JP2006312708A - Thermally conductive molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermally conductive molded product causing no generation of volatile gases and having good plasticity. <P>SOLUTION: The thermally conductive molded product is formed of a polymer composition containing a thermally conductive filler, a non-silicone polymer as a substrate having an allyl group on its end, and a non-silicone oil with kinematic viscosity at 40°C ranging from 70 mm<SP>2</SP>/s to 500 mm<SP>2</SP>/s. In the polymer composition, 200 to 400 parts by weight of the above non-silicone oil is mixed for 100 parts by weight of the above non-silicone polymer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a heat conductive molded body that is used between an exothermic electronic component and a radiator in an electronic device or between an exothermic electronic component and a metal heat transfer plate.

  In recent years, with the improvement in performance of electronic components such as elements typified by a CPU of a computer, the power consumption of the electronic components has increased, and the amount of heat generated by the electronic components has also increased. Therefore, cooling of heat-generating electronic components has become a very important technique for maintaining the performance of electronic components. As such a technique, in order to cool a heat-generating electronic component, a thermally conductive molded body used by being interposed between the electronic component and a cooling member is known. In a high-performance electronic component, since the amount of heat generation is further increased, a heat conductive molded body capable of conducting heat with higher efficiency is demanded.

  As such a heat conductive molded body, conventionally, a material in which a heat conductive filler is blended with a base material made of a silicone polymer has been widely used. For example, Patent Document 1 discloses a heat transfer sheet formed from a material in which a heat conductive material is mixed into a silicone resin and having a groove on at least one surface thereof.

  Since the silicone polymer has a low viscosity when uncured, the heat-conductive filler can be filled at a high ratio. Therefore, by using a silicone polymer as a base material, a molded product exhibiting high thermal conductivity can be obtained. Furthermore, when a silicone polymer is used as the substrate, a flexible heat conductive molded body having a hardness of 60 can be obtained. In addition, in this invention, the value of hardness points out the value measured with the type E durometer based on JISK6253 (ISO7619). Such a flexible thermally conductive molded body can be closely adhered to the electronic component and the cooling member. Therefore, the flexible heat conductive molded body using the silicone polymer can conduct heat efficiently.

  However, a thermally conductive molded body using a silicone polymer has a problem that low molecular weight siloxane which is an unreacted substance contained in the thermally conductive molded body volatilizes due to heat generation of an electronic component. When such low molecular weight siloxane volatilizes and adheres to an electrical contact or the like, it changes to silica, causing poor conduction and contact wear.

In order to avoid this problem, as a base material other than the silicone polymer, an epoxy-based thermally conductive molded body in which a thermally conductive filler is blended with an epoxy polymer has been studied.
However, in a thermally conductive molded body using an epoxy polymer as a base material, a flexible molded body in which the hardness of the molded body is 60 or less cannot be obtained. For this reason, the epoxy-based thermally conductive molded body cannot obtain sufficient adhesion between the electronic component and the cooling member, and cannot efficiently transfer the heat of the electronic component to the cooling member.
Japanese Patent Laid-Open No. 2-166755

  Accordingly, an object of the present invention is to provide a thermally conductive molded article that is free from the generation of volatile gases such as low molecular weight siloxane and has sufficient flexibility to efficiently transfer heat from a heat-generating component.

In order to solve the above problems, the invention described in claim 1 is a thermally conductive molded body formed from a polymer composition, wherein the polymer composition includes a thermally conductive filler, a base as wood, comprising a non-silicone polymer having a terminal allyl group, and a non-silicone oil kinematic viscosity at 40 ° C. is a 70mm ² / s~500mm ² / s, in the polymer composition, 100 parts by weight The gist is that 200 parts by weight to 400 parts by weight of the non-silicone oil is blended with respect to part of the non-silicone polymer.

The invention according to claim 2 is a thermally conductive molded body formed from a polymer composition, and the polymer composition has a thermally conductive filler and a base as an allyl group at a terminal. and a non-polar hydrocarbon-based polymer, and a non-polar hydrocarbon oil is a kinematic viscosity at 40 ° C. is 90mm ² / s~400mm ² / s, in the polymer composition, wherein the non-polar 100 parts by weight The gist is that 200 parts by weight to 400 parts by weight of the non-polar hydrocarbon oil is blended with respect to the hydrocarbon polymer.

  The invention according to claim 3 is the heat conductive molded article according to claim 2, wherein the nonpolar hydrocarbon polymer having an allyl group at the terminal is a polyisobutylene having an allyl group at the terminal. And

The gist of the invention described in claim 4 is that, in the thermally conductive molded article according to claim 2 or 3, the nonpolar hydrocarbon oil is paraffin oil.
The invention according to claim 5 is a thermally conductive molded body formed from a polymer composition, and the polymer composition has a thermally conductive filler and a base material having an allyl group at a terminal. a non-silicone polar polymer, and a polar group-containing non-silicone-based oil is a kinematic viscosity of 70mm ² / s~500mm ² / s at 40 ° C., in the polymer composition, 100 parts by weight of the non-silicone The gist is that 200 parts by weight to 400 parts by weight of the polar group-containing non-silicone oil is blended with the system polar polymer.

  The gist of the invention of claim 6 is that, in the thermally conductive molded article of claim 5, the non-silicone polar polymer having an allyl group at the terminal is a polyacrylate having an allyl group at the terminal. To do.

The gist of the invention described in claim 7 is that, in the thermally conductive molded article according to claim 5 or 6, the polar group-containing non-silicone oil is an ester oil.
The gist of the invention according to claim 8 is that, in the thermally conductive molded article according to any one of claims 1 to 7, the polymer composition further contains a curing agent.

The invention according to claim 9 is a thermally conductive molded body formed from a polymer composition, and the polymer composition has a thermally conductive filler and a base as an allyl group at a terminal. It includes a non-silicone polymer, a non-silicone oil kinematic viscosity is 70mm ² / s~500mm ² / s at 40 ° C., and a red phosphorus coated with a thermosetting resin, the polymer composition , 100 parts by weight of the non-silicone polymer, 200 parts by weight to 400 parts by weight of the non-silicone oil, and 3 parts by weight to 200 parts by weight of the thermosetting resin in a ratio of the red phosphorus alone. The gist is that it is blended with red phosphorus coated with.

The invention according to claim 10 is the thermally conductive molded article according to claim 9, wherein the non-silicone polymer having an allyl group at a terminal is a nonpolar hydrocarbon polymer having an allyl group at a terminal. , non-silicone oil, and summarized in that the kinematic viscosity at 40 ° C. is a non-polar hydrocarbon oil 90mm ² / s~400mm ² / s.

  The invention according to claim 11 is the heat conductive molded article according to claim 10, wherein the nonpolar hydrocarbon polymer having an allyl group at the terminal is polyisobutylene having an allyl group at the terminal. And

The gist of the invention described in claim 12 is that, in the thermally conductive molded article described in claim 10 or 11, the nonpolar hydrocarbon oil is paraffin oil.
The invention according to claim 13 is the thermally conductive molded article according to claim 9, wherein the non-silicone polymer having an allyl group at the terminal is a non-silicone polar polymer having an allyl group at the terminal, non-silicone oil, and summarized in that the kinematic viscosity at 40 ° C. is a polar group-containing non-silicone oils of 70mm ² / s~500mm ² / s.

  The gist of the invention described in claim 14 is that, in the thermally conductive molded article according to claim 13, the non-silicone polar polymer having an allyl group at the terminal is a polyacrylate having an allyl group at the terminal. To do.

The gist of the invention described in claim 15 is that, in the thermally conductive molded article according to claim 13 or 14, the polar group-containing non-silicone oil is an ester oil.
According to a sixteenth aspect of the present invention, in the thermally conductive molded article according to any one of the ninth to fifteenth aspects, the polymer composition is at least one metal hydroxide as a thermally conductive filler. The main point is to include things.

The gist of the invention according to claim 17 is that, in the thermally conductive molded article according to claim 16, the metal hydroxide is aluminum hydroxide.
The gist of the invention according to claim 18 is that, in the thermally conductive molded article according to any one of claims 9 to 17, the polymer composition further contains a curing agent.

  According to the first aspect of the present invention, the thermally conductive molded body hardly generates volatile gas such as low molecular weight siloxane and does not contaminate the inside of the electronic device. In addition, the flexibility of the heat conductive molded body can be improved, whereby heat can be transferred efficiently.

  According to the invention of claim 2, in addition to the effect of claim 1, the blending ratio of the nonpolar hydrocarbon oil is increased by blending the nonpolar hydrocarbon oil with the nonpolar hydrocarbon polymer. And a more flexible thermally conductive molded body can be obtained.

  According to the invention of claim 3, by using polyisobutylene having an allyl group at the terminal as a nonpolar hydrocarbon-based component, the heat resistance, electrical insulation and water resistance of the thermally conductive molded body are improved. be able to.

  According to the invention of claim 4, when the nonpolar hydrocarbon oil is paraffin oil, the oil is bleeded from the obtained heat conductive molded body even when blended in a large amount with the nonpolar hydrocarbon polymer. It becomes difficult to obtain a more flexible heat conductive molded body.

  According to the invention of claim 5, in addition to the effect of claim 1, the blending ratio of the polar group-containing non-silicone oil is adjusted by blending the polar group-containing non-silicone oil with the non-silicone polar polymer. It can be made high and a more flexible heat conductive molded object can be obtained.

  According to the invention of claim 6, by using a polyacrylate having an allyl group at the terminal as the non-silicone polar polymer, the weather resistance, heat resistance, and oil resistance of the thermally conductive molded body can be improved. it can.

  According to the invention of claim 7, by making the polar group-containing non-silicone oil into an ester oil, the oil is difficult to bleed from the thermally conductive molded article even if blended in a large amount in the non-silicone polar polymer. A more flexible thermally conductive molded body can be obtained.

