The case 18 is covered and sealed. This eliminates the influence of the wind generated outside the housing 18.
The base 13 on which the heat insulating material 14 enclosing the heater H and the polymer molded body A and the like are hermetically disposed in an acrylic casing 18 is disposed in a temperature control container 12 made of acrylic resin. The temperature adjustment container 12 is provided with a temperature adjustment opening 12a into which the warm air temperature-controlled by a temperature controller (not shown) is introduced. The temperature adjustment container 12 is adjusted to a predetermined temperature from the temperature adjustment opening 12a. The warm air is blown into the temperature adjustment container 12 to adjust the temperature of the acrylic casing 18 and its internal space.

  In the evaluation testing machine 11 configured as described above, the temperature is adjusted to 20 ° C. and 35 ° C., and the heater H is adjusted to have a wattage of 3.6 W. The temperature at the boundary with the polymer molded product A for evaluation was measured with a thermocouple T over time.

The measurement result of the temperature control temperature 20 ° C. in the evaluation test of the temperature rise suppression is shown in FIG. 2, and the measurement result of the temperature control temperature 35 ° C. is shown in the graph of FIG.
Here, assuming that the use limit temperature of the lithium ion battery of the lithium ion battery mounted on the automobile is 60 ° C., the maximum temperature in the normal use region seems to be 55 ° C. in view of safety. Therefore, in this evaluation test, the time to 55 ° C. was compared under the temperature adjustment of 20 ° C. and the temperature adjustment of 35 ° C. At this time, 20 ° C. and 35 ° C. imitate the environmental temperature outside the vehicle, and evaluate the influence of the temperature outside the vehicle.

Under the temperature adjustment of 20 ° C. shown in the graph of FIG. 2, in Comparative Example 1 in which a heat conductive filler is blended but no heat storage material is blended, the heater H which is a heat release object and the comparative example in 72 minutes The boundary temperature of the polymer molded body according to No. 1 reached 55 ° C.
On the other hand, the heat storage polymer molding A according to Example 1 in which the heat conductive filler and the heat storage material were blended required 94 minutes. That is, the usable time until the temperature reaches 55 ° C. by 22 minutes is increased by 1.3 times compared to Comparative Example 1.

Further, in the measurement under the temperature adjustment of 35 ° C., as shown in the graph of FIG. 3, in Comparative Example 1, the temperature reached 55 ° C. in 31 minutes, whereas in Example 1, the temperature reached 42 minutes and 55 ° C. The time has been extended. That is, the usable time until the temperature reaches 55 ° C. by 9 minutes is increased by 1.4 times compared to Comparative Example 1.
From these results, with respect to temperature rise suppression, in Example 1, compared with Comparative Example 1, the temperature rise at the boundary between the object to be radiated and the heat storage polymer molded body is suppressed, and this tendency is the same even if the environmental temperature changes. It is. That is, the thermal conductivity of Comparative Example 1 is about five times higher than that of Example 1, but Example 1 having heat storage properties is superior from the viewpoint of temperature rise suppression. From this, it was found that using both heat conduction and heat storage greatly contributes to temperature rise suppression and does not depend on the environmental temperature rather than simply improving heat conduction.
Here, regarding the adhesion between the heat dissipation object and the heat storage polymer molded body, the Shore A hardness at room temperature is approximately the same as 32 ° and 30 ° in Example 1 and Comparative Example 1. Both are presumed to show good adhesion.

Next, the heat storage polymer molded body according to Example 2 to Example 9 will be described.
In the heat storage polymer moldings of Examples 2 to 9, SEBS (“G1651HU” manufactured by Kraton Polymer Japan Co., Ltd.) is used as the base polymer, and boron nitride (Momentive Materials Performance Japan) is used as the thermal conductive filler. “PT110” manufactured by a limited liability company, alumina (“CB-A50BC” manufactured by Showa Denko KK), and glass beads (“GB301S manufactured by Potters Barotini, average particle size of 50 μm)” were used. Assuming use in lithium-ion battery batteries mounted on automobiles, lauric acid with a phase change temperature (melting point) of 44 ° C. (“NAA-122” manufactured by NOF Corporation) is used as a heat storage material. did. Furthermore, in Example 3 to Example 5 and Example 7, Diana process oil (“PW380” manufactured by Idemitsu Kosan Co., Ltd.) was used as a softening agent.

