JP6011390B2 - Easily deformable aggregate, heat conductive resin composition, heat conductive member, and heat conductive adhesive sheet - Google Patents

Description

  The present invention relates to a thermally conductive deformable aggregate, a thermally conductive resin composition, and a thermally conductive member that can be suitably used for forming a thermally conductive member for releasing heat from an electronic device.

In recent years, the development of the electronics field has been remarkable, and in particular, electronic devices have become smaller, lighter, higher density, and higher in output, and demands for these performances have become increasingly sophisticated. High insulation and reliability are required to reduce the size and density of electronic circuits, and in particular, there is a strong need to improve heat dissipation to prevent deterioration of electronic devices due to heat generated by higher output of electronic devices. ing.
In the electronics field, a polymer material is suitably used as an insulating material, and in order to improve heat dissipation, it has been desired to improve the thermal conductivity of the polymer material. However, since there is a limit to improving the thermal conductivity of the polymer material, a method has been developed to improve heat dissipation by mixing thermally conductive particles with the polymer material. In recent years, the use as a heat conductive adhesive sheet obtained by molding them into a sheet shape or a pressure sensitive adhesive sheet has been studied.

For example, Patent Document 1 discloses a molding resin containing a nanocomposite polyamide resin in which a layered silicate is uniformly dispersed and a thermally conductive inorganic filler. As the thermally conductive inorganic filler, alumina, magnesium oxide, silica, zinc oxide, boron nitride, silicon carbide, silicon nitride and the like are disclosed.
Thermally conductive inorganic fillers are required to have improved thermal conductivity so that the molded body can be imparted with thermal conductivity with a smaller amount than in the past.

Patent Document 2 obtains spherical composite particles having an average particle diameter of 3 to 85 μm and improved thermal conductivity by granulating and sintering high thermal conductivity particles having an average particle diameter of 10 μm or less. The use of the composite particles has been proposed.
Specifically, after thermally conductive particles such as alumina, aluminum nitride, and crystalline silica are coated with a silane coupling agent or a thermosetting resin, the heat is at least 800 ° C., usually 1000 to 2800 ° C. There has been proposed a method of obtaining spherical composite particles by sintering at a temperature close to the melting point of the conductive particles (see [0009], [0021] to “0022”, [0028] to [0032]).
According to Patent Document 2, it is disclosed that sintering is performed in order to increase the cohesive force of the composite particles. However, as a result of sintering at a temperature close to the melting point of the thermally conductive particles after granulation, the binder used during granulation disappears, and the cohesive force of the composite particles after sintering is never high, rather it is sintered. The later composite particles are brittle, cannot maintain a granulated state, and are easily disintegrated.
Alternatively, if the sintering is sufficiently performed at a temperature equal to or higher than the melting point, the heat conductive particles are fused and integrated, so that a high cohesive force can be obtained. However, as a result of adhesion integration, it becomes huge hard particles.

  Patent Document 3 includes the use of a powder composition comprising inorganic powder such as alumina, magnesium oxide, boron nitride, and aluminum nitride and a thermosetting resin composition, and processed into a powder, a granulated powder, and a granular state. Has been proposed. However, since the inorganic powder used in this method is large in size and uses a thermosetting resin composition, the resin hardens in the aggregate, so that a hard powder with strong bonds can be obtained. It is a body composition.

  In Patent Document 4, a composite particle powder obtained by coating the surface of an alumina particle powder with a surface modifier and then attaching a carbon powder to the surface of the surface modifier-coated particle is set to 1350 to 1750 ° C. in a nitrogen atmosphere. A method for producing aluminum nitride that is heated and fired is disclosed (see claims, [0034], [0042], [0046] to [0049]).

Patent Document 5 discloses a spherical aluminum nitride sintered powder having an average particle size of 10 to 500 μm and a porosity of 0.3% or more. Specifically, a slurry containing an aluminum nitride powder containing 10% by weight or more of a powder having a primary particle size of 0.1 to 0.8 μm and a sintering aid such as lithium oxide or calcium oxide is spray-dried, Furthermore, the manufacturing method of the said spherical aluminum nitride sintered powder baked at 1400-1800 degreeC is described (refer Claim 1, 4, [0035]).
In the case of Patent Documents 4 and 5, as in the case of Patent Document 2, since sintering is performed at a very high temperature and the sintering aid or the like and aluminum nitride are strongly bonded to each other, an aggregate is obtained. For example, hard aluminum nitride, or huge and hard aluminum nitride particles integrated by sintering.

Patent Document 6 discloses the use of secondary aggregated particles obtained by isotropic aggregation of primary particles of flaky boron nitride.
Specifically, after calcining flaky boron nitride at around 1800 ° C., granules formed from primary particles obtained by pulverization are fired at 2000 ° C., and the porosity is 50% or less and the average pore diameter is A method for obtaining a secondary aggregate of 0.05 to 3 μm is disclosed (see [0014], [0026], and “0027]).

  Patent Document 7 discloses the use of a spherical boron nitride aggregate obtained by aggregating irregularly shaped non-spherical boron nitride particles.

  Patent Document 8 discloses the use of a silicon nitride sintered body, and Patent Document 9 discloses the use of a spherical zinc oxide particle powder obtained by sintering.

  On the other hand, as a heat conductive member using heat conductive particles, for example, Patent Documents 10 and 11 disclose heat conductive adhesive sheets using inorganic particles. In order to increase the thermal conductivity of these thermally conductive members, it is effective to increase the packing rate of the particles. However, as the amount of particles increases, the polymer material component decreases. Decrease in material followability occurs. Moreover, especially in the adhesive sheet use, there existed a subject that an adhesive component will reduce by raising a filling rate, and adhesiveness will be lost.

  Therefore, as in Patent Documents 12 and 13, there is a method for controlling the orientation of particles by applying a magnetic field or an electric field to a thermally conductive member in order to form contact (heat transfer path) of particles with a low particle filling rate. It has been reported. However, these methods are not practical when considering industrialization.

  Further, Patent Document 14 reports an attempt to form a tertiary aggregate in which secondary particles are arranged close to each other in a coating film and to exhibit high thermal conductivity with a low filling amount. In this report as well, a silane coupling agent is used as a binder for granulation, and the secondary particles are dried at 150 ° C. for 4 hours or more and subjected to a coupling reaction, thereby producing a granulated product. While improving operability, the flexibility of the particles is lost. Therefore, both thermal conductivity and adhesive strength are insufficient.

  Thus, the heat conductive resin composition and the heat conductive sheet using the conventional heat conductive particles and the secondary particles (aggregates) thereof have high heat conductivity and excellent film formability, It has been difficult to achieve substrate followability and adhesion.

JP 2006-342192 A JP-A-9-59425 JP 2000-239542 A JP 2006-256940 A JP 2006-206393 A JP 2010-157563 A Japanese translation of PCT publication No. 2008-510878 Japanese Patent Laid-Open No. 2007-039306 JP 2009-249226 A JP-A-6-162855 JP 2004-217861 A JP 2006-335957 A JP 2007-332224 A JP 2010-84072 A

  The object of the present invention is to produce a thermally conductive easily deformable aggregate and a thermally conductive member having high thermal conductivity, excellent film formability and substrate followability, and an adhesive sheet having excellent adhesiveness. Therefore, it is providing the heat conductive resin composition.

That is, the present invention includes 100 parts by weight of spherical heat conductive particles (A) having an average primary particle diameter of 0.1 to 10 μm, and 0.1 to 30 parts by weight of an organic binder (B) having a nitrogen atom. The easily deformable aggregate (D) is characterized by having an average particle diameter of 2 to 100 μm and an average compressive force required for a compression deformation rate of 10% of 5 mN or less.
Moreover, this invention contains 20-90 volume% of easily deformable aggregates (D), 10-80 volume% of binder resin (E), and the solvent (F) which melt | dissolves the said binder resin (E). It is related with the said heat conductive resin composition (G) characterized by doing.
Moreover, this invention relates to the said heat conductive resin composition (G) characterized by the organic binder (B) which has a nitrogen atom not melt | dissolving in the said solvent (F).
Further, in the present invention, the organic conductive agent (B) having a nitrogen atom is a water-soluble resin, and the binder resin (E) is a water-insoluble resin. G).
Moreover, this invention relates to the heat conductive member (H) formed by removing a solvent (F) from the said heat conductive resin composition (G).
Moreover, this invention relates to the heat conductive member (I) characterized by pressing the said heat conductive member (H).
Furthermore, this invention relates to the heat conductive adhesive sheet which comprises a peeling film and the said heat conductive member (H), or the heat conductive member (I) of Claim 6.

By using the easily deformable agglomerates of the present invention, the heat conductivity can be imparted to the heat conducting member with a smaller amount of use, or higher heat conductivity can be achieved with the same amount of use as before. It can be applied to the heat conducting member.
In addition, since the thermally conductive resin composition of the present invention uses easily deformable aggregates having high thermal conductivity, the thermal conductivity having high thermal conductivity, excellent film formability, and substrate followability. A member and an adhesive sheet excellent in adhesiveness can be produced.

