JP2020100145A - Laminate - Google Patents

Abstract

To provide a laminate having high thermal conductivity and high adhesive strength between an insulation resin later and a first metal layer.SOLUTION: A laminate includes an insulation resin layer containing inorganic particles (X) having boron nitride (a) and a first metal layer set on the insulation resin layer. Agglomerated particles of particle size D90 in the boron nitride (a) have a strength of 40 mN or more when disintegrated.SELECTED DRAWING: None

Description

The present invention relates to a laminate.

2. Description of the Related Art In recent years, miniaturization and higher performance of electronic and electric devices have been progressing, and mounting density of electronic components has been increasing. Therefore, how to dissipate the heat generated from electronic components in a narrow space has become a problem. Since the heat generated from electronic components is directly connected to the reliability of electronic and electric devices, efficient dissipation of the generated heat is an urgent issue.

As one means for solving the above problems, there is a means for using a ceramic substrate having high thermal conductivity as a heat dissipation substrate for mounting a power semiconductor device or the like. Examples of such a ceramics substrate include an alumina substrate and an aluminum nitride substrate.

However, the means using the ceramic substrate has problems that it is difficult to form a multilayer, the workability is poor, and the cost is very high. Furthermore, since the difference in the coefficient of linear expansion between the ceramic substrate and the copper circuit is large, there is a problem that the copper circuit is easily peeled off during the cooling/heating cycle.

Therefore, a resin composition using plate-like inorganic particles such as boron nitride having a low coefficient of linear expansion has attracted attention as a heat dissipation material. For example, Patent Documents 1 and 2 disclose resin compositions using boron nitride. A technique is known in which an insulating resin layer made of such a resin composition and a laminate in which a metal layer such as copper is laminated on the resin layer are used as a heat dissipation material.

JP, 2014-040533, A JP, 2013-89670, A

For the current circuit pattern of power devices, from the viewpoint of increasing the current and reducing the heat load, a technique for thickening the metal layer such as copper is required. However, when the metal layer is thickened, particularly when the metal layer is processed into a circuit pattern, there is a problem that the adhesive force between the resin layer and the metal layer is small and the resin layer is easily peeled off. In addition, when the adhesive force between the resin layer and the metal layer is small as described above, the adhesion between the two may be deteriorated and the insulation may be deteriorated, especially when heat is applied.
From the above, it is an object of the present invention to provide a laminate having good thermal conductivity and high adhesiveness between a resin layer and a metal layer.

As a result of extensive studies to solve the above problems, a laminate having an insulating resin layer containing inorganic particles (X) containing boron nitride (a) and a first metal layer provided on the insulating resin layer. In the above, it was found that the above-mentioned problems can be solved by a laminated body having a crushing strength of 40 mN or more of crushed aggregated particles of boron nitride (a) having a particle diameter D90. That is, the present invention is as follows.

[1] A laminate including an insulating resin layer containing inorganic particles (X) containing boron nitride (a), and a first metal layer provided on the insulating resin layer, wherein the boron nitride ( A laminate having a crushed strength of 40 mN or more of the agglomerated particles having a particle diameter D90 in a).
[2] The laminate according to the above [1], wherein the aggregated particles of the boron nitride (a) having a particle diameter D50 have a strength of 30 mN or less when crushed.
[3] The laminated body according to the above [1] or [2], wherein the boron nitride (a) is aggregated particles of boron nitride.
[4] The laminated body according to any one of the above [1] to [3], wherein the aspect ratio of the primary particles of the boron nitride (a) is 2 or more.
[5] The inorganic particles (X) further contain boron nitride (b), and the strength at the time of crushing aggregated particles having a particle diameter D90 in the boron nitride (b) is 30 mN or less, [1] to The laminate according to any one of [4].
[6] The layered product according to the above [5], wherein the boron nitride (b) is a boron nitride agglomerated particle.
[7] The laminate according to the above [5] or [6], wherein the aspect ratio of the primary particles of the boron nitride (b) is 2 or more.
[8] The laminated body according to any one of the above [1] to [7], wherein the inorganic particles (X) contain inorganic particles (c) other than the boron nitride.
[9] The laminate according to [8], wherein the inorganic particles (c) are one or more selected from the group consisting of aluminum oxide, aluminum nitride, magnesium oxide, and silicon carbide.
[10] In the above [1] to [9], the insulating resin layer is formed from a resin composition containing inorganic particles (X), a thermosetting compound, and at least one of a thermosetting agent and a curing catalyst. The laminate according to any one of the above.
[11] The laminate according to the above [10], wherein the thermosetting compound contains at least one selected from an epoxy compound, an oxetane compound, an episulfide compound, and a silicone compound.
[12] The laminate according to any one of the above [1] to [11], wherein the insulating resin layer has a thickness of 100 μm or more.
[13] Any one of the above-mentioned [1] to [12], wherein a second metal layer is provided on the surface of the insulating resin layer opposite to the surface on which the first metal layer is provided. Stack of.
[14] An electronic component comprising the laminate according to any one of [1] to [13] above and a semiconductor chip mounted on the laminate.

