JP2009173855A - Thermosetting resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition capable of giving a molded article having high thermal conductivity and high electric insulation and showing excellent mechanical strength. <P>SOLUTION: The thermosetting resin composition includes a thermally conductive filler wherein the thermosetting resin contains a diallyl phthalate monomer and/or a diallyl phthalate oligomer, the content of the thermally conductive filler is 200 to 1,400 pts.wt. based on 100 pts.wt. of the whole thermosetting resin, and the cured material of the composition has thermal conductivity of not less than 1 W/m×K and insulation resistance of not less than 1×10<SP>13</SP>Ω. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a thermosetting resin composition that is used as a material for various electronic devices, heat dissipating parts inside electric devices, and parts that require heat dissipating properties. Typically, the present invention relates to a thermosetting resin composition used as a material for a semiconductor substrate or a light emitter substrate. The present invention also relates to a cured product obtained by curing such a thermosetting resin composition.

In recent years, power electronic devices such as CPUs for personal computers, various information devices, home appliances, and automobile devices have become highly sophisticated and compact, and heat generated from the inside of these electronic devices is increasing. For this reason, preventing damage and malfunction of the device due to this heat generation is a very important issue in terms of device design.
In order to solve such a problem, an electronic component is joined to a heat radiating body such as a heat radiating fin or a heat sink to diffuse heat, thereby suppressing a temperature rise of the apparatus itself. However, since the heat radiator used for this purpose is generally a metal, electrical insulation cannot be ensured. For this reason, a heat-dissipating sheet or grease having an insulating property is often sandwiched between the electric component and the heat-dissipating body.

On the other hand, thermosetting resin compositions are widely used in various fields as materials having an excellent balance of heat resistance, mechanical strength, dimensional accuracy, and cost. However, resin parts generally have poor thermal conductivity. With the recent trend toward miniaturization, it is not possible to secure a sufficient space for heat dissipating parts in the equipment, so the heat dissipating parts have to be made smaller, and therefore the strength of the resin heat dissipating parts tends to decrease due to heat storage inside the equipment. . Therefore, it is required to further improve the heat dissipation, that is, the thermal conductivity while maintaining the strength of the resin product.
For example, Patent Document 1 discloses a molded product obtained by carbonizing a resin component in a molded product including a resin containing various phenol resins such as a solid epoxy resin, a melamine resin, a resol type, and a novolac type, and expanded graphite powder. Describes excellent heat dissipation. In addition, in this document, a resin composition obtained by adding metal powder as necessary to a resin and expanded graphite powder is described as a general-purpose type heat dissipation material, It is described that a molded body obtained from this composition is excellent in heat resistance, heat dissipation and the like.

However, when graphite is added to improve the thermal conductivity, the heat dissipation is improved, but the mechanical strength and electrical insulation are reduced. Therefore, it cannot be used for applications that require high mechanical strength and electrical insulation.
Patent Document 2 includes a phenol resin as a base resin and a reinforcing filler, and has a thermal conductivity of 0.5 W / m · K or more and a bending strength of 150 MPa or more when formed into a molded body. A phenol resin molding material having an Izod impact strength of 30 J / m or more is described. Specifically, as the reinforcing filler, the reinforcing fiber is 15 to 55% by mass of the total amount of the molding material, and the high thermal conductive filler having a thermal conductivity of 10 W / m · K or more is 15 to 45% by mass of the total amount of the molding material. A phenol resin molding material in which a rubber component is blended in an amount of 0.5 to 10% by mass of the total amount of the molding material is described. Further, the reinforcing fiber is at least one selected from glass fiber, carbon fiber, aramid fiber, and cotton fabric fiber, and the high thermal conductive filler is silicon carbide, aluminum nitride, boron nitride, aluminum oxide, beryllium oxide. , Graphite, and at least one selected from diamond.

However, as shown in Patent Document 2, when a high thermal conductive filler such as silicon carbide and aluminum nitride and a rubber component are added to the resin molding material, the thermal conductivity and impact strength are improved, but the rubber component The melt viscosity at the time of molding increases and the moldability is not stable. In addition, since the long-term heat resistance of the molded body is reduced, the molding material is difficult to use as a material for parts that require heat resistance. Further, the addition of the rubber component increases the thermal expansion coefficient and decreases the dimensional accuracy. Therefore, such a molding material can be used as a molding material such as a pulley, but it is difficult to use it for a resin substrate for electronic / electrical parts that particularly require high thermal conductivity and high insulation resistance.
Further, Patent Document 3 contains 50 to 150 parts by mass of glass fiber and 80 to 150 parts by mass of a thermal conductivity-imparting filler with respect to 100 parts by mass of the thermosetting resin, and the thermal conductivity is 0.5 W / m. A thermosetting resin molding material for substrates of electronic parts and electrical parts having a K or higher and an insulation resistance of 1 × 10 ¹² Ω or higher is described.

