JPWO2014167993A1 - Thermally conductive resin composition and thermally conductive sealing body using the same - Google Patents

Abstract

Resin composition having thermal conductivity of 0.5 W / m · K or more, excellent initial adhesive strength to glass epoxy plate, and excellent durability against environmental loads such as cooling and cycling load, and electric and electronic using the same A component sealing body is provided. The total of at least one resin selected from the group consisting of phenol-modified alkylbenzene resin (B1), phenol resin (B2) and epoxy resin (B3) is 0.1 per 100 parts by volume of crystalline polyester resin (A). ~ 100 parts by volume, the thermal conductivity filler (D) having a single thermal conductivity of 10 W / m · K or more contains 10 to 10,000 parts by volume, and the thermal conductivity as a resin composition is 0.5 W / m · K. It is the above, The heat conductive resin composition characterized by the above-mentioned.

Description

  The present invention relates to a heat conductive resin composition, an electric / electronic component sealing body sealed with a heat conductive resin composition, and a method for manufacturing the same.

  Electrical and electronic parts that are widely used in automobiles and electrical appliances must have electrical insulation from the outside in order to achieve their intended purpose. For example, the electric wire is covered with a resin having electrical insulation. In recent years, there has been a rapid increase in applications where it is necessary to pack electrical and electronic parts having a complicated shape in a small capacity, such as a mobile phone, and various methods have been adopted for the electrical insulation. Along with the miniaturization, heat generation problems such as personal computer and display housings, electronic device materials, and interior and exterior of automobiles have been highlighted, and materials with high thermal conductivity are required. For these heat generation countermeasures, countermeasures such as placing a glass epoxy heat sink are common, but at the present time, with the demand for reducing the weight of automobiles, replacement of this glass epoxy board with a heat-dissipating sealing material is possible. It has been demanded.

  When a thermoplastic resin composition is used for these applications, since plastic has a lower thermal conductivity than an inorganic material such as a metal material, it may be a problem that it is difficult to release generated heat. In order to solve such problems, attempts have been widely made to obtain a highly thermally conductive resin composition by highly filling an inorganic compound having high thermal conductivity into a thermoplastic resin.

  However, when trying to mold a high thermal conductivity thermoplastic resin by a commonly used injection molding method, the resin flowing into the mold rapidly cools and solidifies due to its high thermal conductivity, and special conditions of high speed and high pressure There is a problem that it can only be molded. This has a problem that it cannot be used as a sealing material for delicate electronic components. In addition, these high thermal conductivity thermoplastic resins have a problem that adhesiveness is insufficient and necessary airtightness cannot be ensured.

  Patent Documents 1 and 2 propose a hot-melt resin composition for sealing having a melt viscosity that enables sealing at a low pressure without damaging electrical and electronic parts. With this resin composition, a molded product having good initial adhesiveness can be obtained, and the polyester resin composition can be applied to general electric and electronic parts. However, for example, when exposed to -40 ° C and 80 ° C refrigeration cycles many times for a long time, the adhesive strength may be greatly reduced and the sealed state may not be maintained.

  Patent Document 3 shows that a hot melt adhesive composition in which a specific polyester resin and a phenol-modified alkylbenzene resin are blended exhibits good adhesion to tin-plated copper and PET. This adhesive composition also has a problem that the durability of adhesion in a cold cycle such as −40 ° C. for 30 minutes and 80 ° C. for 30 minutes as in automobile applications is insufficient.

  Patent Document 4 exemplifies a method of adding a liquid organic compound at room temperature in order to improve the injection moldability of a thermoplastic resin highly filled with a filler. However, in such a method, there is a problem that a liquid organic compound bleeds out during injection molding and contaminates the mold. Furthermore, there is a problem that it is more difficult to achieve both heat resistance and adhesiveness.

  In Patent Document 5, an invention has been made in which molding fluidity is improved and injection moldability is improved by using a resin that can significantly delay the solidification rate during cooling in the mold. However, although this invention is improved in terms of molding fluidity at the time of injection molding, the filler filling rate is limited to 60% by volume, and it is possible to achieve high thermal conductivity without sufficiently filling the filler. It is a problem in that it is not done. The reason why such a problem occurs is that the wettability between the resin and the filler is not sufficient, so that it is difficult to achieve a high filler filling due to problems such as strand breakage during kneading. Moreover, it is mentioned that injection molding becomes difficult because the melt viscosity of the resin composition is remarkably increased due to the high filler content of 60% by volume or more.

Japanese Patent No. 3553559 JP 2004-83918 A Japanese Patent No. 4389144 Japanese Patent No. 3948240 JP 2009-91440 A

  As described above, the conventional technology has proposed a resin composition for encapsulating electrical and electronic parts having a complicated shape that sufficiently satisfies all the required performance of heat dissipation, good injection moldability, and adhesiveness. There wasn't. Further, in the conventional technique, the adhesiveness is significantly lowered after a 1000 cycle load at -40 ° C. for 30 minutes and 150 ° C. for 30 minutes or a high temperature long time load at 150 ° C. for 1000 hours. That is, a resin composition for sealing electrical and electronic parts that can cope with an environment that requires high durability and heat dissipation against a cold cycle load and a high temperature long time load such as in an automobile engine room has not been realized.

  An object of the present invention is to provide an electrical and electronic component sealing body that has heat dissipation and is excellent in adhesion durability and injection moldability with respect to a thermal cycle load. Moreover, it is providing the manufacturing method and heat conductive resin composition of an electrical / electronic component sealing body suitable for it.

In order to achieve the above object, the present inventors have intensively studied and have proposed the following invention. That is, the present invention relates to 100 parts by volume of the crystalline polyester resin (A), and one or more kinds of resins selected from the group consisting of the phenol-modified alkylbenzene resin (B1), the phenol resin (B2), and the epoxy resin (B3). The total is 0.1 to 100 parts by volume,
The heat conductive filler (D) having a single thermal conductivity of 10 W / m · K or more contains 10 to 10,000 parts by volume, and the thermal conductivity as the resin composition is 0.5 W / m · K or more. The heat conductive resin composition characterized.

  In addition, it is preferable that at least one component selected from the group consisting of a polycarbonate component, a polyalkylene ether glycol component and a polylactone component is copolymerized in the crystalline polyester resin (A) in an amount of 25 to 75% by weight.

The hydroxyl value of the phenol-modified alkylbenzene resin (B1) is preferably 100 equivalents / 10 ⁶ g or more.

Moreover, it is preferable that the said phenol resin (B2) is a novolak-type phenol resin, and a hydroxyl value is 100 equivalent / 10 < ⁶ > g or more.