  In Example 2, 5% by weight of SEBS as a base polymer, 13% by weight of boron nitride as a thermally conductive filler, 39% by weight of alumina as a thermally conductive filler, and 43% of lauric acid as a heat storage material %, The polymer composition is 100% by weight in total. In the formulation of Example 2, the total amount of thermally conductive filler is 1040 parts by weight and the amount of heat storage material is 860 parts by weight with respect to 100 parts by weight of the base polymer. The total amount of the thermally conductive filler and the heat storage material in the polymer composition is 95% by weight.

In Example 3, 5% by weight of SEBS as a base polymer, 13% by weight of boron nitride as a thermally conductive filler, 39% by weight of alumina, 38% by weight of lauric acid as a heat storage material, a process as a softener By blending 5% by weight of oil, the total polymer composition is 100% by weight. That is, the amount of the heat storage material is reduced as compared with Example 2, and the softening agent is added accordingly.
In the formulation of Example 3, the total amount of thermally conductive filler is 1040 parts by weight and the amount of heat storage material is 760 parts by weight with respect to 100 parts by weight of the base polymer. The total amount of the thermally conductive filler and the heat storage material in the polymer composition is 90% by weight.

In Example 4, 5% by weight of SEBS as a base polymer, 13% by weight of boron nitride as a thermally conductive filler, 39% by weight of alumina, 33% by weight of lauric acid as a heat storage material, a process as a softener By blending 10% by weight of oil, the total polymer composition is 100% by weight. That is, the blending amount of the heat storage material is further reduced as compared with Example 3, and the blending amount of the softening agent is increased accordingly.
In the formulation of Example 4, the total amount of thermally conductive filler is 1040 parts by weight and the amount of heat storage material is 660 parts by weight with respect to 100 parts by weight of the base polymer. The total amount of the thermally conductive filler and the heat storage material in the polymer composition is 85% by weight.

In Example 5, 5% by weight of SEBS as a base polymer, 13% by weight of boron nitride as a thermally conductive filler, 39% by weight of alumina, 28% by weight of lauric acid as a heat storage material, a process as a softener By blending 15% by weight of oil, the total polymer composition is 100% by weight. That is, the blending amount of the heat storage material is further reduced as compared with Example 4, and the blending amount of the softening agent is increased accordingly.
In the blending of Example 5, the total amount of heat conductive filler is 1040 parts by weight and the amount of heat storage material is 560 parts by weight with respect to 100 parts by weight of the base polymer. The total amount of the thermally conductive filler and the heat storage material in the polymer composition is 80% by weight.

  Thus, in Examples 3 to 5, the blending amounts of the base polymer and the thermally conductive filler are the same as in Example 2, and only the blending amounts of the heat storage material and the softening agent are different.

In Example 6, 5% by weight of SEBS as a base polymer, 10% by weight of boron nitride as a thermally conductive filler, 30% by weight of alumina, and 55% by weight of lauric acid as a heat storage material were blended. The total polymer composition is 100% by weight. That is, the blending amount of the heat storage material is increased as compared with Example 2, and the blending amounts of boron nitride and alumina as the heat conductive filler are reduced accordingly.
In the formulation of Example 6, the total amount of heat conductive filler is 800 parts by weight and the amount of heat storage material is 1100 parts by weight with respect to 100 parts by weight of the base polymer. The total amount of the thermally conductive filler and the heat storage material in the polymer composition is 90% by weight.