According to invention of Claim 8, the above heat conductive molded objects can be obtained easily.
According to invention of Claim 9, a heat conductive molded object does not generate | occur | produce volatile gases, such as low molecular weight siloxane, and does not pollute the inside of an electronic device. Moreover, the softness | flexibility of a heat conductive molded object can be improved, heat can be efficiently transmitted now, and the outstanding flame retardance can be exhibited. Further, by incorporating red phosphorus coated with a thermosetting resin, the red phosphorus does not inhibit the reaction of the terminal allyl group of the non-silicone polymer, and at the time of molding the thermally conductive molded body or Since no corrosive halogen-based gas is generated during incineration, for example, the life of the molding machine and the mold can be extended and the influence on the environment can be reduced.

  According to the invention of claim 10, in addition to the effect of claim 9, the blending ratio of the nonpolar hydrocarbon oil is increased by blending the nonpolar hydrocarbon oil with the nonpolar hydrocarbon polymer. And a more flexible thermally conductive molded body can be obtained.

  According to the invention of claim 11, by using polyisobutylene having an allyl group at the terminal as the nonpolar hydrocarbon polymer, the heat resistance, electrical insulation and water resistance of the thermally conductive molded body are improved. be able to.

  According to the twelfth aspect of the present invention, the non-polar hydrocarbon oil is paraffin oil, so that even if a large amount is blended with the non-polar hydrocarbon polymer, the oil is bleeded from the obtained heat conductive molded body. It becomes difficult to obtain a more flexible heat conductive molded body.

  According to the invention of claim 13, in addition to the effect of claim 1, the blending ratio of the polar group-containing non-silicone oil is adjusted by blending the polar group-containing non-silicone oil with the non-silicone polar polymer. It can be made high and a more flexible heat conductive molded object can be obtained.

  According to the invention of claim 14, by using a polyacrylate having an allyl group at the terminal as the non-silicone polar polymer, the weather resistance, heat resistance, and oil resistance of the thermally conductive molded body can be improved. it can.

  According to the invention of claim 15, by making the polar group-containing non-silicone oil into an ester oil, the oil is difficult to bleed from the thermally conductive molded article even if blended in a large amount in the non-silicone polar polymer. A more flexible thermally conductive molded body can be obtained.

  According to the invention of claim 16, since the metal hydroxide is blended as the thermally conductive filler, the metal hydroxide releases crystal water at 200 ° C. or higher and absorbs the heat of vaporization. The material is cooled and further flame retardant effects are exhibited.

  According to the invention of claim 17, by incorporating aluminum hydroxide as the metal hydroxide, the manufacturing cost of the heat conductive molded body is greatly reduced, and by the combination of red phosphorus and aluminum hydroxide. Low smoke generation effect is demonstrated.

  According to the eighteenth aspect of the present invention, the heat conductive molded body as described above can be easily obtained.

Hereinafter, the present invention will be described in more detail.
(First embodiment and second embodiment)
The thermally conductive molded body of the first embodiment and the second embodiment includes a thermally conductive filler, a non-silicone polymer having an allyl group at the terminal as a base material, and a non-silicone oil as a plasticizer. It is formed from a polymer composition. In the present invention, the “non-silicone polymer” means a polymer that does not contain a siloxane bond (Si—O) _n in its molecular chain. Specific examples of the non-silicone polymer having an allyl group at the terminal include a nonpolar hydrocarbon polymer having an allyl group at the terminal and a non-silicone polar polymer having an allyl group at the terminal. The “non-silicone oil” means an oil that does not contain a component containing a siloxane bond (Si—O) _n in the molecule. Specific examples of the non-silicone oil include non-polar hydrocarbon oils and polar group-containing non-silicone oils. The non-silicone oils have a kinematic viscosity of 70mm ² / s~500mm ² / s at 40 ° C.. In the polymer composition, 200 to 400 parts by weight of the non-silicone oil is blended with 100 parts by weight of the non-silicone polymer. In the polymer composition, by blending a non-silicone polymer having an allyl group at the terminal and a non-silicone oil having a kinematic viscosity in the above range, the resulting thermally conductive molded product is In addition, volatile gases such as low molecular weight siloxane are hardly generated, and the inside of electronic equipment is not contaminated. Further, in the polymer composition, a non-silicone oil is blended with a non-silicone polymer in a proportion within the above range, whereby the resulting heat conductive molded article has good flexibility and a heat generating component. Adhesion with cooling parts and cooling can be improved and heat can be transferred efficiently.

(First embodiment)
In the first embodiment of the present invention, the thermally conductive molded body has a thermally conductive filler, a nonpolar hydrocarbon polymer having an allyl group at the terminal, and a kinematic viscosity at 40 ° C. of 90 mm ² / s to 400 mm. It is formed from a polymer composition containing a nonpolar hydrocarbon oil that is ² / s. In the polymer composition, 200 parts by weight to 400 parts by weight of the nonpolar hydrocarbon oil is blended with 100 parts by weight of the nonpolar hydrocarbon polymer. The polymer composition may further include a curing agent.

In the present embodiment, the polymer composition contains a nonpolar hydrocarbon polymer having an allyl group at the terminal as a base material. In the present invention, the nonpolar hydrocarbon polymer having an allyl group at the terminal is a hydrocarbon-based polymer having an allyl group (CH ₂ ═CH—CH ₂ —) at the terminal and having no polar functional group. Refers to a molecule. Since the nonpolar hydrocarbon polymer having an allyl group at the terminal does not contain a silicone component, the above-described problem of low molecular weight siloxane generation can be avoided. In addition, by using a nonpolar hydrocarbon polymer having an allyl group at the terminal as a base material, the polymer composition can be heat-cured in the atmosphere by a hydrosilylation reaction or the like. Thereby, productivity of a heat conductive molded object improves and manufacturing cost can be reduced.

  Such a nonpolar hydrocarbon polymer having an allyl group at the terminal can be generally obtained by introducing an allyl group into the terminal of the nonpolar hydrocarbon polymer having excellent weather resistance and chemical resistance. . Specific examples of the nonpolar hydrocarbon polymer having an allyl group at the terminal include polyisobutylene, polyisoprene, polybutadiene, and polybutene having an allyl group at the terminal. Among these, it is preferable to use polyisobutylene having an allyl group at the terminal from the viewpoint of excellent heat resistance, electrical insulation, and water resistance. From the viewpoint of moldability, the nonpolar hydrocarbon polymer having an allyl group at the terminal used in the present invention is liquid at room temperature. The number average molecular weight of such a nonpolar hydrocarbon polymer is preferably in the range of 1000-20000. When the number average molecular weight is in the range of 5000 to 7000, the nonpolar hydrocarbon polymer having an allyl group at the terminal has a relatively low viscosity, so that the heat conductive filler can be filled at a high rate. Therefore, it is particularly preferable.

  In the present embodiment, the polymer composition contains a nonpolar hydrocarbon oil as a plasticizer. In the present invention, the nonpolar hydrocarbon-based oil is an oil mainly composed of a hydrocarbon not substituted with a polar group, and is usually liquid at room temperature and normal pressure (15 ° C., 1013.25 hPa (1 atm)). Refers to things. By using non-polar hydrocarbon polymer having non-polar hydrocarbon polymer having the allyl group, compatibility is improved, and hydrocarbon oil for hydrocarbon polymer having allyl group is enhanced. Becomes easy to disperse. Therefore, the hydrocarbon oil can be blended at a high ratio with respect to the hydrocarbon polymer having an allyl group. Therefore, a more flexible thermally conductive molded body can be obtained. In addition, since the nonpolar hydrocarbon-based oil does not contain a silicone component, the above-described problems due to the generation of low molecular weight siloxane can be avoided.

  Specific examples of such nonpolar hydrocarbon oils include paraffin oil, polyalphaolefin oil, and polybutene oil. Among these, paraffin oil that can be blended in a large amount with respect to the nonpolar hydrocarbon polymer and is excellent in uniform dispersibility is particularly preferable.

The non-polar hydrocarbon-based oils used in the present embodiment has a kinematic viscosity of 90mm ² / s~400mm ² / s at 40 ° C.. In the thermally conductive molded body, such nonpolar hydrocarbon-based oil hardly generates volatile gas in the mounting use temperature range of the thermally conductive molded body, and does not contaminate the inside of the electronic device. In this embodiment, as a volatile gas generation acceleration test from the thermally conductive molded body, when the thermally conductive molded body is left in an atmosphere of 200 ° C. for 1 hour and the weight reduction ratio of the thermally conductive molded body is measured, The weight reduction rate is less than 1%, which is a very small value (see Examples). Therefore, it can be considered that volatile gas is not substantially generated. Nonpolar hydrocarbon oils having a kinematic viscosity at 40 ° C. of less than 90 mm ² / s have high volatility. Therefore, when such oils are used, the amount of volatile gas from the thermally conductive molded body increases and the inside of the electronic equipment is increased. Contaminate. When the kinematic viscosity at 40 ° C. of the nonpolar hydrocarbon-based oil exceeds 400 mm ² / s, the viscosity of the oil increases, so that the polymer composition becomes difficult to process.

  Furthermore, in the polymer composition, 200 parts by weight to 400 parts by weight of a nonpolar hydrocarbon oil is blended with 100 parts by weight of the nonpolar hydrocarbon polymer. Thereby, the flexible heat conductive molded object that the hardness of a sheet | seat becomes 60 or less is obtained. Such a flexible heat conductive molded body improves the adhesion between the heat generating component and the cooling component, and therefore can conduct heat more efficiently. When the blending amount of the nonpolar hydrocarbon oil is less than 200 parts by weight, the hardness of the resulting molded product is increased, and a flexible heat conductive molded product cannot be obtained. When the blending amount of the non-polar hydrocarbon oil exceeds 400 weight, the oil is likely to bleed (exude) from the obtained heat conductive molded body, and there is a possibility that the inside of the electronic device is contaminated.

(Second embodiment)
In the second embodiment of the present invention, the thermally conductive molded body has a thermally conductive filler, a non-silicone polar polymer having an allyl group at the terminal as a base material, and a kinematic viscosity at 40 ° C. as a plasticizer of 70 mm. it is formed from a polymeric composition comprising a polar group-containing non-silicone-based oil is a ² / ^{s~500mm 2} / s. In this polymer composition, 200 parts by weight to 400 parts by weight of the polar group-containing non-silicone oil is blended with 100 parts by weight of the non-silicone polar polymer. The polymer composition may further include a curing agent.