Thermally conductive particles (A) having an average primary particle diameter of 1 μm, thermally conductive particles (A) having an average primary particle diameter of 10 μm, and thermally conductive particles (A) having an average primary particle diameter of 1 μm are treated with nitrogen atoms. It is a figure which shows the relationship between a compressive deformation rate and compressive force of the easily deformable aggregate (D) with an average particle diameter of 10 micrometers aggregated with the organic binder (B) which has. The SEM photograph of the heat conductive particle (A) whose average primary particle diameter is 1 micrometer. A thermosetting sheet containing an easily deformable aggregate (D) having an average particle diameter of 10 μm obtained by aggregating thermally conductive particles (A) having an average primary particle diameter of 1 μm with an organic binder (B) having a nitrogen atom. SEM photograph of the plane. The SEM photograph of the plane of the hardened | cured material which heat-cured the thermosetting sheet of FIG. 3a under pressure. The SEM photograph of the cross section of the hardened | cured material which heat-cured the thermosetting sheet of FIG. 3a under pressure. The SEM photograph of the heat conductive particle (A) with an average primary particle diameter of 10 micrometers.

<Easily deformable aggregate (D)>
The easily deformable aggregate (D) of the present invention comprises 100 parts by weight of spherical heat conductive particles (A) having an average primary particle size of 0.1 to 10 μm and an organic binder (B) 0 having a nitrogen atom. 0.1 to 30 parts by weight, the average particle size is 2 to 100 μm, and the average compressive force required for a compression deformation rate of 10% is 5 mN or less.

The “easy deformability” in the present invention means that an average compressive force required for a compression deformation rate of 10% is 5 mN or less. The average compressive force required for a compressive deformation rate of 10% is an average value of a load for deforming particles by 10% measured by a compression test. For example, a micro compression tester (manufactured by Shimadzu Corporation, MCT -210).
Specifically, a very small amount of sample to be measured is magnified with a microscope, an arbitrary one is selected, the particles to be measured are moved to the lower part of the pressure indenter, a load is applied to the pressure indenter, The measurement target particles are compressed and deformed. The tester includes a detector for measuring a compression displacement of the measurement target particle on an upper portion of the pressurizing indenter. The detector measures the compression displacement of the particles to be measured, and obtains the deformation rate. Then, the compression force required for 10% compression deformation of the particles to be measured (hereinafter also abbreviated as “10% compression deformation force”) is obtained. Similarly, “10% compressive deformation force” is obtained for any other particles to be measured, and the average value of “10% compressive deformation force” for 10 particles to be measured is “average required for 10% compression deformation rate”. Compressive force ".
The easily deformable aggregate (D) of the present invention is a state in which a plurality of small heat conductive particles (A) are aggregated as will be described later. The unit of

FIG. 1 shows a non-aggregated thermally conductive particle (A) as shown in FIGS. 2 and 4 and an easily deformable aggregate (D) in which the thermally conductive particles (A) as shown in FIG. 2 are aggregated. It is a figure which shows the relationship between the compressive deformation rate and compressive force about). The size of the easily deformable aggregate (D) is approximately the same as the size of the thermally conductive particles (A) shown in FIG.
As shown in FIG. 1, the heat conductive particles (A) that are not aggregated require a large force to be deformed only slightly. On the other hand, when the thermally conductive particles (A) having the same size as in FIG. 2 are aggregated to the same size as the thermally conductive particles (A) in FIG. 4, a much smaller force is obtained as shown in FIG. Can be transformed.
That is, the aggregate (D) of the present invention is an “easily deformable” aggregate.
FIG. 3a is a SEM photograph of a plane of a thermosetting sheet which is a kind of the heat conductive member containing the aggregate (D) of the present invention, and FIG. 3b is a diagram showing the heat conductive member (H) heated under pressure. FIG. 3C is a SEM photograph of a plane of the cured product, and FIG. 3C is a SEM photograph of a cross section of the cured product. 3a, b, and c also confirm that the aggregate (D) of the present invention is an “easy deformable” aggregate.
The reason why the aggregate (D) of the present invention is excellent in thermal conductivity because it is “easy to deform” will be described later.

<Thermal conductive particles (A)>
Thermally conductive particles (A) are not particularly limited as long as they have thermal conductivity. For example,
Metal oxides such as aluminum oxide, calcium oxide, magnesium oxide,
Metal nitrides such as aluminum nitride and boron nitride,
Metal hydroxides such as aluminum hydroxide and magnesium hydroxide,
Metal carbonates such as calcium carbonate and magnesium carbonate,
Silicate metal salts such as calcium silicate,
Hydrated metal compounds,
Crystalline silica, amorphous silica, silicon carbide or a composite thereof,
Metals such as gold and silver,
Examples thereof include carbon compounds such as carbon black, graphene, carbon nanotube, and carbon fiber.
These may be used alone or in combination of two or more.

Moreover, the shape of heat conductive particle (A) is not specifically limited, For example, spherical shape, oblate shape, plate shape, polygonal shape, wire shape, indefinite shape etc. are mentioned.
These may be used alone or in combination of two or more.

When used in electronic circuit applications, it is preferable to have insulating properties, and metal oxides and metal nitrides are preferably used. Among these, aluminum oxide, aluminum nitride, and boron nitride are preferable from the viewpoint of thermal conductivity. More preferably used.
When the easily deformable aggregate (D) to be obtained is used for an electronic material application or the like, the thermally conductive particles (A) are more preferably aluminum oxide that is not easily hydrolyzed.
Moreover, if metal nitrides, such as aluminum nitride which performed the process for improving hydrolysis resistance previously, are used and an easily deformable aggregate (D) is obtained, the easily deformable aggregate (D) obtained will be obtained. Can also be used for electronic materials.

It is important that the thermally conductive particles (A) are spherical in terms of the small number of voids and ease of deformation of the easily deformable aggregate (D) to be obtained. That is, when spherical particles are used, a dense easily deformable aggregate (D) with few voids can be obtained. Since the voids in the easily deformable aggregate (D) deteriorate the thermal conductivity, it is important in terms of improving the thermal conductivity to prevent the voids from being generated as much as possible. Moreover, when the heat conductive particles (A) are spherical, the coefficient of friction between the particles of the heat conductive particles (A) in the aggregate is small. As a result, when a force is applied to the aggregate, the positional relationship of the heat conductive particles (A) in the aggregate easily changes, and the aggregate is easily deformed without collapsing.
On the other hand, when plate-like or needle-like thermally conductive particles are used, an agglomerate with many voids is obtained, and the agglomerate between the constituent particles in the agglomerate is large and hardly deforms.

  In the present invention, the term “spherical” refers to, for example, “circularity”. The circularity is an arbitrary number of particles selected from a photograph of the particles taken with an SEM or the like, and represents the area of the particles. When S and the perimeter are L, it can be expressed as (circularity) = 4πS / L2. In order to measure the circularity, various image processing software or an apparatus equipped with image processing software can be used. In the present invention, flow type particle image analyzer FPIA-1000 manufactured by Toa Medical Electronics Co., Ltd. is used. The average circularity is 0.9 to 1 when the average circularity of the particles is measured. Preferably, the average circularity is 0.96-1.

The heat conductive particles (A) used for obtaining the easily deformable aggregate (D) have an average primary particle diameter of 0.1 to 10 μm, and preferably 0.3 to 10 μm. When using one type of thermally conductive particles (A), it is preferable to use particles having an average primary particle size of 0.3 to 5 μm. A plurality of types of thermally conductive particles (A) having different sizes can also be used, and in that case, using a combination of relatively small and relatively large particles reduces the porosity in the aggregate. This is preferable.
If the average primary particle size is too small, the number of contacts between the primary particles in the aggregate increases, and the contact resistance increases, so the thermal conductivity tends to decrease. On the other hand, if the average primary particle size is too large, it tends to collapse even if an aggregate is prepared, and the aggregate itself is difficult to be formed.
In addition, the average primary particle diameter of the heat conductive particles (A) in the present invention is a value when measured with a particle size distribution meter (for example, Mastersizer 2000, manufactured by Malvern Instruments).
In addition, the easily deformable aggregate (D) of the present invention is less likely to collapse. For example, the easily deformable aggregate (D) is placed in a glass sample tube so as to have a porosity of 70%, and is shaken. Even if it shakes for 2 hours, it is supported also because the average particle diameter after shaking is 80% or more of the average particle diameter before shaking.

<Organic binder (B) having nitrogen atom>
The organic binder (B) having a nitrogen atom in the present invention plays a role of “tethering” for binding the heat conductive particles (A) to each other. Further, the non-covalent interaction between the nitrogen atom in the organic binder (B) and the skeleton of the binder resin (E) allows the heat conductive member (H) and the heat conductive member (I). The cohesive force is improved. For example, when used as an adhesive sheet, the adhesive force is improved.
The organic binder (B) having a nitrogen atom is not particularly limited as long as it has a nitrogen atom, and the molecular weight is not limited as long as it can play the role of “tethering”.
Urethane group, thiourethane group, urea group, thiourea group, amide group, thioamide group, imide group, amino group, imino group, cyano group, hydrazino group, hydrazono group, hydrazo group, azino group, diazenyl group, azo group, ammonio And resins having one or more functional groups such as a group, an iminio group, a diazonio group, a diazo group, an azide group, and an isocyanate group. Among them, a resin having a urethane group, an amide group, and an amino group that can easily control the amount of nitrogen element introduced is preferable.