According to the present invention, it is possible to provide a laminate having good thermal conductivity and high adhesion between the insulating resin layer and the first metal layer.

It is a sectional view showing the layered product concerning one embodiment of the present invention typically. It is a sectional view showing the layered product concerning one embodiment of the present invention typically. It is sectional drawing which shows the electronic component of this invention typically.

The laminate of the present invention is a laminate including an insulating resin layer containing inorganic particles (X) containing boron nitride, and a first metal layer provided on the insulating resin layer, wherein the boron nitride It is a laminated body having a strength of 40 mN or more when crushing aggregated particles having a particle diameter D90 in (a).
In the laminate of the present invention, the insulating resin layer contains boron nitride (a) having a strength at the time of crushing aggregated particles of particle diameter D90 of 40 mN or more, whereby the insulating resin layer and the first metal layer are formed. The adhesive strength of is improved. The reason why the adhesive strength is increased is estimated as follows. The peeling between the insulating resin layer and the metal layer is often caused by partial destruction of the insulating resin layer rather than at the interface between the insulating resin layer and the metal layer. By containing inorganic particles containing agglomerated particles having high strength during crushing in the insulating resin layer, destruction of the insulating resin layer is suppressed, and as a result, the adhesive force between the insulating resin layer and the metal layer is increased. it is conceivable that.

<Insulating resin layer>
(Boron nitride)
The insulating resin layer of the present invention contains inorganic particles (X) containing boron nitride (a). Boron nitride is dispersed in the resin in the insulating resin layer and has a function of radiating the heat transferred from the metal layer, so that the insulating resin layer has good thermal conductivity.

Boron nitride (a) is a boron nitride agglomerated particle containing secondary particles obtained by aggregating primary particles of boron nitride, and contains agglomerated particles having a strength during crushing of 40 mN or more. This increases the adhesive force between the insulating resin layer and the first metal layer.
From the viewpoint of improving the adhesive force between the insulating resin layer and the first metal layer, it is preferable that the boron nitride contains aggregated particles having a crushing strength of 45 mN or more, and a crushing strength of 50 mN or more. More preferably, it contains agglomerated particles.

The strength of the aggregated particles of boron nitride (a) having a particle diameter D90 at the time of crushing is 40 mN or more. That is, among the aggregated particles forming the boron nitride (a), the strength of the aggregated particles having a large particle size at the time of crushing is high to a certain extent, so that the adhesive strength between the insulating resin layer and the first metal layer is increased. Cheap.
The strength of the crushed aggregate particles of boron nitride (a) having a particle diameter D50 is preferably 30 mN or less. That is, among the agglomerated particles forming the boron nitride (a), the agglomerated particles having a medium particle size have a small strength at the time of crushing, so that the insulating property of the insulating resin layer is likely to increase.
In boron nitride (a), it is preferable that the crushed strength of aggregated particles having a particle diameter D90 is 40 mN or more, and the crushed strength of aggregated particles having a particle diameter D50 is 30 mN or less. Such an insulating resin layer containing boron nitride (a) has good thermal conductivity, high adhesive strength with the first metal layer, and excellent insulating properties.

In the boron nitride (a), the strength at the time of crushing aggregated particles having a particle diameter D90 is preferably 45 mN or more, more preferably 50 mN or more.
Further, in the boron nitride (a), the strength at the time of crushing agglomerated particles having a particle diameter D90 is preferably 200 mN or less, more preferably 150 mN or less.
In the boron nitride (a), the strength at the time of crushing aggregated particles having a particle diameter D50 is preferably 25 mN or less, more preferably 20 mN or less.

The average particle size of the boron nitride (a) is not particularly limited, but is preferably 5 to 80 μm, more preferably 10 to 70 μm. The average particle size means D50.

The above-mentioned D50 and D90 refer to the values of the diameters corresponding to 50% and 90%, respectively, from the smaller side in the volume-based cumulative fraction of the particle size distribution measurement by the laser diffraction type particle size distribution measuring device.

In the present invention, the strength at the time of crushing aggregated particles contained in inorganic particles such as boron nitride is measured as follows.
Using a micro compression tester, a diamond prism is used as a compression member under the condition of a compression speed of 0.67 mN/sec, and the smooth end face of the compression member is lowered toward each agglomerated particle constituting the inorganic particle. , Load the aggregated particles. The load is gradually increased, and the load when the agglomerated particles are crushed is defined as the crushing strength.
The above-mentioned strength measurement at the time of crushing the agglomerated particles having a particle diameter D90 is carried out by observing inorganic particles such as boron nitride using a microscope, and 10 agglomerated particles having a particle diameter D90 are selected. The strength is calculated and the results are averaged. The aggregated particles having the particle diameter D90 to be measured may be selected from the aggregated particles having an error range of less than 5% from D90.
The strength of the agglomerated particles having the particle diameter D50 at the time of crushing can be measured by replacing “D90” with “D50” in the above description regarding the strength measurement at the time of crushing the agglomerated particles of the particle diameter D90.