  Moreover, the said heat conductive filler (D) consists of 1 type, or 2 or more types of fillers, and when the sum total of the particle frequency of all the fillers is 100%, the particle frequency of a particle size of 1-10 micrometers is 100-0%. And it is preferable that the particle frequency of a particle size of 10-100 micrometers is 0-100%.

  Moreover, it is preferable that the said heat conductive resin composition is 20% or more of the shearing adhesive strength retention after 1000 cycles load of the -40 degreeC 30 minute and 150 degreeC 30 minute cooling cycle with respect to a glass epoxy board.

  Moreover, it is preferable that the said heat conductive resin composition is 0.1 Mpa or more in the shearing adhesive strength with respect to a glass epoxy board.

  After the heat conductive resin composition is heated and kneaded, the resin composition is injected at a temperature of 130 ° C. or higher and 300 ° C. or lower and a resin composition pressure of 0.1 MPa or higher and 100 MPa or lower into a mold in which an electric / electronic component is inserted. A method for producing a thermally conductive encapsulant.

  Moreover, the heat conductive sealing body sealed with the said heat conductive resin composition.

  Moreover, the motor vehicle carrying the components containing the said heat conductive resin composition.

  Since the heat conductive resin composition of the present invention (hereinafter also simply referred to as “resin composition”) is excellent in all of heat dissipation, injection moldability, and adhesiveness, it is used as a sealing material for electrical and electronic component sealing bodies. It can be used suitably.

  The encapsulated body for electric and electronic parts of the present invention comprises a resin or a resin composition that is heated and kneaded in a mold in which the electric and electronic parts are set inside the mold to provide fluidity, and is 0.1 MPa or more and less than 40 MPa. It can be manufactured by injecting and sealing an electric / electronic component with a resin or a resin composition. In other words, compared to injection molding at a high pressure of 40 MPa or higher, which is conventionally used for plastic molding, it is performed at a very low pressure. It is possible to seal a limited electric / electronic component without breaking it. By appropriately selecting a sealing resin or a resin composition, it is possible to obtain a sealed body having a heat radiation property and an adhesion durability that can withstand environmental loads with respect to a glass epoxy plate. The details of the embodiments of the invention will be sequentially described below.

  The thermally conductive resin composition according to the present invention is selected from the group consisting of a phenol-modified alkylbenzene resin (B1), a phenol resin (B2), and an epoxy resin (B3) with respect to 100 parts by volume of the crystalline polyester resin (A). In addition, the total of one or more kinds of resins is 0.1 to 100 parts by volume, and the thermal conductivity filler (D) having a single thermal conductivity of 10 W / m · K or more is 10 to 500 parts by volume. Has a thermal conductivity of 0.5 W / m · K or more.

<Crystalline polyester resin (A)>
The crystalline polyester resin (A) of the present invention has a chemical structure in which a hard segment mainly composed of a polyester segment and a soft segment mainly composed of a polycarbonate and / or polyalkylene ether glycol and / or a polylactone segment are ester-bonded. Is preferred.

  As an example of the soft segment of the crystalline polyester resin (A) of the present invention, the polycarbonate segment can be formed by copolymerizing a polycarbonate component, typically a polycarbonate diol. Due to the copolymerization of the polycarbonate component, it exhibits characteristics such as low melt viscosity, high flexibility and high adhesion. The copolymerization ratio of the polycarbonate component is preferably 25% by weight or more, more preferably 30% by weight or more when the entire soft segment component constituting the crystalline polyester resin (A) is 100% by weight. 35% by weight or more is particularly preferable. Further, it is preferably 75% by weight or less, more preferably 70% by weight or less, and particularly preferably 65% by weight or less. If the copolymerization ratio of the polycarbonate component is too low, the melt viscosity becomes high and high pressure is required for molding, the crystallization rate is high, and short shots are likely to occur. Moreover, when the copolymerization ratio of the polycarbonate component is too high, the heat resistance tends to be insufficient. Moreover, it is preferable that the said polycarbonate component is an aliphatic polycarbonate component which has a poly (alkylene carbonate) component as a main component. Here, the main component is that the poly (alkylene carbonate) component occupies 50% by weight or more of the aliphatic polycarbonate component, more preferably 75% by weight or more, and 90% by weight or more. Further preferred. Moreover, as an alkylene group which comprises poly (alkylene carbonate), a C4-C16 linear alkylene group is preferable, and a longer-chain alkylene group tends to be excellent in cold cycle load durability. Considering availability, it is preferably a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, or a nonamethylene group. Moreover, the copolymer type polycarbonate in which the alkylene group which comprises poly (alkylene carbonate) is 2 or more types of mixtures may be sufficient.

  The polyalkylene ether glycol segment is preferably a polyalkylene ether glycol component, for example, polyethylene glycol (hereinafter also referred to as PEG), polytrimethylene glycol (hereinafter also referred to as PPG), polytetramethylene glycol (hereinafter referred to as PTMG). But is not limited to these. Among these, PTMG is preferable from the viewpoint of heat resistance. The number average molecular weight is preferably 230 or more, more preferably 400 or more, and still more preferably 800 or more. Moreover, it is preferable that it is 5000 or less, and it is more preferable that it is 3000 or less. If the number average molecular weight is less than 230, flexibility may not be imparted and flex resistance may not be exhibited. On the other hand, if it exceeds 5000, compatibility with other copolymerization components may be poor and copolymerization may not be possible. . The copolymerization ratio of the polyalkylene ether glycol component is preferably 25% by weight or more, preferably 30% by weight or more when the entire soft segment component constituting the crystalline polyester resin (A) is 100% by weight. More preferably, it is particularly preferably 35% by weight or more. Further, it is preferably 75% by weight or less, more preferably 70% by weight or less, and particularly preferably 65% by weight or less. If the copolymerization ratio of the polyalkylene ether glycol component is too low, the melt viscosity becomes high and high pressure is required for molding, the crystallization speed is high, and short shots are likely to occur. Moreover, when the copolymerization ratio of the polyalkylene ether glycol component is too high, the heat resistance tends to be insufficient.

  The polylactone segment is preferably a polylactone component, and examples thereof include polycaprolactone, polyvalerolactone, polypropiolactone, polyundecalactone, poly (1,5-oxepan-2-one), and the like. It is not limited to. The copolymerization ratio of the polylactone component is preferably 25% by weight or more, more preferably 30% by weight or more when the total soft segment component constituting the crystalline polyester resin (A) is 100% by weight, It is particularly preferable that the amount be 35% by weight or more. Further, it is preferably 75% by weight or less, more preferably 70% by weight or less, and particularly preferably 65% by weight or less. If the copolymerization ratio of the polylactone component is too low, the melt viscosity becomes high and high pressure is required for molding, the crystallization speed is high, and short shots are likely to occur. Moreover, when the copolymerization ratio of the polylactone component is too high, the heat resistance tends to be insufficient.

