CN105754293A - Resin composition, resin flake, resin flake with metal foil, cured resin flake, structural body and semiconductor device - Google Patents

Abstract

The invention relates to a resin composition, a resin flake, a resin flake with a metal foil, a cured resin flake, a structural body and a semiconductor device for power or a light source.The resin composition comprises epoxy resin containing polyfunctional epoxy resin, a curing agent containing novolac resin with constitutional units shown in general formula (I), and inorganic filling materials containing nitride particles, wherein in the general formula (I), R1 and R2 refer to hydrogen atom or methyl independently, m ranges from 1.5 to 2.5 on a average value basis, and n ranges from 1 to 15 on a average value basis.

Description

Resin combination, resin sheet, with the resin sheet of metal forming, resin cured matter sheet, structure and semiconductor device

The present invention is application number is 201180073184.9 (international application no is PCT/JP2011/069845), the applying date is August 31, denomination of invention in 2011 is " resin combination, resin sheet, with the resin sheet of metal forming, resin cured matter sheet, structure and power with or light source semiconductor device " the divisional application of patent application.

Technical field

The present invention relates to resin combination, resin sheet, with the resin sheet of metal forming, resin cured matter sheet, structure and power with or light source semiconductor device.

Background technology

Along with the development using the miniaturization of electronic equipment of quasiconductor, high capacity, high performance etc., the caloric value from the quasiconductor of high-density installation increases day by day.Such as, for the steady operation of the semiconductor device for controlling the central operation device of computer, electric automobile motors, in order to dispel the heat, radiator, fin become indispensable, component as bonding semiconductor device and radiator etc., it is desirable to the raw material of insulating properties and thermal conductivity can be taken into account.

It addition, the insulant being commonly installed the printed base plate etc. of semiconductor device etc. widely uses organic material.Although these organic material insulating properties are high but thermal conductivity is low, contributes little to the heat radiation of semiconductor device etc..On the other hand, for the heat radiation of semiconductor device etc., sometimes use the inorganic material such as inorganic ceramic.Although these inorganic material thermal conductivities are high but its insulating properties is abundant hardly compared with organic material, it is desirable to can take into account the material of high-insulativity and thermal conductivity.

With above-mentioned relatively, as the material that can take into account insulating properties and heat conductivity, International Publication 02/094905 pamphlet describes the method providing thermosetting resin cured matter that heat conductivity is excellent.By in resin formed anisotropic structures and realize high conduction of heat, utilize mesomorphic skeleton define anisotropic structures epoxy resin cured product thermal conductivity use plate comparison method (steady state method) be 0.68～1.05W/m K.

It addition, in Japanese Unexamined Patent Publication 2008-13759 publication, studied using the composite that the aluminium oxide as inorganic filling material high to the epoxy resin comprising mesomorphic skeleton and thermal conductivity mixes.Such as, the known solidfied material being made up of the compound system of common bisphenol A type epoxy resin and alumina packing, as the thermal conductivity obtained, xenon flicker method is capable of 3.8W/m K, temperature wave thermal analysis system is capable of 4.5W/m K (with reference to Japanese Unexamined Patent Publication 2008-13759 publication).Similarly, it is known that the solidfied material being made up of the compound system of the epoxy resin containing mesomorphic with the firming agent of amine system, aluminium oxide, as thermal conductivity, xenon flicker method is capable of 9.4W/m K, temperature wave thermal analysis system is capable of 10.4W/m K.

Summary of the invention

The problem that invention to solve

But, for the solidfied material recorded in International Publication 02/094905 pamphlet, fail when practicality to obtain sufficient thermal conductivity.It addition, the solidfied material recorded in Japanese Unexamined Patent Publication 2008-13759 publication is owing to employing amine system firming agent, therefore flexibility is poor, has prepreg to be easily broken such problem.

The problem of the present invention is: provide a kind of solidify before have flexibility solidify after be capable of the resin combination of high heat conductance, the resin sheet using this resin combination to constitute, with the resin sheet of metal forming, resin cured matter sheet, structure and power with or light source semiconductor device.

The method of solution problem

1st form of the present invention contains the epoxy resin comprising polyfunctional epoxy resin, comprise the novolac resin with the construction unit represented by following formula (I) firming agent and the inorganic filling material comprising nitride particles.It addition, the functional group number in multifunctional expression a part is more than or equal to 3 in the present invention.

[changing 1]

In formula (I), R¹And R²Representing hydrogen atom or methyl independently of one another, m represents 1.5～2.5 in meansigma methods, and n represents 1～15 in meansigma methods.

Above-mentioned resin combination preferably comprises the above-mentioned inorganic filling material of 50 volume %～85 volume %.

And, above-mentioned resin combination is preferably in the above-mentioned polyfunctional epoxy resin contained in whole epoxy resin more than or equal to 20 mass %.Additionally, from the viewpoint of the crosslink density of resin cured matter and vitrification point, above-mentioned polyfunctional epoxy resin preferably comprises branched structure, in particular, it is preferred that be at least one selected from triphenylmethane type epoxy resin, tetraphenyl ethane type epoxy resin, dihydroxy benzenes phenolic resin varnish type epoxy resin and glycidyl amine type epoxy resin.Particularly be more preferably in the triphenylmethane type epoxy resin and dihydroxy benzenes phenolic resin varnish type epoxy resin comprising branched structure from repetitive select at least one.

From the viewpoint of reduce the softening point of resin combination, above-mentioned polyfunctional epoxy resin preferably further comprises aqueous or semi-solid epoxy resin, and above-mentioned aqueous or semi-solid epoxy resin is preferably at least one selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol A-type and F type blending epoxy, bisphenol-f type phenolic resin varnish, naphthalene diol type epoxy resin and glycidyl amine type epoxy resin.It addition, in the present invention, so-called aqueous, represent that fusing point or softening point are less than room temperature, it addition, so-called semi-solid, represent that fusing point or softening point are less than or equal to 40 DEG C.

Above-mentioned firming agent preferably comprises at least one selected from monokaryon dihydroxy benzenes of 20 mass %～70 mass %.

More preferably in the above-mentioned nitride particles containing 50 volume %～95 volume % in above-mentioned inorganic filling material.Additionally, it is preferred that the condensation product that above-mentioned nitride particles is hexagonal boron or ground product, and the ratio of major diameter and minor axis is less than or equal to 2.

Above-mentioned resin combination preferably further contains coupling agent.It addition, it is also preferred that contain dispersant further.

2nd form of the present invention is a kind of resin sheet, and it is uncured thing or the semi-solid preparation thing of above-mentioned resin combination.

3rd form of the present invention is a kind of resin sheet with metal forming, and it has above-mentioned resin sheet and metal forming.

4th form of the present invention is a kind of resin cured matter sheet, and it is the solidfied material of above-mentioned resin combination.The above-mentioned preferred thermal conductivity of resin cured matter sheet is more than or equal to 10W/m K.

5th form of the present invention is a kind of structure, and it has above-mentioned resin sheet or above-mentioned resin cured matter sheet and the metallic plate arranged in the way of the face with above-mentioned resin sheet or above-mentioned resin cured matter sheet contacts in the one side or two sides of above-mentioned resin sheet or above-mentioned resin cured matter sheet.

6th form of the present invention be the power with above-mentioned resin sheet, above-mentioned resin sheet with metal forming, above-mentioned resin cured matter sheet or above described structure with or light source semiconductor device.

The effect of invention

In accordance with the invention it is possible to provide a kind of solidify before have flexibility solidify after be capable of the resin combination of high heat conductance, the resin sheet using this resin combination to constitute, with the resin sheet of metal forming, resin cured matter sheet, structure and power with or light source semiconductor device.

Accompanying drawing explanation

Fig. 1 indicates that the summary sectional view of the configuration example of the power semiconductor arrangement using the resin sheet with metal forming of the present invention to constitute.

Fig. 2 indicates that the summary sectional view of other configuration example of the power semiconductor arrangement using the resin sheet of the present invention to constitute.

Fig. 3 indicates that the summary sectional view of other configuration example of the power semiconductor arrangement using the resin sheet of the present invention to constitute.

Fig. 4 indicates that the summary sectional view of other configuration example of the power semiconductor arrangement using the resin sheet with metal forming of the present invention to constitute.

Fig. 5 indicates that the summary sectional view of other configuration example of the power semiconductor arrangement using the resin sheet of the present invention to constitute.

Fig. 6 indicates that the summary sectional view of the configuration example of the LED lamp bar using the structure of the present invention to constitute.

Fig. 7 indicates that the summary sectional view of the configuration example of the LED bulb using the structure of the present invention to constitute.

Detailed description of the invention

In this specification, "～" represent the scope comprising numerical value described before and after it respectively as minima and maximum.

It addition, in this manual, " operation " word not only comprises independent operation, even if when can not clearly distinguish with other operation, if the desired effect of this operation can be realized, is then also contained in this term.

Further, in this specification during the amount of each composition in speaking of compositions, when there is the suitable material of multiple and each composition in the composition, unless otherwise specified, it is simply that refer to the total amount of this many kinds of substance existed in the composition.

< resin combination >

The resin combination of the present invention contains the epoxy resin comprising polyfunctional epoxy resin, comprise the novolac resin with the construction unit represented by following formula (I) firming agent and the inorganic filling material comprising nitride particles.By such composition, it is possible to formed there is before solidifying flexibility, solidify after the resin cured matter of the excellent insulating properties of heat conductivity.