Further, in Example 7, 5% by weight of SEBS as a base polymer, 10% by weight of boron nitride as a thermally conductive filler, 30% by weight of alumina, 38% by weight of lauric acid as a heat storage material, and as a softening agent By blending 17% by weight of the process oil, the total polymer composition is 100% by weight. That is, the amount of the heat storage material is reduced as compared with Example 6, and the softening agent is added accordingly.
In the formulation of Example 7, the total amount of heat conductive filler is 800 parts by weight and the amount of heat storage material is 760 parts by weight with respect to 100 parts by weight of the base polymer. The total amount of the thermally conductive filler and the heat storage material in the polymer composition is 78% by weight.

  Thus, in Example 6 and Example 7, the compounding quantity of a base polymer and a heat conductive filler is made the same, and only the compounding quantity of a thermal storage material and a softening agent differs.

In Example 8, 5% by weight of SEBS as a base polymer, 15% by weight of boron nitride as a thermally conductive filler, 35% by weight of glass beads, and 45% by weight of lauric acid as a heat storage material are blended. Thus, the total polymer composition is 100% by weight. In the formulation of Example 8, the total amount of the thermally conductive filler is 1000 parts by weight and the amount of the heat storage material is 900 parts by weight with respect to 100 parts by weight of the base polymer.
Further, in Example 9, 5% by weight of SEBS as a base polymer, 13% by weight of boron nitride as a thermally conductive filler, 40% by weight of glass beads, and 42% by weight of lauric acid as a heat storage material are blended. Thus, the total polymer composition is 100% by weight. In the blending of Example 9, the total amount of heat conductive filler is 1060 parts by weight and the amount of heat storage material is 840 parts by weight with respect to 100 parts by weight of the base polymer.
In Example 2 to Example 7, boron nitride and alumina were used as the thermally conductive filler, whereas in Examples 8 and 9, boron nitride and glass beads were used as the thermally conductive filler.

  In producing the heat storage polymer moldings of Examples 2 to 9, the polymer composition containing the materials in the blending amounts shown in Table 2 was dry blended and heated in an oven at 100 to 150 ° C. for 30 minutes. did. By this heating, lauric acid (NA-122) as a molten heat storage material is uniformly distributed (absorbed) in SEBS as a base polymer, and the whole swells.

  Then, after heating at 100 to 150 ° C. for 30 minutes, it is once taken out from the oven and immediately kneaded and defoamed (manufactured by Shinkey Co., Ltd., “Awatori Nertaro (registered trademark)”, kneading: 2000 rpm × 1 Minute + defoaming: 2000 rpm × 1 minute), and then poured into a concave mold (lower mold) having the same cross section as in Example 1 above, and then engaged with the concave shape of the lower mold The mold (upper mold) was inserted into the lower mold and fixed to the lower mold so that the upper mold did not move. In that state, the mold was again placed in an oven and heated at 100 to 150 ° C. for 30 minutes. At this time, the lower mold and the upper mold were designed to form a molded product in which the polymer composition had a sheet shape with a length of 50 mm, a width of 100 mm, and a thickness of 5 mm. After heating, the whole mold was taken out from the oven, naturally cooled to room temperature, and then removed from the mold to obtain a sheet-like heat storage polymer molded body for evaluation.

For the sheet-like heat storage polymer molded bodies according to Examples 2 to 9 thus obtained, as in the case of Example 1 above, the measurement of hardness and thermal conductivity and the temperature rise suppression effect (target for heat dissipation) The evaluation test of the temperature rise suppression / relaxation effect of the object was conducted.
About hardness, in Example 1 thru | or Example 8, based on JISK6253, the measured value within 1 second was measured using the durometer type A (JIS A hardness meter, the polymer meter Co., Ltd. product). In Example 9, based on JIS K6253, the measured value within 1 second was measured using the durometer type D (JIS D hardness meter, the polymer meter Co., Ltd. product). When measuring the Shore A or Shore D hardness, the measurement was performed at room temperature (25 ° C.) and in two temperature zones when the polymer molded body was heated to 40 ° C.
The method for measuring the thermal conductivity was performed in the same manner as in Example 1 above.
Further, the evaluation test of the temperature rise suppression effect was performed in the same manner as in Example 1. Here, in the evaluation test machine 11 of FIG. 1, the heater H is adjusted to have a wattage of 2.4 W and energized, and the temperature is adjusted to 35 ° C. and the evaluation test is performed in an atmosphere of 35 ° C. went.