The aspect ratio of the primary particles of boron nitride (a) is preferably 2 or more, more preferably 3 or more, and further preferably 4 to 6. When the aspect ratio is 2 or more, the major axis of boron nitride (a) becomes long, and the thermal conductivity can be improved. In addition, in this specification, an aspect ratio means a major axis/minor axis.

The content of boron nitride (a) is preferably 10 to 100% by mass, more preferably 20 to 90% by mass, and further preferably 30 to 70% by mass, based on the total amount of the inorganic particles (X). When the content of the boron nitride (a) is as described above, the insulating resin layer has good thermal conductivity and the adhesive force with the first metal layer tends to be high.
The content of the inorganic filler (X) is preferably 10 to 95% by mass, more preferably 30 to 90% by mass, and further preferably 60 to 90% by mass based on the total amount of the insulating resin layer.

The inorganic particles (X) contained in the insulating resin layer of the present invention preferably contain boron nitride (b) in addition to boron nitride (a). The boron nitride (b) is preferably boron nitride agglomerated particles from the viewpoint of enhancing thermal conductivity and insulating properties. The strength of the crushed aggregate particles of boron nitride (b) having a particle diameter D90 is preferably 30 mN or less. By using boron nitride (b) having a large particle size and containing agglomerated particles of low strength together with the above-mentioned boron nitride (a), the thermal conductivity of the insulating resin layer and the adhesiveness with the first metal layer Is improved, and the insulating property is further improved.
The strength of the aggregated particles of the boron nitride (b) having a particle diameter D90 at the time of crushing is preferably 20 mN or less, more preferably 10 mN or less.
The strength of the aggregated particles of boron nitride (b) having a particle diameter D50 at the time of crushing is preferably 30 mN or less, more preferably 20 mN or less, and further preferably from the viewpoint of improving the insulating property of the insulating resin layer. It is 10 mN or less.

The average particle diameter of boron nitride (b) is not particularly limited, but is preferably 5 to 80 μm, more preferably 10 to 70 μm.

The aspect ratio of the primary particles of boron nitride (b) is preferably 2 or more, more preferably 3 or more, and further preferably 4 to 6. When the aspect ratio is 2 or more, the major axis of boron nitride (b) becomes long, and the thermal conductivity can be improved.

The mass ratio of boron nitride (b) to boron nitride (a) in the inorganic particles (X) contained in the insulating resin layer is preferably 0.2 to 5, and more preferably 0.5 to 2. It is more preferably 0.8 to 1.2. Within such a range, the thermal conductivity and insulating properties of the insulating resin layer and the adhesiveness with the first metal layer are improved.

The content of boron nitride (b) is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, based on the total amount of the inorganic particles (X).

The boron nitrides (a) and (b) are preferably boron nitride agglomerated particles as described above.
The boron nitride agglomerated particles are preferably manufactured by using primary particles of boron nitride as a material. The boron nitride used as the material of the boron nitride agglomerated particles is not particularly limited, and includes hexagonal boron nitride, cubic boron nitride, boron nitride produced by a reduction nitriding method of a boron compound and ammonia, a boron compound and melamine, and the like. Examples thereof include boron nitride produced from a nitrogen compound, boron nitride produced from sodium borohydride and ammonium chloride, and the like.

As the boron nitride agglomerated particles, hexagonal boron nitride agglomerated particles are preferable. The hexagonal boron nitride agglomerated particles are produced using hexagonal boron nitride as a material, and easily contain agglomerated particles having a crushing strength of 40 mN or more, and are excellent in thermal conductivity.
The hexagonal boron nitride agglomerated particles are obtained by mixing 100 parts by mass of a crude hexagonal boron nitride powder containing 20 to 90% by mass of boron nitride and 10 to 80% by mass of boron oxide with a carbon source of 9 to 15 parts by mass in terms of carbon. After molding, it is preferably obtained by a method of firing in an atmosphere containing nitrogen gas.

The above-mentioned crude hexagonal boron nitride powder can be suitably obtained by mixing a compound containing oxygen and boron and a compound having an amino group, molding, and then heating and pulverizing.
Examples of the compound containing oxygen and boron include orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ), tetraboric acid (H ₂ B ₄ O ₇ ), and boric anhydride (B ₂ O ₃ ). Among them, orthoboric acid is preferable because it has good miscibility with a compound having an amino group.
Examples of the compound having an amino group include aminotriazine compounds, guanidine compounds, urea and the like. Examples of the aminotriazine compound include melamine, guanamine, benzoguanamine, and condensates of these, melam, melem, and melon.

Examples of the carbon source include graphite, carbon black, boron carbide, saccharides, melamine, and phenol resin, with graphite being preferred.