  The soft segment of the crystalline polyester resin (A) used in the present invention includes one or more kinds of segments selected from the group consisting of the polycarbonate segment, the polyalkylene ether glycol segment, and the polylactone segment, and the total is 25. It is preferred that it is copolymerized by ˜75% by weight.

  Further, as a hard segment of the crystalline polyester resin (A) used in the present invention, heat-resistant crystals such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), etc. Preferred is a polyester segment. More preferred are PBT and PBN. When other crystalline polyesters are used, heat resistance may be insufficient, durability, and low temperature characteristics may deteriorate. These hard segments can be used alone or in combination of two or more.

  On the other hand, in the crystalline polyester resin (A) used in the present invention, a small amount of an aromatic copolymer component can be used as long as it is within a range that maintains a low melt viscosity. Preferred examples of the aromatic copolymer component include aromatic dicarboxylic acids such as isophthalic acid and orthophthalic acid, and aromatic glycols such as ethylene oxide adduct and propylene oxide adduct of bisphenol A. In particular, by introducing an aliphatic component having a relatively high molecular weight such as dimer acid or dimer diol, good mold releasability may be obtained by rapid solidification after molding.

  Copolymerizing aliphatic or alicyclic dicarboxylic acid having 10 or more carbon atoms and / or aliphatic or alicyclic diol having 10 or more carbon atoms such as dimer acid, hydrogenated dimer acid, dimer diol, hydrogenated dimer diol. be able to. Thereby, a block-like segment can be introduce | transduced into the crystalline polyester resin (A) of this invention. The amount of copolymerization is preferably 2 mol% or more, more preferably 5 mol% or more, more preferably, when the total of all acid components and all glycol components of the crystalline polyester resin (A) is 200 mol%. It is 10 mol% or more, most preferably 20 mol% or more. The upper limit is 70 mol% or less, preferably 60 mol% or less, more preferably 50 mol% or less in consideration of handling properties such as heat resistance and blocking.

  The number average molecular weight of the crystalline polyester resin (A) of the present invention is preferably 3000 or more, more preferably 5000 or more, and further preferably 7000 or more. The upper limit of the number average molecular weight is preferably 50000 or less, more preferably 40000 or less, and still more preferably 30000 or less. When the number average molecular weight is less than 3,000, the hydrolysis resistance of the thermally conductive resin composition and the retention of strong elongation under high temperature and high humidity may be insufficient. When the number average molecular weight exceeds 50,000, the melt viscosity at 220 ° C. May be higher.

  The crystalline polyester resin (A) of the present invention is desirably a saturated polyester resin that does not contain an unsaturated group. If it is an unsaturated polyester, there is a possibility that crosslinking occurs at the time of melting, and the melt stability may be inferior.

  Further, the crystalline polyester resin (A) of the present invention may be a polyester having a branch by copolymerizing a trifunctional or higher polycarboxylic acid or polyol such as trimellitic anhydride or trimethylolpropane as necessary. .

  In the present invention, the crystallinity means that a temperature is raised from −150 ° C. to 250 ° C. at 20 ° C./min using a differential scanning calorimeter (DSC) and shows a clear melting peak in the temperature raising process. .

<Phenol-modified alkylbenzene resin (B1)>
The phenol-modified alkylbenzene resin (B1) used in the heat conductive resin composition of the present invention is not particularly limited, but is preferably a phenol-modified xylene resin, more preferably an alkylphenol-modified alkylbenzene resin. The xylene resin is a multimer composition having a basic structure in which xylene is cross-linked by a methylene group or an ether bond, and can be typically obtained by heating meta-xylene and formaldehyde in the presence of sulfuric acid. The phenol-modified alkylbenzene resin (B1) of the present invention preferably has a number average molecular weight in the range of 450 to 40,000. The hydroxyl value is preferably 100 equivalents / 10 ⁶ g or more, more preferably 1000 equivalents / 10 ⁶ g or more, and still more preferably 5000 equivalents / 10 ⁶ g or more. Also, preferably not more than 20000 equivalents / 10 ⁶ g, more preferably 15000 or less equivalent / 10 ⁶ g. If the hydroxyl value is too low, the adhesion to the glass epoxy material tends to be poor, and if the hydroxyl value is too high, the water absorption tends to increase and the insulating property tends to be lowered. In addition, the hydroxyl value mentioned here is measured by JIS K1557-1: 2007A method.

<Phenolic resin (B2)>
Although the phenol resin (B2) used for the resin composition of this invention is not specifically limited, It is preferable that it is resin obtained by reaction of phenols and aldehydes. A novolac type phenol resin or a cresol type phenol resin may be used, but a novolac type phenol resin is more preferable. Moreover, what has a number average molecular weight in the range of 450-40,000 is preferable. Examples of phenols that can be used as starting materials for phenol resins include bifunctional compounds such as o-cresol, p-cresol, p-tert-butylphenol, p-ethylphenol, 2,3-xylenol, and 2,5-xylenol. Phenol, phenol, m-cresol, m-ethylphenol, trifunctional phenol such as 3,5-xylenol or m-methoxyphenol, tetrafunctional phenol such as bisphenol A or bisphenol F, or one of these various phenols Species or two or more can be used in combination. Moreover, as formaldehyde used for manufacture of a phenol resin, 1 type (s) or 2 or more types, such as formaldehyde, paraformaldehyde, a trioxane, can be used together. Other examples include phenol-modified resins such as phenol aralkyl and phenol-modified alkylbenzene resins. Of these, those having good compatibility with the crystalline polyester resin (A) are particularly preferable in order to exhibit high adhesive strength. In order to obtain a phenol resin having good compatibility with the crystalline polyester resin (A), it is preferable that the melt viscosity is close and a hydroxyl group is present. Further, the phenol resin (B2) used in the present invention preferably has a hydroxyl value of 100 equivalents / 10 ⁶ g or more, more preferably 500 equivalents / 10 ⁶ g or more, and 1000 equivalents / 10 ⁶ g or more. More preferably. Further, preferably 10000 or less equivalent / 10 ⁶ g, more preferably not more than 5000 equivalents / 10 ⁶ g. If the hydroxyl value is too low, the adhesion to the glass epoxy material tends to be poor, and if the hydroxyl value is too high, the water absorption tends to increase and the insulating property tends to be lowered. In addition, the hydroxyl value mentioned here is measured by JIS K1557-1: 2007A method.