The left column of Table 2 shows the blending contents of Examples 2 to 9, and the right column of Table 2 collectively shows the measurement results of Shore A hardness or Shore D hardness and thermal conductivity. In addition, the numerical value shown in the left orchid of Table 2 shows each compounding component by a weight part and weight%.
Moreover, the time-dependent measurement result of the thermocouple T in the evaluation test of the temperature rise suppression effect is shown in the graph of FIG.

  As in the case of the first embodiment, assuming that the maximum temperature in the normal use region of the lithium ion battery of the lithium ion battery mounted on the automobile is 55 ° C. in consideration of safety, the heater which is a heat dissipation object in FIG. Looking at the time until the temperature of the thermocouple T at the boundary between H and the heat storage polymer molded body A (heat storage polymer molded body of Examples 2 to 9) reaches 55 ° C., the base polymer, In Example 2 and Example 6 containing only boron nitride and alumina as the heat storage material and the thermally conductive filler, the time required to reach 55 ° C. is 180 minutes (10800 seconds) or more, and the temperature rise suppression effect It is understood that it is excellent. Further, in Example 8 in which only the base polymer, the heat storage material, and boron nitride and glass beads as the heat conductive filler are blended, the time required to reach 55 ° C. is about 180 minutes (10800 seconds). It turns out that it is excellent in the inhibitory effect.

And also in Example 3 thru | or Example 5, compared with Example 2, the compounding quantity of a thermal storage material was reduced and the softening agent was added. Although the rate decreased, the time required to reach 55 ° C. due to the decrease in hardness was approximately 148 minutes in Example 3, approximately 167 minutes in Example 4, approximately 175 minutes in Example 5, and a high rise. A temperature suppressing effect was shown.
In particular, in Examples 3 to 5, although the blending amounts of the heat storage material and the softening agent are different, the thermal conductivity is substantially the same because the blending amount of the heat conductive filler is the same. As the blending amount of the softening agent was increased and the blending amount of the softening agent was increased, the Shore A hardness decreased, and this Shore A hardness showed a very small value under the measurement at a high temperature of 40 ° C. The lower the Shore A hardness, the longer the time required to reach 55 ° C., and the higher the temperature rise suppression effect.
Furthermore, also in Example 7, compared with Example 6, the amount of heat storage material was reduced and a softening agent was added, so although the thermal conductivity was lower than in Example 6, the hardness was reduced. The time required to reach 55 ° C. was 151 minutes, and a high temperature rise suppression effect was shown.

Further, in Example 9 containing only the base polymer, the heat storage material, and boron nitride and glass beads as the heat conductive filler, the time required to reach 55 ° C. because the Shore D hardness at room temperature is 60. Was 149 minutes, and a high temperature rise suppression effect was shown.
In addition, from Example 2 and Example 6, increasing the blending amount of the heat storage material and decreasing the blending amount of the heat conductive filler also decreases the thermal conductivity, but also decreases the Shore A hardness.
In Example 5 and Example 7, the Shore A hardness at normal temperature is the same, but in Example 5 where the amount of heat conductive filler is larger than in Example 7 and the amount of heat storage material is less, Since the conductivity was high and the Shore A hardness at 40 ° C. was low, the time required to reach 55 ° C. was long, and the temperature rise suppression effect was high.