In the production of the hexagonal boron nitride agglomerated particles, it is preferable to mix the crude hexagonal boron nitride powder and the carbon source and then mold the mixture into an appropriate shape. By molding, preferably by pressure molding, boron nitride agglomerated particles containing agglomerated particles having high strength during crushing are easily generated. The density after molding is preferably 0.5 g/cm ³ or more, more preferably 0.8 g/cm ³ or more, from the viewpoint of facilitating the production of boron nitride agglomerated particles containing agglomerated particles having high strength during crushing. More preferably, it is 1 g/cm ³ or more. The density after molding is preferably 2 g/cm ³ or less, more preferably 1.8 g/cm ³ or less, and further preferably 1.5 g/cm ³ or less.

After molding the mixture of the crude hexagonal boron nitride powder and the carbon source, by firing, the boron oxide contained in the crude hexagonal boron nitride powder reacts with the carbon contained in the carbon source, and the strength during crushing Aggregated particles of boron nitride containing agglomerated particles having a high value can be obtained.
The firing is preferably performed in a nitrogen gas atmosphere. The firing temperature is preferably 1000 to 2200° C., and the firing time is preferably 1 to 20 hours.

The method for producing the boron nitride agglomerated particles is not limited to the above-described production method, and a spray drying method, a fluidized bed granulation method, or the like may be used. The spray drying method can be classified into a two-fluid nozzle method, a disk method (also called a rotary method), an ultrasonic nozzle method, and the like depending on the spray method, and any of these methods can be applied. The ultrasonic nozzle method is preferable from the viewpoint that the total pore volume can be controlled more easily.

The insulating resin layer of the present invention preferably contains inorganic particles (c) in addition to the above-mentioned boron nitride.
The inorganic particles (c) are preferably one or more selected from the group consisting of aluminum oxide, aluminum nitride, magnesium oxide, and silicon carbide, and more preferably aluminum oxide. By containing such inorganic particles (c), the content of the above-mentioned boron nitride (a) and boron nitride (b) blended as necessary can be reduced, and as a result, an insulating resin layer and The adhesive strength with the first metal layer can be improved.

The mass ratio of the inorganic particles (c) to the boron nitride (a) is preferably 0.2 to 5, more preferably 0.5 to 2, and further preferably 0.8 to 1.2. preferable. Within such a range, the thermal conductivity of the insulating resin layer and the adhesiveness with the first metal layer are improved.

The average particle size of the inorganic particles (c) is preferably 0.1 to 80 μm, more preferably 0.5 to 70 μm.
The content of the inorganic particles (c) is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, based on the total amount of the inorganic particles (X).

(Resin composition)
The insulating resin layer of the present invention is formed from a resin composition containing the above-mentioned inorganic particles (X), a thermosetting compound, and at least one of a thermosetting agent and a curing catalyst.
The thermosetting compound preferably contains at least one selected from an epoxy compound, an oxetane compound, an episulfide compound, and a silicone compound. Of these, epoxy compounds are preferable.

As the epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a phenol novolac type epoxy compound, a biphenyl type epoxy compound, a biphenyl novolac type epoxy compound, a biphenol type epoxy compound, a naphthalene type epoxy compound, Fluorene type epoxy compounds, phenol aralkyl type epoxy compounds, naphthol aralkyl type epoxy compounds, dicyclopentadiene type epoxy compounds, anthracene type epoxy compounds, adamantane skeleton epoxy compounds, tricyclodecane skeleton epoxy compounds, naphthylene ether type epoxies Examples thereof include compounds and epoxy compounds having a triazine nucleus in the skeleton.
The epoxy compound is preferably a bisphenol A type epoxy compound.

Examples of the oxetane compound include 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 3-methyl -3-glycidyl oxetane, 3-ethyl-3-glycidyl oxetane, 3-methyl-3-hydroxymethyl oxetane, 3-ethyl-3-hydroxymethyl oxetane, di{1-ethyl(3-oxetanyl)}methyl ether, etc. Can be mentioned.

The episulfide compound is not particularly limited as long as it has an episulfide group, and examples thereof include compounds in which the oxygen atom of the epoxy group of the epoxy compound is replaced with a sulfur atom.
Specific examples of the above-mentioned episulfide compound include bisphenol-type episulfide compounds (compounds obtained by substituting oxygen atoms of epoxy groups of bisphenol-type epoxy compounds with sulfur atoms), hydrogenated bisphenol-type episulfide compounds, dicyclopentadiene-type episulfide compounds, and biphenyl. Type episulfide compounds, phenol novolac type episulfide compounds, fluorene type episulfide compounds, polyether modified episulfide compounds, butadiene modified episulfide compounds, triazine episulfide compounds, naphthalene type episulfide compounds and the like. Of these, naphthalene type episulfide compounds are preferable.
The substitution of oxygen atoms with sulfur atoms may be carried out in at least a part of the epoxy groups, or the oxygen atoms of all epoxy groups may be replaced with sulfur atoms.