<Epoxy resin (B3)>
Although the epoxy resin (B3) used for the resin composition of this invention is not specifically limited, It is preferable that it is an epoxy resin which has an average of at least 1.1 or more glycidyl groups in a molecule | numerator. For example, glycidyl ether type such as bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, novolak glycidyl ether, brominated bisphenol A diglycidyl ether, glycidyl ester type such as hexahydrophthalic acid glycidyl ester, dimer acid glycidyl ester, triglycidyl isocyanate Nurate, glycidylhindantoin, tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, triglycidylmetaaminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidylmetaxylenediamine, diglycidyltribromoaniline, tetraglycidylbisaminomethylcyclohexane, etc. Glycidylamine or 3,4-epoxy B hexyl methyl carboxylate, epoxidized polybutadiene, include an alicyclic or aliphatic epoxides such as epoxidized soybean oil, it can be used in combination of these by itself or two or more kinds. Of these, those having good compatibility with the crystalline polyester resin (A) are particularly preferable in order to exhibit high adhesion. The preferred number average molecular weight of the epoxy resin (B3) is 450 to 40,000. If the number average molecular weight is less than 450, the resin composition is very easy to soften and the mechanical properties may be inferior. If it exceeds 40,000, the compatibility with the crystalline polyester resin (A) is lowered, and the adhesion may be impaired.

  In the present invention, by blending one or more kinds of resins selected from the group consisting of phenol-modified alkylbenzene resin (B1), phenolic resin (B2) and epoxy resin (B3) into the heat conductive resin composition, When sealing a component, excellent properties such as good initial adhesion and adhesion durability against a thermal cycle can be imparted. One or more kinds of resins selected from the group consisting of phenol-modified alkylbenzene resin (B1), phenol resin (B2) and epoxy resin (B3) are stress relaxation effects due to crystallization delay of crystalline polyester resin (A), crystals It is considered that the effect as a dispersion aid of the water-soluble polyester resin (A) and the polyolefin resin (C) and the effect of improving the wettability to the base material by introducing a functional group are exhibited. The total blending amount of at least one resin selected from the group consisting of the phenol-modified alkylbenzene resin (B1), the phenol resin (B2) and the epoxy resin (B3) in the present invention is 100 volume of the crystalline polyester resin (A). The amount is preferably 0.1 part by volume or more, more preferably 1 part by volume or more, and still more preferably 3 parts by volume or more. Moreover, it is preferable that it is 100 volume parts or less, It is more preferable that it is 50 volume parts or less, It is still more preferable that it is 40 volume parts or less. If the blending ratio of at least one resin selected from the group consisting of phenol-modified alkylbenzene resin (B1), phenol resin (B2) and epoxy resin (B3) is too low, stress relaxation effect due to crystallization delay cannot be exhibited. In addition, the function of the polyolefin resin (C) and the crystalline polyester resin (A) as a dispersion aid may not be exhibited. Moreover, if the blending ratio of one or more resins selected from the group consisting of the phenol-modified alkylbenzene resin (B1), the phenol resin (B2), and the epoxy resin (B3) is too high, the productivity of the heat conductive resin composition is increased. In addition, the flexibility characteristics as a sealing body may be inferior.

<Polyolefin resin (C)>
The resin composition of the present invention may contain a polyolefin resin (C). Adhesion can be improved by including polyolefin (C). Moreover, it is preferable to use a low crystalline polyolefin resin. Low crystalline polyolefin resin density than ordinary polyolefin resin is in a low tendency, ones density is less than 0.75 g / cm ³ or more 0.91 g / cm ³ are preferred. By using such a low crystallinity and low density polyolefin resin as the polyolefin resin (C), the polyolefin resin (C) can be easily finely divided with respect to the originally incompatible crystalline polyester resin (A). It can be dispersed and mixed, and a homogeneous resin composition can be obtained with a general twin screw extruder. Further, by using a polyolefin resin (C) having a low density and low crystallinity, it appropriately acts on the temporal relaxation of the residual stress generated in the crystalline polyester resin (A) during the injection molding, and is sealed. As a stopping resin, it exhibits desirable characteristics such as long-term adhesion durability and reduction of stress generated by environmental load. As the polyolefin resin (C) having such characteristics, polyethylene and ethylene copolymers are particularly preferable because they are easily available and inexpensive and do not adversely affect the adhesion to metals and films. More specific examples include low density polyethylene, ultra-low density polyethylene, linear low density polyethylene, ethylene-α-olefin copolymer, ethylene propylene elastomer, ethylene-butene copolymer, and the like. Or two or more types can be used in combination.

  Moreover, what does not contain polar groups, such as a carboxyl group and a glycidyl group, in polyolefin resin (C) is preferable. If a polar group is present, the compatibility with the crystalline polyester resin (A) changes, and the strain energy during crystallization of the crystalline polyester resin (A) may not be relaxed. Generally, a polyolefin having a polar group tends to have a higher compatibility with a polyester resin than a polyolefin having no polar group. However, in the present invention, when the compatibility is increased, the adhesive deterioration with time tends to increase. .

  Further, the polyolefin resin (C) of the present invention has a melt mass flow rate (hereinafter sometimes abbreviated as MFR) measured under the condition D of JIS K 7210-1999 (test temperature 190 ° C., nominal load 2.16 kg). It is preferably ˜20 g / 10 minutes. If the MFR is less than 5, the melt viscosity is too high, the compatibility with the crystalline polyester resin (A) may decrease, and the adhesion may be impaired. If the MFR is 20 or more, the viscosity is low and the resin composition is extremely low. It tends to soften and may have poor mechanical properties.

  In the present invention, blending the polyolefin resin (C) with the heat conductive resin composition has excellent characteristics such as good initial adhesiveness and adhesive durability against environmental load such as a thermal cycle when encapsulating electrical and electronic parts. Demonstrate. The polyolefin resin (C) is considered to exhibit a strain energy relaxation effect due to crystallization and enthalpy relaxation of the crystalline polyester resin (A). The preferred blending amount of the polyolefin resin (C) is 0 to 100 parts by volume, more preferably 0.1 to 90 parts by volume, even more preferably 3 to 100 parts by volume of the crystalline polyester resin (A). It is -80 volume part, Most preferably, it is 5-70 volume part. If it exceeds 100 parts by volume, adhesiveness and resin physical properties may be deteriorated, the crystalline polyester resin (A) and the polyolefin resin (C) undergo macro phase separation, and the elongation at break decreases. It may adversely affect the moldability, such as not being able to obtain a smooth surface.