In the present embodiment, the polymer composition contains a non-silicone polar polymer having an allyl group at the terminal as a base material. In the present invention, the non-silicone polar polymer having an allyl group at the end has an allyl group (CH ₂ ═CH—CH ₂ —) at the end of the molecular chain and a siloxane bond (Si—O in the molecular chain). ) A polymer not containing _n and having a polar group. Since the non-silicone polar polymer having an allyl group at the terminal does not contain a silicone component, the above-described problem of low molecular weight siloxane generation can be avoided. In addition, by using a non-silicone polar polymer having an allyl group at the terminal as a base material, the polymer composition can be heat-cured in the atmosphere by a hydrosilylation reaction or the like. Thereby, productivity of a heat conductive molded object improves and manufacturing cost can be reduced.

  Specific examples of the non-silicone polar polymer having an allyl group at the terminal include polyacrylates, polyamides, and polyesters having an allyl group at the terminal. Especially, it is preferable to use the polyacrylate which has an allyl group at the terminal from the point which is excellent in a weather resistance, heat resistance, and oil resistance. From the viewpoint of moldability, the non-silicone polar polymer having an allyl group at the terminal used in the present invention is liquid at room temperature. The number average molecular weight of such a non-silicone polar polymer is preferably in the range of 5000-30000. When the number average molecular weight is in the range of 10,000 to 20,000, the non-silicone polar polymer having an allyl group at the terminal has a relatively low viscosity, and therefore, the heat conductive filler can be filled at a high rate. Is particularly preferred.

In the present embodiment, the polymer composition contains a polar group-containing non-silicone oil as a plasticizer. In the present invention, the polar group-containing non-silicone oil is an oil mainly composed of a compound having a polar group but not containing a siloxane bond (Si-O) _n. .25 hPa). A non-silicone polar polymer having an allyl group can be obtained by using a polar group-containing non-silicone oil having the same polarity as the non-silicone polar polymer having an allyl group. On the other hand, the polar group-containing non-silicone oil can be easily dispersed, and the polar group-containing non-silicone oil can be blended at a high ratio with respect to the non-silicone polar polymer having an allyl group. Therefore, a more flexible thermally conductive molded body can be obtained. Further, since the polar group-containing non-silicone oil does not contain a silicone component, the above-described problems due to the generation of low molecular weight siloxane can be avoided.

  Specific examples of such polar group-containing non-silicone oils include ester oils and acrylic oils. Among these, ester oils that can be blended in a large amount with respect to the non-silicone polar polymer and are excellent in uniform dispersibility are particularly preferable.

Further, the polar group-containing non-silicone oil used in the present embodiment has a kinematic viscosity of 70mm ² / s~500mm ² / s at 40 ° C.. In the thermally conductive molded body, such a polar group-containing non-silicone oil hardly generates volatile gas in the mounting use temperature range of the thermally conductive molded body and does not contaminate the inside of the electronic device. In this embodiment, as a volatile gas generation acceleration test from the thermally conductive molded body, the thermally conductive molded body is left in an atmosphere of 200 ° C. for 1 hour, and the weight reduction rate of the thermally conductive molded body is measured. The reduction rate is a very small value of less than 1%, and it can be considered that volatile gas is not substantially generated (see Examples). Since the polar group-containing non-silicone oil having a kinematic viscosity at 40 ° C. of less than 70 mm ² / s has high volatility, the use of such oil increases the amount of volatile gas from the thermally conductive molded body. The inside is polluted. If the kinematic viscosity at 40 ° C. of the polar group-containing non-silicone oil exceeds 500 mm ² / s, the viscosity of the oil increases, and the polymer composition becomes difficult to process.

  Furthermore, in the polymer composition, 200 parts by weight to 400 parts by weight of a polar group-containing non-silicone oil is blended with 100 parts by weight of the non-silicone polar polymer. Thereby, the flexible heat conductive molded object that the hardness of a sheet | seat becomes 60 or less is obtained. Such a flexible heat conductive molded body improves the adhesion between the heat generating component and the cooling component, and therefore can conduct heat more efficiently. When the blending amount of the polar group-containing non-silicone oil is less than 200 parts by weight, the hardness of the resulting molded product is increased, and a flexible heat conductive molded product cannot be obtained. When the blending amount of the polar group-containing non-silicone oil exceeds 400 weight, the oil is likely to bleed (exude) from the obtained heat conductive molded article, and the electronic device may be contaminated.

Although it does not specifically limit as a hardening | curing agent used in 1st embodiment and 2nd embodiment, The hardening | curing agent which has Si-H group is an allyl group terminal double immediately by heating in presence of a platinum catalyst. This is preferable because it undergoes an addition reaction to bond. For example, it has a dimethylsiloxane structure (— (CH ₃ ) Si (CH ₃ ) O—) as a basic skeleton, and in the molecular chain, some of the methyl groups in the structure are replaced with hydrogen to form Si—H groups You may use the hardening agent which has become. In such a curing agent, the dimethylsiloxane structure may be further modified with an organic substance in order to impart compatibility with the substrate. When such a curing agent containing an Si—H group is added to the polymer composition of the present invention, a non-silicone polymer (nonpolar hydrocarbon polymer / non-polar polymer having an allyl group as a base material). The polymer composition can be heated and cured in the air by a hydrosilylation reaction with a non-silicone polar polymer). Thereby, productivity of a heat conductive molded object improves and manufacturing cost can be reduced. Moreover, since the addition amount of the curing agent in the polymer composition is very small (for example, about 5 to 10 parts by weight with respect to 100 parts by weight of the nonpolar / non-silicone polar polymer), The entire amount reacts with the hydrocarbon-based polymer having an allyl group at the terminal and is incorporated into the polymer. Therefore, even if the curing agent has a dimethylsiloxane structure, it is considered that unreacted low-molecular siloxane is not generated. In addition, any curing agent capable of crosslinking a polymer containing a double bond, such as a peroxide curing agent, can be used.

  Examples of the thermally conductive filler used in the first embodiment and the second embodiment include metal oxides, metal nitrides, metal carbides, and metal hydroxides that have high thermal conductivity and are electrically insulating. A powder is mentioned. Specific examples include powders such as aluminum oxide, boron nitride, aluminum nitride, magnesium oxide, zinc oxide, silicon carbide, quartz, and aluminum hydroxide, but are not limited thereto. Moreover, you may use powder, such as carbon fiber, diamond, and graphite, which has high heat conductivity and conductivity.

The polymer composition of the present invention may further contain an appropriate amount of a catalyst, a curing retarder, a deterioration inhibitor and the like for the purpose of improving productivity, weather resistance, heat resistance and the like.
In the present invention, the polymer composition may be formed into an arbitrary shape. For example, the polymer composition can be formed into a sheet shape to form a heat conductive sheet.

Examples of the molding method of the present invention include, but are not limited to, a method of injecting a polymer composition into a mold and a method of casting the polymer composition on a substrate.
The heat conductive molded object of this invention can be used for the heat-transfer sheet | seat etc. which are pinched | interposed between an electronic component and a heat radiating member, and transmit the heat which generate | occur | produces from an electronic component to a heat radiating member.

(Third embodiment and fourth embodiment)
The thermally conductive molded body of the third embodiment and the fourth embodiment includes a thermally conductive filler, a non-silicone polymer having the allyl group at the end as a base material, and the non-silicone oil as a plasticizer. And a polymer composition containing red phosphorus coated with a thermosetting resin. The definition of the non-silicone polymer having an allyl group at the end is the same as in the first and second embodiments described above, the nonpolar hydrocarbon polymer having an allyl group at the end, and the allyl group at the end. Specific examples include non-silicone polar polymers. The definition of the non-silicone oil is the same as in the first embodiment and the second embodiment, and specific examples include nonpolar hydrocarbon oils and polar group-containing nonsilicone oils. In the polymer composition, 3 parts by weight to 200 parts by weight with respect to 100 parts by weight of the non-silicone polymer in a ratio of 200 parts by weight to 400 parts by weight of the non-silicone oil and the red phosphorus alone. And red phosphorus coated with the thermosetting resin. In the polymer composition, by blending a non-silicone polymer having an allyl group at the terminal and a non-silicone oil, the resulting heat conductive molded body is mounted at the time of its mounting for the same reason as described above. It does not pollute the electronic equipment and can transfer heat efficiently. Further, by blending red phosphorus coated with a thermosetting resin with a non-silicone polymer in a proportion within the above range, the resulting thermally conductive molded body is obtained from US Under Lighters Laboratories Inc. (Under). Excellent flame retardancy equivalent to the UL94V-0 grade defined in the UL standard established by (Writers Laboratories Inc) can be obtained. Since red phosphorus is coated with resin, it does not inhibit the crosslinking reaction of non-silicone polymers having an allyl group at the end.
(Third embodiment)
In the third embodiment of the present invention, the thermally conductive molded body has a thermally conductive filler, a nonpolar hydrocarbon polymer having an allyl group at the terminal, and a kinematic viscosity at 40 ° C. of 90 mm ² / s to 400 mm. It is formed from a polymer composition containing a nonpolar hydrocarbon oil of ² / s and red phosphorus coated with a thermosetting resin. In this polymer composition, 3 parts by weight with respect to 100 parts by weight of the nonpolar hydrocarbon polymer in a ratio of 200 parts by weight to 400 parts by weight of the nonpolar hydrocarbon oil and the red phosphorus alone. ~ 200 parts by weight of red phosphorus coated with the thermosetting resin is blended. The polymer composition may further include a curing agent.

  In the present embodiment, the polymer composition contains a nonpolar hydrocarbon polymer having an allyl group at the terminal as a base material. The definition, physical properties, specific examples, preferable limitations, and reasons for limitation of the nonpolar hydrocarbon polymer having an allyl group at the terminal are the same as in the first embodiment. The nonpolar hydrocarbon-based polymer can avoid the problem of low molecular weight siloxane generation for the same reason as in the first embodiment, and heat conduction is achieved by heating and curing the polymer composition in the air. The productivity of the molded product can be improved and the manufacturing cost can be reduced.