However, since the molding material of Patent Document 3 has a low content ratio of the filler with thermal conductivity, practically sufficient heat dissipation characteristics cannot be obtained in the molded body.
In addition, as shown in Patent Documents 2 and 3, when the reinforcing material such as glass fiber is contained in the molding material at a ratio as high as the content ratio of the high thermal conductive filler, the mechanical strength is improved. As a result, the thermal conductivity is lowered and sufficient heat dissipation characteristics cannot be obtained. Moreover, since many filler materials other than resin are contained, the viscosity of a molding material is high, ie, fluidity | liquidity is bad, As a result, molding processability worsens.
JP 2001-122663 A JP 2004-339352 A JP 2007-77325 A

  This invention makes it a subject to provide the thermosetting resin composition from which the molded article which has high thermal conductivity and electrical insulation, and was excellent in mechanical strength is obtained.

The present inventors have repeated research to solve the above problems, and are thermosetting resin compositions containing a thermally conductive filler, wherein the thermosetting resin contains a diallyl phthalate monomer and / or a diallyl phthalate oligomer. The content ratio of the heat conductive filler is about 200 to 1400 parts by weight with respect to 100 parts by weight of the total amount of the thermosetting resin, and the heat conductivity of the cured product of this composition is about 1 W / m · K. As described above, the thermosetting resin composition having a volume resistivity of about 1 × 10 ¹³ Ω · cm or more was found to be excellent in mechanical strength while maintaining such high thermal conductivity and insulation. .
The present invention has been completed based on the above findings, and provides the following thermosetting resin composition.

Item 1. A thermosetting resin composition containing a heat conductive filler, wherein the thermosetting resin contains a diallyl phthalate monomer and / or a diallyl phthalate oligomer, and the content ratio of the heat conductive filler is a thermosetting resin. 200 to 1400 parts by weight with respect to 100 parts by weight of the total amount, and the cured product of this composition has a thermal conductivity of 1 W / m · K or more and a volume resistivity of 1 × 10 ¹³ Ω · cm or more. A thermosetting resin composition.
Item 2. The heat according to item 1, further comprising 1 to 15 parts by weight of at least one reinforcing material selected from the group consisting of insulating whiskers and glass fibers with respect to 100 parts by weight of the total amount of the thermosetting resin composition. Curable resin composition.
Item 3. Item 3. The thermosetting resin composition according to Item 1 or 2, which contains at least one selected from the group consisting of boron nitride, aluminum nitride, magnesium oxide, and alumina as the thermally conductive filler.
Item 4. Item 4. The thermosetting material according to Item 3, wherein the thermally conductive filler is an aluminum nitride filler whose particle surface is coated with silicon oxide and / or a magnesium oxide filler whose particle surface is coated with a double oxide of silicon and magnesium. Resin composition.
Item 5. Diallyl phthalate monomer and / or diallyl phthalate oligomer consists of diallyl isophthalate monomer and / or diallyl isophthalate oligomer and diallyl orthophthalate monomer and / or diallyl orthophthalate oligomer, and the total amount of diallyl phthalate monomer and / or diallyl phthalate oligomer Item 5. The thermosetting resin composition according to any one of Items 1 to 4, wherein the ratio of the diallyl orthophthalate monomer and / or diallyl orthophthalate oligomer is 5 to 50% by weight.
Item 6. Item 6. The item according to any one of Items 1 to 5, wherein the thermosetting resin contains diallyl phthalate oligomer or further diallyl phthalate monomer, and the ratio of diallyl phthalate oligomer to the total amount of diallyl phthalate monomer and diallyl phthalate oligomer is 10 to 100% by weight. Thermosetting resin composition.
Item 7. The thermosetting resin composition according to any one of Items 1 to 6, wherein the ratio of the diallyl phthalate monomer and / or diallyl phthalate oligomer to the total amount of the thermosetting resin is 60% by weight or more.
Item 8. Item 8. The thermosetting resin composition according to any one of Items 1 to 7, wherein the unsaturated polyester resin is contained in an amount of 40% by weight or less based on the total amount of the thermosetting resin.
Item 9. Item 9. The thermosetting resin composition according to any one of Items 1 to 8, wherein the epoxy resin is contained in an amount of 3 to 35% by weight based on the total amount of the thermosetting resin.
Item 10. Item 10. A cured product obtained by curing the thermosetting resin composition according to any one of items 1 to 9.
Item 11. Item 11. A heat dissipation member comprising the cured product according to item 10.

The thermosetting resin composition of the present invention is obtained by adding a large amount of a heat conductive filler to a thermosetting resin containing a diallyl phthalate monomer and / or a diallyl phthalate oligomer, thereby providing high thermal conductivity and high electrical insulation. It combines the properties and excellent mechanical strength. Among them, it is characterized by containing a large amount of heat conductive filler, and is particularly excellent in heat conductivity. Moreover, since the thermosetting resin contains a diallyl phthalate monomer and / or a diallyl phthalate oligomer, it is excellent in dimensional accuracy and heat resistance.
Since the composition of the present invention has such excellent characteristics, a substrate for mounting a product or component material close to a heat source in the field of automobiles, home appliances, etc., and a driving component that generates heat inside an electronic / electrical device It can be used for a wide range of applications such as

Hereinafter, the present invention will be described in detail.
The thermosetting resin composition of the present invention is a thermosetting resin composition containing a thermally conductive filler, wherein the thermosetting resin contains a diallyl phthalate monomer and / or a diallyl phthalate oligomer, The content ratio of the conductive filler is about 200 to 1400 parts by weight with respect to 100 parts by weight of the total amount of the thermosetting resin, the thermal conductivity of the cured product of this composition is about 1 W / m · K or more, and the volume resistivity Is about 1 × 10 ¹³ Ω · cm or more.