  Thus, also in Example 2 thru | or Example 9, the temperature rise of the boundary surface of the thermal radiation object H and the thermal storage polymer molded object A is suppressed, and especially a PVC resin as a base polymer, and boron nitride as a heat conductive filler The temperature at the boundary between the heat dissipation object H and the heat storage polymer molded body A is 55 ° C. than in Example 1 in which heat storage capsules containing myristyl myristate as a heat storage material and DINP as a plasticizer are blended. It took a long time to reach, and the temperature rise of the heat dissipating object (heater H) was remarkably suppressed and alleviated. Moreover, from Example 3 thru | or Example 5, when the hardness was low, it turned out that the high temperature increase inhibitory effect is acquired by the adhesiveness of the thermal radiation object H and the thermal storage polymer molded object A improving.

  Even if a styrene-based thermoplastic elastomer such as SEBS is used as the base polymer, it can be used because the melting temperature is relatively low and it is not necessary to use high-temperature conditions during molding, as with polyvinyl chloride resin. The selection range of the heat storage material is widened. In addition, styrene-based thermoplastic elastomers such as SEBS are environmentally friendly without the risk of generating harmful substances such as dioxins during incineration, unlike polyvinyl chloride resin. Furthermore, alumina (aluminum oxide) as a thermally conductive filler is relatively easily available and inexpensive, has a low specific gravity, and has a high thermal conductivity. Further, glass as a thermally conductive filler is also relatively easy to obtain, is inexpensive, has a low specific gravity, has a good thermal conductivity, and also has a function as a reinforcing filler.

  Thus, according to the heat storage polymer molded body according to the first to ninth embodiments, the heat storage filler and the heat storage material are arranged by suppressing the hardness of the heat storage polymer molded body within a predetermined low hardness range. The adhesion between the object to be radiated (heater H) and the heat storage polymer molded article is good, and the temperature increase of the object to be radiated (heater H) can be remarkably suppressed and alleviated. Therefore, for example, when the battery is brought into contact with a secondary battery such as a lithium ion battery mounted on an automobile, the operable time of the secondary battery can be extended. As a result, it is possible to suppress a decrease in the function and life of the battery and to extend the life.

Here, regarding the hardness (°), from Example 1 to Example 9, if the Shore A hardness is 30 ° or more and the Shore D hardness is 60 ° or less at room temperature, the adhesion to the heat dissipation object is good. It is good and has a high effect of suppressing and mitigating the temperature rise of the heat dissipation object. In addition, as shown in Table 2, Shore A hardness becomes small, so that the temperature of a thermal storage polymer molded object becomes high.
And, according to the experimental study by the present inventor, when an attempt is made to obtain a Shore A hardness of less than 30 at room temperature, the moldability when the molded body is formed by injection molding or extrusion molding is lowered. On the other hand, when the Shore D hardness at room temperature exceeds 60, the adhesiveness with the object to be radiated is deteriorated, and when the object to be radiated swells, the stress cannot be absorbed and the increase of the internal pressure can be suppressed. It becomes difficult.
Therefore, when the Shore A hardness at normal temperature is 30 or more and the Shore D hardness is in the range of 60 or less, the moldability is good and good adhesion to the heat dissipation object can be secured, and the heat dissipation object expands. In some cases, the stress can be absorbed efficiently. In the above, the Shore A hardness of 30 to 95 is particularly optimal.

At this time, from Examples 1 to 9, the composition of the heat conductive filler is in the range of 20 to 1060 parts by weight with respect to 100 parts by weight of the base polymer, and the composition of the heat storage material is 100 parts by weight of the base polymer. If it is within the range of 40 parts by weight to 1100 parts by weight, it is possible to mold with the required strength, ensuring both desired thermal conductivity and heat storage and low hardness, and temperature difference from the surroundings. Even in a small environment, the temperature increase of the heat dissipation object is reliably suppressed and alleviated.
Further, if the total blending amount of the heat conductive filler and the heat storage material in the polymer composition is 95% by weight or less, the Shore A hardness of the heat storage polymer molded body at room temperature is 30 or more and the Shore D hardness is 60 or less. Within the range.