  In the present embodiment, the polymer composition contains a nonpolar hydrocarbon oil as a plasticizer. By using the same nonpolar hydrocarbon oil for the nonpolar hydrocarbon polymer having an allyl group, it is possible to obtain a more flexible thermally conductive molded article for the same reason as in the first embodiment. Can do. In addition, since the nonpolar hydrocarbon-based oil does not contain a silicone component, the above-described problems due to the generation of low molecular weight siloxane can be avoided. Specific examples, physical properties, preferable limitations, and reasons for limitation of such nonpolar hydrocarbon oil are the same as those in the first embodiment.

  In the present embodiment, the polymer composition contains red phosphorus coated with a thermosetting resin as a flame retardant. Examples of thermosetting resins that coat red phosphorus include phenolic resins, furan resins, xylene / formaldehyde resins, ketone / formaldehyde resins, urea resins, melamine resins, aniline resins, alkyd resins, unsaturated polyester resins, and epoxy resins. It is done. The red phosphorus coated with the thermosetting resin is blended so as to be 3 parts by weight to 200 parts by weight with respect to 100 parts by weight of the non-silicone polymer having an allyl group at the terminal. Yes. If the proportion of red phosphorus coated with the thermosetting resin is less than 3 parts by weight, the flame retardant effect is not exhibited, and if it exceeds 200 parts by weight, the production cost of the thermally conductive molded body increases.

In the polymer composition, with respect to 100 parts by weight of the nonpolar hydrocarbon polymer, in addition to red phosphorus coated with the thermosetting resin in the blending ratio, 200 parts by weight to 400 parts by weight of non-phosphorus polymer Polar hydrocarbon oil is blended. As a result, the sheet has a hardness of 60 or less and has flexibility, and even in the case of a thin sheet-like molded body having a thickness of less than 1.0 mm, excellent equivalent to the UL94V-0 grade. Thus, a heat conductive molded article having flame retardancy can be obtained. Such a heat conductive molded body that is flexible and excellent in flame retardance can conduct heat more efficiently because adhesion between the heat generating component and the cooling component is improved. The reason for limiting the blending amount of the nonpolar hydrocarbon oil is the same as in the first embodiment.
(Fourth embodiment)
In the fourth embodiment of the present invention, the thermally conductive molded body has a thermally conductive filler, a non-silicone polar polymer having an allyl group at the end as a base material, and a kinematic viscosity at 40 ° C. as a plasticizer of 70 mm. and ^{2 / s~500mm 2 / s} of the polar group-containing non-silicone-based oil, it is formed from a polymeric composition comprising a red phosphorus coated with a thermosetting resin. In this polymer composition, 3 parts by weight in a proportion of 200 parts by weight to 400 parts by weight of the non-silicone oil containing polar group and 100 parts by weight of the red phosphorus with respect to 100 parts by weight of the non-silicone polar polymer. ~ 200 parts by weight of red phosphorus coated with the thermosetting resin is blended. The polymer composition may further include a curing agent.

  In the present embodiment, the polymer composition contains a non-silicone polar polymer having an allyl group at the terminal as a base material. Since the non-silicone polar polymer having an allyl group at the terminal does not contain a silicone component, the above-described problem of low molecular weight siloxane generation can be avoided. In addition, by using a non-silicone polar polymer having an allyl group at the terminal as the base material, the productivity of the thermally conductive molded body is improved and the manufacturing cost is reduced for the same reason as in the second embodiment. can do. Specific examples, physical properties, preferable limitations and reasons for the non-silicone polar polymer having an allyl group at the terminal are the same as in the second embodiment.

  In the present embodiment, the polymer composition contains a polar group-containing non-silicone oil as a plasticizer. By using the polar group-containing non-silicone oil having the same polarity as the non-silicone polar polymer having the polarity and the allyl group, for the same reason as in the second embodiment, A flexible heat conductive molded body can be obtained. Further, since the polar group-containing non-silicone oil does not contain a silicone component, the above-described problems due to the generation of low molecular weight siloxane can be avoided. Specific examples, physical properties, preferable limitations, and reasons for limitation of such polar group-containing non-silicone oil are the same as in the second embodiment.

Also in this embodiment, the said polymer composition contains the red phosphorus coat | covered with the thermosetting resin similar to 3rd embodiment as a flame retardant.
In the polymer composition, with respect to 100 parts by weight of the non-silicone polar polymer, 200 parts by weight to 400 parts by weight of the polar group-containing non-silicone oil and 3 parts by weight to 200 parts by weight of red phosphorus alone. It contains red phosphorus coated with a part by weight of thermosetting resin. Thereby, even in the case of a thin sheet-like molded body having a flexibility such that the hardness of the sheet is 60 or less and a thickness of less than 1.0 mm, it corresponds to the UL94V-0 grade. A thermally conductive molded body having excellent flame retardancy is obtained. Such a heat conductive molded body that is flexible and excellent in flame retardance can conduct heat more efficiently because adhesion between the heat generating component and the cooling component is improved. The reason for limiting the blending amount of the polar group-containing non-silicone oil is the same as in the second embodiment.

  Although it does not specifically limit as a hardening | curing agent used in 3rd embodiment and 4th embodiment, The hardening | curing agent which has Si-H group is an allyl group terminal double immediately by heating in presence of a platinum catalyst. Preferred for addition reaction to the bond. However, this reaction can be inhibited when normal red phosphorus that is not surface treated to impart flame retardancy is used. Therefore, in the third embodiment and the fourth embodiment, the use of red phosphorus coated with a thermosetting resin prevents the reaction from being inhibited. Specific examples and physical properties of the curing agents of the third embodiment and the fourth embodiment are the same as those of the first embodiment and the second embodiment.

  Specific examples of the thermally conductive filler of the third embodiment and the fourth embodiment are the same as those of the first embodiment and the second embodiment. Among these thermally conductive fillers, it is considered that the combustion substances are cooled to release crystal water at 200 ° C. or higher and absorb the heat of vaporization, and in this respect, an effect as a flame retardant aid is expected. Therefore, metal hydroxide is preferable. Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, and calcium hydroxide. Of the metal hydroxides, aluminum hydroxide is particularly preferred because it is not only very cheap, but also has a low smoke generation effect when used in combination with a red phosphorus flame retardant.

  Hereinafter, the present invention will be described in more detail with reference to examples.

Thermally conductive sheet of the first embodiment (Example 1)
In Example 1, as a nonpolar hydrocarbon polymer having an allyl group at the terminal, polyisobutylene having an allyl group at the terminal (EP200A, number average molecular weight = 5000, manufactured by Kaneka Corporation) 300 parts by weight of paraffinic oil (PW-90 manufactured by Idemitsu Kosan Co., Ltd.) having a kinematic viscosity of 90 mm ² / s as a hydrogen-based oil and 800 parts by weight of aluminum hydroxide having an average particle size of 44 μm as a heat conductive filler 400 parts by weight of aluminum hydroxide having an average particle diameter of 8 μm, 5 parts by weight of a curing agent (CR300, manufactured by Kaneka Corporation) having a dimethylsiloxane structure modified with an organic substance as a curing agent, and an anti-aging agent (NOCRACK NS -7, 1 part by weight of Ouchi Shinsei Chemical Co., Ltd.) and a retarder (ME-75, GE Toshiba Silicone Co., Ltd.) 0.5 parts by weight of a chemical company) and 0.1 parts by weight of a platinum catalyst (PT-CS-3.2cS, manufactured by Ferro (USA)) and mixed with a vibration stirrer to form a polymer A composition was prepared. The polymer composition was formed into a sheet, vacuum degassed, and then heated in a 130 ° C. atmosphere for 1 hour to cure the polymer composition to obtain a heat conductive sheet.

(Example 2)
In Example 2, the nonpolar hydrocarbon oil is the same as Example 1 except that the non-polar hydrocarbon oil is changed to 300 parts by weight of paraffin oil (PW-150, manufactured by Idemitsu Kosan Co., Ltd.) having a kinematic viscosity of 40 ° C. of 150 mm ² / s. A polymer composition of composition was prepared. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 1.

(Example 3)
Example 3 is the same as Example 1 except that the nonpolar hydrocarbon oil is changed to 300 parts by weight of paraffin oil (PW-380, manufactured by Idemitsu Kosan Co., Ltd.) having a kinematic viscosity of 40 ° C. of 400 mm ² / s. A polymer composition having the following composition was prepared. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 1.

Example 4
In Example 4, the blending amount of paraffin oil (PW-90 Idemitsu Kosan Co., Ltd.) having a kinematic viscosity of 90 mm ² / s at 40 ° C. was changed to 200 parts by weight, and blending of aluminum hydroxide having an average particle size of 44 μm A polymer composition having the same composition as in Example 1 was prepared except that the amount was changed to 600 parts by weight and the amount of aluminum hydroxide having an average particle size of 8 μm was changed to 300 parts by weight. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 1.

(Example 5)
In Example 5, the blending amount of paraffin oil (PW-90 made by Idemitsu Kosan Co., Ltd.) having a kinematic viscosity of 90 mm ² / s at 40 ° C. was changed to 400 parts by weight, and blending of aluminum hydroxide having an average particle size of 44 μm A polymer composition having the same composition as in Example 1 was prepared except that the amount was changed to 1000 parts by weight and the amount of aluminum hydroxide having an average particle size of 8 μm was changed to 500 parts by weight. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 1.

(Comparative Example 1)
In Comparative Example 1, except that a non-polar hydrocarbon oil is 40 ° C. kinematic viscosity was changed to paraffin oil (manufactured by PW-30 manufactured by Idemitsu Kosan Co., Ltd.) 300 parts by weight of 30 mm ² / s, Example 1 the same as A polymer composition of composition was prepared. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 1.

(Comparative Example 2)
In Comparative Example 2, the same as Example 1 except that the nonpolar hydrocarbon oil was changed to 300 parts by weight of paraffin oil (PS-430 manufactured by Idemitsu Kosan Co., Ltd.) having a kinematic viscosity of 40 ° C. of 440 mm ² / s. A polymer composition of composition was prepared. An attempt was made to produce a thermally conductive sheet from the polymer composition by the same method as in Example 1. However, in Comparative Example 2, because the paraffin oil has a large kinematic viscosity at 40 ° C., the viscosity of the prepared polymer composition was increased, and the polymer composition could not be kneaded and formed into a sheet shape. .