Thermosetting resin “Thermosetting resin” in the present invention is an uncured thermosetting resin.
<Diallyl phthalate>
By using a resin containing a diallyl phthalate monomer and / or a diallyl phthalate oligomer as a thermosetting resin, even if a large amount of the thermally conductive filler is blended, the compatibility with the thermally conductive filler is good. Defects such as these are not likely to occur, and the viscosity can be adjusted. For this reason, the molded object which was extremely excellent in heat conductivity can be produced.
The diallyl phthalate monomer and / or oligomer (hereinafter sometimes referred to as “diallyl phthalate”) may be any of diallyl orthophthalate, diallyl isophthalate, and diallyl terephthalate. Diallyl phthalate can be used alone or in combination of two or more. The diallyl phthalate oligomer may be a copolymer oligomer composed of two or three kinds of diallyl orthophthalate monomer, diallyl isophthalate monomer, and diallyl terephthalate monomer. Further, the benzene ring of diallyl phthalate may be substituted with a halogen atom such as a chlorine atom, a bromine atom or an iodine atom. Further, in diallyl phthalate, all or part of unsaturated bonds present in the molecule may be hydrogenated. Further, the diallyl phthalate oligomer may be a copolymer oligomer of these monomers and a different monomer having a C═C double bond such as a styrene monomer.

Among the diallyl phthalates, diallyl isophthalate is preferable in terms of excellent heat resistance and mechanical strength. Further, since diallyl isophthalate has a low viscosity at the time of melting, the dispersibility of the heat conductive filler is good. In view of ease of handling, the diallyl isophthalate oligomer preferably has a weight average molecular weight of about 20,000 to 50,000, an iodine value of about 75 to 90, and a softening point of about 50 to 80 ° C.
Further, diallyl orthophthalate is preferable in that it has excellent heat resistance and excellent dimensional stability, moldability, and processability. The diallyl orthophthalate oligomer preferably has a weight average molecular weight of about 10,000 to 30,000, an iodine value of about 55 to 65, and a softening point of about 70 to 85 ° C. in consideration of the viscosity of the resin.
It is preferable to use diallyl orthophthalate in combination with diallyl isophthalate, which makes it excellent in heat resistance and mechanical strength, as well as in dimensional stability and moldability. When diallyl isophthalate and diallyl orthophthalate are used in combination, the ratio of diallyl orthophthalate to the total amount of diallyl isophthalate and diallyl orthophthalate is preferably about 5 to 50% by weight, and about 10 to 30% by weight More preferably. If it is the said range, it will become a composition with the balance of favorable heat resistance and favorable moldability.

Furthermore, it is preferable to use a diallyl phthalate oligomer and a diallyl phthalate monomer in combination. In this case, the impregnation property to the heat conductive filler is improved, and the viscosity at the time of melt-kneading or molding is reduced to reduce the heat conductivity. The dispersibility of the conductive filler can be improved. For this reason, defects such as voids are less likely to occur inside the molded product. The monomer may be the same type as the monomer constituting the oligomer, or may be a different type. In particular, by adding a diallyl isophthalate monomer, the heat resistance, the dispersibility of the thermally conductive filler due to low viscosity, and the moldability can be combined more reliably.
The ratio of diallyl phthalate oligomer to the total amount of diallyl phthalate is preferably about 10 to 100% by weight, more preferably about 30 to 98% by weight, and still more preferably about 60 to 97% by weight. The balance is diallyl phthalate monomer. If it is the range of the said ratio, while being excellent in the dispersibility and moldability of a heat conductive filler, it will be excellent in dimensional stability.

The molecular weight of the diallyl phthalate oligomer may usually be about 10,000 to 50,000. If it is the said range, a thermosetting resin will bridge | crosslink and a composition will not gelatinize.
The ratio of diallyl phthalate (total amount of diallyl phthalate monomer and diallyl phthalate oligomer) to the total amount of the thermosetting resin is preferably about 60% by weight or more, more preferably about 70% by weight or more, and still more preferably about 80% by weight or more. About 85% by weight or more is even more preferred. As the thermosetting resin, only diallyl phthalate may be substantially contained. If it is the said range, since a heat conductive filler can fully be mix | blended, the outstanding heat dissipation characteristic is acquired. Moreover, if it is the said range, it will be excellent in heat resistance and voltage resistance.