[changing 2]

In formula (I), R¹And R²Representing hydrogen atom or methyl independently of one another, m represents 1.5～2.5 in meansigma methods, and n represents 1～15 in meansigma methods.

Generally, epoxy resin and firming agent the conduction of heat of the epoxy resin cured product obtained is by phonon control, and thermal conductivity is 0.15W/m K～0.22W/m about K.This due to: epoxy resin cured product is amorphous state, is absent from being called the structure of ordered structure；And cause covalent bond and the metal of the harmonious property of lattice vibration, ceramic phase ratio few.Therefore, in epoxy resin cured product, the scattering of phonon is big, and for the mean free path of phonon, compared with the 100nm of such as crystallinity silicon dioxide, epoxy resin cured product is as short as about 0.1nm, becomes the reason of lower thermal conductivity.

The mesomorphic that utilizes as shown in above-mentioned International Publication 02/094905 pamphlet forms anisotropic structures, it is believed that the crystal arrangement of epoxy molecule suppresses the static scattering of phonon, causes that thermal conductivity improves.But, the dissolubility by force, in a solvent of the most of crystallinity of epoxy monomer containing mesomorphic is low, sometimes for special condition when using as resin combination.Accordingly, it would be desirable to without mesomorphic and hold diffluent epoxy monomer in a solvent.

The present inventor etc. find: increasing the covalent bond quantity of the harmonious property causing lattice vibration in order to improve thermal conductivity, reduce dynamic phon scattering, the raising for thermal conductivity is effective, this completes the present invention.Cause the structure that the covalent bond quantity of the harmonious property of lattice vibration is many, it is possible to be shortened by the distance between the branch point of resin matrix and constitute tiny grid and obtain.It is to say, the structure that molecular weight between preferred crosslinking points is little in thermosetting resin.By such composition, crosslink density uprises, even if do not form anisotropic structures in without the epoxy resin cured product of mesomorphic, the raising for thermal conductivity is also effective.

In resin combination after hardening, tiny grid is constituted for the distance that shortens between the branch point of resin matrix, in the present invention, specifically, use polyfunctional epoxy resin as epoxy resin, use has the novolac resin of the construction unit represented by above-mentioned formula (I) as firming agent, uses nitride particles as inorganic filling material.

(epoxy resin)

The resin combination of the present invention comprises polyfunctional epoxy resin as epoxy resin.By comprising polyfunctional epoxy resin, it is possible to increase crosslink density.Polyfunctional epoxy resin can be modulated by the epoxy monomer of multifunctional type.

Above-mentioned polyfunctional epoxy resin can also branch off structure for linear chain structure, but branch off structure and there is at side chain or end the polyfunctional epoxy resin of skeleton of reactive epoxy radicals, branch becomes crosslinking points so that molecular weight reduction between crosslinking points, crosslink density uprises, it is preferred to, particularly comprise branched structure preferably in polymeric repetitive.

For this situation, the epoxy resin with the repetitive shown in following formula (II) is compared to explanation with the epoxy resin with the repetitive shown in following formula (III).

The epoxy resin (epoxide equivalent 165g/eq) with the repetitive shown in following formula (II) is linear chain structure.On the other hand, comprise further branched structure (2) and branch pendant moiety reactive epoxy end groups (1) and with above-mentioned formula (II) be substantially equal epoxide equivalent the epoxy resin (epoxide equivalent 168g/eq) with the repetitive shown in following formula (III) in, infer that the grid of crosslinking becomes thinner, it may be desirable that crosslink density uprises further.

[changing 3]

[changing 4]

Using the epoxy resin with the repetitive shown in above-mentioned formula (II) or (III) (reactive epoxy end groups (1): para-position) and as the novolac resin (binding site of m=2.0, n=2, OH base a: position, R of the construction unit represented by the formula (I) with the present invention of firming agent¹And R²=hydrogen atom) structural formula of reactant when carrying out ideal response is shown in formula (IV) and (V).Known: with as formula (I) compared with the sizing grid of the following formula (IV) of the reactant of formula (II), less with the grid of the following formula V of the reactant of the formula (III) branching off structure as formula (I).Accordingly, as above-mentioned polyfunctional epoxy resin, it is however preferred to have the epoxy resin of the repetitive shown in above-mentioned formula (III).

[changing 5]

[changing 6]

It addition, for the epoxy backbone comprising repetitive, in such as above-mentioned formula (III), it is assumed that two ends carry out hydrogen atom and epoxidation phenol in conjunction with time, it is also possible to comprise the skeleton of the following formula (VI) shown in n=1.

[changing 7]

It addition, the material that the preferred epoxide equivalent of above-mentioned polyfunctional epoxy resin is little.Epoxide equivalent is little, represents that crosslink density raises.In particular, it is preferred that epoxide equivalent is less than or equal to 200g/eq, more preferably less than or equal to 170g/eq.

It addition, above-mentioned polyfunctional epoxy resin does not preferably have residues such as having neither part nor lot in the alkyl of crosslinking, phenyl.It is believed that: have neither part nor lot in the residue of reaction be converted in phonon conduction the reflection of phonon, the warm-up movement of residue and become the reason of phon scattering.

As above-mentioned polyfunctional epoxy resin, for instance, phenol novolac epoxy resins, triphenylmethane type epoxy resin, tetraphenyl ethane type epoxy resin, dihydroxy benzenes phenolic resin varnish and glycidyl amine type epoxy resin can be enumerated.From the viewpoint of branched structure, be more preferably from triphenylmethane type epoxy resin, tetraphenyl ethane type epoxy resin and glycidyl amine type epoxy resin select at least one, from the viewpoint of crosslink density, it is preferred that there is the triphenylmethane type epoxy resin of the branched structure in repetitive with reactive terminal.Even if it addition, be the firming agent of straight chain type structure, from the viewpoint of crosslink density, it is also preferred that have the dihydroxy benzenes phenolic resin varnish type epoxy resin of the reactive terminal more than 1 in repetitive.

Above-mentioned polyfunctional epoxy resin contains more than or equal to 20 mass % preferably in whole epoxy resin, is preferably more than or equal to 30 mass %, it is preferred that containing more than or equal to 50 mass %.

The epoxy resin of the present invention preferably further comprises aqueous or semi-solid epoxy resin.Aqueous and semi-solid epoxy resin brings the effect of the softening point reducing resin combination sometimes.In aqueous and semi-solid epoxy resin, from the viewpoint of reduce the effect of softening point, it is preferable that liquid epoxy resin.

As this aqueous or semi-solid epoxy resin, for instance be preferably used from bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol A-type and F type blending epoxy, bisphenol F phenolic type epoxy resin, naphthalene diol type epoxy resin and glycidyl amine type epoxy resin select at least one.

From the viewpoint of the reducing effect of softening point, as aqueous or semi-solid epoxy resin, it is preferred to use at least one selected from bisphenol f type epoxy resin, bisphenol A-type and F type blending epoxy, bisphenol-f type phenolic resin varnish and glycidyl amine type epoxy resin.

Aqueous or semi-solid epoxy resin majority is difunctional epoxy resin, when difunctional epoxy resin monomer, owing to not branching off structure, making crosslink density reduce by extending between crosslinking points, addition therefore should not made many.Therefore, the aqueous or semi-solid epoxy resin of two senses preferably comprise whole epoxy resin less than or equal to 50 mass %, be more preferably contains less than or equal to 30 mass %, it is preferred that containing less than or equal to 20 mass %.

From the viewpoint of above-mentioned, in order to suppress the reduction of crosslink density, it is preferred to use as bisphenol-f type phenolic resin varnish or the glycidyl amine type epoxy resin of polyfunctional aqueous or semi-solid epoxy resin.Polyfunctional aqueous or semi-solid epoxy resin preferably comprise whole epoxy resin less than or equal to 50 mass %, be more preferably contains less than or equal to 30 mass %, it is preferred that containing less than or equal to 20 mass %.

But modified function recited herein, skeleton are an example, are not limited.

(firming agent)

The resin combination of the present invention comprises the novolac resin with the construction unit represented by following formula (I) as firming agent.

From the viewpoint of above-mentioned MOLECULE DESIGN, the novolac resin used as the firming agent of the present invention preferably selects the structure that hydroxyl equivalent is less in the same manner as epoxy resin.Thus, the concentration as the hydroxyl of reactive group uprises.It addition, novolac resin is it is also preferred that try one's best without the residue having neither part nor lot in crosslinking in the same manner as epoxy resin.

From the viewpoint of above, the novolac resin used as firming agent has the construction unit represented by following formula (I).

[changing 8]

In formula (I), R¹And R²Representing hydrogen atom or methyl independently of one another, m represents 1.5～2.5 in meansigma methods, and n represents 1～15 in meansigma methods.

The hydroxyl equivalent of preferred above-mentioned novolac resin is little, and in the novolac resin of the construction unit having represented by formula (I), owing to m is calculated as more than or equal to 1.5 with meansigma methods, therefore hydroxyl equivalent suitably reduces.On the other hand, if excessively reducing hydroxyl equivalent, the solidfied material obtained easily becomes fragile, and therefore m is calculated as less than or equal to 2.5 with meansigma methods.Therefore, the m of above-mentioned formula (I) is calculated as 1.5～2.5 with meansigma methods, more preferably 1.7～2.2.