(Comparative Example 3)
In Comparative Example 3, the 40 ° C. kinematic viscosity change the amount of 90 mm ² / s of the paraffin oil (manufactured by PW-90 manufactured by Idemitsu Kosan Co., Ltd.) to 150 parts by weight, the amount of aluminum hydroxide having an average particle diameter of 44μm Was changed to 500 parts by weight, and a polymer composition having the same composition as Example 1 was prepared except that the amount of aluminum hydroxide having an average particle size of 8 μm was changed to 250 parts by weight. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 1.

(Comparative Example 4)
In this comparative example 4, the blending amount of paraffin oil (PW-90 Idemitsu Kosan Co., Ltd.) having a kinematic viscosity of 90 mm ² / s at 40 ° C. was changed to 450 parts by weight, and blending of aluminum hydroxide having an average particle size of 44 μm A polymer composition having the same composition as in Example 1 was prepared except that the amount was changed to 1100 parts by weight and the amount of aluminum hydroxide having an average particle size of 8 μm was changed to 550 parts by weight. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 1.

About the heat conductive sheet obtained in Examples 1-5 and Comparative Examples 1-4, hardness (JIS K6253 conformity, type E durometer) and thermal resistance value were measured. The thermal resistance value is determined by placing test pieces (size: thickness 1.0 mm × length 10 mm × width 10 mm) of each thermally conductive molded body on a heat generation substrate (heat generation amount Q: 4 W). A heat sink (FH60-30 manufactured by Alpha Co., Ltd.) is pressed into contact with a constant load (2 kgf / cm ² ). A fan (air volume: 0.01 (kg / sec), wind pressure: 49 (Pa)) is attached to the top of the heat sink, and a temperature sensor is connected to the heat sink and the heat generating substrate. In this state, the heating substrate is energized. After 5 minutes, the temperature of the heat generating substrate (θ _j1 ) and the temperature of the heat sink (θ _i0 ) were measured, and the measured values were applied to the following formula to calculate the thermal resistance value. The following relationship is established between the thermal resistance value and the thermal conductivity, and the thermal resistance value can be converted into thermal conductivity.

Thermal resistance value (° _{C./W)=(θ j1} −θ _j0 ) / heat generation amount Q
= Thickness (m) in the heat passing direction of the test piece / (Heat passing cross-sectional area (m ² ) × heat conductivity (W / m · K))
The heat conductive sheets obtained in Examples 1 to 5 and Comparative Examples 1 to 4 were subjected to a volatile gas generation acceleration test. Each thermally conductive sheet was measured for a change in weight after being left at a constant temperature of 200 ° C. for 1 hour using a thermogravimetric measuring device (TGA-50, Shimadzu Corporation).

The above measurement results are shown in Tables 1 and 2.
The heat conductive sheets of Examples 1 to 5 had a hardness of 54 or less and a thermal resistance value of 4.2 (° C./W) or less. Therefore, since these heat conductive sheets have high heat conductivity and are highly flexible, they have good adhesion to other members and can transmit heat more efficiently. A thermally conductive molded product was obtained with high productivity and at a low price. Also, in the volatile gas generation acceleration test, since the reduction ratio of the sheet weight is less than 1%, it is considered that there is almost no generation of low molecular weight siloxane and other volatile gases. Further, these thermally conductive sheets did not cause bleed phenomenon during mounting.

  On the other hand, in the heat conductive sheet of Comparative Example 1, the weight of the heat conductive molded body was reduced by 5% in the volatile gas generation acceleration test. Therefore, in the mounting, this heat conductive sheet may generate volatile gas and contaminate the inside of the electronic device. In addition, it is considered that the heat conductive sheet of Comparative Example 3 hardly generates volatile gas because the reduction ratio of the weight of the heat conductive molded body in the volatile gas generation acceleration test is small. In addition, no bleeding phenomenon occurred in the mounting. However, since the hardness of the sheet is 61, which is inferior in flexibility, even if the thermal resistance value of the sheet itself is relatively good, sufficient adhesion with the mounting target cannot be obtained when mounted, which is efficient. You may not be able to transfer heat to your. The heat conductive sheet of Comparative Example 4 is considered to generate little volatile gas because the weight reduction ratio of the heat conductive molded body in the volatile gas generation acceleration test is small. However, since this thermally conductive sheet has caused a bleed phenomenon, there is a possibility that the inside of the electronic device is contaminated during mounting.

第２実施形態の熱伝導性シート
（実施例６）
実施例６においては、末端基にアリル基を有する非シリコーン系極性高分子として末端にアリル基を有するポリアクリレート（ＳＡ１００Ａ 数平均分子量＝２００００ 株式会社カネカ製）１００重量部に、極性基含有非シリコーン系オイルとして４０℃動粘度が７０ｍｍ^２／ｓのポリオールエステルオイル（ＨＡＴＣＯＬ２３６２ ＨＡＴＣＯ社（米国）製）を３００重量部と、熱伝導性充填剤として平均粒径４４μｍの水酸化アルミニウムを８００重量部および平均粒径８μｍの水酸化アルミニウムを４００重量部と、硬化剤として有機物で変性したジメチルシロキサン構造を有する硬化剤（ＣＲ５００ 株式会社カネカ製）を１０重量部と、老化防止剤（ノクラックＮＳ−７、大内新興化学工業）を３重量部と、白金触媒（ＰＴ−ＣＳ−３．２ｃＳ、Ｆｅｒｒｏ社（米国）製）を０．５重量部とを配合し、振動攪拌器により混合して高分子組成物を調製した。この高分子組成物をシート状に成形し、真空脱泡した後に、１３０℃雰囲気で１時間加熱して、前記高分子組成物を硬化することにより熱伝導性シートを得た。

Thermally conductive sheet of the second embodiment (Example 6)
In Example 6, a polar group-containing non-silicone was added to 100 parts by weight of a polyacrylate (SA100A number average molecular weight = 20000, manufactured by Kaneka Corporation) having an allyl group at the terminal as a non-silicone polar polymer having an allyl group at the terminal group. 40 ° C. kinematic viscosity of 70 mm ² / s of the polyol ester oil (HATCOL2362 Hatco Corporation (USA)) as a system oil and 300 parts by weight, 800 parts by weight of aluminum hydroxide having an average particle diameter of 44μm as the thermally conductive filler and 400 parts by weight of aluminum hydroxide having an average particle diameter of 8 μm, 10 parts by weight of a curing agent having a dimethylsiloxane structure modified with an organic substance as a curing agent (CR500, manufactured by Kaneka Corporation), an anti-aging agent (NOCRACK NS-7, 3 parts by weight of Ouchi Shinsei Chemical Industry) and platinum catalyst (PT-CS-3) .2 cS, manufactured by Ferro (USA), 0.5 parts by weight, and mixed with a vibration stirrer to prepare a polymer composition. The polymer composition was molded into a sheet and vacuum degassed, and then heated in a 130 ° C. atmosphere for 1 hour to cure the polymer composition, thereby obtaining a heat conductive sheet.

(Example 7)
In Example 7, except that the polar group-containing non-silicone oil is 40 ° C. kinematic viscosity was changed to 120 mm ² / s of the polyol ester oil (HATCOL2372 Hatco Corporation (USA)) 300 parts by weight, same as in Example 6 A polymer composition having the following composition was prepared. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 1.

(Example 8)
Example 8 is the same as Example 6 except that the polar group-containing non-silicone oil was changed to 300 parts by weight of an acrylic oil (UP1021 manufactured by Toa Gosei Co., Ltd.) having a kinematic viscosity at 40 ° C. of 400 mm ² / s. A polymer composition of composition was prepared. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 1.

Example 9
Example 9 is the same as Example 6 except that the polar group-containing non-silicone oil was changed to 300 parts by weight of an acrylic oil (UP1020 manufactured by Toa Gosei Co., Ltd.) having a kinematic viscosity at 40 ° C. of 500 mm ² / s. A polymer composition of composition was prepared. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 1.

(Example 10)
In Example 10, 40 ° C. kinematic viscosity of 70 mm ² / s of the polyol ester oil (HATCOL2362 Hatco Corporation (USA)) was changed to 200 parts by weight the amount of the amount of aluminum hydroxide having an average particle diameter of 44μm Was changed to 600 parts by weight, and a polymer composition having the same composition as Example 6 was prepared except that the amount of aluminum hydroxide having an average particle size of 8 μm was changed to 300 parts by weight. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 1.

(Example 11)
In Example 11, 40 ° C. kinematic viscosity of 70 mm ² / s of the polyol ester oil (HATCOL2362 Hatco Corporation (USA)) was changed to 400 parts by weight the amount of the amount of aluminum hydroxide having an average particle diameter of 44μm Was changed to 1000 parts by weight, and a polymer composition having the same composition as Example 6 was prepared, except that the amount of aluminum hydroxide having an average particle size of 8 μm was changed to 500 parts by weight. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 6.

(Comparative Example 5)
In Comparative Example 5, the same as Example 6 except that the polar group-containing non-silicone oil was changed to 300 parts by weight of a polyol ester oil (HATCOL 2352 manufactured by HATCO (USA)) having a kinematic viscosity at 40 ° C. of 30 mm ² / s. A polymer composition having the following composition was prepared. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 6.

(Comparative Example 6)
In Comparative Example 6, the same composition as in Example 6 except that the polar group-containing non-silicone oil was changed to 300 parts by weight of an ester oil (Ketjenrub 165 manufactured by Akzo Nobel) having a kinematic viscosity at 40 ° C. of 750 mm ² / s. A polymer composition was prepared. An attempt was made to produce a thermally conductive sheet from the polymer composition by the same method as in Example 6. However, since the kinematic viscosity of the polyester-based oil is large, the viscosity of the polymer composition increases, and the polymer composition cannot be kneaded and formed into a sheet shape.