Examples of the resin having a urethane group include a reaction product obtained by reacting a polyfunctional isocyanate and a polyfunctional polyol.
The polyfunctional isocyanate is a compound having two or more isocyanate groups,
For example, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2, 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate Aromatic diisocyanates such as tobenzene, dianisidine diisocyanate, 4,4′-diphenyl ether diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate;
Trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate An aliphatic diisocyanate such as neat, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate;
ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1,4 -Aromatic aliphatic diisocyanates such as tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate;
3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4- Cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1,3 Examples thereof include alicyclic diisocyanates such as -bis (isocyanatomethyl) cyclohexane and 1,4-bis (isocyanatomethyl) cyclohexane.
Moreover, the polyfunctional isocyanate which has 3 or more isocyanates, such as the trimethylol propane adduct body of the said diisocyanate, the burette body which reacted with water, and the trimer which has an isocyanurate ring, can be mentioned.
A polyfunctional polyol is a compound having two or more hydroxyl groups,
For example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, 1,3-butanediol, 1,4-butanediol, polybutylene glycol, 3 -Methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,9-nonanediol, cyclohexanedimethanol, hydrogenated bisphenol A, polycaprolactone diol, trimethylolethane, polytrimethylolethane, Trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, arabito Le, polyhydric alcohols such as xylitol, galactitol, glycerol, polyglycerol, polytetramethylene glycol;
2,2-bis (hydroxymethyl) butyric acid [dimethylolbutanoic acid], 2,2-bis (hydroxymethyl) propionic acid [dimethylolpropionic acid], 2,2-bis (hydroxyethyl) propionic acid, 2,2 -Bis (hydroxypropyl) propionic acid, tartaric acid, dihydroxymethylacetic acid, bis (4-hydroxyphenyl) acetic acid, 4,4-bis (p-hydroxyphenyl) pentanoic acid, 2,4-dihydroxybenzoic acid, 3,5- Acidic group-containing low molecular weight polyhydric alcohols such as dihydroxybenzoic acid and homogentisic acid;
Polyether polyols such as polyethylene oxide, polypropylene oxide, block copolymer or random copolymer of ethylene oxide / propylene oxide;
Polyester polyols which are condensates of the polyhydric alcohol or polyether polyol and polybasic acids such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, isophthalic acid;
Examples include caprolactone-modified polyols such as caprolactone-modified polytetramethylene polyol, polyolefin polyols, hydrogenated polybutadiene polyols, polycarbonate polyols, and other polymer polyols such as polybutadiene polyols.

The resin having an amide group is obtained by polymerizing a reaction product obtained by reacting a polyfunctional primary or secondary amine with a polyfunctional polyol, or an unsaturated double bond compound having an amide group. Reaction products obtained.
The polyfunctional primary or secondary amine is a compound having two or more primary amino groups or secondary amino groups,
For example, aliphatic polyamines such as ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, 1,2-diaminopropane;
A polyether skeleton diamine such as Jeffamine EDR148 from Sun Techno Chemical;
1,3-bisaminomethylcyclohexane, 1-cyclohexylamino-3-aminopropane, 3-aminomethyl-3,3,5-trimethyl-cyclohexylamine, NBDA (norbornane diamine) manufactured by Mitsui Toatsu Chemical Co., Ltd. A polyamine having an alicyclic hydrocarbon group such as a diamine having a norbornane skeleton represented by N-aminoethylpiperazine;
A polyamine having an aliphatic hydrocarbon group bonded to an aromatic hydrocarbon group such as metaxylylenediamine or tetramethylxylylenediamine;
Examples include polyamide amines and polyurethane amines having amino groups at the molecular ends of polyamide and polyurethane.
As the polyfunctional polyol, the above-mentioned polyfunctional polyol can be used.
Examples of unsaturated double bond compounds having an amide group include (meth) acrylamide, N-methyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and N-methylol. (Meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-methylenebis (meth) acrylamide, N-isopropylacrylamide, N, N-dimethylaminopropylacrylamide and the like can be mentioned. .

Examples of the resin having an amino group include a reaction product obtained by polymerizing an unsaturated double bond compound having an amino group, and a reactive organism obtained by ring-opening polymerization of a cyclic compound having an amino group. .
Examples of the unsaturated double bond compound having an amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, N- (meth) acryloylmorpholine, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, allylamine, and the like can be mentioned.
Examples of the cyclic compound having an amino group include ethyleneimine.

  As the organic binder (B) having a nitrogen atom, one kind may be used alone, or two or more kinds may be mixed and used.

  Moreover, it is preferable that the organic binder (B) which has a nitrogen atom is insoluble in a solvent (F). The term “insoluble” as used herein means that precipitation is visually confirmed when 1 g of an organic binder (B) having a nitrogen atom is put in 100 g of a solvent (F) and stirred at 25 ° C. for 24 hours. Since the organic binder (B) having a nitrogen atom plays a role of “tethering” for binding the thermally conductive particles, in the thermally conductive resin composition, it is insoluble in the solvent (F). This is because the easily deformable aggregate (D) can maintain the aggregated state.

In addition, the organic binder (B) having a nitrogen atom is preferably a water-soluble resin. When the heat conductive member (I) described later is an adhesive sheet, it can be suitably used. The term “water-soluble” as used herein means that precipitation is not visually confirmed when 1 g of resin is added to 100 g of water and stirred at 25 ° C. for 24 hours.
The water-soluble resin is not particularly limited, and examples thereof include polyethyleneimine, polyallylamine, polyacrylamide, and polyvinylpyrrolidone.

  The easily deformable aggregate (D) of the present invention contains 0.1 to 30 parts by weight of the organic binder (B) having the nitrogen atom with respect to 100 parts by weight of the heat conductive particles (A). It is preferable to contain 1-10 weight part. If the amount is less than 0.1 part by weight, the heat conductive particles (A) cannot be sufficiently bound, and a sufficient strength for maintaining the form cannot be obtained. When the amount is more than 30 parts by weight, the effect of binding the thermally conductive particles (A) is increased, but the binder enters between the thermally conductive particles (A) more than necessary, and the thermal conductivity. It is not preferable because there is a risk of inhibiting the

2-100 micrometers is preferable and, as for the average particle diameter of the easily deformable aggregate (D) of this invention, More preferably, it is 5-50 micrometers. When the average particle diameter is smaller than 2 μm, the number of the heat conductive particles (A) constituting the aggregate (D) is decreased, the effect as the aggregate is low, and the deformability is inferior. When the average particle diameter exceeds 100 μm, the weight of the easily deformable aggregate (D) per unit volume increases, and the degree of freedom in the film thickness of the thermally conductive member that settles or forms when used as a dispersion. This is not preferable because problems such as disappearance occur.
In addition, the average particle diameter of the easily deformable aggregate (D) in the present invention is a value when measured with a particle size distribution meter (for example, Mastersizer 2000 manufactured by Malvern Instruments).

The specific surface area of the easily deformable aggregate (D) is not particularly limited, but is preferably 10 m ² / g or less, and more preferably 5 m ² / g or more. When it is larger than 10 m ² / g, the binder resin (E) is adsorbed on the particle surface or inside the agglomerates, and tends to decrease film formability and adhesive strength, which is not preferable.

  The specific surface area is a value measured by a BET specific surface area meter (for example, BELSORP-mini manufactured by Nippon Bell Co., Ltd.).

Such an easily deformable aggregate (D) of the present invention includes, for example, an organic binder having 100 parts by weight of spherical heat conductive particles (A) having an average primary particle size of 0.1 to 10 μm and a nitrogen atom. (B) A slurry containing 0.1 to 30 parts by weight and a solvent (C) for dissolving the organic binder (B) having nitrogen atoms is obtained, and then the solvent (C) is removed from the slurry. Can be obtained.
Alternatively, it is obtained by mixing 100 parts by weight of the heat conductive particles (A) and 0.1 to 30 parts by weight of the organic binder (B) having a nitrogen atom, or 100 parts by weight of the heat conductive particles (A). An organic binder solution containing 0.1 to 30 parts by weight of an organic binder (B) having a nitrogen atom and a solvent (C) for dissolving the organic binder (B) having a nitrogen atom It can also be obtained by removing the solvent (C) after spraying or while spraying.
In order to obtain an easily deformable aggregate (D) having a uniform composition, the heat conductive particles (A) and the organic binder (B) having a nitrogen atom are mixed in advance in a solvent (C) to form a slurry. It is preferable that the solvent (C) is removed after the step.