<Unsaturated polyester>
The thermosetting resin may contain an unsaturated polyester. By containing unsaturated polyester, processability improves. When the unsaturated polyester is contained, the amount used is preferably about 40% by weight or less, more preferably about 5 to 35% by weight, even more preferably about 10 to 30% by weight, based on the total amount of the thermosetting resin. preferable. If it is the said range, while the effect of addition of unsaturated polyester is fully acquired, the molded article which has practical hardness is obtained.
As unsaturated polyester, the liquid or solid known unsaturated polyester can be used without a restriction | limiting. The unsaturated polyester is obtained by dehydration polycondensation of a polybasic unsaturated organic acid and a polyhydric alcohol, and can be thermally cured by reaction with diallyl phthalate.

Examples of the unsaturated organic acid component include maleic acid, fumaric acid, itaconic acid, phthalic acid, adipic acid, and citraconic acid. Examples of the polyhydric alcohol component include ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, 1,3-butanediol, 1,6-hexanediol, glycerin, bisphenol A, hydrogenated bisphenol A, and the like.
A part of the unsaturated organic acid in the unsaturated polyester may be replaced with a saturated organic acid.

  Moreover, you may use air curable unsaturated polyester as unsaturated polyester. Examples of the air-curable unsaturated polyester include, as an organic acid component, tetrahydrophthalic acid, 3,6-endomethylenetetraphthalic acid, methyl-3,6-endomethylenetetraphthalic acid as the above acid component and other acid components. An unsaturated polyester obtained by using a mixture in which an aliphatic cyclic unsaturated acid such as the above is used and / or a mixture in which allyl glycidyl ether or the like is used as an alcohol component in addition to the alcohol component. Is mentioned.

The unsaturated polyester preferably has a number average molecular weight of about 800 to 10,000, more preferably about 1,000 to 10,000. If the number average molecular weight of the unsaturated polyester is in the above range, it has an appropriate viscosity, so that a molded product having sufficient strength can be obtained and the processability is also good.
Unsaturated polyester can be used individually by 1 type or in combination of 2 or more types.

As a curing agent for diallyl phthalate or unsaturated polyester, a known compound can be used without limitation as a curing agent for these resins. Examples of such known curing agents include benzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5 di (t-butylperoxy) hexane, 1,3-bis (t-butylperoxy). Isopropyl) benzene, t-butylperoxy 2-ethylhexyl monocarbonate, t-butylperoxyisopropyl monocarbonate, t-butylperoxybenzoate, n-butyl 4,4-bis (t-butylperoxy) valerate, 2, Examples thereof include peroxides such as 2-di (t-butylperoxy) butane and t-butylcumyl peroxide. Of these, 1,6-bis (t-butylperoxycarbonyloxy) hexane, dicumyl peroxide, and t-butylperoxy 2-ethylhexyl monocarbonate are preferable in that the curing agent itself and the odor of the decomposition residue are less than others. A hardening | curing agent can be used individually by 1 type or in combination of 2 or more types.
The amount of the curing agent used is preferably about 0.5 to 10 parts by weight and more preferably about 1 to 3 parts by weight with respect to 100 parts by weight of the total amount of the thermosetting resin to be cured.

<Epoxy resin>
Moreover, the epoxy resin may be contained in the thermosetting resin composition. Any known epoxy resin can be used without limitation. Among them, an epoxy resin having a softening point of about 110 ° C. or less and an epoxy equivalent of about 10,000 or less is preferable. Examples of such epoxy resins include condensation products of epichlorohydrin and polyhydric alcohols or polyphenols, condensation products of epichlorohydrin and phenol novolac, cycloaliphatic epoxy compounds, glycidyl ester epoxy compounds, heterocyclic epoxies. Compounds, epoxy compounds derived from polyolefin polymers or copolymers, epoxy compounds obtained by (co) polymerization of glycidyl methacrylate, epoxy compounds obtained from glycerides of highly unsaturated fatty acids, polyalkylene ether type epoxy compounds (nuclear) And epoxy group-containing compounds such as bromine-containing or fluorine-containing epoxy compounds. Among these, bisphenol type epoxy resins and phenol novolac type epoxy resins are preferable. An epoxy resin can be used individually by 1 type or in combination of 2 or more types.
Epoxy resins are used extensively in sealing materials by taking advantage of their heat resistance, but adding them to thermosetting resin compositions improves peel strength or bending strength, and degrades heat resistance and water resistance. It is difficult to obtain a molded body.

When the epoxy resin is used, the amount used is preferably about 3 to 35% by weight, more preferably about 5 to 20% by weight, based on the total amount of the thermosetting resin. If it is the said range, while the effect of an epoxy resin addition is fully acquired, workability is favorable.
As a curing agent in the case of using an epoxy resin, an acid anhydride compound that does not inhibit the curing of diallyl phthalate monomer or oligomer or unsaturated polyester can be used. Such compounds include solid acid anhydrides at room temperature such as maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, methylcyclohexenedicarboxylic anhydride. Products; methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methyl endomethylenetetrahydrophthalic anhydride, hydrogenated methyl nadic anhydride, etc. . Among these, maleic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride are preferable, and maleic anhydride is more preferable. The epoxy resin curing agent can be used alone or in combination of two or more.