(Comparative Example 7)
In Comparative Example 7, 40 ° C. kinematic viscosity of 70 mm ² / s of the polyol ester oil (HATCOL2362 Hatco Corporation (USA)) was changed to 150 parts by weight the amount of the amount of aluminum hydroxide having an average particle diameter of 44μm A polymer composition having the same composition as in Example 6 was prepared except that the amount of aluminum hydroxide having an average particle diameter of 8 μm was changed to 250 parts by weight. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 6.

(Comparative Example 8)
In Comparative Example 8, 40 ° C. kinematic viscosity of 70 mm ² / s of the polyol ester oil (HATCOL2362 Hatco Corporation (USA)) was changed to 450 parts by weight the amount of the amount of aluminum hydroxide having an average particle diameter of 44μm Was changed to 1100 parts by weight, and a polymer composition having the same composition as Example 6 was prepared except that the amount of aluminum hydroxide having an average particle size of 8 μm was changed to 550 parts by weight.

  In Examples 6, 10 and 11, and Comparative Examples 7 and 8, the total amount of polyacrylate having an allyl group at the terminal and polyol ester oil, and the total amount of thermally conductive filler The ratio is adjusted to be constant (polyacrylate + polyol ester oil: thermally conductive filler = 1: 3).

  For the heat conductive sheets obtained in Examples 6 to 11 and Comparative Examples 5 to 8, the hardness (JIS K6253 compliant, type E durometer) and heat resistance value measurement, and the volatile gas generation acceleration test were performed by the methods described above. I did it. The results are shown in Tables 3 and 4.

  The heat conductive sheets of Examples 6 to 11 had a hardness of 49 or less and a thermal resistance value of 3.8 (° C./W) or less. Therefore, since these heat conductive sheets have high heat conductivity and are highly flexible, they have good adhesion to other members and can transmit heat more efficiently. A thermally conductive molded product was obtained with high productivity and at a low price. Also, in the volatile gas generation acceleration test, since the reduction ratio of the sheet weight is less than 1%, it is considered that there is almost no generation of low molecular weight siloxane and other volatile gases. Further, these thermally conductive sheets did not cause bleed phenomenon during mounting.

  In the heat conductive sheet of Comparative Example 5, the weight of the heat conductive sheet was reduced by 5.1% in the volatile gas generation acceleration test, so that the volatile gas may contaminate the electronic device in the mounting. Conceivable.

  The heat conductive sheet of Comparative Example 7 is considered to generate little volatile gas because the weight reduction rate of the heat conductive molded body in the volatile gas generation acceleration test is small. In addition, no bleeding phenomenon occurred in the mounting. However, since the hardness of the sheet is 61, which is inferior in flexibility, even if the thermal resistance value of the sheet itself is relatively good, sufficient adhesion with the mounting target cannot be obtained when mounted, which is efficient. You may not be able to transfer heat to your.

  The heat conductive sheet of Comparative Example 8 is considered to generate little volatile gas because the weight reduction ratio of the heat conductive molded body in the volatile gas generation acceleration test is small. However, since this thermal conductive sheet has caused a bleed phenomenon in mounting, there is a possibility that the inside of the electronic device is contaminated.

第３実施形態の熱伝導性シート
（実施例１２）
実施例１２においては、末端にアリル基を有する非極性炭化水素系高分子として末端にアリル基を有するポリイソブチレン（ＥＰ２００Ａ、数平均分子量＝５０００、株式会社カネカ製）１００重量部に、非極性炭化水素系オイルとして４０℃動粘度が９０ｍｍ^２／ｓであるパラフィンオイル（ＰＷ−９０ 出光興産株式会社製）を３００重量部と、熱伝導性充填剤として平均粒径４４μｍの水酸化アルミニウムを８００重量部および平均粒径８μｍの水酸化アルミニウムを４００重量部と、難燃剤として熱硬化性樹脂で被覆された赤燐を５重量部と、硬化剤として有機物で変性したジメチルシロキサン構造を有する硬化剤（ＣＲ３００、株式会社カネカ製）を５重量部と、老化防止剤（ノクラックＮＳ−７、大内新興化学工業株式会社製）を１重量部と、白金触媒（ＰＴ−ＣＳ−３．２ＣＳ、Ｆｅｒｒｏ社（米国）製）を０．１重量部とを配合し、振動攪拌器により混合して高分子組成物を調製した。該高分子組成物をシート状に成形し、真空脱泡後、１３０℃雰囲気で１時間加熱することにより前記高分子組成物を硬化させて熱伝導性シートを得た。

Thermally conductive sheet of the third embodiment (Example 12)
In Example 12, 100 parts by weight of polyisobutylene having an allyl group at the end (EP200A, number average molecular weight = 5000, manufactured by Kaneka Corporation) as a nonpolar hydrocarbon polymer having an allyl group at the end 300 parts by weight of paraffinic oil (PW-90 manufactured by Idemitsu Kosan Co., Ltd.) having a kinematic viscosity of 90 mm ² / s as a hydrogen-based oil and 800 parts by weight of aluminum hydroxide having an average particle size of 44 μm as a heat conductive filler 400 parts by weight of aluminum hydroxide having an average particle size of 8 μm, 5 parts by weight of red phosphorus coated with a thermosetting resin as a flame retardant, and a curing agent having a dimethylsiloxane structure modified with an organic substance as a curing agent ( 5 parts by weight of CR300 (manufactured by Kaneka Corporation) and an anti-aging agent (NOCRACK NS-7, manufactured by Ouchi Shinsei Chemical Co., Ltd.) 1 part by weight and 0.1 part by weight of a platinum catalyst (PT-CS-3.2CS, manufactured by Ferro (USA)) were blended and mixed with a vibration stirrer to prepare a polymer composition. The polymer composition was formed into a sheet, vacuum degassed, and then heated in a 130 ° C. atmosphere for 1 hour to cure the polymer composition to obtain a heat conductive sheet.

(Example 13)
In Example 13, a polymer composition having the same composition as Example 12 was prepared, except that the blending ratio of red phosphorus coated with a thermosetting resin as a flame retardant was changed to 3 parts by weight. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 12.

(Example 14)
In Example 14, a polymer composition having the same composition as in Example 12 was prepared, except that the blending ratio of red phosphorus coated with a thermosetting resin as a flame retardant was changed to 200 parts by weight. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 12.

(Example 15)
In Example 15, the heat conductive filler was changed to 800 parts by weight of aluminum hydroxide having an average particle diameter of 8 μm and 400 parts by weight of aluminum oxide having an average particle diameter of 20 μm, and coated with a thermosetting resin as a flame retardant. A polymer composition having the same composition as Example 12 was prepared, except that the red phosphorus content was changed to 40 parts by weight. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 12.

(Example 16)
In Example 16, the heat conductive filler was changed to 800 parts by weight of magnesium hydroxide having an average particle diameter of 1 μm, and the blending ratio of red phosphorus coated with a thermosetting resin as a flame retardant was changed to 40 parts by weight. A polymer composition having the same composition as in Example 12 was prepared except that. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 12.

(Example 17)
Example 17 is the same as Example 12 except that the nonpolar hydrocarbon oil was changed to 300 parts by weight of paraffin oil (PW-150 manufactured by Idemitsu Kosan Co., Ltd.) having a kinematic viscosity at 40 ° C. of 150 mm ² / s. A polymer composition of composition was prepared. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 12.

(Example 18)
Example 18 is the same as Example 12 except that the nonpolar hydrocarbon oil was changed to 300 parts by weight of paraffin oil (PW-380, manufactured by Idemitsu Kosan Co., Ltd.) having a kinematic viscosity of 40 ° C. of 400 mm ² / s. A polymer composition of composition was prepared. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 12.

(Example 19)
In Example 19, the blending amount of paraffin oil (PW-90, manufactured by Idemitsu Kosan Co., Ltd.) having a kinematic viscosity of 90 mm ² / s at 40 ° C. was changed to 200 parts by weight, and blending of aluminum hydroxide having an average particle size of 44 μm A polymer composition having the same composition as Example 12 was prepared, except that the amount was changed to 600 parts by weight and the amount of aluminum hydroxide having an average particle diameter of 8 μm was changed to 300 parts by weight. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 12.

(Example 20)
In Example 20, the blending amount of paraffin oil (PW-90, manufactured by Idemitsu Kosan Co., Ltd.) having a kinematic viscosity of 90 mm ² / s at 40 ° C. was changed to 400 parts by weight, and blending of aluminum hydroxide having an average particle size of 44 μm A polymer composition having the same composition as in Example 12 was prepared except that the amount was changed to 1000 parts by weight and the amount of aluminum hydroxide having an average particle size of 8 μm was changed to 500 parts by weight. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 12.

(Comparative Example 9)
In Comparative Example 9, a polymer composition having the same composition as Example 12 was prepared, except that the flame retardant was changed to 5 parts by weight of normal red phosphorus that was not subjected to surface treatment. An attempt was made to produce a thermally conductive sheet from the polymer composition by the same method as in Example 12. However, in Comparative Example 9, since red phosphorus not coated with a thermosetting resin is blended, the above-described hydrosilylation reaction between the allyl group and the Si—H group of the curing agent is inhibited, and the polymer composition The product was not cured and could not be formed into a sheet.

(Comparative Example 10)
In Comparative Example 10, a polymer composition having the same composition as in Example 12 was prepared, except that the amount of red phosphorus coated with the thermosetting resin as a flame retardant was changed to 2 parts by weight. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 12.

(Comparative Example 11)
In Comparative Example 11, the amount of aluminum hydroxide having an average particle size of 44 μm was changed to 600 parts by weight, and the amount of aluminum hydroxide having an average particle size of 8 μm was changed to 300 parts by weight, and thermosetting as a flame retardant. The amount of red phosphorus coated with a functional resin is changed to 240 parts by weight, and the amount of paraffin oil (PW-90 made by Idemitsu Kosan Co., Ltd.) with a kinematic viscosity at 40 ° C. of 90 mm ² / s is changed to 400 parts by weight. A polymer composition having the same composition as in Example 12 was prepared except that. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 12.