  The resin composition of the present invention does not correspond to any of the crystalline polyester resin (A), the phenol-modified alkylbenzene resin (B1), the phenol resin (B2), the epoxy resin (B3), and the polyolefin resin (C). Other resins such as polyester, polyamide, polyolefin, polycarbonate, acrylic, ethylene vinyl acetate, isocyanate compounds, curing agents such as melamine, fillers such as talc and mica, pigments such as carbon black and titanium oxide, antimony trioxide, A flame retardant such as brominated polystyrene may be blended at all. By blending these components, adhesiveness, flexibility, durability and the like may be improved. The crystalline polyester resin (A) at that time is preferably contained in an amount of 1% by volume or more, more preferably 5% by volume or more, and further preferably 7% by volume with respect to the entire heat conductive resin composition according to the present invention. That's it. When the content of the crystalline polyester resin (A) is less than 1% by volume, the crystalline polyester resin (A) itself has excellent molding fluidity, adhesion, adhesion durability and elongation retention for electrical and electronic parts. May decrease.

  Furthermore, when the thermally conductive resin composition according to the present invention is exposed to a high temperature and high humidity environment for a long period of time, it is preferable to add an antioxidant. For example, as a hindered phenol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,1,3-tri (4-hydroxy-2-methyl- 5-t-butylphenyl) butane, 1,1-bis (3-t-butyl-6-methyl-4-hydroxyphenyl) butane, 3,5-bis (1,1-dimethylethyl) -4-hydroxy- Benzenepropanoic acid, pentaerythrityltetrakis (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3- (1,1-dimethylethyl) -4-hydroxy-5-methyl-benzenepropano Icic acid, 3,9-bis [1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4 , 10-tetraoxaspiro [5.5] undecane, 1,3,5-trimethyl-2,4,6-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) benzene, phosphorus As the system, 3,9-bis (p-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, tri (monononylphenyl) phosphite, triphenoxyphosphine, isodecylphosphite, isodecylphenylphosphite , Diphenyl 2-ethylhexyl phosphite, dinonylphenylbis (nonylphenyl) ester phosphoric acid, 1,1,3-tris (2- Til-4-ditridecyl phosphite-5-t-butylphenyl) butane, tris (2,4-di-t-butylphenyl) phosphite, pentaerythritol bis (2,4-di-t-butylphenyl phosphite) ), 2,2′-methylenebis (4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, thioether 4,4′-thiobis [2-tert-butyl-5-methylphenol] bis [3- (dodecylthio) propionate], thiobis [2- (1,1-dimethylethyl) -5-methyl-4,1 -Phenylene] bis [3- (tetradecylthio) -propionate], pentaerythritol tetrakis (3-n-do Decylthiopropionate) and bis (tridecyl) thiodipropionate, and these can be used alone or in combination of two or more. The addition amount is preferably 0.1% by volume or more and 5% by volume or less with respect to the whole sealing resin composition. If it is less than 0.1% by volume, the effect of preventing thermal deterioration may be poor. If it exceeds 5% by volume, the adhesiveness and the like may be adversely affected.

Examples of the method for determining the composition and composition ratio of the crystalline polyester resin (A) include ¹ H-NMR and ¹³ C-NMR in which the polyester resin is dissolved in a solvent such as deuterated chloroform, and measurement after methanolysis of the polyester resin. Examples include quantification by gas chromatography (hereinafter sometimes abbreviated as methanolysis-GC method). In the present invention, when there is a solvent that can dissolve the crystalline polyester resin (A) and is suitable for ¹ H-NMR measurement, the composition and composition ratio are determined by ¹ H-NMR. When there is no suitable solvent or when the composition ratio cannot be specified only by ¹ H-NMR measurement, ¹³ C-NMR or methanolysis-GC method is adopted or used in combination.

  As a method for producing the crystalline polyester resin (A) of the present invention, a known method can be used. For example, the above-mentioned dicarboxylic acid and diol components are esterified at 150 to 250 ° C. and then reduced in pressure while being reduced in pressure. A target polyester resin can be obtained by polycondensation at ˜300 ° C. Alternatively, the target polyester resin is obtained by transcondensation at 230 ° C. to 300 ° C. under reduced pressure after a transesterification reaction at 150 ° C. to 250 ° C. using a derivative such as dimethyl ester of dicarboxylic acid and a diol component. be able to.

  Further, in order to mold without causing thermal degradation of the crystalline polyester resin (A), rapid melting at 210 to 240 ° C. is required, so the upper limit of the melting point of the crystalline polyester resin (A) is 210. ° C is desirable. The lower limit is preferably 5 to 10 ° C. higher than the heat resistant temperature required for the corresponding application.

<Thermal conductive filler (D)>
The heat conductive filler (D) is composed of one kind or two or more kinds of fillers, and when the total particle frequency of all fillers is 100%, the particle frequency of a particle diameter of 1 to 10 μm is 100 to 0%, and The particle frequency with a particle size of 10 to 100 μm is preferably 0 to 100%, more preferably the particle frequency with a particle size of 1 to 10 μm is 90 to 10% and the particle frequency with a particle size of 10 to 100 μm. 10 to 90%, more preferably the particle frequency of 1 to 10 μm is 80 to 20%, and the particle frequency of 10 to 100 μm is 20 to 80%, particularly preferably 1 to 10 μm. The particle frequency of 70 to 30%, the particle frequency of 10 to 100 μm is 30 to 70%, most preferably the particle frequency of 1 to 10 μm is 60 to 40%, and , 10-100 μm grains Particle frequency of 40 to 60%. Moreover, the preferable compounding quantity of a heat conductive filler (D) is 10-1000 volume parts with respect to 100 volume parts of crystalline polyester resin (A), More preferably, it is 50-800 volume parts, More preferably It is 100-600 volume parts, Most preferably, it is 150-500 volume parts. If it is less than 10 parts by volume, the thermal conductivity may not be exhibited. If it exceeds 1000 parts by volume, the adhesiveness and the resin physical properties may be deteriorated.
The particle frequency of the filler will be described below.

  As the heat conductive filler (D) to be blended in the heat conductive resin composition of the present invention, it is preferable to use an electrically insulating filler having a thermal conductivity of 10 W / m · K or more. If it is less than 10 W / m · K, the effect of improving the thermal conductivity of the thermally conductive resin composition is inferior. The thermal conductivity of the single substance is preferably 12 W / m · K or more, more preferably 15 W / m · K or more, still more preferably 20 W / m · K or more, particularly preferably 30 W / m · K or more. It is done. The upper limit of the thermal conductivity of the heat conductive filler (D) alone is not particularly limited, and it is preferably as high as possible. Generally, it is preferably 3000 W / m · K or less, more preferably 2500 W / m · K or less. Used.

  The heat conductive filler (D) can contain one kind or two or more kinds of fillers. The term “two or more types of fillers” means that two or more types of fillers differ in material type, shape, average particle size, particle size distribution, surface treatment agent, and the like.