It addition, as the m of hydroxyl unit number in meansigma methods, for instance, as raw material and with the resorcinol of the phenol of equimolar unitary and binary, it is possible to average unit number is adjusted to 1.5～2.5.

In the novolac resin of the construction unit having represented by formula (I), due to R¹And R²It is each independently hydrogen atom or methyl, therefore defines the structure as far as possible without the residue having neither part nor lot in crosslinking.

Further, from the viewpoint of the softening point of above-mentioned novolac resin, the n of above-mentioned formula (I) is calculated as 1～15 with meansigma methods, from the viewpoint of the kinematic viscosity when crimping etc. being processed into the resin combination of lamellar is heated, n is preferably calculated as 1～10 with meansigma methods.

Additionally, n is in meansigma methods, namely, as the firming agent skeleton comprising repetitive, comprise such as in formula (I) the phenol (-Ph-(OH) m) of two aterminal hydrogen atom and m unit in conjunction with time the n=1 that obtains shown in the compound of following formula (VII), the n compound more than 15, n can be 1～15 as meansigma methods.

[changing 9]

Furthermore it is possible to for by synthesizing that to make novolac resin be the different mixture of molecular weight thus as meansigma methods n with 1～15 situation about obtaining, it is also possible to for using novolac resin mixing different for molecular weight thus as meansigma methods, n is adjusted to 1～15 situation.

For the aldehyde of synthesis and the ketone of novolac resin, from the viewpoint of the preferred formaldehyde of hydroxyl equivalent, but consider that thermostability can select acetaldehyde, acetone can be selected from being readily synthesized consideration.Further, in order to take into account hydroxyl equivalent and thermostability, it is possible to and with in formaldehyde, acetaldehyde and acetone at least two or more.

By upper, above-mentioned novolac resin is preferably as the monokaryon of monomer and have the phenolic compounds of 2 yuan of phenolic hydroxyl groups and the novolac resin obtained as the formaldehyde of aldehyde, acetaldehyde or condensation of acetone.

It addition, have the novolac resin of construction unit represented by above-mentioned formula (I), as long as having the construction unit represented by formula (I) in molecule, it is also possible to have other structure further.To be modified as purpose, for instance, it is possible at molecular memory in the condensed ring structure etc. of the phenolic compounds such as alkyl phenol, aralkyl skeleton, ton skeleton as the skeleton from phenolic compounds.It addition, the novolac resin with the construction unit represented by above-mentioned formula (I) can also be able to be block copolymer for atactic polymer.

There is the novolac resin of construction unit represented by above-mentioned formula (I), the containing ratio of the construction unit represented by preferred intramolecular formula (I) is more than or equal to 50 mass %, it is more preferably greater than or equal to 70 mass %, is further preferably greater than or equal to 80 mass %.

The hydroxyl equivalent of the novolac resin with the construction unit represented by above-mentioned formula (I) is preferably less than or equal to 100g/eq, more preferably less than or equal to 80g/eq, from the viewpoint of crosslink density, more preferably less than or equal to 70g/eq.

In order to modified, above-mentioned firming agent can contain other novolac resin, monokaryon further and have the phenolic compounds (monomer) of the above hydroxyl of binary, aralkyl resin etc..The more high hydroxyl equivalent of first number of phenolic hydroxyl group is more little, but the too high tendency having resin cured matter easily to become fragile of crosslink density.On the other hand, if above-mentioned firming agent contains above-mentioned monomer, then resin cured matter can be suppressed to become fragile.It is left unreacted monomer when firming agent containing above-mentioned monomer by adding monomer or synthesis in above-mentioned firming agent and obtains.

As such monomer, it is preferred to there is the phenolic compounds of the raw material of the novolac resin of construction unit represented by above-mentioned formula (I) for synthesis, it is possible to comprise other monokaryon phenolic compounds further.In this monokaryon phenolic compounds, it is preferred to monokaryon dihydric phenolic compounds (monokaryon dihydroxy benzenes).Monokaryon dihydroxy benzenes can be used alone or two or more kinds may be used.If adding monokaryon dihydroxy benzenes, then can be reduced the softening point of resin combination, the reduction of crosslink density be suppressed for low-level effect simultaneously, it is thus preferred to.

As above-mentioned monokaryon dihydroxy benzenes, catechol, resorcinol, hydroquinone can be enumerated, in these 3 kinds, it is preferable that not easily oxidized resorcinol.Skeleton recited herein is an example, is not limited.

At least one total containing ratio selected from above-mentioned monokaryon dihydroxy benzene compound, from the viewpoint of thermal conductivity and softening point, preferably in whole firming agent are 20 mass %～70 mass %, particularly from the viewpoint of the crosslink density of the flexibility of prepreg and solidfied material is preferably 30 mass %～50 mass %.If in above-mentioned scope, then can suppress to have neither part nor lot in the quantity of the functional group of crosslinking such that it is able to suppress the dynamic scattering of phonon, it is suppressed that the thermal conductivity of resin cured matter reduces.

The hydroxyl equivalent overall as above-mentioned firming agent is preferably less than or equal to 80g/eq, more preferably less than or equal to 70g/eq.

The content of the firming agent in the resin combination of the present invention, it is preferable that be adjusted relative to mode close to 1 of the ratio of the epoxide equivalent of above-mentioned epoxy resin according to the hydroxyl equivalent of firming agent.The ratio of above-mentioned equivalent is closer to 1, and crosslink density is more high, it is possible to expect the minimizing effect of the dynamic scattering of phonon.Specifically, above-mentioned equivalent proportion (hydroxyl equivalent/epoxide equivalent) is preferably 0.8～1.2, more preferably 0.9～1.1, and more preferably 0.95～1.05.

But, when use causes the imidazoles system curing accelerator of chain polymerization of epoxy radicals, amine system curing accelerator as curing accelerator, owing to being difficult to remaining unreacted epoxy radicals, therefore can excessively add above-mentioned epoxy resin relative to above-mentioned firming agent.

(inorganic filling material)

From the viewpoint of thermal conductivity, the resin combination of the present invention comprises nitride particles as inorganic filling material.As nitride particles, for instance, the particles such as boron nitride, silicon nitride, aluminium nitride can be enumerated, it is preferred to boron nitride.If using above-mentioned boron nitride as inorganic filling material in resin combination, then can suppress the reduction of vitrification point.Its reason is thought as follows.

Known: to be typically used as the aluminium oxide of inorganic filling material, aluminium hydroxide, silicon oxide etc., there is on the surface of particle hydroxyl, although denier but water can be adsorbed, absorption water resistance hinder curing reaction to make crosslink density reduce.Therefore, comprise the epoxy resin cured product of the inorganic filling material being main component with these aluminium oxidies, aluminium hydroxide, silicon oxide etc., low with vitrification point compared with the epoxy resin cured product of inorganic filling material.Particularly in the epoxy resin of the high crosslink density of the present invention, it is believed that its impact performance is notable.

On the other hand, boron nitride polarity is little, and surface does not have hydroxyl, therefore, it is difficult to absorption water, the solidification to epoxy resin that these hydroxyls, absorption water become reason will not be caused to hinder, thus the curing reaction of epoxy monomer and firming agent carries out, it is possible to give high crosslink density.It is thus regarded that, comprise with boron nitride be main component the vitrification point of epoxy resin cured product of inorganic filling material equal with epoxy resin cured product without inorganic filling material.

Additionally, whether resin combination contains boron nitride, energy dispersion-type X-ray analytic process (EDX) such as can be used to confirm, combine especially by with scanning electron microscope (SEM), it is also possible to confirm the distribution of the boron nitride in resin combination cross section.

The crystal shape of above-mentioned boron nitride can be any one in hexagonal crystal (hexagonal), cubic crystal (cubic), rhombohedron brilliant (rhombohedral), but considers from being easily controlled particle diameter, it is preferable that hexagonal crystal.Furthermore it is possible to and with the different boron nitride of two or more crystal shape.

From the viewpoint of thermal conductivity and varnish viscosity, above-mentioned hexagonal boron particle is preferably size-reduced or cohesion processing material.Shape of particle as above-mentioned hexagonal boron, round shape, spherical, flakey, aggregated particle etc. can be enumerated, but the shape as the high particle of fillibility, it is preferable that the ratio of major diameter and minor axis is less than or equal to 3, be more preferably less than or equal to the round shape of 2, spherical, it is preferred that spherical.Particularly through the above-mentioned hexagonal boron of cohesion processing, there is a large amount of gap, easily damage deformation by pressure because applying pressure, even if therefore considering the coating of the varnish of resin combination and reduce the filling rate of inorganic filling material, it is also possible to by utilizing pressurization etc. to be compressed improving the filling rate of essence after coating.For shape of particle, from the viewpoint of easily form heat conduction path by the contact each other of the high inorganic filling material of thermal conductivity, think compared with spherical, round shape, lepidiod contact point are more, but consider from the thixotropy viscosity taking into account above-mentioned fillibility and resin combination, it is preferable that spherical particle.It addition, the different above-mentioned boron nitride particles of shape of particle can be used alone a kind and and can also use two or more.