(Comparative Example 12)
In Comparative Example 12, the same as Example 12 except that the nonpolar hydrocarbon oil was changed to 300 parts by weight of paraffin oil (PW-32 manufactured by Idemitsu Kosan Co., Ltd.) having a kinematic viscosity of 40 ° C. of 30 mm ² / s. A polymer composition of composition was prepared. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 12.

(Comparative Example 13)
In Comparative Example 13, the same as Example 12 except that the nonpolar hydrocarbon oil was changed to 300 parts by weight of paraffin oil (PS-430, manufactured by Idemitsu Kosan Co., Ltd.) having a kinematic viscosity of 40 ° C. of 440 mm ² / s. A polymer composition of composition was prepared. An attempt was made to produce a thermally conductive sheet from the polymer composition by the same method as in Example 12. However, in Comparative Example 13, the viscosity of the polymer composition prepared due to the large 40 ° C. kinematic viscosity of paraffin oil increased, and the polymer composition could not be kneaded and formed into a sheet.

(Comparative Example 14)
In Comparative Example 14, the blending amount of paraffin oil (PW-90 manufactured by Idemitsu Kosan Co., Ltd.) having a kinematic viscosity of 90 mm ² / s at 40 ° C. was changed to 150 parts by weight, and the blending amount of aluminum hydroxide having an average particle size of 44 μm Was changed to 500 parts by weight, and a polymer composition having the same composition as Example 12 was prepared except that the amount of aluminum hydroxide having an average particle size of 8 μm was changed to 250 parts by weight. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 12.

(Comparative Example 15)
In Comparative Example 15, the blending amount of paraffin oil (PW-90 manufactured by Idemitsu Kosan Co., Ltd.) having a kinematic viscosity of 90 mm ² / s at 40 ° C. was changed to 450 parts by weight, and the blending amount of aluminum hydroxide having an average particle size of 44 μm Was changed to 1100 parts by weight, and a polymer composition having the same composition as Example 12 was prepared except that the amount of aluminum hydroxide having an average particle size of 8 μm was changed to 550 parts by weight. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 12.

  About the heat conductive sheet obtained in Examples 12 to 20 and Comparative Examples 9 to 15, the hardness (based on JIS K6253, type E durometer) and the measurement of the heat resistance value, and the volatile gas generation acceleration test were performed by the method described above. went.

  Regarding flame retardancy, each thermal conductive sheet is subjected to a combustion test using the apparatus shown in FIG. 1 in accordance with UL94V which defines the flammability of plastic materials in the UL (Under Writer Laboratories Inc) standard which is a US safety standard. And evaluated. Specifically, the test piece 1 (length 127 mm × width 12.7 mm × thickness 1.0 mm or 0.5 mm) of each thermally conductive sheet supported by the clamp 4 is burner 2 (caliber: 10 mm, length: After approximately 10 seconds of indirect flame on a flame 2a of about 10 cm), the combustion time of each test piece 1 was recorded apart from the flame 2a. After extinction of each test piece 1, the flame 2a was again indirectly flamed for 10 seconds, and then separated from the flame 2a, the burning time of each test piece 1 was recorded. Furthermore, the retention time (glowing time) of the fire type after the second flame contact and the presence or absence of a dripping material that ignites the absorbent cotton 3 disposed below the test piece 1 were recorded. The above operation was performed for each test piece 1 as one set 5 times. The obtained results were compared with the criteria shown in Table 5 below to determine the flame retardant grade of each thermally conductive sheet.

The above measurement results are shown in Tables 6 and 7.
The thermal conductive sheets of Examples 12 to 20 have a hardness of 55 or less and a thermal resistance value of 4.3 (° C./W) or less, and also have excellent flame retardancy equivalent to the UL94V-0 grade. Was. Therefore, since these heat conductive sheets have high heat conductivity and are highly flexible, they have good adhesion to other members and can transmit heat more efficiently. Furthermore, these heat conductive sheets have excellent flame retardancy even in a very thin sheet-like molded body having a thickness of 0.5 mm. A thermally conductive molded product was obtained with high productivity and at a low price. Also, in the volatile gas generation acceleration test, since the reduction ratio of the sheet weight is less than 1%, it is considered that there is almost no generation of low molecular weight siloxane and other volatile gases. Further, these thermally conductive sheets did not cause bleed phenomenon during mounting.

  On the other hand, since the heat conductive sheet of Comparative Example 10 has a small proportion of red phosphorus coated with a thermosetting resin, the heat conductive sheet having a thickness of 0.5 mm is equivalent to the UL94V-0 grade. Flame retardancy was not obtained. The heat conductive sheet of Comparative Example 11 had a high blending ratio of red phosphorus coated with a thermosetting resin. Therefore, not only the cost was increased, but also the viscosity increased in the manufacturing process and the moldability was poor. In addition, the thermal resistance value has increased. In the thermally conductive sheet of Comparative Example 12, the weight of the thermally conductive molded body was reduced by 5% in the volatile gas generation acceleration test. Therefore, in the mounting, this heat conductive sheet may generate volatile gas and contaminate the inside of the electronic device. It is considered that the heat conductive sheet of Comparative Example 14 hardly generates volatile gas because the reduction ratio of the weight of the heat conductive molded body in the volatile gas generation acceleration test is small. The thermal conductive sheet of Comparative Example 14 did not cause a bleeding phenomenon in the mounting, but the sheet hardness was 62 and inferior in flexibility. Therefore, even though the thermal resistance value of the sheet itself was relatively good, the mounting In such a case, there is a possibility that sufficient adhesion to the mounting target cannot be obtained and heat cannot be transferred efficiently. The heat conductive sheet of Comparative Example 15 is considered to generate little volatile gas because the weight reduction rate of the heat conductive molded body in the volatile gas generation acceleration test is small. However, since this thermally conductive sheet has caused a bleed phenomenon, there is a possibility that the inside of the electronic device is contaminated during mounting.

第４実施形態の熱伝導性シート
（実施例２１）
実施例２１においては、末端基にアリル基を有する非シリコーン系極性高分子として末端にアリル基を有するポリアクリレート（ＳＡ１００Ａ 数平均分子量＝２００００ 株式会社カネカ製）１００重量部に、極性基含有非シリコーン系オイルとして４０℃動粘度が７０ｍｍ^２／ｓのポリオールエステルオイル（ＨＡＴＣＯＬ２３６２ ＨＡＴＣＯ社（米国）製）を３００重量部と、熱伝導性充填剤として平均粒径４４μｍの水酸化アルミニウムを８００重量部および平均粒径８μｍの水酸化アルミニウムを４００重量部と、難燃剤として熱硬化性樹脂で被覆された赤燐を５重量部と、硬化剤として有機物で変性したジメチルシロキサン構造を有する硬化剤（ＣＲ５００ 株式会社カネカ製）を１０重量部と、老化防止剤（ノクラックＮＳ−７、大内新興化学工業）を３重量部と、白金触媒（ＰＴ−ＣＳ−３．２ｃＳ、Ｆｅｒｒｏ社（米国）製）を０．５重量部とを配合し、振動攪拌器により混合して高分子組成物を調製した。この高分子組成物をシート状に成形し、真空脱泡した後に、１３０℃雰囲気で１時間加熱して、前記高分子組成物を硬化することにより熱伝導性シートを得た。

Thermally conductive sheet of the fourth embodiment (Example 21)
In Example 21, a polar group-containing non-silicone was added to 100 parts by weight of a polyacrylate having an allyl group at the end as a non-silicone polar polymer having an allyl group at the end group (SA100A number average molecular weight = 20000, manufactured by Kaneka Corporation). 40 ° C. kinematic viscosity of 70 mm ² / s of the polyol ester oil (HATCOL2362 Hatco Corporation (USA)) as a system oil and 300 parts by weight, 800 parts by weight of aluminum hydroxide having an average particle diameter of 44μm as the thermally conductive filler and 400 parts by weight of aluminum hydroxide having an average particle size of 8 μm, 5 parts by weight of red phosphorus coated with a thermosetting resin as a flame retardant, and a curing agent having a dimethylsiloxane structure modified with an organic substance as a curing agent (CR500 stock) 10 parts by weight of company Kaneka) and anti-aging agent (NOCRAK NS-7, 3 parts by weight of Ouchi Shinsei Chemical Co., Ltd.) and 0.5 parts by weight of platinum catalyst (PT-CS-3.2cS, manufactured by Ferro (USA)) are mixed and mixed with a vibration stirrer to form a polymer. A composition was prepared. The polymer composition was molded into a sheet and vacuum degassed, and then heated in a 130 ° C. atmosphere for 1 hour to cure the polymer composition, thereby obtaining a heat conductive sheet.

(Example 22)
In Example 22, a polymer composition having the same composition as Example 21 was prepared except that the amount of red phosphorus coated with the thermosetting resin as a flame retardant was changed to 3 parts by weight. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 21.

(Example 23)
In Example 23, a polymer composition having the same composition as in Example 21 was prepared, except that the amount of red phosphorus coated with the thermosetting resin as a flame retardant was changed to 200 parts by weight. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 21.

(Example 24)
In Example 24, except that the polar group-containing non-silicone oil is 40 ° C. kinematic viscosity was changed to 120 mm ² / s of the polyol ester oil (HATCOL2372 Hatco Corporation (USA)) 300 parts by weight, same as in Example 21 A polymer composition having the following composition was prepared. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 21.

(Example 25)
Example 25 is the same as Example 21 except that the polar group-containing non-silicone oil was changed to 300 parts by weight of an acrylic oil (UP1020 manufactured by Toa Gosei Co., Ltd.) having a kinematic viscosity at 40 ° C. of 500 mm ² / s. A polymer composition of composition was prepared. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 21.

(Example 26)
In Example 26, the blending amount of polyol ester oil (HATCOL 2362 HATCO (USA)) having a kinematic viscosity at 40 ° C. of 70 mm ² / s was changed to 200 parts by weight, and blending of aluminum hydroxide having an average particle size of 44 μm was performed. A polymer composition having the same composition as Example 21 was prepared except that the amount was changed to 600 parts by weight and the amount of aluminum hydroxide having an average particle size of 8 μm was changed to 300 parts by weight. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 21.