The silicone compound may be either a condensation curing type silicone compound or an addition reaction curing type silicone compound, but an addition reaction curing type silicone compound is preferable. The addition reaction-curable silicone compound is preferably, for example, one containing an alkenyl group-containing organopolysiloxane and a hydrogen organopolysiloxane.

The content of the thermosetting compound in the resin composition is, based on the total amount of the resin composition, preferably 5 to 80% by mass, more preferably 8 to 60% by mass, and 10 to 40% by mass. More preferably,

The resin composition for forming the insulating resin layer of the present invention contains a thermosetting compound and at least one of a thermosetting agent and a curing catalyst.
When an epoxy compound, an oxetane compound, an episulfide compound or the like is used as the thermosetting compound, a thermosetting agent may be used, and when a silicone compound is used as the thermosetting compound, a curing catalyst may be used.

The heat curing agent is not particularly limited, and a cyanate ester compound (cyanate ester curing agent), a phenol compound (phenol heat curing agent), an amine compound (amine heat curing agent), a thiol compound (thiol heat curing agent), an imidazole compound , Phosphine compounds, acid anhydrides, active ester compounds and dicyandiamide.

The cyanate ester compound is not particularly limited, and examples thereof include novolac type cyanate ester resins, bisphenol type cyanate ester resins, and prepolymers obtained by partially trimming these. Examples of the novolac type cyanate ester resin include a phenol novolac type cyanate ester resin and an alkylphenol type cyanate ester resin. Examples of the bisphenol type cyanate ester resin include a bisphenol A type cyanate ester resin, a bisphenol E type cyanate ester resin, and a tetramethylbisphenol F type cyanate ester resin.

The commercial product of the cyanate ester compound is not particularly limited, and a phenol novolac type cyanate ester resin (“PT-30” and “PT-60” manufactured by Lonza Japan Co., Ltd.) and a bisphenol type cyanate ester resin trimerized are prepared. Examples thereof include polymers (“BA-230S”, “BA-3000S”, “BTP-1000S” and “BTP-6020S” manufactured by Lonza Japan Co., Ltd.).

The phenol compound is not particularly limited, and examples thereof include novolac type phenol, biphenol type phenol, naphthalene type phenol, dicyclopentadiene type phenol, aralkyl type phenol and dicyclopentadiene type phenol.

Commercially available phenol compounds are not particularly limited, and include novolac type phenol (“TD-2091” manufactured by DIC), biphenyl novolac phenol (“MEHC-7851” manufactured by Meiwa Kasei Co., Ltd.), and aralkyl type phenol compound (Meiwa Kasei). "MEH-7800" manufactured by the company) and phenol having an aminotriazine skeleton ("LA1356" and "LA3018-50P" manufactured by DIC) and the like.

The amine compound is not particularly limited, and hexamethylenediamine, octamethylenediamine, decamethylenediamine, 3,9-bis(3-aminopropyl)2,4,8,10-tetraspiro[5.5]undecane, bis (4-aminocyclohexyl)methane, metaphenylenediamine, diaminodiphenyl sulfone and the like can be mentioned.

The thiol compound is not particularly limited and includes trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate and dipentaerythritol hexa-3-mercaptopropionate.

The imidazole compound is not particularly limited, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine and 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric Examples thereof include acid addition products.

The phosphine compound is not particularly limited, and examples thereof include an alkylphosphine compound and an arylphosphine compound.
Examples of the alkylphosphine compound include triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine, tri-n-hexylphosphine, tri-n-octylphosphine, tricyclohexylphosphine and tris(3-hydroxypropyl)phosphine. Are listed.
Examples of the arylphosphine compound include tribenzylphosphine, triphenylphosphine, tri-p-tolylphosphine, bisdiphenylphosphenoethane, bisdiphenylphosphinobutane and the like.

The acid anhydride is not particularly limited, and phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic acid anhydride, nadic acid anhydride, glutaric anhydride. Acid, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride and the like can be mentioned.

The active ester compound is not particularly limited, and examples of commercially available products include "HPC-8000", "HPC-8000-65T" and "EXB9416-70BK" manufactured by DIC.

The blending amount of the thermosetting agent is appropriately selected, but is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and preferably 50 parts by mass or less, with respect to 100 parts by mass of the thermosetting compound. It is more preferably 30 parts by mass or less.

Examples of the curing catalyst include catalysts for hydrosilylation reaction in which the above-mentioned alkenyl group-containing organopolysiloxane and hydrogen organopolysiloxane are reacted. Specific examples include tin-based catalysts, platinum-based catalysts, rhodium-based catalysts and palladium-based catalysts. Of these, platinum-based catalysts are preferable.
When a curing catalyst is used, the content of the curing catalyst is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and further preferably 100 parts by mass of the thermosetting compound. Is 0.05 parts by mass or more, and preferably 0.5 parts by mass or less.

The content of the resin obtained by reacting the thermosetting compound with at least one of the thermosetting agent and the curing catalyst is preferably 5 to 80% by mass, more preferably 10 to 70% by mass in the insulating resin layer. 15 to 50 mass% is more preferable.