Moreover, when using an epoxy resin, in addition to a hardening | curing agent, an epoxy resin hardening accelerator can be used. Since the reaction of the acid anhydride with the epoxy resin is accelerated by the anionic polymerization curing agent, the anionic polymerization curing agent can be used as a curing accelerator. As anionic polymerization type curing agents, tertiary amines, a part of secondary amines, imidazoles, metal salts of carboxylic acids, etc. are known, and any of these can be used. Benzyldimethylamine, 2-methylimidazole of imidazoles, 2-ethyl-4-methylimidazole, 2-undecylimidazole and the like are preferable.
The thermosetting resin in the composition of the present invention may contain other thermosetting resins as long as the effects of the present invention are not hindered.

Thermally conductive fillers As thermally conductive fillers, metal nitrides such as boron nitride, aluminum nitride, and silicon nitride; metal oxides such as magnesium oxide, alumina, beryllium oxide, titanium oxide, zirconium oxide, and zinc oxide; Examples thereof include metal hydroxides such as magnesium, aluminum hydroxide, barium hydroxide, and calcium hydroxide; metal carbides such as boron carbide, aluminum carbide, and silicon carbide. These fillers exhibit high thermal conductivity despite good electrical insulation.

Of these, metal nitrides such as boron nitride and aluminum nitride are preferred because of their high thermal conductivity. In addition, metal oxides are preferable and magnesium oxide and alumina are more preferable because they are inexpensive and have good dispersibility. In terms of cost performance, magnesium oxide and alumina are preferable.
Further, the amount of moisture adsorption, chemical composition, average particle size, bulk density, whiteness, oil absorption, pH, surface area, equilibrium moisture absorption capacity and the like based on the difference in the synthesis method are not particularly limited. Furthermore, the thing which improved the compatibility and dispersibility to resin by processing the surface with a silane type or titanate type coupling agent or stearic acid can also be used conveniently.
The magnesium oxide filler and the aluminum nitride filler can improve the moisture resistance of the filler by covering the surface with an oxide or a double oxide.
Silica does not have sufficient thermal conductivity when used alone as the thermal conductive filler of the present invention, but it can be used in combination with other thermal conductive fillers to supplement the thermal conductivity of the cured product. Or mechanical strength such as bending strength and impact strength can be improved.

In the present invention, by using a magnesium oxide filler in which the surface of magnesium oxide powder or particles is coated with a double oxide of silicon (Si) and magnesium (Mg), moisture resistance, mechanical strength, And the dispersibility to resin can be improved and the thermosetting resin composition excellent in the electrical insulation characteristic and heat conductivity can be obtained. Magnesium oxide, the surface of which is coated with such an oxide, can be obtained by mixing a silicon compound and magnesium oxide powder, filtering off solids, drying and firing.
In addition, in the present invention, by using an aluminum nitride filler whose surface is coated with silicon nitride aluminum nitride powder or particles, the moisture resistance, mechanical strength, and dispersibility in the resin are easily improved, and the electric insulation characteristics And the thermosetting resin composition excellent in thermal conductivity can be obtained. Aluminum nitride whose surface is coated with such an oxide can be obtained by mixing a silicon compound and an aluminum nitride powder, filtering off solids, drying and firing.

A heat conductive filler may be used individually by 1 type, and may use it in combination of 2 or more types from which a material and a characteristic differ.
The use amount of the heat conductive filler (total heat conductive filler excluding silica) may be about 200 to 1400 parts by weight with respect to 100 parts by weight of the total amount of the thermosetting resin, and about 200 to 900 parts by weight. About 200 to 550 parts by weight is more preferable. If it is the said range, while being able to obtain the thermosetting resin hardened | cured material which has heat conductivity sufficient practically, the dispersion | distribution workability of a filler is also favorable.

Other Components The thermosetting resin composition of the present invention may contain various additives that are generally blended with rubbers and resins, if necessary. Examples of such additives include peptizers such as aromatic mercaptan-based, aromatic disulfide-based, aromatic mercaptan-zinc-based, etc .; organic acid-based, nitroso compound-based, sulfenamide-based scorch inhibitor; paraffin -Based, aromatic, naphthenic, liquid rubber-based plasticizers; rosin derivative-based, terpene-based natural resin-based tackifiers; coumarone (indene) resin-based, petroleum resin-based, alkylphenol resin-based, xylene / formaldehyde Synthetic resin tackifiers such as halogen resins; flame retardants such as halogen, metal hydrate, silicon, and phosphorus; antioxidants; thermal stabilizers; light stabilizers; ultraviolet absorbers; lubricants; Examples thereof include a crosslinking agent; a crosslinking aid; a vulcanization anti-reversion agent; a silane coupling agent; a titanate coupling agent.
Moreover, the thermosetting resin composition of this invention can contain the well-known additive normally used for a thermosetting resin composition. Examples of such additives include fillers, acid acceptors, reinforcing agents, stabilizers, anti-aging agents, lubricants, pressure-sensitive adhesives, pigments, flame retardants, UV absorbers, foaming agents, and vulcanization modifiers. It is done. Further, in order to improve the strength and rigidity of the molded product, a reinforcing material such as a crosslinking agent, a coupling agent, and a short fiber may be included.