(Example 27)
In Example 27, 40 ° C. kinematic viscosity of 70 mm ² / s of the polyol ester oil (HATCOL2362 Hatco Corporation (USA)) was changed to 400 parts by weight the amount of the amount of aluminum hydroxide having an average particle diameter of 44μm Was changed to 1000 parts by weight, and a polymer composition having the same composition as Example 21 was prepared except that the amount of aluminum hydroxide having an average particle size of 8 μm was changed to 500 parts by weight. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 21.

(Comparative Example 16)
In Comparative Example 16, a polymer composition having the same composition as that of Example 21 was prepared except that the amount of red phosphorus coated with the thermosetting resin as a flame retardant was changed to 2 parts by weight. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 21.

(Comparative Example 17)
In Comparative Example 17, a polymer composition having the same composition as Example 21 was prepared, except that the amount of red phosphorus coated with the thermosetting resin as a flame retardant was changed to 240 parts by weight. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 21.

(Comparative Example 18)
In Comparative Example 18, the same as Example 21 except that the polar group-containing non-silicone oil was changed to 300 parts by weight of a polyol ester oil having a kinematic viscosity at 40 ° C. of 30 mm ² / s (made by HATCOL 2352 HATCO (USA)). A polymer composition having the following composition was prepared. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 21.

(Comparative Example 19)
In Comparative Example 19, the same composition as in Example 21 except that the polar group-containing non-silicone oil was changed to 300 parts by weight of an ester oil (Ketjenrub 165 manufactured by Akzo Nobel) having a kinematic viscosity at 40 ° C. of 750 mm ² / s. A polymer composition was prepared. An attempt was made to produce a thermally conductive sheet from the polymer composition by the same method as in Example 21. However, in Comparative Example 19, since the kinematic viscosity at 40 ° C. of the oil was large, the viscosity of the prepared polymer composition was large, and the polymer composition could not be kneaded and formed into a sheet shape.

(Comparative Example 20)
In Comparative Example 20, 40 ° C. kinematic viscosity of 70 mm ² / s of the polyol ester oil (HATCOL2362 Hatco Corporation (USA)) was changed to 150 parts by weight the amount of the amount of aluminum hydroxide having an average particle diameter of 44μm A polymer composition having the same composition as in Example 21 was prepared except that the amount of aluminum hydroxide having an average particle diameter of 8 μm was changed to 250 parts by weight. A heat conductive sheet was obtained from the polymer composition by the same method as in Example 21.

(Comparative Example 21)
In Comparative Example 21, 40 ° C. kinematic viscosity of 70 mm ² / s of the polyol ester oil (HATCOL2362 Hatco Corporation (USA)) was changed to 450 parts by weight the amount of the amount of aluminum hydroxide having an average particle diameter of 44μm Was changed to 1100 parts by weight, and a polymer composition having the same composition as Example 21 was prepared, except that the amount of aluminum hydroxide having an average particle size of 8 μm was changed to 550 parts by weight.

  About the heat conductive sheets obtained in Examples 21 to 27 and Comparative Examples 16 to 21, the hardness (based on JIS K6253, type E durometer) and the measurement of the thermal resistance value, the volatile gas generation acceleration test, and A flame retardancy test was performed. The results are shown in Table 8 and Table 9.

  The heat conductive sheets of Examples 21 to 27 have a hardness of 49 or less, a thermal resistance value of 3.8 (° C./W) or less, and excellent flame retardancy equivalent to the UL94V-0 grade. It was. Therefore, these thermal conductive sheets have high thermal conductivity and are highly flexible, so that they have good adhesion to other members, can transmit heat more efficiently, and have excellent flame resistance. Can have sex. A thermally conductive molded product was obtained with high productivity and at a low price. Also, in the volatile gas generation acceleration test, since the reduction ratio of the sheet weight is less than 1%, it is considered that there is almost no generation of low molecular weight siloxane and other volatile gases. Further, these thermally conductive sheets did not cause bleed phenomenon during mounting.

  Since the heat conductive sheet of Comparative Example 16 has a small proportion of red phosphorus coated with a thermosetting resin, the heat conductive sheet having a thickness of 0.5 mm is flame retardant equivalent to the UL94V-0 grade. Sex was not obtained.

  The heat conductive sheet of Comparative Example 17 had a high blending ratio of red phosphorus coated with a thermosetting resin. Therefore, not only was the cost high, but the viscosity increased in the manufacturing process and the moldability was poor. In addition, the thermal resistance value has increased.

  In the heat conductive sheet of Comparative Example 18, in the volatile gas generation acceleration test, the weight of the heat conductive sheet was reduced by 5.1%. Therefore, in mounting, the volatile gas may contaminate the electronic device. Conceivable.

  The heat conductive sheet of Comparative Example 20 is considered to generate little volatile gas because the weight reduction ratio of the heat conductive molded body in the volatile gas generation acceleration test is small. Although the thermal conductive sheet of Comparative Example 20 did not cause a bleed phenomenon in mounting, the sheet had a hardness of 61 and poor flexibility, so that the thermal resistance value of the sheet itself was relatively good. In such a case, there is a possibility that sufficient adhesion to the mounting target cannot be obtained and heat cannot be transferred efficiently.

  The heat conductive sheet of Comparative Example 21 is considered to generate little volatile gas because the weight reduction ratio of the heat conductive molded body in the volatile gas generation acceleration test is small. However, since this thermal conductive sheet has caused a bleed phenomenon in mounting, there is a possibility that the inside of the electronic device is contaminated.

  In the examples and comparative examples in the third embodiment and the fourth embodiment described above, the total amount of the non-silicone polymer having the allyl group at the terminal and the non-silicone oil, and the total amount of the heat conductive filler The ratio is adjusted to be constant (non-silicone polymer + non-silicone oil: heat conductive filler = 1: 3), but other ratios may be used.

The figure which shows the apparatus which evaluates a flame retardance.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Test piece, 2 ... Burner, 3 ... Absorbent cotton, 4 ... Clamp.

Claims (18)

A thermally conductive molded body formed from a polymer composition, wherein the polymer composition is
A thermally conductive filler;
As a substrate, a non-silicone polymer having an allyl group at the terminal,
And a non-silicone oils have a kinematic viscosity at 40 ° C. is 70mm ² / s~500mm ² / s, in the polymer composition, with respect to the non-silicone polymer of 100 parts by weight, 200 parts by weight to 400 parts by weight of the non-silicone oil is blended. A thermally conductive molded body formed from a polymer composition, wherein the polymer composition is
A thermally conductive filler;
As a base material, a nonpolar hydrocarbon polymer having an allyl group at the end, and
And a non-polar hydrocarbon oil of kinematic viscosity at 40 ° C. at 90mm ² / s~400mm ² / s, in the polymer composition, with respect to the non-polar hydrocarbon-based polymer of 100 parts by weight, 200 to 400 parts by weight of the non-polar hydrocarbon oil is blended.   The thermally conductive molded article according to claim 2, wherein the nonpolar hydrocarbon polymer having an allyl group at the terminal is a polyisobutylene having an allyl group at the terminal.   The thermally conductive molded article according to claim 2 or 3, wherein the nonpolar hydrocarbon oil is paraffin oil. A thermally conductive molded body formed from a polymer composition, wherein the polymer composition is
A thermally conductive filler;
As a base material, a non-silicone polar polymer having an allyl group at the end, and
And a polar group-containing non-silicone-based oil is a kinematic viscosity of 70mm ² / s~500mm ² / s at 40 ° C., in the polymer composition, with respect to the non-silicone-polar polymer 100 parts by weight, 200 to 400 parts by weight of the polar group-containing non-silicone oil is blended.   6. The thermally conductive molded article according to claim 5, wherein the non-silicone polar polymer having an allyl group at the terminal is a polyacrylate having an allyl group at the terminal.   The thermally conductive molded article according to claim 5 or 6, wherein the polar group-containing non-silicone oil is an ester oil.     The thermally conductive molded article according to any one of claims 1 to 7, wherein the polymer composition further contains a curing agent. A thermally conductive molded body formed from a polymer composition, wherein the polymer composition is
A thermally conductive filler;
As a substrate, a non-silicone polymer having an allyl group at the terminal,
A non-silicone oil kinematic viscosity is 70mm ² / s~500mm ² / s at 40 ° C.,
A non-silicone oil in an amount of 200 parts by weight to 400 parts by weight with respect to 100 parts by weight of the non-silicone polymer in the polymer composition. A heat conductive molded body comprising 3 to 200 parts by weight of red phosphorus coated with the thermosetting resin in a proportion of the red phosphorus alone. Non-silicone polymer having an allyl group at the terminal is a non-polar hydrocarbon polymer having an allyl group at the end, non-silicone-based oil has a kinematic viscosity at 40 ° C. is 90mm ² / s~400mm ² / s The thermally conductive molded article according to claim 9, which is a nonpolar hydrocarbon-based oil.   11. The thermally conductive molded article according to claim 10, wherein the nonpolar hydrocarbon polymer having an allyl group at the terminal is polyisobutylene having an allyl group at the terminal.   The thermally conductive molded article according to claim 10 or 11, wherein the nonpolar hydrocarbon oil is paraffin oil. Non-silicone polymer having an allyl group at the terminal is a non-silicone polar polymer having an allyl group at the end, non-silicone oil, kinematic viscosity at 40 ℃ of 70mm ² / s~500mm ² / s The thermally conductive molded article according to claim 9, which is a polar group-containing non-silicone oil.   14. The thermally conductive molded article according to claim 13, wherein the non-silicone polar polymer having an allyl group at a terminal is a polyacrylate having an allyl group at a terminal.   The heat conductive molded article according to claim 13 or 14, wherein the polar group-containing non-silicone oil is an ester oil.   The thermally conductive molded article according to any one of claims 9 to 15, wherein the polymer composition contains at least one kind of metal hydroxide as a thermally conductive filler.   The thermally conductive molded article according to claim 16, wherein the metal hydroxide is aluminum hydroxide.   The thermally conductive molded article according to claim 9, wherein the polymer composition further contains a curing agent.

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