The resin composition may contain other components such as a dispersant, a chelating agent and an antioxidant in addition to the above components.
The insulating resin layer is formed by semi-curing or curing a resin composition containing at least one of the above-mentioned inorganic particles (X), thermosetting compound, thermosetting agent and curing catalyst. This resin composition may contain a solvent from the viewpoint of adjusting its viscosity. The solvent is not particularly limited, and examples thereof include toluene and methyl ethyl ketone, and these can be used alone or in combination of two or more kinds.

The thickness of the insulating resin layer is preferably 50 μm or more, more preferably 80 μm or more, further preferably 100 μm or more, and preferably 600 μm or less, more preferably 400 μm or less. ..

The laminate of the present invention includes the above-mentioned insulating resin layer (also referred to as a first insulating resin layer) and a first metal layer described later provided on the insulating resin layer. A second insulating resin layer may be provided on the surface of the insulating resin layer opposite to the surface on which the first metal layer is provided.
The composition of the second insulating resin layer may be the same as or different from the composition of the first insulating resin layer described above.

<First metal layer>
Since the first metal layer of the present invention exerts the function as a heat conductor, its thermal conductivity is preferably 10 W/(m·K) or more. Examples of the material forming the first metal layer include aluminum, copper, gold, silver, and a graphite sheet. From the viewpoint of more effectively increasing the thermal conductivity, aluminum, copper, or gold is preferable, and aluminum or copper is more preferable.

The thickness of the first metal layer of the present invention is preferably 200 μm or more. By setting the thickness to 200 μm or more, the thermal resistance can be reduced. The thickness of the metal layer is more preferably 250 μm or more, further preferably 300 μm or more, and usually 2000 μm or less.
In the present invention, the relatively thick first metal layer is used, but since the specific insulating resin layer is used as described above, the adhesion between the insulating resin layer and the first metal layer is The force is high, and the first metal layer can be prevented from peeling off from the insulating resin layer.

<Second metal layer>
In the laminated body of the present invention, a second metal layer is provided on the surface of the above-mentioned insulating resin layer (first insulating resin layer) opposite to the surface on which the first metal layer is provided. Is preferred.
That is, as one embodiment of the laminated body of the present invention, for example, as schematically shown in FIG. 1, the laminated body 10 includes a first metal layer 12, a first insulating resin layer 14, and a second metal layer. The layer 16 is a laminated body in which the layers are laminated in this order.
In addition, a second insulating resin layer is provided on the surface of the insulating resin layer (first insulating resin layer) of the present invention opposite to the surface on which the first metal layer is provided, and the second insulating resin layer is It may be disposed between the first insulating resin layer and the second metal layer. In such an embodiment, for example, as schematically shown in FIG. 2, the first metal layer 22, the first insulating resin layer 24B, the second insulating resin layer 24A, and the second metal layer 26 are The laminated body 20 laminated|stacked in order is mentioned. In addition, the second metal layer is preferably used as a base material such as a metal base plate.
By providing the second metal layer in this way, heat generated from a heating element such as a semiconductor chip can be transferred from the first metal layer to the second metal layer via the resin layer and radiated. ..

Examples of the material used for the second metal layer include aluminum, copper, gold, silver and a graphite sheet. From the viewpoint of enhancing thermal conductivity, aluminum, copper, or gold is preferable, and aluminum or copper is preferable.
The thickness of the second metal layer is not particularly limited, but is preferably 0.3 to 5 mm, more preferably 0.5 to 4.5 mm, and further preferably 0.8 to 4 mm. ..

(Manufacture of laminated body)
The laminate of the present invention can be obtained, for example, by applying the resin composition to the surface of the first metal layer and then heating and curing the resin composition. The heating may be performed at a temperature of about 180 to 210° C., and the press treatment may be performed during the heating.
When the laminated body of the present invention is a laminated body in which the second metal layer is provided on the surface of the insulating resin layer opposite to the surface on which the first metal layer is provided, the laminated body is formed as follows. Can be manufactured.
The resin composition is applied onto the second metal layer and, if necessary, semi-cured, and then the first metal layer is attached so as to come into contact with the resin composition, and the pressure is increased to a certain degree (for example, 180 It can be manufactured by performing a press treatment of applying a pressure of about 8 to 25 MPa at ˜210° C. It is also possible to sandwich the first and second metal layers on both sides of a sheet made of the resin composition and perform the above-mentioned press treatment to produce the sheet.
When the first insulating resin layer and the second insulating resin layer are used, the laminated body may be obtained by applying a resin composition which will be the second insulating resin layer onto the second metal layer, for example. After semi-curing in accordance with the above, a resin composition to be the first insulating resin layer is further applied thereon, and semi-cured if necessary. After that, the first metal layer can be attached to the resin composition so as to be in contact with the resin composition, and the above-mentioned press treatment can be performed to manufacture. In addition, both surfaces of the laminated sheet of the sheet made of the resin composition that becomes the first insulating resin layer and the sheet made of the resin composition that becomes the second insulating resin layer are provided with the first metal layer and the second metal layer. It can also be manufactured by performing the above-mentioned press treatment by sandwiching each.