  About the shape of a heat conductive filler (D), the thing of a various shape is applicable. For example, particles, fine particles, nanoparticles, aggregated particles, tubes, nanotubes, wires, rods, needles, plates, irregular shapes, rugby balls, hexahedrons, large particles and fine particles are combined Various shapes such as a composite particle shape can be exemplified. These heat conductive fillers (D) may be natural products or synthesized ones. In the case of a natural product, there are no particular limitations on the production area and the like, which can be selected as appropriate.

A heat conductive filler (D) can be suitably selected with the following calculation formulas. For example, when n types of heat conductive fillers (D) are used, each filler is D ₁ , D ₂ , D ₃ ,... D _n , the total weight of these is 100% by weight, and the total particle frequency is 100 %. When the particle frequency with a particle size of 1 to 10 μm is obtained by (Equation 1) and the particle frequency with a particle size of 10 to 100 μm is obtained by (Equation 2), the particle frequency by (Equation 1) is 100 to 0%. And the particle frequency according to (Equation 2) is preferably 0 to 100%. More preferably, the particle frequency according to (Formula 1) is 90 to 10%, the particle frequency according to (Formula 2) is 10 to 90%, and more preferably, the particle frequency according to (Formula 1) is 80 to 20%, and ( The particle frequency according to (Equation 2) is 20 to 80%, particularly preferably the particle frequency according to (Equation 1) is 70 to 30%, and the particle frequency according to (Equation 2) is 30 to 70%, most preferably ( The particle frequency according to Formula 1) is 70 to 30%, and the particle frequency according to Formula 2 is 30 to 70%. It is preferable that the particle frequency of the filler satisfies these ranges, so that the filler filling rate and the thermal conductivity can be improved more efficiently than the case where these ranges are not satisfied even with the same blending amount. The particle diameter range is as described above, but more preferably 1 μm or more and less than 10 μm and 10 μm or more and 100 μm or less.

If use filler is one (Formula 1), to D ₁ of the term of (formula 2), to D ₂ are similarly two cases, and so in the case of three up to D _3, the number of types Consider the sum of the particle frequencies up to the corresponding term. However, the particle size and particle frequency handled in (Equation 1) and (Equation 2) indicate the particle size and particle frequency of the heat conductive filler alone before blending with the resin. That is, regardless of the shape of the heat conductive filler (D), in the case of an aggregate, the particle diameter and particle frequency of the aggregate are targeted. When the aspect ratios of the fillers are different, such as a tube shape, a nanotube shape, a wire shape, a rod shape, a needle shape, a plate shape, a rugby ball shape, and a hexahedron shape, the average value of the major axis and the minor axis is used. However, this is not the case when it is an aggregate. When none of these applies, the average particle size per particle and the particle frequency are targeted. In addition, the average particle diameter and particle frequency in this invention shall be measured using particle size distribution measuring apparatuses, such as a laser scattering particle size distribution analyzer.

(Formula 1)
{(Mixing ratio of heat conductive filler D ₁ [mass%]) / 100 × (particle frequency of ₁ to 10 μm of heat conductive filler D ₁ [%]) / 100
+ (Mixing ratio of heat conductive filler D ₂ [% by mass]) / 100 × (particle frequency of 1 to 10 μm of heat conductive filler D ₂ [%]) / 100
+ (Mixing ratio of heat conductive filler D ₃ [% by mass]) / 100 × (particle frequency of 1 to 10 μm of heat conductive filler D ₃ [%]) / 100
+ ...
+ (Mixing ratio of the heat conductive filler _{D n} [wt%]) / 100 × (1~10μm particle frequency of the thermally conductive filler _{D n [%]) / 100} } × 100} × 100
(Formula 2)
{(Mixing ratio of heat conductive filler D ₁ [mass%]) / 100 × (10-100 μm particle frequency of heat conductive filler D ₁ [%]) / 100
+ (Mixing ratio of heat conductive filler D ₂ [mass%]) / 100 × (particle frequency of heat conductive filler D ₂ at 10 to 100 μm [%]) / 100
+ (Mixing ratio of heat conductive filler D ₃ [mass%]) / 100 × (particle frequency of heat conductive filler D ₃ of 10 to 100 μm [%]) / 100
+ ...
+ (Mixing ratio of the heat conductive filler _{D n} [wt%]) / 100 × (particle frequency of 10~100μm thermally conductive filler _{D n [%]) / 100} } × 100} × 100

  Specific examples of the thermally conductive filler (D) exhibiting electrical insulation include metal oxides such as glass oxide epoxy, magnesium oxide, silicon oxide, beryllium oxide, copper oxide, cuprous oxide, boron nitride, and glass nitride epoxy. Metal nitride such as silicon nitride, metal carbide such as silicon carbide and zinc oxide, metal carbonate such as magnesium carbonate, insulating carbon material such as diamond, metal hydroxide such as epoxy glass hydroxide and magnesium hydroxide An oxide can be illustrated.

  Among them, since it has excellent electrical insulation, metal nitrides such as boron nitride, glass nitride epoxy, silicon nitride, metal oxides such as glass oxide epoxy, magnesium oxide, beryllium oxide, and zinc oxide, metal carbonates such as magnesium carbonate Insulating carbon materials such as metal hydroxides such as glass hydroxide epoxy and magnesium hydroxide, and diamond can be more preferably used. These can be used alone or in combination.

  These heat conductive fillers (D) have been surface-treated with various surface treatment agents such as a silane treatment agent in order to enhance the adhesion at the interface between the resin and the inorganic compound or to facilitate workability. May be. It does not specifically limit as a surface treating agent, For example, conventionally well-known things, such as a silane coupling agent and a titanate coupling agent, can be used. Among them, an epoxy group-containing silane coupling agent such as epoxy silane, an amino group-containing silane coupling agent such as aminosilane, polyoxyethylene silane, and the like are preferable because they hardly reduce the physical properties of the resin. The surface treatment method of the inorganic compound is not particularly limited, and a normal treatment method can be used.

  The heat conductive resin composition of the present invention optimizes the particle size of the heat conductive filler (D) in order to achieve both high heat conductivity and high flow. The idea is that by inserting small particles between large particles, the filling rate is increased and the contact area is increased, so that the amount of filler is reduced with respect to the target thermal conductivity, and as a result, high flow is achieved. .

  The thermal conductivity of the thermally conductive resin composition according to the present invention is preferably 0.5 W / m · K or more, more preferably 1.0 W / m · K or more, and 1.5 W / m. -It is more preferable that it is K or more, and it is especially preferable that it is 2.0 W / m.K or more. Less than 0.5 W / m · K is not preferable because the thermal conductivity effect is poor. Although an upper limit is not specifically limited, Since it depends on the heat conductivity of a heat conductive filler (D), it is generally 3000 W / m * K or less, Furthermore, it is 2500 W / m * K or less.