As described above, the heat storage polymer molded body according to Example 1 is composed of a base polymer made of PVC resin as a thermoplastic resin, boron nitride as a thermal conductive filler, and myristyl myristate as a heat storage material. A polymer composition containing a heat storage capsule encapsulated in a resin capsule and DINP as a plasticizer is formed into a sheet shape.
In addition, the heat storage polymer molded body according to Example 2 to Example 9 is a base polymer made of SEBS, boron nitride as a thermal conductive filler, alumina (aluminum oxide), glass beads, lauric acid as a heat storage material, A polymer composition containing process oil as a softening agent is formed into a sheet shape.

  According to the heat storage polymer molded body according to the present Example 1 to Example 9, a heat conduction path is secured by the thermally conductive filler, and heat of the heat dissipation object is easily conducted when contacting the heat dissipation object, The heat conducted from the object to be radiated can be diffused in the heat conduction path and stored in the heat storage material, so that the temperature rise can be remarkably suppressed and reduced. Moreover, even in an environment where the temperature of the surrounding (outside of the housing) environment is high and the temperature difference from the surrounding (outside of the housing) is small, the heat storage performance by the heat storage material is effectively exhibited, resulting in a temperature difference from the surroundings. Can reduce temperature rise. Furthermore, since the heat conduction path is secured by the heat conductive filler, it is possible to dissipate to the outside (outside the housing), so that the heat of the object to be radiated can be effectively stored and radiated.

  In addition, in the blending composition and molding of the polymer composition in the heat storage polymer molded body of the above embodiment, it is assumed that it is used in a lithium ion battery mounted as a power source for automobiles, and is brought into contact with the lithium ion battery to take measures against heat However, the present invention is not limited to this example, and the base polymer, the thermal conductive filler, the mixing ratio of the heat storage material, and the polymer composition are not limited to this example. The forming form can be variously changed.

  In addition, the polymer composition in the heat storage polymer molded body of the present invention includes various stabilizers such as a dispersant, a flame retardant, an antioxidant, a heat stabilizer, an ultraviolet light inhibitor, a weathering agent, and a light stabilizer as necessary. , Additives such as thickeners, lubricants, mold release agents, flame retardants, coupling agents, nucleating agents, light diffusing agents, foaming agents, antistatic agents, crosslinking agents, anti-coloring agents, pigments, dyes, coloring agents, etc. It is also possible to add.

And when implementing this invention, it is not limited to the said Example about the structure of another part of a thermal storage polymer molded object, a component, a mixing | blending, a manufacturing method, etc.
It should be noted that the numerical values given in the embodiments and examples of the present invention are not all critical values, and certain numerical values are values determined from manufacturing cost, easy manufacturing, etc. Since it indicates a preferable preferable value, even if the numerical value is slightly changed within the allowable value, its implementation is not denied.

  A Thermal storage polymer molding

Claims (4)

A thermoplastic base polymer, a thermally conductive filler, and a latent heat storage material composed of paraffins or fatty acids that absorb heat when the phase changes from a solid phase to a liquid phase, and 100 weights of the thermoplastic base polymer The heat conductive filler is in a range of 20 parts by weight to 1060 parts by weight, and the heat storage material is molded in a range of 560 parts by weight to 1100 parts by weight with respect to parts , A heat storage polymer molded article having a Shore A hardness of 30 or more and a Shore D hardness of 60 or less. Polymer composition comprising a thermoplastic base polymer made of polyvinyl chloride resin , a thermally conductive filler, and a latent heat storage material made of paraffins or fatty acids that absorb heat when the phase changes from a solid phase to a liquid phase A heat storage polymer molded article obtained by molding a product and having a Shore A hardness of 30 or more and a Shore D hardness of 60 or less.   The heat storage polymer molded body according to claim 1 or 2, wherein the heat storage material is a latent heat storage material having a phase change temperature in a range of 20 ° C or higher and lower than 50 ° C.   The heat storage polymer according to any one of claims 1 to 3, wherein the total amount of the thermally conductive filler and the heat storage material in the polymer composition is 95% by weight at the maximum. Molded body.

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