As the reinforcing material, glass fibers, electrically insulating whiskers such as aluminum nitride, silicon carbide, and silicon nitride can be used. The amount used in the case of adding such a reinforcing material may be about 1 to 15 parts by weight, preferably about 2 to 13 parts by weight, with respect to 100 parts by weight of the total amount of the thermosetting resin composition. 3 to 11 parts by weight is more preferable.
Physical Properties The composition of the present invention has a cured product having a thermal conductivity of 1 W / m · K or more and a volume resistivity of 1 × 10 ¹³ Ω · cm or more.
The cured product referred to here is the same operation as in the examples described later, to obtain a thermosetting resin composition by mixing each component, knead, cool, coarsely pulverize, heat and pressure It is a cured product obtained by molding. The thermal conductivity and volume resistivity are values measured by the methods described in the examples.
The heat conductivity and volume resistivity of the said range can be obtained by adjusting suitably the kind and usage-amount of each component in a composition in the range mentioned above.

Production method The thermosetting resin composition of the present invention is prepared by mixing each component, a mixer; a wet disperser using a medium such as a ball mill, a sand mill, and a bead mill; an ultrasonic disperser such as a homogenizer; It can be obtained by uniformly mixing each component using an apparatus capable of dispersing under a shearing force, such as a pressure disperser. In addition, the thermosetting resin composition of the present invention may be produced by pulverizing a kneaded material that is heated and melted and kneaded using a pressure kneader, a mixing roll, a twin screw extruder, or the like, using a power mill or the like. The molding material thus obtained can be applied to any of injection molding, transfer molding, compression molding and the like.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.
Examples 1-13 and Comparative Examples 1-4
The following components were mixed for 1-2 minutes using a Henschel mixer. The obtained mixture was kneaded with a 9-inch diameter mixing roll at a roll temperature of 80 to 100 ° C. for 5 minutes, taken out, cooled, and coarsely pulverized with a power mill. The obtained composition was molded with a mold at 170 ° C. under a pressure of 30 kgf / cm ² and a curing time of 5 minutes to obtain a heat radiating plate (100 mm × 100 mm × 4 mm).

Ingredients used : diallyl phthalate:
・ Diallyl orthophthalate oligomer (Daiso Corp .: Daiso Dup)
・ Diallyl isophthalate oligomer (Daiso: Daiso isopap)
・ Diallyl orthophthalate monomer (Daiso)
・ Diallyl isophthalate monomer (Daiso)
・ Diallyl terephthalate monomer (Daiso)
Epoxy resin:
・ Orthocresol novolac resin (manufactured by Toto Kasei Co., Ltd .: YDCN704)
Epoxy resin curing agent:
・ Hardening accelerator for maleic anhydride epoxy resin:
-Benzylmethylamine-Hexamethylenetetramine diallyl phthalate curing agent:
・ Dicumyl peroxide ・ tert-butylperoxyisopropyl monocarbonate Thermally conductive filler:
-Amorphous alumina (manufactured by Showa Denko KK, average particle size: 4.6 μm)
・ Spherical alumina (manufactured by Showa Denko KK, average particle size: 11 μm)
Magnesium oxide (manufactured by Tateho Chemical Co., Ltd .: surface silica / magnesium double oxide coating, average particle size: 25 μm)
Boron nitride (Showa Denko, average particle size: 10 μm)
Aluminum nitride (Toyo Aluminum Co., Ltd .: surface silica coating, average particle size: 1.2 μm)
・ Silica (Electrochemical Industry Co., Ltd .: Spherical silica)
Reinforcement:
・ Glass fiber (Nittobo Glass, fiber diameter: 11 μm, average fiber length: 3 mm)
・ Potassium titanate whisker (Otsuka Chemical Co., Ltd.)
Silane coupling agent:
・ Acryloxy silane coupling agent (Shin-Etsu Chemical Co., Ltd.)
・ Epoxysilane-based silane coupling agent (Shin-Etsu Chemical Co., Ltd.)
The types and amounts used of the components used in each example are as follows.

Example 1
Diallyl isophthalate oligomer 91.2 parts by weight Diallyl isophthalate monomer 4.8 parts by weight Dicumyl peroxide 1.92 parts by weight Amorphous alumina 304.0 parts by weight Acryloxy silane coupling agent 3.0 parts by weight Others 1.0 parts by weight

Example 2
Diallyl isophthalate oligomer 77.0 parts by weight Diallyl isophthalate monomer 3.0 parts by weight Dicumyl peroxide 1.6 parts by weight Amorphous alumina 320.4 parts by weight Acryloxy silane coupling agent 3.2 parts by weight Other 1.0 parts by weight

Example 3
Diallyl isophthalate oligomer 87.0 parts by weight Diallyl isophthalate monomer 4.6 parts by weight Dicumyl peroxide 1.82 parts by weight Spherical alumina 288.4 parts by weight Glass fiber 20.0 parts by weight Acryloxy silane coupling agent 2.9 parts by weight Others 1.0 parts by weight