<Solvent (C)>
The solvent (C) is for dissolving the heat conductive particles (A) and dissolving the organic binder (B) having a nitrogen atom.
The solvent (C) is not particularly limited as long as it can dissolve the organic binder (B) having a nitrogen atom, and can be appropriately selected depending on the type of the organic binder (B) having a nitrogen atom. As the solvent (C), for example, ester solvents, ketone solvents, glycol ether solvents, aliphatic solvents, aromatic solvents, alcohol solvents, ether solvents, water and the like can be used. A mixture of more than one can also be used.

The solvent (C) preferably has a lower boiling point from the viewpoint of easy removal, and preferably has a boiling point of 110 ° C. or lower, such as water, ethanol, methanol, ethyl acetate, or the like.
Further, the amount of the solvent (C) used is preferably small in terms of ease of removal, but is appropriately changed according to the solubility of the organic binder (B) having a nitrogen atom and the drying apparatus. can do.

The method for removing the solvent (C) from the slurry is not particularly limited, and the easily deformable aggregate (D) can be produced using a commercially available apparatus. For example, it can be selected from methods such as spray drying, stirring drying, and stationary drying. Among them, spray drying can be suitably used from the viewpoint that a relatively round and easily deformable aggregate (D) having a uniform particle diameter can be obtained with high productivity.
Specifically, the solvent (C) may be volatilized and removed while spraying the slurry in the form of a mist. Spray conditions and volatilization conditions can be selected as appropriate.

<Thermal conductive resin composition (G)>
Next, the heat conductive resin composition (G) will be described. It is preferable that a heat conductive resin composition (G) contains an easily deformable aggregate (D), binder resin (E), and a solvent (F).

<Binder resin (E)>
The binder resin (E) is not particularly limited as long as it can form a heat conductive member.
Polyurethane resin, polyester resin, polyester urethane resin, alkyd resin, butyral resin, acetal resin, polyamide resin, acrylic resin, styrene-acrylic resin, styrene resin, nitrocellulose, benzylcellulose, cellulose (tri) acetate, casein, shellac, gilsonite , Gelatin, styrene-maleic anhydride resin, polybutadiene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinylidene fluoride resin, polyvinyl acetate resin, ethylene vinyl acetate resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / Vinyl acetate / maleic acid copolymer resin, fluorine resin, silicone resin, epoxy resin, phenoxy resin, phenol resin, maleic acid resin, urea resin, melamine resin, benzoguanami Resin, ketone resin, petroleum resin, rosin, rosin ester, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, carboxymethylethylcellulose, carboxymethyl One or more selected from the group consisting of nitrocellulose, ethylene / vinyl alcohol resin, polyolefin resin, chlorinated polyolefin resin, modified chlorinated polyolefin resin, and chlorinated polyurethane resin can be used as appropriate. .
Among these, epoxy resins are preferably used from the viewpoints of insulation and heat resistance when used as urethane resins and electronic parts from the viewpoint of flexibility.
In addition, it is preferable that the organic binder (B) which has a nitrogen atom which comprises an easily deformable aggregate (D) is non-curable in order to ensure easy deformability. However, the binder resin (E) contained in the thermally conductive resin composition (G) and the thermally conductive member (H) is cured by the binder resin (E) itself or by reaction with an appropriate curing agent. Things can be used.

Moreover, it is preferable that binder resin (E) is a water-insoluble resin. The term “water-insoluble” as used herein means that when 1 g of resin is added to 100 g of water and stirred at 25 ° C. for 24 hours, precipitation is visually confirmed. Specifically, the organic bond having the nitrogen atom is used. Examples other than the water-soluble resin in the adhesive (B) are mentioned.
The binder resin (E) is preferably a water-insoluble resin when imparting adhesiveness to the heat conductive member (I) described later.

<Solvent (F)>
The solvent (F) is used for uniformly dispersing the easily deformable aggregate (D) and the binder resin (E) in the thermally conductive resin composition (G).

The solvent (F) used is one that can dissolve the binder resin (E) and does not dissolve the organic binder (B) having a nitrogen atom constituting the easily deformable aggregate (D). It is important to choose. When the heat conductive resin composition (G) is obtained, if the solvent (F) that dissolves the organic binder (B) having nitrogen atoms is used, the aggregation state of the easily deformable aggregate (D) is maintained. It may not be possible.
For example, when a water-soluble resin such as polyacrylamide or polyvinylpyrrolidone is selected as the organic binder (B) having a nitrogen atom, as the solvent (F) when obtaining the heat conductive resin composition (G), A non-aqueous solvent such as toluene or xylene may be selected.
When a water-insoluble resin such as a water-insoluble polyurethane resin or water-insoluble polyamide resin is selected as the organic binder (B) having a nitrogen atom, a solvent for obtaining the heat conductive resin composition (G) As (F), an aqueous solvent such as water or alcohol may be selected.
Here, “insoluble” means that 1 g of an organic binder (B) having a nitrogen atom is placed in 100 g of a solvent (F), stirred at 25 ° C. for 24 hours, and precipitation is confirmed visually. To do.

  The content of the easily deformable aggregate (D) in the thermally conductive resin composition (G) can be appropriately selected according to the target thermal conductivity and application, but in order to obtain high thermal conductivity. Is preferably 20 to 90% by volume based on the solid content of the thermally conductive resin composition (G). More preferably, it is in the range of 30 to 80% by volume. If the content is less than 20% by volume, the effect of adding the easily deformable aggregate (D) is thin and sufficient thermal conductivity cannot be obtained. On the other hand, when it exceeds 90% by volume, the content of the binder resin (E) is relatively reduced, and the formed heat conductive member (H) and the heat conductive member (I) become brittle, or the heat conductive member. There is a possibility that voids may be formed in (I), and there is a possibility that the thermal conductivity gradually decreases while using the thermal conductive member (I). The volume% here means the weight ratio of the thermally conductive particles (A), the organic binder (B) having a nitrogen atom, and the binder resin (E) to the solid content in the thermally conductive resin composition (G). And the theoretical value calculated based on the specific gravity.

  The easily deformable aggregate (D) may be used alone, or may have a different average particle size, a different type of heat conductive particles (A) or a different average primary particle size, or may be configured. A plurality of organic binders (B) having different types and amounts of nitrogen atoms may be used in combination.

Moreover, the heat conductive resin composition (G) can also use together the heat conductive particle which has not aggregated. By also using thermally conductive particles that are not agglomerated, the gap between the easily deformable aggregates (D) is filled, or when the easily deformable aggregates (D) are deformed, heat conduction is caused. The gap between the conductive particles (A) can be filled, and further improvement in thermal conductivity can be expected.
Examples of the thermally conductive particles that can be used in combination include those exemplified as the thermally conductive particles (A).

<Manufacture of heat conductive resin composition (G)>
The thermally conductive resin composition (G) is preferably produced by stirring and mixing the easily deformable aggregate (D), the binder resin (E), and, if necessary, the solvent (F). Common stirring methods can be used for stirring and mixing, for example, disperse, scandex, paint conditioner, sand mill, rake machine, medialess disperser, three rolls, bead mill, etc. It can be carried out.

  After stirring and mixing, it is preferable to go through a defoaming step in order to remove bubbles from the heat conductive resin composition (G). The method of defoaming is not particularly limited and can be performed using a general method, and examples thereof include vacuum defoaming and ultrasonic defoaming.

<Additives>
Various additives can be added to the heat conductive resin composition (G) as necessary. Examples of the various additives include a coupling agent for improving the adhesion to the substrate, an ion scavenger for enhancing the insulation reliability at the time of moisture absorption, a leveling agent, a flame retardant, and other fillers. Although it does not specifically limit as a flame retardant, For example, aluminum hydroxide, magnesium hydroxide, etc. are mentioned.
These may use 1 type and can also use multiple types together.

<Thermal conductive member (H), thermal conductive member (I)>
Next, the heat conductive member (H) and the heat conductive member (I) will be described.
A thermally conductive resin composition (G) containing an easily deformable aggregate (D), a binder resin (E), and a solvent (F) is obtained, and the solvent (F) is obtained from the thermally conductive resin composition (G). It can remove and a heat conductive member (H) can be obtained. Next, heat is applied to the thermally conductive member (H) to improve the thermal conductivity of the thermally conductive member (H) by applying pressure to the contained easily deformable aggregate (D). Conductive member (I) can be obtained.
For example, by using the heat conductive resin composition (G), an adhesive or sticky heat conductive sheet (heat conductive member (H)) is obtained, and the heat dissipation target article and the heat dissipation member The heat conductive sheet and the heat radiating member are bonded to each other by applying pressure while sandwiching the heat conductive sheet, and the heat conductive member (I) having improved heat conductivity of the heat conductive sheet is used. The heat of the article can be efficiently transmitted to the heat radiating member.
Further, a heat conductive sheet (heat conductive member (H)) having no adhesion or tackiness is obtained from the heat conductive resin composition (G), and instead of the above-mentioned adhesive or tacky heat conductive sheet. By using for the heat | fever, the heat | fever of the articles | goods of heat dissipation object can be efficiently transmitted to a heat radiating member.