It addition, in view of the fillibility of inorganic filling material, in order to fill gap, it is also possible to and with the inorganic filling material beyond boron nitride.As long as the inorganic compound with insulating properties is just not particularly limited, but it is preferably the material with high heat conductance.As the object lesson of the inorganic filling material beyond boron nitride, beryllium oxide, aluminium oxide, magnesium oxide, silicon oxide, aluminium nitride, silicon nitride, Talcum, Muscovitum, aluminium hydroxide, barium sulfate etc. can be enumerated.Wherein, from the viewpoint of thermal conductivity, it is preferable that aluminium oxide, aluminium nitride, silicon nitride.

Volume average particle size as above-mentioned inorganic filling material, it is not particularly limited, from the viewpoint of mouldability, it is preferably less than or equal to 100 μm, consider to be more preferably 20 μm～100 μm from thixotropic viewpoint of heat conductivity and varnish, further from the viewpoint of insulating properties, more preferably 20 μm～60 μm.

Above-mentioned inorganic filling material can be the material that display has the particle size distribution of simple spike, it is also possible to have 2 materials with the particle size distribution of superiors for display.In the present invention, from the viewpoint of filling rate, it is preferred to display has 2 inorganic filling materials with the particle size distribution of superiors.

As above-mentioned display, there are 2 particle size distribution with the inorganic filling material of the particle size distribution of superiors, such as, when display has the particle size distribution at 3 peaks, it is preferable that have 0.1 μm as little particle～0.8 μm mean diameter, as in particle 1 μm～8 μm mean diameters, as 20 μm～60 μm mean diameters of big particle.By being such inorganic filling material, the filling rate of inorganic filling material improves further, and thermal conductivity improves further.From the viewpoint of fillibility, the mean diameter that big particle is preferably 30 μm～50 μm, middle particle is preferably the 1/4～1/10 of the mean diameter of big particle, and little particle is preferably the 1/4～1/10 of the mean diameter of middle particle.

Above-mentioned nitride particles uses preferably as above-mentioned big particle.Above-mentioned middle particle, above-mentioned little particle can be nitride particles, it is also possible to for other particle, consider from thixotropic viewpoint of thermal conductivity with varnish, it is preferred to aluminium oxide particles.

The containing ratio of the above-mentioned nitride particles in above-mentioned inorganic filling material total amount, from the viewpoint of mouldability, it is preferably 50 volume %～95 volume %, from the viewpoint of fillibility, it is more preferably 60 volume %～95 volume %, from the viewpoint of heat conductivity, more preferably 65 volume %～92 volume %.

Additionally, the content of the inorganic filling material in the resin combination of the present invention, from the viewpoint of mouldability, it is preferably 50 volume %～85 volume %, from the viewpoint of heat conductivity, it is more preferably 60 volume %～85 volume %, considers from thixotropic viewpoint of varnish, more preferably 65 volume %～75 volume %.If in the content of the inorganic filling material of volume reference in above-mentioned scope, then there is before can forming solidification flexibility, solidify after the resin cured matter of the excellent insulating properties of heat conductivity.

It addition, the content of the volume reference of inorganic filling material in resin combination, it is carried out as follows mensuration.First, measure the quality (Wc) of the resin combination of 25 DEG C, in atmosphere this resin combination is burnt till 2 hours at 400 DEG C, then burn till 3 hours at 700 DEG C, resinous principle is decomposed, burns and after removing, measure the quality (Wf) at inorganic filling material 25 DEG C remaining.Then, use electronic hydrometer or density bottle, obtain the density (df) of the inorganic filling material of 25 DEG C.Then, the density (dc) of the resin combination of same method mensuration 25 DEG C is used.Then, obtain the volume (Vc) of resin combination and the volume (Vf) of the inorganic filling material of remaining, as shown in (formula 1), with the volume of the inorganic filling material of remaining divided by resin combination volume, thus obtaining the volume ratio (Vr) of inorganic filling material.

(formula 1)

Vc=Wc/dc

Vf=Wf/df

Vr=Vf/Vc

Vc: the volume (cm of resin combination³), Wc: the quality (g) of resin combination

Dc: the density (g/cm of resin combination³)

Vf: the volume (cm of inorganic filling material³), Wf: the quality (g) of inorganic filling material

Df: the density (g/cm of inorganic filling material³)

Vr: the volume ratio of inorganic filling material

It addition, above-mentioned inorganic filling material, as long as the scope at above-mentioned volume ratio is contained within, just it is not particularly limited as quality ratio.Specifically, when above-mentioned resin combination is set to 100 mass parts, above-mentioned inorganic filling material can contain with the scope of 1 mass parts～99 mass parts, it is preferable that contains with the scope of 50 mass parts～97 mass parts, more preferably 80 mass parts～95 mass parts.By making the content of above-mentioned inorganic filling material in above-mentioned scope, it is possible to realize higher thermal conductivity.

(other composition)

The resin combination of the present invention is except mentioned component, it is also possible to comprise other composition as required.As other composition, curing accelerator, coupling agent, dispersant, organic solvent can be enumerated.

Particularly when above-mentioned epoxy resin, above-mentioned firming agent be not there is nitrogen-atoms, there is the material of alkalescence, from the viewpoint of the curing reaction of sufficiently conducted resin combination, it is preferable that add above-mentioned curing accelerator.It addition, in the molecule of above-mentioned epoxy resin, when resin combination comprises nitrogen-atoms, owing to the effect same with amine system curing accelerator can be expected, therefore can without curing accelerator.

As above-mentioned curing accelerator, it is possible to use phosphorus system curing accelerators such as triphenylphosphine (north Xinghua length of schooling TPP), PPQ (Xinghua, north length of schooling)；The salt system curing accelerators such as TPP-MK (Xinghua, north length of schooling)；The organic boron system curing accelerators such as EMZ-K (Xinghua, north length of schooling)；The imidazoles system curing accelerators such as 2E4MZ (four countries' chemical conversion industry system), 2E4MZ-CN (four countries' chemical conversion industry system), 2PZ-CN (four countries' chemical conversion industry system), 2PHZ (four countries' chemical conversion industry system)；Triethylamine, N, accelerine, curing accelerator such as system such as amine such as 4-(N, N-dimethylamino) pyridine, hexamethylenetetramine etc.；Deng.Particularly phosphorus system curing accelerator, salt system curing accelerator can suppress the homopolymerization of epoxy monomer, thus easily carry out the reaction of firming agent and epoxy resin, it is thus preferred to.From matching design aspect, at epoxide equivalent/hydroxyl equivalent more than 1, when being particularly greater than or equal to 1.2, produce unreacted epoxy radicals, it is likely to become the reason of the phon scattering making thermal conductivity reduce as mentioned above, therefore in such a situation it is preferred to add and can make the imidazoles system curing accelerator of epoxy radicals homopolymerization, amine system curing accelerator.

It addition, by making resin combination comprise coupling agent, the contingency of the resinous principle comprising epoxy resin and novolac resin and inorganic filling material improves further, it is possible to realize higher thermal conductivity and higher cementability.

As above-mentioned coupling agent, as long as there is the functional group with resinous principle coupling and the compound with the functional group of inorganic filling material coupling is just not particularly limited, it is possible to use normally used coupling agent.

As the functional group with above-mentioned resinous principle coupling, epoxy radicals, amino, sulfydryl, urea groups, N-phenyl amino etc. can be enumerated.From the viewpoint of storage stability, above-mentioned coupling agent preferably has the functional group of the slow epoxy radicals of response speed or N-phenyl amino.

Additionally, as the functional group with above-mentioned inorganic filling material coupling, alkoxyl, hydroxyl etc. can be enumerated, as the coupling agent with this functional group, can enumerate have dialkoxy silicane, trialkoxy silane silane series coupling agent, there is the titanate esters system coupling agent of alkoxy titanates.

As silane coupler, specifically include, for example: 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl group triethoxysilane, 3-glycidoxypropyl dimethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, APTES, 3-(2-amino-ethyl) aminopropyltriethoxywerene werene, 3-TSL 8330, 3-(2-amino-ethyl) TSL 8330, N-phenyl-3-TSL 8330, 3-sulfydryl triethoxysilane, 3-ureidopropyltriethoxysilane etc..

Alternatively, it is also possible to use the silane coupler oligomer (chemical conversion CoatedSand company of Hitachi system) representated by SC-6000KS2.

Titanate esters system coupling agent can be used in end and have the titanate coupling agent (aginomoto become more meticulous length of schooling PLAINACTKR44) of amino.

These coupling agents can be used alone a kind, or and can also use two or more.

Content as the coupling agent in above-mentioned resin combination, it does not have limit especially, from the viewpoint of heat conductivity, it is preferable that be 0.02 mass %～0.83 mass % relative to the gross mass of resin combination, more preferably 0.04 mass %～0.42 mass %.

It addition, from the viewpoint of heat conductivity, insulating properties, the content of coupling agent is 0.02 mass %～1 mass % preferably with respect to inorganic filling material, more preferably 0.05 mass %～0.5 mass %.

Additionally, by making resin combination comprise dispersant, inorganic filling material dispersibility in comprising the resinous principle of epoxy resin and novolac resin improves further, by making inorganic filling material be uniformly dispersed, it is possible to realize higher thermal conductivity and higher cementability.