Example 4
Diallyl isophthalate oligomer 80.9 parts by weight Diallyl isophthalate monomer 4.3 parts by weight Dicumyl peroxide 1.70 parts by weight Spherical alumina 274.8 parts by weight Glass fiber 40.0 parts by weight Acryloxy silane coupling agent 2.7 parts by weight Others 1.0 parts by weight

Example 5
Diallyl isophthalate oligomer 104.0 parts by weight Diallyl isophthalate monomer 5.0 parts by weight Dicumyl peroxide 2.18 parts by weight Magnesium oxide 291.2 parts by weight Glass fiber 30.0 parts by weight Other 1.5 parts by weight

Example 6
Diallyl orthophthalate oligomer 45.0 parts by weight Diallyl isophthalate oligomer 46.0 parts by weight Dicumyl peroxide 1.82 parts by weight Magnesium oxide 309.2 parts by weight Glass fiber 30.0 parts by weight Other 1.5 parts by weight

Example 7
Diallyl orthophthalate oligomer 21.0 parts by weight Diallyl isophthalate oligomer 91.0 parts by weight Diallyl terephthalate monomer 10.8 parts by weight
tert-Butylperoxyisopropyl monocarbonate 2.46 parts by weight Boron nitride 257.2 parts by weight Glass fiber 20.0 parts by weight Acryloxy silane coupling agent 2.5 parts by weight Other 1.5 parts by weight

Example 8
Diallyl orthophthalate oligomer 23.5 parts by weight Diallyl isophthalate oligomer 64.6 parts by weight Diallyl terephthalate monomer 5.9 parts by weight
tert-Butylperoxyisopropyl monocarbonate 1.76 parts by weight Amorphous alumina 226.0 parts by weight Boron nitride 60.0 parts by weight Glass fiber 20.0 parts by weight Acryloxy silane coupling agent 2.3 parts by weight Other 1.5 parts by weight

Example 9
Diallyl orthophthalate oligomer 20.0 parts by weight Diallyl isophthalate oligomer 55.0 parts by weight Diallyl terephthalate monomer 5.0 parts by weight Orthocresol novolac resin 14.0 parts by weight Maleic anhydride 6.0 parts by weight Benzylmethylamine 0.005 parts by weight Dicumyl peroxide 1.5 parts by weight Amorphous alumina 187.6 Part by weight Boron nitride 92.4 parts by weight Glass fiber 20.0 parts by weight Epoxysilane silane coupling agent 2.0 parts by weight Other 1.5 parts by weight

Example 10
Diallyl isophthalate oligomer 75.0 parts by weight Diallyl isophthalate monomer 5.0 parts by weight
tert-Butylperoxyisopropyl monocarbonate 1.5 parts by weight Amorphous alumina 231.0 parts by weight Aluminum nitride 60.0 parts by weight Potassium titanate whisker 15.0 parts by weight Acryloxy silane coupling agent 2.9 parts by weight Other 1.5 parts by weight

Example 11
Diallyl isophthalate oligomer 82.0 parts by weight Diallyl isophthalate monomer 5.5 parts by weight Dicumyl peroxide 1.5 parts by weight Amorphous alumina 172.6 parts by weight Aluminum nitride (amorphous) 92.4 parts by weight Silica (average particle size: 5.0 μm) 20.0 parts by weight titanic acid Potassium whisker 15.0 parts by weight Acryloxy silane coupling agent 2.9 parts by weight Other 1.5 parts by weight

Example 12
Diallyl isophthalate oligomer 80.0 parts by weight Diallyl isophthalate monomer 5.0 parts by weight Orthocresol novolac resin 5.0 parts by weight Maleic anhydride 2.0 parts by weight Benzylmethylamine 0.002 parts by weight Dicumyl peroxide 1.7 parts by weight Spherical alumina 268.0 parts by weight Glass fiber 40.0 parts by weight Epoxy silane silane coupling agent 2.7 parts by weight Other 1.5 parts by weight

Example 13
Diallyl isophthalate oligomer 90.0 parts by weight Diallyl terephthalate monomer 7.2 parts by weight Orthocresol novolac resin 15.3 parts by weight Maleic anhydride 6.3 parts by weight Benzylmethylamine 0.001 part by weight Dicumyl peroxide 2.0 parts by weight Boron nitride (amorphous) 128.0 parts by weight Spherical alumina 120.0 parts by weight Glass fiber 20.0 parts by weight Epoxysilane-based silane coupling agent 2.5 parts by weight Other 1.5 parts by weight

Comparative Example 1
Diallyl isophthalate oligomer 200.0 parts by weight Dicumyl peroxide 10.0 parts by weight Amorphous alumina 172.0 parts by weight Glass fiber 240.0 parts by weight Others 20.0 parts by weight

Comparative Example 2
Diallyl isophthalate oligomer 100.0 parts by weight Diallyl isophthalate monomer 10.0 parts by weight Dicumyl peroxide 2.2 parts by weight Silica (average particle size: 6.5 μm) 290.0 parts by weight Acryloxy silane coupling agent 2.9 parts by weight Other 1.5 parts by weight