Alternatively, a thermally conductive resin composition (G) containing an easily deformable aggregate (D) and a binder resin (E) is obtained, and pressure is applied to the thermally conductive resin composition (G). The thermally conductive member (I) can be obtained by deforming the easily deformable aggregate (D).
For example, a heat conductive sheet or the like (thermal conductive member (I)) can be obtained from the thermal conductive resin composition (G) by applying pressure.

  Articles for heat dissipation include articles used in building materials, vehicles, aircraft, ships, etc., as well as various electronic parts such as integrated circuits, IC chips, hybrid packages, multi-modules, power transistors and LED substrates. Thus, there is an article that is easily heated and requires the heat to be released to the outside in order to prevent durability and performance deterioration.

By the way, in order to realize high thermal conductivity, it is important to form more heat conduction paths in the direction in which heat is to be transmitted.
In the easily deformable aggregate (D) of the present invention, since the heat conductive particles (A) are aggregated, the distance between the particles is close and the heat conduction path is formed in advance, so that the heat conduction is efficiently performed. be able to.
In addition, since the easily deformable aggregate (D) of the present invention is “easy to deform”, high thermal conductivity can be realized. That is, when a force is applied to the easily deformable aggregate (D), the easily deformable aggregate (D) does not collapse, and the heat conductive particles (A) in the easily deformable aggregate (D) are not separated. By improving the adhesion, a previously formed heat conduction path can be enhanced. In addition, since the position of the thermally conductive particles (A) constituting the easily deformable aggregate (D) can be easily changed, the easily deformable aggregate (D) is formed between the heat radiation target article and the heat dissipation member. Follows the shape of the interface, the contact area between the heat radiation target article or heat radiating member and the heat conductive particles (A) increases, and the heat inflow area and the heat propagation path can be dramatically increased.

Further details will be described with reference to the drawings.
FIG. 3a shows an easily deformable aggregate having an average particle diameter of 10 μm, which is obtained by aggregating the heat conductive particles (A) having an average primary particle diameter of 1 μm shown in FIG. 2 with an organic binder (B) having a nitrogen atom. FIG. 3B and FIG. 3C are SEM photographs of a plane and a cross section, respectively, of a cured product obtained by thermosetting the thermosetting sheet under pressure. By applying pressure to the thermosetting sheet, the thermally conductive particles (A) in the easily deformable aggregate (D) are more closely adhered to each other, and more thermally conductive particles (A) are present on the surface of the cured product. It can be confirmed that the shape of the interface is followed.
On the other hand, non-aggregated thermally conductive particles (A) as shown in FIG. 4 having the same size as the easily deformable aggregate (D) shown in FIG. Since it does not have deformability, the above change can hardly be confirmed before and after pressurization of the thermosetting sheet.
Thus, since the easily deformable aggregate (D) of the present invention is “easy to deform”, it is excellent in thermal conductivity and has high thermal conductivity even with a smaller amount of use. Therefore, the heat conductive resin composition (G) of the present invention can obtain a heat conductive member (H) and a heat conductive member (I) excellent in substrate followability and film formability, By having a nitrogen atom in the organic binder (B), an adhesive sheet excellent in adhesiveness can be obtained.

The thermal conductivity (W / m · K) of the present invention is the thermal diffusivity (mm2 / s) representing the speed at which heat is conducted through the sample, and the specific heat capacity (J / (g · K)) and density of the measured sample. It can be obtained by the following formula multiplied by (g / cm3).
Thermal conductivity (W / m · K)
= Thermal diffusivity (mm2 / s) x specific heat capacity (J / (g · K)) x density (g / cm3)

  For the measurement of thermal diffusivity, for example, a periodic heating method, a hot disk method, a temperature wave analysis method, a flash method, or the like can be selected according to the shape and purpose of the measurement sample. The thermal diffusivity was measured by the flash method using LFA447 NanoFlash (manufactured by NETZSCH).

<Heat conductive adhesive sheet>
A thermal conductive adhesive sheet will be described as an example of one of the thermal conductive members.
The thermally conductive sheet can be formed by coating and drying a thermally conductive resin composition (G) containing a solvent (F) on a substrate. In addition, a heat conductive sheet may be called a heat conductive film.

  The coating method is not particularly limited, and a known method can be used. For example, knife coating, die coating, lip coating, roll coating, curtain coating, bar coating, gravure coating, flexo coating, dip coating, spray coating , Spin coating and the like.

  As the substrate, for example, a plastic film such as a polyester film, a polyethylene film, a polypropylene film, or a polyimide film, a film obtained by releasing the plastic film (hereinafter referred to as a release film), or the like can be used. Furthermore, metals such as aluminum, copper, stainless steel, and beryllium copper, and foils of these alloys can be used as a substrate.

  The thickness of the heat conductive layer can be appropriately determined according to the application, but it exists between a heat source and a heat sink, such as an adhesive sheet or an adhesive sheet, and is used to release heat. From the viewpoint of thermal conductivity and various physical properties, the thickness is usually 10 to 200 μm, preferably 30 to 150 μm. In addition, when used as a package that does not collect heat from a heat source, such as a housing, the thickness may be 200 μm or more, and in some cases, about 1 mm in view of strength and the like.

Subsequently, another base material is superimposed on the surface of the heat conductive layer of the heat conductive sheet, and the heat conductive member, which is the precursor member, is heated and pressed by heating, thereby increasing the heat conductivity of the heat conductive sheet. (I).
When the thermally conductive resin composition (G) is applied to the release film and dried, another release film is layered on the surface of the heat conductive layer and pressed under heat to be sandwiched between the two release films. The obtained sheet-like heat conductive member (I) can be obtained, and the release film can be peeled off to isolate the sheet-like heat conductive member (I). Alternatively, another base material other than the release film can be stacked on the surface of the heat conductive layer, and pressure-pressed under heating to obtain the heat conductive member (I).

  The pressure press treatment is not particularly limited, and a known press processor can be used. Moreover, although the temperature at the time of a press can be selected suitably, if it uses as a thermosetting adhesive sheet, it is desirable to heat above the temperature which the thermosetting of binder resin (E) occurs. If necessary, it can be pressed under vacuum.

  Although the pressure at the time of a press can be suitably selected if the pressure which can deform | transform the easily deformable aggregate (D) can be applied, it is preferable that it is 1 MPa or more.

  Moreover, a highly heat-conductive molding can also be obtained by molding the heat conductive resin composition (G) containing no solvent (F) under pressure.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, a following example does not restrict | limit the right range of this invention at all. In the examples, “parts”, “%”, and “vol%” represent “parts by weight”, “wt%”, and “volume%”, respectively, and Mw represents a weight average molecular weight.
The average primary particle size, circularity, average particle size, average compressive force required for a compression deformation rate of 10%, resistance to collapse, and the like were determined as follows.

<Average primary particle size>
It measured using the particle size distribution meter master sizer 2000 by Malvern Instruments. The measurement conditions were a dry unit and an air pressure of 2.5 bar, and the feed rate was optimized by the sample.

<Circularity>
The average circularity of the particles was measured using a flow type particle image analyzer FPIA-1000 manufactured by Toa Medical Electronics Co., Ltd. Specifically, about 5 mg of particles to be measured are dispersed in 10 ml of toluene to prepare a dispersion, and the dispersion is irradiated with ultrasonic waves (20 kHz, 50 W) for 5 minutes. The dispersion concentration is 5,000 to 20,000 / Measurement was performed with the above apparatus as μl, and the circularity of the circle-equivalent diameter particle group was measured to obtain the average circularity.

<Average particle size>
It measured using the particle size distribution meter master sizer 2000 by Malvern Instruments. The measurement conditions were a dry unit and an air pressure of 2.5 bar, and the feed rate was optimized by the sample.

<Average compression force required for 10% compression deformation>
The average compressive force required for a compressive deformation rate of 10% was a random compression tester (manufactured by Shimadzu Corporation, MCT-210), and a load for deforming particles by 10% was randomly selected within the measurement region. It measured about the particle | grains and made it the average value.

<Difficult to collapse: maintenance ratio of average particle diameter after shaking test>
The easily deformable aggregate (D) is put in a glass sample tube so as to have a porosity of 70%, shaken with a shaker for 2 hours, and then the particle size distribution is measured. It was confirmed using 80% or more of the average particle diameter as an index.

<Synthesis example of binder resin>
(Resin synthesis example 1)
Polyester polyol (made by Kuraray Co., Ltd.) obtained from terephthalic acid, adipic acid and 3-methyl-1,5-pentanediol in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube. Kuraray polyol P-1011 ", Mn = 1006) 401.9 parts by weight, 12.7 parts by weight of dimethylolbutanoic acid, 151.0 parts by weight of isophorone diisocyanate, 40.0 parts by weight of toluene, 90 ° C under nitrogen atmosphere, It was made to react for 3 hours, 300.0 weight part of toluene was added to this, and the urethane prepolymer solution which has an isocyanate group was obtained.
Next, 27.8 parts by weight of isophorone diamine, 3.2 parts by weight of di-n-butylamine, 342.0 parts by weight of 2-propanol, and 396.0 parts by weight of toluene have the obtained isocyanate group. 815.1 parts by weight of urethane prepolymer solution was added, reacted at 70 ° C. for 3 hours, diluted with 144.0 parts by weight of toluene and 72.0 parts by weight of 2-propanol, solid content 30%, Mw = 54,000. A solution E-1 of polyurethane polyurea resin having an acid value of 8 mg KOH / g was obtained.