As above-mentioned dispersant, it is possible to suitably select from normally used material.Include, for example ED-113 (nanmu this chemical conversion Co., Ltd. system), DISPERBYK-106 (BYK-ChemieGmbH system), DISPERBYK-111 (BYK-ChemieGmbH system), AJISPERPN-411 (aginomoto become more meticulous length of schooling), REB122-4 (Hitachi's chemical conversion industry system) etc..It addition, these dispersants can also individually or and use two or more.

Content as the dispersant in above-mentioned resin combination, it does not have limit especially, from the viewpoint of heat conductivity, it is preferable that be 0.01 mass %～2 mass % relative to inorganic filling material, more preferably 0.1 mass %～1 mass %.

(manufacture method of resin combination)

Manufacture method as the resin combination of the present invention, it is possible to use the manufacture method of the resin combination generally carried out without particular limitation.Such as, can pass through to mix inorganic filling material and coupling agent as required, add and make epoxy resin and firming agent dissolve or be dispersed in the material of suitable organic solvent gained, and mix other compositions such as the curing accelerator that adds as required and obtain.

As the organic solvent dissolving or disperseing firming agent, it is possible to the novolac resin etc. according to using suitably selects.For example, it is possible to the alcohols such as methanol, ethanol, 1-propanol, 2-propanol, n-butyl alcohol, 2-propanol, cellosolve, methyl cellosolve is preferably used；The ketone series solvents such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), Ketohexamethylene, Ketocyclopentane；The ester series solvent such as butyl acetate, ethyl lactate；The ether systems such as dibutyl ethers, oxolane, methyltetrahydrofuran；The nitrogen series solvent such as dimethylformamide, dimethyl acetylamide.

It addition, as the method for blending epoxy, firming agent and inorganic filling material etc., it is possible to the dispersion machines such as appropriately combined common blender, puddle mixer, three-roll grinder, ball mill and carry out.

< resin sheet >

The resin sheet of the present invention can obtain by above-mentioned resin combination is shaped to lamellar.Above-mentioned resin sheet is constituted owing to comprising above-mentioned resin combination, and the storage stability before therefore solidifying and the heat conductivity after solidification are excellent.It addition, the resin sheet of the present invention can be uncured thing, it is also possible to for semi-solid preparation thing.Here, semi-solid preparation typically refers to the state being referred to as B scalariform state, and the viscosity under room temperature (25 DEG C) is 10⁴～10⁵Pa s, and the decrease in viscosity at 100 DEG C is to 10²～10³The state of Pa s.It addition, viscosity can use twist mode Measurement of Dynamic Viscoelasticity device etc. to be measured.

It addition, the resin sheet of the present invention can arrange the resin bed being made up of above-mentioned resin combination on supporter.The thickness of above-mentioned resin bed suitably can select according to purpose, it it is such as 50 μm～500 μm, from the viewpoint of thermal resistance, can be thinner, additionally from the viewpoint of insulating properties, it is possible to for thicker, as the thickness that can take into account thermal resistance and insulating properties, it is preferably 70 μm～300 μm, more preferably 100 μm～250 μm.

As above-mentioned supporter, insulating properties supporter and conductive support body can be enumerated.As insulating properties supporter, the plastic foils etc. such as poly tetrafluoroethylene, polyethylene terephthalate film, polybutylene terephthalate, PEN, polyethylene film, polypropylene screen, polymethylpentene film, polyamide membrane, polyimide film can be enumerated.As conductive support body, it is possible to use the metal such as Copper Foil, aluminium foil, metal evaporation plastic foil.

For above-mentioned insulating properties supporter, it is possible to carry out the surface treatments such as priming paint coating, UV process, Corona discharge Treatment, milled processed, etch processes, demoulding process as required.For above-mentioned conductive support body, it is also possible to carry out the surface treatments such as priming paint coating, coupling processing, UV process, etch processes, demoulding process.Particularly when requiring metal forming and the adaptation of the resin bed being made up of above-mentioned resin combination, it is possible on the alligatoring face obtained by milled processed, electrolysis paper tinsel, resin bed is set.

It addition, above-mentioned supporter can only be arranged in the one side of resin sheet, it is also possible to be arranged on two sides.

The thickness of above-mentioned supporter is not particularly limited, can according to the thickness of resin composition layer, resin sheet purposes, manufacture equipment and suitably knowledge based on those skilled in the art determine, but from the operability excellence aspect of economy and resin sheet, it is preferred to 10 μm～150 μm, be more preferably 40 μm～110 μm.

The resin sheet of the present invention, for instance, it is possible to by above-mentioned resin combination is coated on above-mentioned supporter, it is dried and manufactures.Coating process and drying means about resin combination are not particularly limited, it is possible to suitably select commonly used approach.Such as, coating process can enumerate comma coating, die coating, dip coated etc..

As above-mentioned drying means, can use box warm air drying machine and coating machine that multisection type warm air drying machine etc. when processing continuously, can be used when batch process.Additionally, for being used for dry heating condition also without special restriction, but when using warm air drying machine, from the viewpoint of prevent the expansion of the coating material of resin combination, it is preferable that the warm air being included in drying machine is heated the operation of process than within the scope of the boiling point lower temperature of solvent.

When above-mentioned resin sheet is semi-solid preparation thing, the method as semi-solid preparation is not particularly limited, it is possible to suitably select commonly used approach, for instance, make above-mentioned resin combination semi-solid preparation by heat treated.Heating treatment method for semi-solid preparation is not particularly limited.

Temperature range for above-mentioned semi-solid preparation, it is possible to the epoxy resin according to constituting resin combination suitably selects.From the viewpoint of the intensity of B rank sheet, it is preferable that carried out some curing reactions in advance by heat treatment, heat treated temperature range is preferably 80 DEG C～150 DEG C, more preferably 100 DEG C～120 DEG C.Additionally, time as the heat treated for semi-solid preparation is not particularly limited, suitably can select from the viewpoint of the curing rate of the resin of B rank sheet and the mobility of resin, cementability, preferably to be heated more than or equal to 1 minute and less than or equal to 30 minutes, more preferably 3 minutes to 10 minutes.

After above-mentioned resin sheet semi-solid preparation, it is possible to more than 2 resin sheets are overlapping, heat and pressurize, make resin sheet thermo-compressed.Heating-up temperature during thermo-compressed can select according to the softening point of resin, fusing point, it is preferred to 80 DEG C～180 DEG C, more preferably 100 DEG C～150 DEG C.It addition, pressurization during thermo-compressed preferably carries out under vacuo, more preferably pressurize with 4MPa～20MPa under vacuo, it is preferred that pressurize with 5MPa～15MPa.

< resin cured matter sheet and manufacture method > thereof

The resin cured matter sheet of the present invention obtains by making above-mentioned resin composition.Thereby, it is possible to constitute the resin cured matter that heat conductivity is excellent.It is not particularly limited as by the method for resin composition, it is possible to suitably select commonly used approach, for instance, make above-mentioned resin composition by heat treated.

As the method being heated above-mentioned resin combination processing, it does not have limit especially, it addition, for heating condition also without special restriction.

But, usual multifunctional type epoxy resin cure speed is fast, therefore solidifies the functional groups such as the epoxy radicals of easy remained unreacted, hydroxyl under high temperature, has the tendency of the raising effect being difficult to obtain thermal conductivity.Therefore, from the viewpoint of realize higher thermal conductivity, it is preferable that be included in the temperature range near the active temperature of curing reaction (hereinafter sometimes referred to " specific range of temperatures ") to be heated the operation of process.Here, refer near the active temperature of curing reaction in differential thermal analysis from the temperature peak temperature to reaction heat solidifying heating producing epoxy resin.

Above-mentioned specific range of temperatures suitably can select according to the epoxy resin constituting resin combination, it is preferred to 80 DEG C～180 DEG C, more preferably 100 DEG C～150 DEG C.By being heated process in such temperature range, it is possible to realize higher thermal conductivity.When less than or equal to 150 DEG C, it is possible to suppress to solidify and too fast carries out, when more than or equal to 80 DEG C, resin melting and solidify.

It addition, as the time of the heat treated in specific range of temperatures, it does not have limit especially, it is preferable that to be heated more than or equal to 30 seconds and less than or equal to 15 minutes.

In the present invention, except the heat treated in specific range of temperatures, it is preferable that at least 1 operation being heated processing under further high temperature is set.Thereby, it is possible to improve the elastic modelling quantity of solidfied material, thermal conductivity, bonding force further.Heat treated under further high temperature carries out at 120 DEG C～250 DEG C, carries out at 120 DEG C～200 DEG C.If temperature is too high, resin aoxidizes and easily becomes painted reason.It addition, the time of this heat treated is preferably 30 minutes～8 hours, more preferably 1 hour～5 hours.Further, this heat treated processes with the multistage from low temperature to high temperature preferably within the scope of said temperature.

It addition, as the method by the solidfied material sheet material of above-mentioned resin combination, can enumerate and will carry out the method solidified after above-mentioned resin sheet molding, cut into slices carrying out after resin composition and the method etc. of sheet material.

< structure, resin sheet > with metal forming

The structure of the present invention has above-mentioned resin sheet or above-mentioned resin cured matter sheet (being sometime collectively referred to as " sheet material of the present invention " below) and the metallic plate arranged in the way of the face with above-mentioned resin sheet or above-mentioned resin cured matter sheet contacts in the one side of sheet material or two sides of the present invention.