Comparative Example 3
Diallyl isophthalate oligomer 17.1 parts by weight Diallyl isophthalate monomer 6.9 parts by weight Dicumyl peroxide 0.4 parts by weight Spherical alumina 341.6 parts by weight Epoxysilane silane coupling agent 3.4 parts by weight Other 1.5 parts by weight

Comparative Example 4
Orthocresol novolac resin 83.5 parts by weight Hexamethylenetetramine 12.5 parts by weight Amorphous alumina 304.0 parts by weight Glass fiber 20.0 parts by weight Other 1.5 parts by weight

Physical property evaluation The following physical property test was done about the heat sink obtained by each said Example and comparative example.
Bending strength: The bending strength was measured according to JISK7203.
Charpy impact strength: Charpy impact strength was measured according to JISK7111.
Thermal conductivity: The thermal diffusivity was measured according to the thermal diffusivity measurement of JISR1611, and the specific heat was measured according to JISK7123. Furthermore, the product of thermal diffusivity, specific heat, and density was defined as thermal conductivity.
Volume resistance: Insulation resistance was measured according to JISK6271.
Molded state: The molded plate was visually observed, and the molded state was evaluated according to the following criteria.
○: Good fillability and curability and no defects.
Δ: Fillability and curability are good, but some whiskers, bubbles, cracks, etc. occurred.
X: The curing time is long, or the filling property is poor and many defects are generated.
XX: The molded body could not be molded well.

The results are shown in Table 1 below.

As is clear from Table 1, the heat dissipation plate obtained in Comparative Example 1 in which the amount of the thermally conductive filler used was small had a low thermal conductivity. The heat sink obtained by Comparative Example 2 had low thermal conductivity. The heat radiating plate obtained in Comparative Example 3 had a low volume resistivity and a very poor molding state. Moreover, the heat sink obtained by the comparative example 4 which used only an epoxy resin as a thermosetting resin had a low volume resistivity, and its shaping | molding state was also bad.
On the other hand, the heat sink obtained by Examples 1-13 which hardened the composition of this invention had high heat conductivity and volume resistivity, and its formation state was also favorable. In addition, practically sufficient bending strength and impact strength were exhibited, and when glass fiber or whisker was added as a filler, even higher bending strength was exhibited.

  The cured product obtained by curing the composition of the present invention has extremely high thermal conductivity while maintaining heat resistance, mechanical strength, and electrical insulation equivalent to or higher than those of conventional thermosetting resin molding materials. The composition of the present invention is suitably used for materials such as substrates for electronic components or electrical components.

Claims (11)

A thermosetting resin composition containing a heat conductive filler, wherein the thermosetting resin contains a diallyl phthalate monomer and / or a diallyl phthalate oligomer, and the content ratio of the heat conductive filler is a thermosetting resin. 200 to 1400 parts by weight with respect to 100 parts by weight of the total amount, and the cured product of this composition has a thermal conductivity of 1 W / m · K or more and a volume resistivity of 1 × 10 ¹³ Ω · cm or more. A thermosetting resin composition.   Furthermore, 1-15 weight part of at least 1 sort (s) of reinforcing material chosen from the group which consists of an insulating whisker and glass fiber is contained with respect to 100 weight part of whole quantity of a thermosetting resin composition. Thermosetting resin composition.   The thermosetting resin composition according to claim 1 or 2, comprising at least one selected from the group consisting of boron nitride, aluminum nitride, magnesium oxide, and alumina as the heat conductive filler.   The thermosetting according to claim 3, wherein the thermally conductive filler is an aluminum nitride filler whose particle surface is coated with silicon oxide and / or a magnesium oxide filler whose particle surface is coated with a double oxide of silicon and magnesium. Resin composition.   Diallyl phthalate monomer and / or diallyl phthalate oligomer consists of diallyl isophthalate monomer and / or diallyl isophthalate oligomer and diallyl orthophthalate monomer and / or diallyl orthophthalate oligomer, and the total amount of diallyl phthalate monomer and / or diallyl phthalate oligomer The thermosetting resin composition according to any one of claims 1 to 4, wherein the ratio of the diallyl orthophthalate monomer and / or diallyl orthophthalate oligomer is 5 to 50% by weight.   The diallyl phthalate oligomer or further the diallyl phthalate monomer is contained as the thermosetting resin, and the ratio of the diallyl phthalate oligomer to the total amount of the diallyl phthalate monomer and the diallyl phthalate oligomer is 10 to 100% by weight. Thermosetting resin composition.   The thermosetting resin composition according to any one of claims 1 to 6, wherein the ratio of diallyl phthalate monomer and / or diallyl phthalate oligomer to the total amount of the thermosetting resin is 60% by weight or more.   The thermosetting resin composition according to any one of claims 1 to 7, wherein the unsaturated polyester resin is contained in an amount of 40% by weight or less based on the total amount of the thermosetting resin.   The thermosetting resin composition according to any one of claims 1 to 8, wherein the epoxy resin is contained in an amount of 3 to 35% by weight based on the total amount of the thermosetting resin.   Hardened | cured material obtained by hardening the thermosetting resin composition in any one of Claims 1-9.   A heat dissipation member comprising the cured product according to claim 10.