(Resin synthesis example 2)
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, dropping device, introduction tube, and nitrogen introduction tube, 292.1 parts by weight of polycarbonate diol (Kuraray polyol C-2090: manufactured by Kuraray Co., Ltd.), tetrahydrophthalic anhydride (Licacid TH: manufactured by Shin Nippon Rika Co., Ltd.) 44.9 parts by weight and 350.0 parts by weight of toluene as a solvent were charged, and the mixture was heated to 60 ° C. with stirring in a nitrogen stream, and dissolved uniformly. Subsequently, the flask was heated to 110 ° C. and reacted for 3 hours. Then, after cooling to 40 ° C., 62.9 parts by weight of bisphenol A type epoxy resin (YD-8125: manufactured by Tohto Kasei Co., Ltd.) and 4.0 parts by weight of triphenylphosphine as a catalyst were added, and the temperature was raised to 110 ° C. , Reacted for 8 hours. After cooling to room temperature, the solid content was adjusted to 35% with toluene to obtain a carboxyl group-containing modified ester resin E-2 solution having Mw = 25000.

(Resin synthesis example 3)
A four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel was charged with 98.5 parts by weight of butyl acrylate, 1.5 parts by weight of acrylic acid, and 150.0 parts by weight of ethyl acetate. The mixture was heated to 70 ° C. under substitution, and 0.15 parts by weight of azobisisobutyronitrile was added to initiate polymerization. 0.13 parts by weight of azobisisobutyronitrile was added for another 2 hours from 3 hours after the start of polymerization until 5 hours after every other hour. Thereafter, 150.0 parts by weight of ethyl acetate was added to terminate the polymerization, and an acrylic resin E-3 having a solid content of 25% and Mw = 84000 was obtained.

<Example of easily deformable aggregate (D)>
(Example 1: (D-1))
Alumina particles (“AO-502” manufactured by Admatechs Co., Ltd., average primary particle size: about 1 μm, average circularity: 0.99): 100 parts by weight, 4% by weight aqueous solution of poly (ethyleneimine) with Mw = 1800: 125 parts by weight (solid content: 5 parts by weight) and ion-exchanged water: 25 parts by weight were stirred with a disper at 1000 rpm for 1 hour to obtain a slurry.
This slurry is spray-dried in a mini-spray dryer (“B-290” manufactured by Nihon Büch Co., Ltd.) in an atmosphere of 125 ° C., and the average compressive force required for an average particle size of about 10 μm and a compression deformation rate of 10% is about 0.00. An easily deformable aggregate D-1 having a maintenance rate of 4 mN and an average particle diameter after the shaking test of 95% was obtained.

(Example 2: (D-2))
Alumina particles (“CB-P02” manufactured by Showa Denko KK, average primary particle size: about 2 μm, average circularity: 0.98): 100 parts by weight, 4 wt% aqueous solution of poly (allylamine) with Mw = 5000: 50 wt. Parts (solid content: 2 parts by weight) and ion-exchanged water: 100 parts by weight In the same manner as in Example 1, the average compression force required for an average particle diameter of about 15 μm and a compression deformation rate of 10%: about 0 An easily deformable aggregate D-2 having a maintenance rate of 3 mN and an average particle diameter after the shaking test of 92% was obtained.

(Example 3: (D-3))
Alumina particles (“AO-509” manufactured by Admatechs Co., Ltd., average primary particle size: about 10 μm, average circularity: 0.99): 100 parts, 4 wt% aqueous solution of poly (diallylamine hydrochloride) with Mw = 50000: 12 In the same manner as in Example 1 except that 5 parts by weight (solid content: 0.5 part by weight) and ion-exchanged water: 137.5 parts by weight were used, the average particle size was about 40 μm and the compression deformation rate was 10%. Average compressive force required: about 3.2 mN, maintenance rate of average particle diameter after shaking test: 90% easily deformable aggregate D-3 was obtained.

(Example 4: (D-4))
Aluminum nitride (“H grade” manufactured by Tokuyama Corporation, average primary particle size: about 1 μm, average circularity: 0.97): 100 parts by weight, 4 wt% aqueous solution of poly (N-isopropylacrylamide) with Mw = 10000: 50 Except for using parts by weight (solid content: 2 parts by weight) and ion-exchanged water: 100 parts by weight, the average compressive force required for an average particle size of about 15 μm and a compression deformation rate of 10% is about the same as in Example 1. An easily deformable aggregate D-4 having a maintenance rate of 2 mN and an average particle diameter after the shaking test of 96% was obtained.

(Example 5: (D-5))
Alumina particles (“CB-P05” manufactured by Showa Denko KK, average primary particle size: about 5 μm, average circularity: 0.99): 100 parts by weight, 20% by weight aqueous solution of poly (vinylpyrrolidone) with Mw = 5000: Except for using 25 parts by weight (solid content: 10 parts by weight) and ion-exchanged water: 125 parts by weight, in the same manner as in Example 1, the average compressive force required for an average particle diameter of about 30 μm and a compression deformation rate of 10%: About 1 mN, an easily deformable aggregate D-5 having an average particle diameter maintenance rate after shaking test of 92% was obtained.

(Example 6: (D-6))
Instead of the 4% by weight aqueous solution of poly (ethyleneimine) in Example 1, a 20% by weight toluene solution of polyurethane resin (Toyobo Co., Ltd .: Byron UR-1400): 10 parts by weight (solid content: 2 parts by weight) Used in the same manner as in Example 1 except that 140 parts by weight of toluene was used instead of ion-exchanged water and the spray drying temperature was changed from 125 ° C. to 140 ° C., so that the average particle diameter was about 20 μm and the compression deformation rate was 10%. Average compressive force required: about 0.5 mN, easy-to-deform agglomerate D-6 having an average particle size retention rate after shaking test of 93% was obtained.

(Example 7: (D-7))
After obtaining the same slurry as in Example 1, it was dried with stirring in a high speed mixer ("LFS-2" manufactured by Earth Technica Co., Ltd.) to remove moisture, and the average particle size was about 100 µm, and the compression deformation rate was 10 An easily deformable aggregate D-7 having an average compressive force required for%: about 3 mN and an average particle diameter maintenance rate after shaking test of 98% was obtained.

(Comparative Example 1: (D′-1))
Instead of “CB-P02” in Example 2, alumina particles (“CB-A20S” manufactured by Showa Denko KK, average primary particle size: about 20 μm, average circularity: 0.98, and compression deformation rate of 10% are required. Except for using an average compressive force of about 220 mN), an easily deformable aggregate was obtained using a 4 wt% aqueous solution of poly (allylamine) with Mw = 5000 for the alumina particles in the same manner as in Example 2. However, a product D′-1 that was easily disintegrated and did not form an aggregate was obtained.

(Comparative Example 2: (D′-2))
Although an attempt was made to obtain an easily deformable aggregate in the same manner as in Example 1 except that poly (ethyleneimine) having Mw = 1800 of Example 1 was not used and ion-exchanged water was changed to 150 parts by weight, disintegration was attempted. It was easy to do and the product D'-2 which does not comprise the state of an aggregate was obtained.

(Comparative Example 3: (D′-3))
In the same manner as in Example 1 except that the 4 wt% aqueous solution of poly (ethyleneimine) with Mw = 1800 in Example 1 was 1250 parts by weight (solid content: 50 parts by weight) and the ion-exchanged water was 50 parts by weight, An easily deformable aggregate D′-3 having an average particle diameter of about 20 μm, an average compression force required for a compression deformation ratio of 10%: about 0.8 mN, and an average particle diameter maintenance ratio after a shaking test of 12% was obtained.

(Comparative Example 4: (D′-4))
Instead of the 4 wt% aqueous solution of poly (ethyleneimine) in Comparative Example 3, a silane coupling agent (“KBM-04” manufactured by Shin-Etsu Chemical Co., Ltd.), tetramethoxysilane (10 wt% solution): 20 parts by weight (solid content: 2 The slurry was obtained in the same manner as in Comparative Example 3 except that the ion-exchanged water was changed to 130 parts by weight. The slurry was spray-dried and cured in an atmosphere of 125 ° C., and the average particle size was about 15 μm. An easily compressible agglomerate D′-4 having an average compressive force required for a deformation rate of 10%: about 42 mN and an average particle size after a shaking test of 75% was obtained.

(Comparative Example 5: (D′-5))
A slurry similar to that of Comparative Example 4 was obtained, and the slurry was spray-dried in an atmosphere of 125 ° C., and then sintered at 2100 ° C., which is equal to or higher than the melting point of alumina, and an average required for an average particle size of about 15 μm and a compression deformation rate of 10% An easily deformable agglomerate D′-5 having a compressive force of about 200 mN and an average particle diameter maintenance rate after the shaking test of 98% was obtained.