As above-mentioned metallic plate, copper coin, aluminium sheet, iron plate etc. can be enumerated.It addition, the thickness of metallic plate or heat sink is not particularly limited.It addition, as metallic plate, it is possible to use the metal formings such as Copper Foil, aluminium foil, tinfoil paper.It addition, in the present invention, the material in the one side of above-mentioned resin sheet or two sides with above-mentioned metal forming is called the resin sheet with metal forming.

The thickness of above-mentioned metallic plate, it is preferable that be appropriately configured according to the heat conductivity etc. of occupation mode, metallic plate, in particular, it is preferred that average thickness is 5 μm～300 μm, more preferably 15 μm～200 μm, it is preferred to 30 μm～150 μm.

Above described structure can obtain the manufacture method of the operation of duplexer and manufacture by being included at least one side upper configuration metallic plate of the sheet material of the present invention.As the method configuring metallic plate on the sheet material of the present invention, it is possible to use commonly used approach without particular limitation.Include, for example the method etc. of metallic plate of fitting at least one side of the sheet material of the present invention.Pressurization and laminating etc. can be enumerated as applying method.The condition of pressurization and laminating suitably can select according to the composition of resin sheet.

It addition, above described structure can have metallic plate in the one side of the sheet material of the present invention, another side has adherend.In this approach, owing to clamping above-mentioned resin sheet or above-mentioned resin cured matter sheet between adherend and metallic plate, after therefore solidifying, adherend is excellent with the heat conductivity of metallic plate.It is not particularly limited as above-mentioned adherend, as the material of adherend, for instance the composite etc. of metal, resin, pottery and the mixture as them can be enumerated.

Above described structure may be used for the semiconductor device of power use or light source.Fig. 1～Fig. 7 is denoted as the configuration example of the power semiconductor arrangement of sheet material composition of the use present invention of above described structure example, LED lamp bar and LED bulb.

In FIG, the resin sheet 112 of stacking semi-solid preparation and the resin sheet 110 with metal forming of metal support 114 of protective layer of the resin sheet 112 as semi-solid preparation are used.In detail, Fig. 1 indicates that the summary sectional view of the configuration example of power semiconductor arrangement 100, this power semiconductor arrangement 100 is constituted as follows: be arranged on the lead frame 106 of copper or copper alloy by power semiconductor chip 102 across solder layer 104, sealing resin 108 is used to carry out sealing immobilization, the resin sheet 112 of the semi-solid preparation in the resin sheet 110 with metal forming of the present invention is crimped with lead frame 106 and solidifies, metal support 114 is configured to the protective layer of the resin sheet 112 of semi-solid preparation, and be arranged on radiator 120 across the heat conducting materials such as Heat sink grease 122.

By getting involved the resin sheet 110 with metal forming of the present invention such that it is able to form electric insulation between lead frame 106 and radiator 120, the heat produced can be dispelled the heat efficiently in radiator 120 in power semiconductor chip 102 simultaneously.It addition, for above-mentioned lead frame 106, in order to improve thermal diffusivity, it is possible to use thick metallic plate.Above-mentioned radiator 120 can use there is the copper of heat conductivity, aluminum is constituted, by forming cooling sheet, water route further, it is possible to efficiently underground heat be transferred in air, in water or other fluid.It addition, as power semiconductor chip, IGBT, MOS-FET, diode, integrated circuit etc. can be enumerated.

It addition, in Fig. 2～7 below, for Fig. 1 it is stated that component give same-sign and the description thereof will be omitted.

Use the resin sheet 112 of semi-solid preparation in fig. 2.In detail, Fig. 2 indicates that the summary sectional view of the configuration example of power semiconductor arrangement 150, this power semiconductor arrangement 150 is constituted as follows: be arranged in copper lead frame 106 by power semiconductor chip 102 across solder layer 104, sealing resin 108 is used to carry out sealing immobilization, obtain so-called single semiconductor device, the resin sheet 112 of the semi-solid preparation of the present invention is crimped on radiator 120 and heat cure, configure across heat conducting material 122 with this single semiconductor device.By getting involved the resin sheet 112 of the present invention, insulating properties and thermal diffusivity can be taken into account in the same manner as Fig. 1.

Fig. 3 indicates that the summary sectional view of the configuration example of power semiconductor arrangement 160, this power semiconductor arrangement 160 is constituted as follows: be arranged in across solder layer 104 on copper or copper alloy ieadf iotaame 106 by power semiconductor chip 102, copper or copper alloy ieadf iotaame 106 are crimped on radiator 120 across the resin sheet 112 of the present invention, use sealing resin 108 to seal.Insulating properties and thermal diffusivity can be taken into account in the same manner as Fig. 1.

Fig. 4 indicates that the summary sectional view of the configuration example of the power semiconductor arrangement 200 configuring radiator 120 on the two sides of power semiconductor chip 102 and constitute.The resin sheet 110 with metal forming of the present invention is configured respectively between radiator 120 and lead frame 106.It addition, dividing plate 107 is arranged between power semiconductor chip 102 and lead frame 106 across solder layer 104.By such composition, it is possible to obtain cooling effect higher compared with the one side cooling structure of Fig. 1～Fig. 3.

Fig. 5 indicates that the summary sectional view of the configuration example of the power semiconductor arrangement 210 configuring cooling component on the two sides of power semiconductor chip 102 and constitute.Owing to the resin sheet 112 of the present invention is bonding with radiator 120 by lead frame 106, therefore do not need dividing plate 107, it is possible to obtain constituting higher cooling effect than Fig. 4.

Fig. 6 indicates that the summary sectional view of an example of the composition of the LED lamp bar 300 using structure 115 to constitute, and this structure 115 obtains between the Copper Foil 116 of circuit and aluminium sheet 118 by being clipped in be formed by the resin cured matter sheet 112 of the present invention.

LED lamp bar 300 is by configuring outer housing 132, heat conducting material 122, the structure 115 of the present invention and the single parts 130 of LED successively and constitute.Across the resin cured matter sheet 112 of the Copper Foil 116 and the present invention that form circuit, there is aluminum electrical insulating property as the single parts 130 of LED of heater can dispel the heat efficiently simultaneously.By making outer housing 132 for metal system, it is possible to work as radiator.

Fig. 7 indicates that the summary sectional view of an example of the composition of the LED bulb 400 using structure 115 to constitute, and this structure 115 obtains between the Copper Foil 116 of circuit and aluminium sheet 118 by being clipped in be formed by the resin cured matter sheet 112 of the present invention.LED bulb 400 has LED drive circuit 142, and across bulb shell 140, side's configuration lamp holder 146, the opposing party configures heat conducting material 122, the structure 115 of the present invention, the single parts 130 of LED successively, covers the single parts 130 of LED with lens 144.By the single parts 130 of LED as heater are arranged on bulb shell 140 across the structure 115 of the present invention, it is possible to dispel the heat efficiently.

Embodiment

Specifically describe the present invention by the examples below, but the invention is not restricted to these embodiments.It addition, unless otherwise specified, then " part " and " % " is quality criteria.

The kind of epoxy resin described in embodiment, novolac resin, inorganic filling material, additive and solvent is as follows with abbreviation or model.

(epoxy monomer)

TPM-Ep: triphenylmethane type epoxy resin (Japan chemical medicine EPPN-502H, multifunctional branching type solid epoxy, epoxide equivalent 168g/eq)

PhN-Ep: bisphenol F phenolic type epoxy resin (Mitsubishi Chemical jER152, multifunctional straight chain type liquid epoxy resin, epoxide equivalent 165g/eq)

BisAF-Ep: aqueous bisphenol A type epoxy resin and bisphenol f type epoxy resin mixture (Nippon Steel chemistry ZX-1059, two functional-type liquid epoxy resins, epoxide equivalent 165g/eq)

(firming agent)

ReN: resorcinol novolac resin (composite, dihydric phenol type novolac resin (m=2), hydroxyl equivalent: 62g/eq, formula (I) R¹: H, R²: H)

RCN: resorcinol catechol novolac resin (composite, dihydric phenol type novolac resin (m=2), hydroxyl equivalent: 62g/eq, formula (I) R¹: H, R²: H)

XLC: phenol phenylene aralkyl resin (Mitsui Chemicals XLC-LL, multifunctional type solid aralkyl-type resin, hydroxyl equivalent: 175g/eq)

Res: resorcinol (with the pure medicine reagent of light, binary monokaryon phenolic compounds, hydroxyl equivalent 55g/eq)

(inorganic filling material)

(boron nitride, water island alloy are iron for HP-40；Volume average particle size 40 μm, hexagonal crystal, cohesion, length-width ratio 1.5)

PT-110 (boron nitride, figure Japan advanced in years system；Volume average particle size 43 μm, hexagonal crystal, flakey, length-width ratio 10)

AA-18 (aluminium oxide, Sumitomo Chemical system；Volume average particle size 18 μm)

AA-3 (aluminium oxide, Sumitomo Chemical system；Volume average particle size 3 μm)

AA-04 (aluminium oxide, Sumitomo Chemical system；Volume average particle size 0.4 μm)

ShapalH (aluminium nitride moral mountain system；Volume average particle size 0.5 μm)

(curing accelerator)

TPP: triphenylphosphine (with Guang Chun medicine company system)

(coupling agent)

PAM:N-phenyl-3-TSL 8330 (chemical industrial company of SHIN-ETSU HANTOTAI system, KBM-573)

(dispersant)

BYK-106 (Bi Ke chemistry Japanese firm system)

REB122-4 (Hitachi's chemical conversion industry system, ethyl lactate 45% solution)

(solvent)

CHN: Ketohexamethylene

(supporter)

PET: the polyethylene terephthalate film (Tengsen Industrial Co., Ltd's system, FILMBYNA75E-0010CTR-4) that the one side demoulding processes

GTS: electrolytic copper foil (Furukawa Co., Ltd. system, thickness 80 μm, GTS grade)

[synthesis of novolac resin]

(synthesis of ReN)

In the removable flask of the 1L with blender, cooler and thermometer, measure 110g (1mol) resorcinol, 45g (about 0.5mol, F/P=0.5) 37% formalin, 1.1g as the oxalic acid of catalyst, 50g as after the water of solvent, stirring content while heating oil bath to 120 DEG C, carrying out backflow and carrying out reaction in 3 hours.Afterwards, pull down cooler and distillator is installed, water being distilled off and is warming up to 150 DEG C.At 150 DEG C, continuous stirring is reacted 12 hours further.After reaction terminates, heating, to 170 DEG C, under reduced pressure makes unreacted resorcinol distil 8 hours and remove.After monomer removes, move to stainless steel cask, cool down and obtain resorcinol novolac resin (ReN).