  In the present invention, the adhesive strength between the specific member and the heat conductive resin composition is obtained by preparing a measurement sample piece in which the heat conductive resin composition is bonded by molding between two plate-like members. Determination is made by measuring the shear peel strength. The method for preparing the test specimen for measurement and the method for measuring the shear peel strength are performed according to the methods described in the examples described later.

  The heat conductive resin composition of this invention is shape | molded by inject | pouring into the metal mold | die which set the electrical / electronic component. More specifically, in the case of using a screw type hot melt molding process applicator, it is heated and melted at around 200 to 280 ° C., injected into a mold through an injection nozzle, and then molded after a certain cooling time. A molded object can be obtained by removing the object from the mold.

  The type of the applicator for hot melt molding is not particularly limited, and examples thereof include a vertical extrusion molding machine IMC-18F9 manufactured by Imoto Seisakusho.

  In order to describe the present invention in more detail, examples and comparative examples are given below, but the present invention is not limited to the examples. In addition, each measured value described in the Example and the comparative example was measured by the following method.

<Measurement of melting point and glass transition temperature>
Using a differential scanning calorimeter “DSC220” manufactured by Seiko Denshi Kogyo Co., Ltd., put 5 mg of a measurement sample in a glass epoxy pan, seal it with a lid, hold once at 250 ° C. for 5 minutes, and then quench rapidly with liquid nitrogen Then, the temperature was measured from −150 ° C. to 250 ° C. at a temperature increase rate of 20 ° C./min. The inflection point of the obtained curve was defined as the glass transition temperature, and the endothermic peak as the melting point.

<Adhesive strength test> (Evaluation of initial adhesiveness and thermal cycle durability)
Method for Producing Adhesive Strength Test Piece A 1.6 mm thick glass epoxy plate (FR-4 manufactured by Nikkan Kogyo Co., Ltd.) is cut into a size of 25 mm wide × 70 mm long and 25 mm wide × 40 mm long, and the surface is wiped with acetone. The oil was removed. Next, this glass epoxy plate was fixed inside a mold for preparing a shear adhesion test sample (FIG. 1). Next, the resin composition was injected from the gate using a screw type hot melt molding applicator (Imoto Seisakusho type low pressure extrusion molding machine IMC-18F9) to perform molding. The molding conditions were a molding resin temperature of 250 ° C., a molding pressure of 5 MPa, a holding pressure of 5 MPa, a cooling time of 15 seconds, and a discharge rotation set to 100% (maximum discharge was 100% and about 3 cc / second). The molded product was released to obtain an adhesive strength test piece.

Evaluation of Initial Adhesiveness The adhesion test piece was stored in an atmosphere of 23 ° C. and 50% relative humidity for 3 hours to 100 hours. Next, the shear bond strength was measured. The tensile speed was 500 mm / min.
Evaluation criteria A: Shear bond strength 2.0 MPa or more
○: Shear adhesive strength less than 2.0 MPa 1.0 MPa or more
Δ: Shear adhesive strength less than 1.0 MPa 0.1 MPa or more
X: Shear adhesive strength less than 0.1 MPa

Cooling cycle test For an adhesive strength test piece produced in the same manner as the initial adhesiveness was evaluated, 1000 cycles with one cycle being placed in an environment of −40 ° C. for 30 minutes and then 150 ° C. for 30 minutes. Then, the shear bond strength was measured, and the shear adhesion retention rate was calculated. The shear adhesion retention rate is a value defined by the following mathematical formula (3).

Evaluation criteria A: Shear bond strength retention 80% or more
○: Shear bond strength retention rate of less than 80% and 50% or more
Δ: Shear bond strength retention less than 50% 20% or more
X: Shear adhesive strength retention of less than 20%

Low pressure moldability evaluation method Using a flat plate mold, a flat plate (100 mm x 100 mm x 10 mm) made of a resin composition was molded using a low pressure molding applicator IMC-18F9 manufactured by Imoto Seisakusho as an applicator for hot melt molding. The gate position was the center of a 100 mm × 100 mm surface.
Molding conditions: Molding resin temperature 250 ° C., molding pressure 5 MPa, holding pressure 5 MPa, cooling time 15 seconds, discharge rotation 100% setting Evaluation criteria A: Completely filled, without burrs or sink marks.
○: Although completely filled, some burrs are generated.
Δ: Filled without short shot, but there is a sink.
X: There is a short shot.

Production Example of Crystalline Polyester Resin (A3) In a reaction vessel equipped with a stirrer, a thermometer, and a condenser for distillation, 100 moles of terephthalic acid 1,75 parts of butanediol, terephthalic acid and 1,4- 0.25% by weight of tetrabutyl titanate was charged with respect to the total weight of butanediol, and an esterification reaction was performed at 170 to 220 ° C. for 2 hours. After completion of the esterification reaction, 25 mol parts of polytetramethylene glycol “PTMG1000” (Mitsubishi Chemical Co., Ltd.) having a number average molecular weight of 1000 and 0.5% of hindered phenol antioxidant “Irganox 1330” (Ciba Geigy Co., Ltd.) were added. The weight was charged and the temperature was raised to 250 ° C., while the pressure in the system was slowly reduced to 665 Pa at 250 ° C. over 60 minutes. Further, a polycondensation reaction was performed at 133 Pa or less for 30 minutes to obtain a crystalline polyester resin (A3). The crystalline polyester resin (A3) had a melting point of 190 ° C. and a melt viscosity of 500 dPa · s. The results are shown in Table 1.

  Crystalline polyester resins (A1), (A2), and (A4) were produced in the same manner as the crystalline polyester resin (A3). The composition and physical property values are shown in Table 1.

Abbreviations in the table are as follows.
PBT: polybutylene terephthalate PBN: polybutylene naphthalate PCD: polycarbonate diol PTMG1000: polytetramethylene glycol, number average molecular weight 1000

Example 1
100 parts by volume of crystalline polyester resin (A3), 40 parts by volume of phenol resin (B2-1), 160 parts by volume of thermally conductive filler (D1), 100 parts by volume of thermally conductive filler (D2), uniformly After mixing, a heat conductive resin composition was obtained by melt-kneading at a die temperature of 220 ° C. to 240 ° C. using a twin screw extruder. The thermal conductive resin composition was evaluated for initial shear adhesion, cold cycle durability and low-pressure moldability by the method described separately. In <shear bond strength test>, the initial bond strength was 1.2 MPa, after the thermal cycle test, 1.2 MPa, and the shear bond strength retention was 100%. The evaluation results are shown in Table 2.

Examples 2-6, Comparative Examples 1-5
In the same manner as in Example 1, except that the formulation was changed as shown in Tables 2 to 3, a thermally conductive resin composition was produced and evaluated. The evaluation results are shown in Tables 2 to 3.