(Comparative Example 6: (D′-6))
100 parts by weight of alumina particles (manufactured by Sumitomo Chemical Co., Ltd., “AL-33”, average primary particle size: about 12 μm, average circularity: 0.9), epoxy resin composition (manufactured by Japan Epoxy Resin, “Epicoat 1010”) Except for using 2 parts by weight of toluene and 148 parts by weight of toluene, an attempt was made to obtain an easily deformable aggregate in the same manner as in Example 1, but the product D did not easily form agglomerate because it was easily disintegrated. '-6 was obtained.

Abbreviations in Table 1 are shown below.
H ₂ O: ion exchange water

  As shown in Table 1, in order to produce an aggregate, it is necessary to use an organic binder (B) having an average primary particle diameter of the heat conductive particles (A) of 10 μm or less and having nitrogen atoms. It is. Moreover, the solvent (C) should just dissolve an organic binder. Comparative Examples 1, 2, and 6 cannot form an aggregate. Further, as shown in Comparative Example 3, when the amount of the organic binder (B) is too large, the aggregates are further aggregated when shaken, and are deteriorated by impact. In addition, as shown in Comparative Examples 4 and 5, when the Si coupling agent is used as an organic binder or sintered at a melting point of alumina or higher, the thermally conductive particles (A) are firmly bound to each other. When it is made, it turns out that it becomes scarce easily.

<Examples of thermally conductive resin composition (G), thermally conductive member (H), thermally conductive member (I), thermally conductive adhesive sheet>
(Example 8)
37.1 parts by weight of easily deformable aggregate D-1 (average particle size 10 μm) obtained in Example 1 and 30% toluene / 2-propanol of polyurethane polyurea resin E-1 obtained in Resin Synthesis Example 1 Disperse stirring 31.5 parts by weight of the solution and 3.15 parts by weight of 50% MEK solution of bisphenol A type epoxy resin (“Epicoat 1001” manufactured by Japan Epoxy Resin Co., Ltd.), 6.5 parts by weight of 2-propanol After adjusting the viscosity with 25.8 parts by weight of toluene, ultrasonic degassing was performed to obtain a thermally conductive resin composition having a content of easily deformable aggregates of 50 vol%.
The obtained thermally conductive resin composition was applied to a release-treated sheet (a release-treated polyethylene terephthalate film having a thickness of 75 μm) using a comma coater, and dried by heating at 100 ° C. for 2 minutes. A heat conductive member (H) having a thickness of 50 μm was obtained. The thermal conductivity obtained by the method described later was 3 (W / m · K).
The thermally conductive member (H) is pressed at 150 ° C. and 2 MPa for 1 hour, whereby the thermally conductive layer has a thickness of 45 μm and a thermal conductivity of 6.6 (W / m · K) ( A thermally conductive adhesive sheet comprising I) was obtained.
Further, the heat-transmitting member (H) from which the release-treated sheet was peeled was sandwiched between a 40 μm copper foil and a 250 μm aluminum plate and pressed at 150 ° C. and 2 MPa for 1 hour. The adhesive force of the sheet | seat calculated | required by the method mentioned later was 18 N / cm.

Example 9
37.1 parts by weight of easily deformable aggregate D-2 (average particle size 15 μm) obtained in Example 2 and 30% toluene / 2-propanol of the polyurethane polyurea resin E-1 obtained in Resin Synthesis Example 1 Disperse stirring 31.5 parts by weight of the solution and 3.15 parts by weight of 50% MEK solution of Epicoat 1031S (manufactured by Japan Epoxy Resin Co., Ltd.) as a curing agent, 6.5 parts by weight of 2-propanol, and 25. After adjusting the viscosity with 8 parts by weight, ultrasonic defoaming was performed to obtain a heat conductive resin composition having a content of easily deformable aggregates of 70 vol%.
The obtained heat conductive resin composition was treated in the same manner as in Example 8 to obtain a heat conductive member (H) having a heat conductive layer thickness of 65 μm and a heat conductivity of 3.0 (W / m · K). Further, pressing was performed in the same manner as in Example 8 to obtain a thermal conductive member (I) having a thermal conductive layer thickness of 60 μm, thermal conductivity of 5.8 (W / m · K), and adhesive strength of 20 N / cm. Obtained.

(Example 10)
32.4 parts by weight of easily deformable aggregate D-3 (average particle size 40 μm) obtained in Example 3 and 30% toluene / 2-propanol of the polyurethane polyurea resin E-1 obtained in Resin Synthesis Example 1 Disperse stirring 50.4 parts by weight of the solution and 5.0 parts by weight of 50% MEK solution of Epicoat 1031S (manufactured by Japan Epoxy Resin Co., Ltd.) as a curing agent, 6.5 parts by weight of 2-propanol, and 25.8 of toluene. After adjusting the viscosity with parts by weight, ultrasonic degassing was performed to obtain a thermally conductive resin composition having a content of easily deformable aggregates of 40 vol%.
The obtained heat conductive resin composition was treated in the same manner as in Example 8 to obtain a heat conductive member (H) having a heat conductive layer thickness of 60 μm and a heat conductivity of 2.5 (W / m · K). Further, pressing was performed in the same manner as in Example 8 to obtain a heat conductive member (I) having a heat conductive layer thickness of 55 μm, a heat conductivity of 5.5 (W / m · K), and an adhesive strength of 22 N / cm. Obtained.

(Example 11)
35% toluene solution of 36.0 parts by weight of easily deformable aggregate D-4 (average particle size 15 μm) obtained in Example 4 and carboxyl group-containing modified ester resin E-2 obtained in Resin Synthesis Example 2 36.0 parts by weight and 1 part by weight of Chemite PZ (manufactured by Nippon Shokubai Co., Ltd.) as a heat curing aid are mixed and stirred with a disper. After the adjustment, ultrasonic degassing was performed to obtain a thermally conductive resin composition having a content of easily deformable aggregates of 50 vol%.
A heat conductive member (H) having a heat conductive layer thickness of 50 μm and a heat conductivity of 4.5 (W / m · K) was obtained from the obtained heat conductive resin composition in the same manner as in Example 8. Further, pressing was performed in the same manner as in Example 8 to obtain a heat conductive member (I) having a heat conductive layer thickness of 44 μm, a heat conductivity of 8.3 (W / m · K), and an adhesive force of 15 N / cm. Obtained.

(Example 12)
22.8 parts by weight of easily deformable aggregate D-5 (average particle size 30 μm) obtained in Example 5 and 68.8% 25% ethyl acetate solution of acrylic resin E-3 obtained in Resin Synthesis Example 3 Part by weight and 1.72 parts by weight of Chemite PZ (manufactured by Nippon Shokubai Co., Ltd.) as a heat curing aid are mixed and stirred with a disper. After adjusting the viscosity with 11.0 parts by weight of methyl ethyl ketone (MEK), ultrasonic desorption is performed. It foamed and the heat conductive resin composition of 25 vol% of content rate of an easily deformable aggregate was obtained.
A heat conductive member (H) having a heat conductive layer thickness of 50 μm and a heat conductivity of 1.8 (W / m · K) was obtained from the obtained heat conductive resin composition in the same manner as in Example 8. Further, pressing was performed in the same manner as in Example 8 to obtain a heat conductive member (I) having a heat conductive layer thickness of 45 μm, a heat conductivity of 3.1 (W / m · K), and an adhesive force of 16 N / cm. Obtained.

(Example 13)
12. 38.3 parts by weight of easily deformable aggregate D-6 (average particle size 20 μm) obtained in Example 6 and aqueous emulsion resin (Polysol AX-590, manufactured by Showa Denko KK, solid content 49%) 8 parts by weight was mixed and stirred with a disper, and after adjusting the viscosity with 48.0 parts by weight of water, ultrasonically degassed to obtain a thermally conductive resin composition having a content of easily deformable aggregates of 60 vol%. .
A heat conductive member (H) having a heat conductive layer thickness of 50 μm and a heat conductivity of 1.8 (W / m · K) was obtained from the obtained heat conductive resin composition in the same manner as in Example 8. Further, pressing was performed in the same manner as in Example 8 to obtain a heat conductive member (I) having a heat conductive layer thickness of 45 μm, a heat conductivity of 3.1 (W / m · K), and an adhesive force of 18 N / cm. Obtained.

(Example 14)
61.6 parts by weight of easily deformable aggregate D-7 (average particle size 100 μm) obtained in Example 7 and 18.7 parts by weight of polyester urethane resin Byron UR6100 (manufactured by Toyobo Co., Ltd.), a curing agent as a curing agent Disperse stir with 0.08 parts by weight of epoxy-based curing agent Tetrad X (Mitsubishi Gas Chemical Co., Ltd.), adjust the viscosity with 20.0 parts by weight of toluene, and then defoam ultrasonically to easily deformable aggregates A heat conductive resin composition having a content of 65 vol% was obtained.
The obtained heat conductive resin composition was treated in the same manner as in Example 8 to obtain a heat conductive member (H) having a heat conductive layer thickness of 110 μm and a heat conductivity of 2.8 (W / m · K). Further, pressing was performed in the same manner as in Example 8 to obtain a heat conductive member (I) having a heat conductive layer thickness of 100 μm, a heat conductivity of 6.5 (W / m · K), and an adhesive force of 16 N / cm. Obtained.