Resorcinol novolac resin (ReN) carries out molecular weight determination by GPC, and monomer containing ratio is 8 mass %, and the number-average molecular weight of the reaction product outside demonomerization is 900.Pass through¹The mensuration of HNMR, it is known that on average comprise 2.0 hydroxyls in repetitive.By with the number-average molecular weight molecular weight 122 divided by the construction unit of formula (I), calculating average repeat unit number n is 7.4.It addition, hydroxyl equivalent is 62g/eq.

(synthesis of RCN)

In the removable flask of the 3L with blender, cooler and thermometer, add 627g resorcinol, 33g catechol, 316.2g37% formalin, 15g oxalic acid, 300g water, heat in oil bath and be warming up to 100 DEG C.Reflux 104 DEG C of front and back, carry out reaction in 4 hours at a reflux temperature.Afterwards, water is distilled off by the temperature in flask to 170 DEG C.Keep 170 DEG C while successive reaction 8 hours.After reaction, under reduced pressure carry out concentration in 20 minutes, the water etc. in removing system, obtain resorcinol novolac resin (RCN).

Resorcinol catechol novolac resin (RCN) carries out molecular weight determination by GPC, and monomer containing ratio is 8 mass %, and the number-average molecular weight of the reaction product outside demonomerization is 600.Pass through¹The mensuration of HNMR, it is known that on average comprise 1.8 hydroxyls in repetitive.Hydroxyl equivalent is 62g/eq.It addition, confirmed any one represented ton skeleton derivative of following formula (VIIIa)～(VIIId) that structure, result comprise more than at least one by FD-MS.Ignore ton skeleton derivative, with the number-average molecular weight molecular weight 119 divided by the construction unit of formula (I), thus calculating average repeat unit number n is 5.0.

[changing 10]

[changing 11]

[changing 12]

[changing 13]

(evaluation methodology of firming agent)

For firming agent obtained above, it is carried out as follows the mensuration of physics value.

(molecular weight determination)

The mensuration of number-average molecular weight (Mn), uses Hitachi Co., Ltd high performance liquid chromatography L6000 and Shimadzu Seisakusho Ltd. data analysis device C-R4A to carry out.Analyze and use TOSOH Co., Ltd G2000HXL and G3000HXL with GPC post.Sample solution concentration is 0.2 mass %, moves and uses oxolane mutually, is measured with flow velocity 1.0ml/min.Use polystyrene standard sample to make standard curve, use it to calculate number-average molecular weight with polystyrene conversion value.

(hydroxyl equivalent)

Hydroxyl equivalent uses chloroacetic chloride-potassium hydroxide titration measuring.Further, since the color of solution is dark-coloured, therefore titration end-point judge the development process not by use indicator, but undertaken by potential difference titration.Specifically, use its excessive reagent of water decomposition after pyridine solution makes the glycoloyl chlorination of mensuration resin, use the acetic acid that potassium hydroxide/methanol solution titration generates.

[manufacture of the epoxy resin cured product without inorganic filling material]

< reference example 1 >

The stainless steel disc of the diameter 5cm processed through the demoulding weighs 100 parts of TPM-Ep as polyfunctional epoxy resin, 37 parts of ReN as firming agent, 0.3 part of TPP as curing accelerator, while adding heat fusing with 150 DEG C while after mixing, placing at 150 DEG C and solidify for 1 hour on hot plate.The secondary carried out further 160 DEG C, 2 hours and 190 DEG C, 2 hours takes off resin cured matter from stainless steel disc, obtains epoxy resin cured product after solidifying.The result of Measurement of Dynamic Viscoelasticity is, there is rubber-like flat site when more than or equal to 300 DEG C, and the minima of storage modulus is 230MPa at 340 DEG C.

< reference example 2 >

As the epoxy resin of embodiment 1, use 66 parts of BisAF-Ep to replace TPM-Ep, as firming agent, use 71 parts of XLC to replace ReN, in addition, similarly operate, obtain resin cured matter.

[calculating of the crosslink density of reference example 1 and 2]

Use following method, calculate the crosslink density of the solidfied material of the resin composition of reference example 1 and 2.Comparison reference example 1 and reference example 2 are it can be seen that the crosslink density of solidfied material of resin composition of reference example 1 is high about 12 times more than.

The crosslink density of resin cured matter, it is possible to according to classical rubber elasticity theory, is obtained by (formula 2) by the storage modulus minima (E ' min) of the rubber-like flat site of resin cured matter.

(formula 2)

[several 1]

$n=\frac{\mathrm{\&rho;}}{M_c}=\frac{{E^{\&prime;}}_{\min }}{3\mathrm{\&phi;}RT}$

N: crosslink density (mol/cm³), Mc: mean molecule quantity (g/mol) between crosslinking points

E ' min: storage tensile modulus minima (Pa), ρ: density (g/cm³)

Front coefficientR: gas constant (J/K mol)

The absolute temperature (K) of T:E ' min

(manufacture of structure)

< embodiment 1 >

nullIn the polyethylene bottle of 250mL，Weigh 10.0g (100 parts) TPM-Ep as polyfunctional epoxy resin host、3.7g (37 parts) ReN is as firming agent、0.11g (1.1 parts) TPP is as curing accelerator、56g (560 parts) HP-40、11.3g (113 parts) AA-04 is as inorganic filling material、0.07g (0.7 part) PAM is as coupling agent、0.1g (1 part) BYK-106 and 1.6g (16 parts) REB122-4 is as dispersant、50g (500 parts) CHN is as solvent、After the alumina balls of 100g (1000 parts) diameter 5mm，Cover the lid of polyethylene bottle，Ball mill is used to mix 30 minutes with revolution 100 revs/min，Obtain resin composition Chinese varnish.

Using gap is the applicator of 400 μm, after being coated on by the resin composition Chinese varnish obtained on the stripping surface of PET film (Tengsen Industrial Co., Ltd's system, 75E-0010CTR-4), rapidly at the box baking oven inner drying 10 minutes of 100 DEG C.

Then, cut out 2 square drying sheets of 10cm, make resin facing to overlapping 2 drying sheets medially, carry out thermo-compressed by vacuum hotpressing (hot plate 150 DEG C, pressure 10MPa, vacuum≤1kPa, 1 minute time of process), obtain the resin sheet that thickness is 200 μm of resin composition layer, i.e. B rank sheet.

PET film is peeled off from the two sides of the B rank sheet obtained, two sides is clamped with the side, alligatoring face of the GTS Copper Foil of 80 μ m-thick, undertaken crimping and solidifying by vacuum hotpressing (hot plate temperature 150 DEG C, vacuum≤1kPa, pressure 10MPa, 10 minutes time of process), afterwards, in box baking oven, carry out 2 hours, the secondary solidification of 2 hours at 190 DEG C at 160 DEG C, two sides must be arrived and be provided with the structure of Copper Foil.

< comparative example 1 >

Use 6.6g (66 parts) BisAF-Ep to replace the epoxy resin TPM-Ep of embodiment 1, use 7.1g (71 parts) XLC to replace ReN as firming agent, in addition, similarly operate, obtain resin cured matter.

< comparative example 2 >

84.9g (849 parts) AA-18,30.9g (309 parts) AA-3 and 12.9g (129 parts) AA-04 is used to replace inorganic filling material HP-40 and AA-04 of embodiment 1, in addition, operate similarly to Example 1, obtain resin cured matter.

< comparative example 3 >

84.9g (849 parts) AA-18,30.9g (309 parts) AA-3 and 12.9g (129 parts) AA-04 is used to replace inorganic filling material HP-40 and AA-04 of comparative example 1, in addition, operate in the same manner as comparative example 1, obtain resin cured matter.

[removing the making of the resin sheet solidfied material sample of Copper Foil]

Being immersed in the etching solution of 20% aqueous solution of sodium peroxydisulfate by the resin sheet solidfied material of the two sides band Copper Foil obtained, process to Copper Foil is completely dissolved.Complete after Copper Foil removes, fully to be washed by lamellar solidfied material, at 120 DEG C dry 4 hours, using the sample of gained as the resin sheet solidfied material sample removing Copper Foil.