The polyolefin resin, phenol resin, phenol-modified alkylbenzene resin, epoxy resin, and heat conductive filler used in Tables 2 and 3 are as follows.
Phenol-modified alkylbenzene resin (B1-1): Nikanol (registered trademark) HP-150, manufactured by Fudo Co., Ltd., phenol-modified alkylbenzene resin.
Phenol-modified alkylbenzene resin (B1-2): Nikanol (registered trademark) HP-100, manufactured by Fudou Co., Ltd., phenol-modified alkylbenzene resin.
Phenol resin (B2-1): CKM 2400 Showa High Polymer Co., Ltd., novolac type phenol resin, hydroxyl value 9000 equivalents / 10 ⁶ g.
Epoxy resin (B3-1): JER1007K manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin Number average molecular weight 2900
Epoxy resin (B3-2): JER1010K, manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, number average molecular weight 5500
Polyolefin (C1): Exelen (registered trademark) VL EUL731, manufactured by Sumitomo Chemical Co., Ltd., ethylene-α-olefin copolymer, density 0.90, MFR 10 g / 10 min.
Polyolefin (C2): Admer (registered trademark) SF-600, manufactured by Mitsui Chemicals, adhesive polyolefin, density 0.88, MFR 3.3 g / 10 min.
Thermal conductive filler (D)
(D1): Alumina powder (LS-210B manufactured by Nippon Light Metal Co., Ltd., thermal conductivity 20 to 40 W / m · K as a simple substance, average particle size 3.2 μm, volume resistivity 10 ¹² to 10 ¹⁴ Ω · cm, Specific gravity 3.98,
Particle frequency: [1-10 μm] 95%, [10-100 μm] 0%, [Others] 5%)
(D2): Alumina powder (LS-110F manufactured by Nippon Light Metal Co., Ltd., thermal conductivity 20 to 40 W / m · K as a simple substance, average particle size 1.1 μm, volume resistivity 10 ¹² to 10 ¹⁴ Ω · cm, Specific gravity 3.98,
Particle frequency: [1-10 μm] 60%, [10-100 μm] 0%, [Others] 40%)
(D3): Alumina powder (Nippon Light Metal Co., Ltd. V325F, single body thermal conductivity 20-40 W / m · K, average particle size 12 μm, volume resistivity 10 ¹² to 10 ¹⁴ Ω · cm, specific gravity 3.98. ,
Particle frequency: [1-10 μm] 35%, [10-100 μm] 55%, [Others] 10%)
(D4): Magnesia powder (RF-50-C manufactured by Ube Materials Co., Ltd., single unit thermal conductivity 42 to 60 W / m · K, average particle size 56.6 μm, volume resistivity 10 ¹⁷ Ω · cm, Specific gravity 3.58,
Particle frequency: [1-10 μm] 0%, [10-100 μm] 95%, [Others] 5%)
(D5): Magnesia powder (RF-10C-C manufactured by Ube Materials Co., Ltd., single unit thermal conductivity 42 to 60 W / m · K, average particle size 6.6 μm, volume resistivity 10 ¹⁷ Ω · cm, Specific gravity 3.58,
Particle frequency: [1-10 μm] 60%, [10-100 μm] 35%, [Others] 5%)

  In Comparative Example 1, in <shear bond strength test>, initial adhesion to the glass epoxy plate was 0.05 MPa, and after the thermal cycle test, the initial adhesion and thermal cycle durability were NG. In <Low Pressure Molding Evaluation>, good results were obtained. The evaluation results are shown in Table 3.

The resin composition of the present invention has excellent initial adhesive strength to a glass epoxy material, exhibits high adhesion durability even after being subjected to a thermal cycle load, and is also excellent in maintaining elongation at 150 ° C. atmosphere. Therefore, it is useful as a heat conductive resin composition. In addition, the thermally conductive electrical and electronic component encapsulant of the present invention exhibits durability against severe environmental loads at high temperatures (150 ° C.) and cooling cycles, and is useful for heat dissipation applications. The electrical and electronic component sealing body of the present invention is useful as, for example, automobiles, communications, computers, various connectors for household appliances, harnesses or electronic components, switches having a printed circuit board, and molded products of sensors.

Claims (10)

For 100 parts by volume of the crystalline polyester resin (A),
The total of one or more kinds of resins selected from the group consisting of phenolic-modified alkylbenzene resin (B1), phenolic resin (B2) and epoxy resin (B3) is 0.1 to 100 parts by volume,
The heat conductive filler (D) having a single thermal conductivity of 10 W / m · K or more contains 10 to 10,000 parts by volume, and the thermal conductivity as the resin composition is 0.5 W / m · K or more. The heat conductive resin composition characterized.   One or more components selected from the group consisting of a polycarbonate component, a polyalkylene ether glycol component and a polylactone component are copolymerized in the crystalline polyester resin (A) in an amount of 25 to 75% by weight. Item 2. The heat conductive resin composition according to Item 1. The heat conductive resin composition according to claim 1 or 2, wherein the phenol-modified alkylbenzene resin (B1) has a hydroxyl value of 100 equivalents / 10 ⁶ g or more. The thermally conductive resin composition according to any one of claims 1 to 3, wherein the phenol resin (B2) is a novolac type phenol resin and has a hydroxyl value of 100 equivalents / 10 ⁶ g or more.   When the heat conductive filler (D) is composed of one kind or two or more kinds of fillers, and the sum of the particle frequencies of all fillers is 100%, the particle frequency with a particle diameter of 1 to 10 μm is 100 to 0%, and The heat conductive resin composition according to any one of claims 1 to 4, wherein a particle frequency of a particle size of 10 to 100 µm is 0 to 100%.   The heat conductive resin according to any one of claims 1 to 5, which has a shear bond strength retention of 20% or more after 1000 cycles of a cooling cycle of -40 ° C for 30 minutes and 150 ° C for 30 minutes with respect to the glass epoxy plate. Composition.   The heat conductive resin composition in any one of Claims 1-6 whose shear adhesive strength with respect to a glass epoxy board is 0.1 Mpa or more.   After the heat conductive resin composition according to any one of claims 1 to 7 is heated and kneaded, the resin composition temperature is 130 ° C or higher and 300 ° C or lower and the resin composition pressure is placed in a mold in which an electric / electronic component is inserted. The manufacturing method of the heat conductive sealing body inject | poured at 0.1 Mpa or more and 100 Mpa or less.   The heat conductive sealing body sealed with the heat conductive resin composition in any one of Claims 1-7. The motor vehicle carrying the components containing the heat conductive resin composition in any one of Claims 1-7.