The above-described laminated body of the present invention is used, for example, in an electronic device, as a radiator arranged between a heat-generating component and a heat-radiating component and installed between a CPU and a fin, or an inverter of an electric vehicle. It is used as a heat sink for power cards.
It can also be used as an electronic component including the laminate of the present invention and a semiconductor chip mounted on the laminate.
FIG. 3 is a sectional view schematically showing an example of an electronic component using the laminated body of the present invention.
The electronic component 30 includes a laminated body 39 in which a first metal layer 33, an insulating resin layer 32, and a second metal layer 31 are laminated in this order, a connection conductive portion 34, a semiconductor chip 35, a lead 37 ( 37a, 37b), a wire (metal wiring) 36, and a sealing resin 38.
The connection conductive portion 34 is arranged between the semiconductor chip 35 and the first metal layer 33 and joins them. The connection conductive portion 34 is preferably formed of solder.
The first metal layer 33 is soldered to the upper surface of the other end of the lead 37a whose one end extends outward from the side surface of the electronic component 30. Further, the semiconductor chip 35 is electrically connected to another lead 37b arranged so as to face the lead 37a by a wire 36. By energizing the leads 37a, 37b, the first metal layer 33 is formed. The electric current is designed to flow. Further, the first metal layer 33 may be patterned by etching or the like.

The heat generated from the semiconductor chip 35 is transferred from the first metal layer 33 to the second metal layer 31 via the insulating resin layer 32. As described above, the insulating resin layer in the laminated body of the present invention has excellent thermal conductivity, so that heat generated from the semiconductor chip 35 can be efficiently transferred to the second metal layer 31. Furthermore, since the adhesive strength between the first metal layer and the insulating resin layer is high, they are unlikely to peel off, and good product performance can be maintained.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
[Raw materials used in Examples and Comparative Examples]
<Thermosetting compound>
・Mitsubishi Epichemical Co., Ltd. "Epicote 828US", epoxy compound <heat curing agent>
・"Dicyandiamide" manufactured by Tokyo Chemical Industry Co., Ltd.
・"2MZA-PW" manufactured by Shikoku Kasei Co., Ltd., isocyanuric modified solid dispersion type imidazole <aggregated boron nitride particles>
・Showa Denko's "high strength" average particle diameter 40μm, aspect ratio 4
・Showa Denko's "UHP-G1H" average particle diameter 40 μm, aspect ratio 7
・"HP-40" manufactured by Mizushima Gokin Co., Ltd., average particle diameter 40 µm, aspect ratio 5
・"PTX60H" manufactured by Momentive Co., Ltd. average particle diameter 60 µm, aspect ratio 13
<Alumina>
・Showa Denko's "AS50" average particle size 10 μm

(Strength when crushing aggregated particles)
With respect to the inorganic particles (boron nitride agglomerated particles and alumina) used in each of the Examples and Comparative Examples, the strength at the time of crushing agglomerated particles having particle diameters corresponding to D90 and D50 was measured as follows.
D90 and D50 of each inorganic particle used in each Example and Comparative Example were measured using a laser diffraction particle size distribution analyzer (“AEROS” manufactured by Malvern Instruments Ltd.).
Using a micro compression tester ("HM-2000" manufactured by Fischer Instruments Co., Ltd.), a diamond prism is used as a compression member under the condition of a compression speed of 0.67 mN/sec, and the smooth end surface of the compression member is treated with inorganic particles. A load was applied to the agglomerated particles by descending towards the individual agglomerated particles that made up. The load was gradually increased, and the load when the agglomerated particles were crushed was defined as the strength during crushing.
For crushing strength measurement of agglomerated particles having a particle diameter D90, inorganic particles such as boron nitride are observed using a microscope, 10 agglomerated particles having a particle diameter D90 are selected, and the strength at crushing is determined for each. The measurement was performed and the results were averaged. The agglomerated particles having a particle diameter D90 were selected from the agglomerated particles having a particle diameter within an error range of less than 5% from D90.
The strength at the time of crushing the agglomerated particles having the particle diameter D50 was the same as the strength at the time of crushing the agglomerated particles having the particle diameter D90 described above. That is, in the above description regarding the strength measurement at the time of crushing aggregated particles having a particle diameter D90, “D90” was replaced with “D50” for measurement.
Table 1 shows the strength of the aggregated particles having the particle diameters D90 and D50 measured as described above at the time of crushing.