(evaluation of thermal diffusivity)

Cut out the square sample of 10mm from the resin sheet solidfied material sample removing Copper Foil, use NETZSCH company NanoflashLFA447 type, by the flicker method mensuration thermal diffusivity at the thickness direction of the resin sheet solidfied material removing Copper Foil of 25 DEG C.

(evaluation of specific heat)

Cut out several pieces in the mode that weight is 20～40mg be about the square sample of 3mm from the resin sheet solidfied material sample removing Copper Foil.Use differential scanning calorimetry (DSC) (PERKINELMER company Pyris-1), using sapphire as base sample, measure the specific heat of the resin sheet solidfied material removing Copper Foil of 25 DEG C.

(evaluation of density)

Use Archimedes method density measuring device (Alfamirage company SD-200L), measure the density of the resin sheet solidfied material removing Copper Foil of 25 DEG C.

(evaluation of thermal conductivity)

Above-mentioned thermal diffusivity, specific heat and the density obtained is substituted into (formula 3), obtains the thermal conductivity of the thickness direction of resin cured matter sheet.

λ=α Cp ρ (formula 3)

λ: thermal conductivity (W/m K), α: thermal diffusivity (mm²/s)

Cp: specific heat (J/kg K), ρ: density (g/cm³)

[mensuration of storage modulus and vitrification point]

From the sample of the resin sheet solidfied material cut-out length 33mm × width 5mm removing Copper Foil, use RheometricScientific company SOLIDSANALYZERII, under stretch mode, measure the temperature dependency of the storage modulus of 30～350 DEG C.

Read the peak temperature vitrification point (Tg) as Measurement of Dynamic Viscoelasticity of tan δ.Experimental condition is set in programming rate 5 DEG C/min, frequency 10Hz, span 21mm, stretcher strain amount 0.1%, air atmosphere.

[table 1]

(result)

If by the result of embodiment 1 and comparative example 1 it can be seen that the main component being inorganic filling material with boron nitride, then, when the crosslink density of matrix resin is about 13 times, thermal conductivity raises 3 one-tenth.

On the other hand, if by the result of comparative example 2 and comparative example 3 it can be seen that the main component being inorganic filling material with aluminium oxide, even if then the crosslink density of matrix resin is about 12 times, thermal conductivity also only improves 1 one-tenth.Reason is thought: the vitrification point of comparative example 2 reduces 45 DEG C compared with embodiment 1, and therefore the absorption water resistance of aluminium oxide hinders curing reaction, and crosslink density reduces.

[manufacture of structure]

< embodiment 2～12, comparative example 4～5 >

According to the step of embodiment 1, coordinate the material shown in table 2, obtain resin cured matter.It addition, the curing accelerator of material do not recorded as table 2, coupling agent, dispersant, commensurability with embodiment 1 coordinate.

(evaluation methodology)

For resin combination obtained above, operate as described above, measure thermal conductivity and the vitrification point of resin cured matter.It addition, the flexibility of evaluating resin compositions and the insulation breakdown voltage of resin cured matter that formed by resin combination as follows.Show the result in table 2.

(flexible appraisal)

B rank sheet cut-out length 100mm, the width 10mm that will make, removes the PET film on surface.Sample is attached to and overlaps with on multistage aluminum and fixture that diameter is 20～140mm, the plectane of 20mm class interval, at 25 DEG C not damaged flexible most path be evaluated as ◎ when being 20mm, good, zero it is evaluated as during 40mm or 60mm, be evaluated as △ during 80mm or 100mm, for practical boundary, be evaluated as during more than or equal to 120mm ×, defective.

(insulation breakdown voltage determination)

Metal container is placed the resin sheet solidfied material sample removing Copper Foil, electrode (aluminum flat round electrode, diameter 25mm, contact surface 20mm) is set to lamellar.Then, inject fluoride liquid insulating oil (3M company FC-40), use when impregnated in fluoride liquid and always grind electricity DAC-6032C processed, measure the insulation breakdown voltage at 25 DEG C.Condition determination is set to frequency 50Hz, the boosting of the constant speed of rate of rise 500V/ second.

[table 2]

Embodiment 1～12, compared with comparative example 1～5, has the flexibility of excellence, shows high heat conductance after solidification before solidification.

Confirming in further detail, in the comparison of embodiment 1, embodiment 12 and comparative example 4, TPM-Ep, PhN-Ep, BisAF-Ep hydroxyl equivalent is substantially equal, and use level is also substantially equal, but thermal conductivity differs widely.TPM-Ep has the branched structure of reactive terminal and the resin matrix that crosslink density is high in repetitive, therefore compared with the Bis-AF of the PhN-Ep of multifunctional type linear chain structure and two senses, shows the effect that thermal conductivity improves.

The result of comparative example 1,4,5, thermal conductivity reduces compared with embodiment 1, and reason is thought: the crosslink density of composition epoxy resin is low.

Further, by the comparison of the result of embodiment 1～5 it can be seen that by adding difunctional epoxy resin or monokaryon dihydric phenolic compounds, flexibility improves, if combination difunctional epoxy resin and monokaryon dihydric phenolic compounds, sufficient flexibility can be obtained.Thinking on the other hand, by adding difunctional epoxy resin or monokaryon dihydric phenolic compounds, crosslink density reduces, and thermal conductivity reduces compared with embodiment 1.It is additionally contemplated that, the RCN used due to embodiment 6 and 7 comprises monomer, therefore obtains the soft bating effect equal with embodiment 4 and 5.

According to embodiment 8～10 as a result, it is possible to say: compared with embodiment 1,6,7, it is possible to reduce boron nitride and the ratio of aluminium oxide is increased to 34 volume % of inorganic filling material.

According to embodiment 11 as a result, it is possible to say: compared with embodiment 1, if using the aluminium nitride having than aluminium oxide more high heat conductance as small particle size filler, then can improve the thermal conductivity of resin cured matter.

Symbol description

102: power semiconductor chip, 104: solder layer, 106: distribution metallic plate (lead frame, bus), 107: dividing plate, 108: sealing resin, 110: with the resin sheet of metal forming, 112: resin sheet or resin cured matter sheet, 114: metal foil support body, 115: structure, 116: completed the metal forming of circuit fabrication, 118: metallic plate, 120: radiator, 122: heat conducting material (Heat sink grease, fin, phase transformation sheet), the single parts of 130:LED, 132: outer housing, 140:LED bulb shell, 142:LED drive circuit, 144: lens, 146: lamp holder.

Claims (16)

1. a resin combination, containing the epoxy resin, the firming agent comprising the novolac resin with the construction unit represented by following formula (I) and the inorganic filling material comprising nitride particles that comprise polyfunctional epoxy resin,

In formula (I), R¹And R²Representing hydrogen atom or methyl independently of one another, m represents 1.5～2.5 in meansigma methods, and n represents 1～15 in meansigma methods.

2. resin combination according to claim 1, containing the described inorganic filling material of 50 volume %～85 volume %.

3. the resin combination according to claim 1 or claim 2, containing the described polyfunctional epoxy resin more than or equal to 20 mass % in whole epoxy resin.

4. the resin combination according to any one of claim 1～claim 3, described polyfunctional epoxy resin is at least one selected from triphenylmethane type epoxy resin, tetraphenyl ethane type epoxy resin, dihydroxy benzenes phenolic resin varnish type epoxy resin and glycidyl amine type epoxy resin.

5. the resin combination according to any one of claim 1～claim 4, described epoxy resin comprises aqueous or semi-solid epoxy resin further, and described aqueous or semi-solid epoxy resin is at least one selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol A-type and F type epoxy resin, bisphenol F phenolic type epoxy resin, naphthalene diol type epoxy resin and glycidyl amine type epoxy resin.

6. the resin combination according to any one of claim 1～claim 5, described firming agent comprises at least one selected from monokaryon dihydroxy benzenes of 20 mass %～70 mass %.

7. the resin combination according to any one of claim 1～claim 6, contains the described nitride particles of 50 volume %～95 volume % in described inorganic filling material.

8. the resin combination according to any one of claim 1～claim 7, described nitride particles is condensation product or the ground product of hexagonal boron, and the ratio of major diameter and minor axis is less than or equal to 2.

9. the resin combination according to any one of claim 1～claim 8, contains coupling agent further.

10. the resin combination according to any one of claim 1～claim 9, contains dispersant further.

11. a resin sheet, the uncured thing of its resin combination according to any one of claim 1～claim 10 or semi-solid preparation thing.

12. with a resin sheet for metal forming, it has the resin sheet described in claim 11 and metal forming.

13. a resin cured matter sheet, the solidfied material of its resin combination according to any one of claim 1～claim 10.

14. resin cured matter sheet according to claim 13, the thermal conductivity of thickness direction is more than or equal to 10W/m K.

15. a structure, it has the resin cured matter sheet described in the resin sheet described in claim 11 or claim 13 or claim 14 and the metallic plate arranged in the way of the face with described resin sheet or described resin cured matter sheet contacts in the one side or two sides of described resin sheet or described resin cured matter sheet.

16. power with or a light source semiconductor device, its have described in the resin sheet described in claim 11, claim 12 with the resin cured matter sheet described in the resin sheet of metal forming, claim 13 or claim 14 or the structure described in claim 15.