(Example 1)
Epoxy resin (Epicoat 828US) 19.7% by mass, dicyandiamide 0.7% by mass as a thermosetting agent, 2MZA-PW 0.4% by mass, boron nitride agglomerated particles as boron nitride (a) (high strength product) Was mixed so as to be 79.2% by mass to obtain a resin composition.
The resin composition is applied onto a release PET sheet (thickness 40 μm) so as to have a thickness of 200 μm, and dried in an oven at 50° C. for 10 minutes to form a sheet of the resin composition on the release PET sheet. Formed. After that, the release PET sheet was peeled off, and both sides of the sheet made of the resin composition were covered with the first metal layer (copper plate, thickness 500 μm) and the second metal layer (aluminum plate, thickness 1.0 mm). The sandwiched body was vacuum-pressed under the conditions of a temperature of 150° C. and a pressure of 10 MPa to produce a laminate in which the first metal layer, the insulating resin layer, and the second metal layer were laminated in this order. The evaluation results are shown in Table 2.

(Examples 2 to 6, Comparative Examples 1 to 4)
A laminate was obtained in the same manner as in Example 1 except that the composition of the resin composition was as shown in Table 2. The evaluation results are shown in Table 2.

<Evaluation>
The laminates of Examples and Comparative Examples were evaluated as follows.
<Insulation: Initial>
A circular electrode of φ2 was formed on each of the laminates (6 cm×6 cm) prepared in Examples and Comparative Examples, and a voltage was applied to the electrodes at a speed of 20 kV/min. The breakdown voltage of the measurement sample was defined as the dielectric breakdown voltage, and the insulation was evaluated according to the following criteria.
[Criteria for insulation]
⊚: Dielectric breakdown voltage is 10 kV or more ◯: Dielectric breakdown voltage is 5 kV or more and less than 10 kV ×: Dielectric breakdown voltage is less than 5 kV <thermal conductivity>
After cutting each laminate of Examples and Comparative Examples into 1 cm square, the thermal conductivity was measured by a laser flash method using a measurement sample in which carbon black was sprayed on both sides. The results are shown in Table 2 below.
<Adhesive strength>
A chuck was attached to an end of the first metal layer (copper plate) of each of the laminates of Examples and Comparative Examples, and a "Micro Autograph MST-I" manufactured by Shimadzu Corporation was used, and a pulling speed was 50 mm under an atmosphere of 23°C. The 90° peel strength was measured in /min.

Since the laminated body of each of the above-described examples includes the insulating resin layer containing boron nitride (a) containing aggregated particles having a crushing strength of 40 mN or more, the insulating resin layer has high adhesive force and thermal conductivity. It turns out that the rate is also excellent.
On the other hand, the laminate of each comparative example using the insulating resin layer containing no boron nitride containing aggregated particles having a strength during crushing of 40 mN or more has at least the adhesive force of the insulating resin layer and the thermal conductivity. One result was bad.

10, 20 laminated body 12, 22 first metal layer 14 resin layer 16, 26 second metal layer 24A second resin layer 24B first resin layer 30 electronic component 31 second metal layer 32 insulating resin layer 33 First metal layer 34 Connection conductive portion 35 Semiconductor chip 36 Wires 37a, 37b Lead 38 Sealing resin 39 Laminated body

Claims (14)

A laminate comprising an insulating resin layer containing inorganic particles (X) containing boron nitride (a), and a first metal layer provided on the insulating resin layer, wherein the boron nitride (a) comprises: A laminate having a strength at the time of crushing aggregated particles having a particle diameter D90 of 40 mN or more. The laminate according to claim 1, wherein the aggregated particles of the boron nitride (a) having a particle diameter D50 have a strength of 30 mN or less when crushed. The laminate according to claim 1, wherein the boron nitride (a) is a boron nitride agglomerated particle. The laminate according to any one of claims 1 to 3, wherein the boron nitride (a) primary particles have an aspect ratio of 2 or more. The inorganic particles (X) further contain boron nitride (b), and the strength at the time of crushing aggregated particles having a particle diameter D90 in the boron nitride (b) is 30 mN or less. The laminated body according to. The laminate according to claim 5, wherein the boron nitride (b) is boron nitride agglomerated particles. The layered product according to claim 5 or 6, wherein an aspect ratio of the primary particles of the boron nitride (b) is 2 or more. The laminate according to any one of claims 1 to 7, wherein the inorganic particles (X) contain inorganic particles (c) other than the boron nitride. The laminate according to claim 8, wherein the inorganic particles (c) are one or more selected from the group consisting of aluminum oxide, aluminum nitride, magnesium oxide, and silicon carbide. The laminate according to claim 1, wherein the insulating resin layer is formed from a resin composition containing inorganic particles (X), a thermosetting compound, and at least one of a thermosetting agent and a curing catalyst. body. The laminate according to claim 10, wherein the thermosetting compound contains at least one selected from an epoxy compound, an oxetane compound, an episulfide compound, and a silicone compound. The laminate according to claim 1, wherein the insulating resin layer has a thickness of 100 μm or more. The laminate according to claim 1, wherein a second metal layer is provided on the surface of the insulating resin layer opposite to the surface on which the first metal layer is provided. An electronic component comprising: the laminate according to any one of claims 1 to 13; and a semiconductor chip mounted on the laminate.