(Comparative Example 7)
36.0 parts by weight of spherical aluminum oxide powder having an average primary particle diameter of 1 μm (manufactured by Admatechs Co., Ltd., AO-502) and 30% toluene / 2- 2 of the polyurethane polyurea resin E-1 obtained in Resin Synthesis Example 1 Disperse stirring 36.0 parts by weight of a propanol solution and 3.6 parts by weight of a 50% MEK solution of bisphenol A type epoxy resin Epicoat 1001 (manufactured by Japan Epoxy Resin Co., Ltd.) as a curing agent, 2-propanol 5.7 After adjusting the viscosity with parts by weight and 22.7 parts by weight of toluene, ultrasonic degassing was performed to obtain a resin composition with an aluminum oxide content of 50 vol%.
The obtained resin composition was applied to a release-treated sheet (a release-treated polyethylene terephthalate film having a thickness of 75 μm) using a comma coater, dried by heating at 100 ° C. for 2 minutes, and the thickness of the heat conductive layer was 50 μm. A thermal conductive member (H) having a thermal conductivity of 0.5 (W / m · K) was obtained.
Further, the release treatment sheet was stacked on this coating layer and pressed at 150 ° C. and 2 MPa for 1 hour to obtain a sheet having a thickness of 45 μm. The thermal conductivity of this sheet was as low as 0.8 (W / m · K).
Further, the heat-transmitting member (H) from which the release-treated sheet was peeled was sandwiched between a 40 μm copper foil and a 250 μm aluminum plate and pressed at 150 ° C. and 2 MPa for 1 hour. The obtained sample had an adhesive strength of 16 N / cm.

(Comparative Example 8)
36.0 parts by weight of spherical aluminum oxide powder (CB-A20S, manufactured by Showa Denko KK) having an average primary particle diameter of 20 μm, and 30% toluene / 2--2- of the polyurethane polyurea resin E-1 obtained in Resin Synthesis Example 1 Disperse stirring 36.0 parts by weight of a propanol solution and 3.6 parts by weight of a 50% MEK solution of bisphenol A type epoxy resin Epicoat 1001 (manufactured by Japan Epoxy Resin Co., Ltd.) as a curing agent, 2-propanol 5.7 After adjusting the viscosity with parts by weight and 22.7 parts by weight of toluene, ultrasonic degassing was performed to obtain a resin composition with an aluminum oxide content of 50 vol%.
In the same manner as in Comparative Example 7, the obtained resin composition was used to obtain a heat conductive member (H) having a heat conductive layer thickness of 50 μm and a heat conductivity of 0.4 (W / m · K). The sheet was pressed in the same manner as in Comparative Example 7 to obtain a sheet having a thickness of 45 μm, a thermal conductivity of 0.7 (W / m · K), and an adhesive strength of 15 N / cm.

(Comparative Example 9)
Aggregate D′-3 (average particle diameter: 20 μm) obtained in Comparative Example 3 (38.3 parts by weight) and polyurethane polyurea resin E-1 obtained in Resin Synthesis Example 1 in 30% toluene / 2-propanol solution 27 Disperse stirring 0.0 part by weight and 2.7 parts by weight of 50% MEK solution of bisphenol A type epoxy resin Epicoat 1001 (manufactured by Japan Epoxy Resin Co., Ltd.) as a curing agent, 7.0 parts by weight of 2-propanol, After adjusting the viscosity with 28.0 parts by weight of toluene, ultrasonic degassing was performed to obtain a resin composition having an aggregate content of 60 vol%.
In the same manner as in Comparative Example 7, the obtained resin composition was used to obtain a heat conductive member (H) having a heat conductive layer thickness of 60 μm and a heat conductivity of 0.3 (W / m · K). The sheet was pressed in the same manner as in Comparative Example 7 to obtain a sheet having a thickness of 50 μm, a thermal conductivity of 0.4 (W / m · K), and an adhesive strength of 15 N / cm.

(Comparative Example 10)
Aggregate D′-4 (average particle size 15 μm) 38.3 parts by weight obtained in Comparative Example 4 and 30% toluene / 2-propanol solution 27 of polyurethane polyurea resin E-1 obtained in Resin Synthesis Example 1 Disperse stirring 0.0 part by weight and 2.7 parts by weight of 50% MEK solution of bisphenol A type epoxy resin Epicoat 1001 (manufactured by Japan Epoxy Resin Co., Ltd.) as a curing agent, 7.0 parts by weight of 2-propanol, After adjusting the viscosity with 28.0 parts by weight of toluene, ultrasonic degassing was performed to obtain a resin composition having an aggregate content of 60 vol%.
In the same manner as in Comparative Example 7, the obtained resin composition was used to obtain a heat conductive member (H) having a heat conductive layer thickness of 60 μm and a heat conductivity of 0.2 (W / m · K). The sheet was pressed in the same manner as in Comparative Example 7 to obtain a sheet having a thickness of 50 μm, a thermal conductivity of 0.4 (W / m · K), and an adhesive strength of 2 N / cm.
In addition, this sheet had many cracks due to the particles being crushed.

(Comparative Example 11)
38.3 parts by weight of D′-5 (average particle size 15 μm) prepared in Comparative Example 5 and 27.0 parts by weight of 35% toluene solution of carboxyl group-containing modified ester resin E-2 obtained in Resin Synthesis Example 2 Then, 2.7 parts by weight of a 50% MEK solution of bisphenol A type epoxy resin Epicoat 1001 (manufactured by Japan Epoxy Resin Co., Ltd.) as a curing agent was dispersed with stirring, 7.0 parts by weight of 2-propanol, and 28.0 of toluene. After adjusting the viscosity with parts by weight, ultrasonic degassing was performed to obtain a resin composition having a non-aggregate content of 60 vol%.
In the same manner as in Comparative Example 7, the obtained resin composition was used to obtain a heat conductive member (H) having a heat conductive layer thickness of 60 μm and a heat conductivity of 0.7 (W / m · K). The sheet was pressed in the same manner as in Comparative Example 7 to obtain a sheet having a thickness of 50 μm, a thermal conductivity of 0.9 (W / m · K), and an adhesive force of 1 N / cm.
In addition, this sheet had many cracks due to the particles being crushed.

<Evaluation of thermal conductive member and adhesive sheet>
(Measurement method of thermal conductivity)
A sample sample was cut into a 15 mm square, and the sample surface was gold-deposited and coated with carbon spray. Then, the thermal diffusivity in a sample environment at 25 ° C. was measured with a Xenon flash analyzer LFA447 NanoFlash (manufactured by NETZSCH). The specific heat capacity was measured using a high-sensitivity differential scanning calorimeter DSC220C manufactured by SII Nano Technology. Furthermore, the density was calculated using an underwater substitution method.

(Measurement method of adhesive strength)
Adhesive sheet (sample of three layers: Cu foil (40 μm) / thermal conductive member (I) / aluminum plate (250 μm)) having thermal conductive member (I) is applied to TENSILON UCT-1T (made by ORIENTEC) Then, the adhesive force was measured under the conditions of 5 kgf and a pulling speed of 50 mm / min.

Abbreviations in Table 2 are shown below.
Tol: Toluene IPA: 2-propanol MEK: Methyl ethyl ketone

As shown in Table 2, the thermally conductive resin composition (G) containing the easily deformable aggregate (D) of the present invention is obtained by pressing the thermally conductive member (I) excellent in thermal conductivity. provide. As shown in Comparative Examples 7 to 11, a resin composition that does not contain the easily deformable aggregate (D) in the thermally conductive resin composition (G) cannot exhibit sufficient thermal conductivity. Further, as shown in Comparative Example 8, even when the aggregate is broken during the production of the resin composition, since the resin content is large, there is no sufficient heat conduction path, and high heat conductivity cannot be expressed. Furthermore, as shown in Comparative Examples 10 and 11, if an organic binder containing no nitrogen atom is used, sufficient adhesive strength cannot be obtained.

Claims (7)

100 parts by weight of spherical thermally conductive particles (A) having an average primary particle size of 0.1 to 10 μm,
0.1-30 parts by weight of an organic binder (B) having at least one functional group selected from the group consisting of an imino group, an amide group and an amino group,
An easily deformable aggregate (D) having an average particle diameter of 2 to 100 μm and an average compressive force required for a compression deformation rate of 10% of 5 mN or less.
(However, cases (a) and (b) below are excluded.
(A) An easily deformable aggregate comprising 100 parts by weight of alumina particles having an average primary particle diameter of 5 μm and 10 parts by weight of polyvinylpyrrolidone, having an average particle diameter of 40 μm and an average compressive force of 2 mN.
(A) An easily deformable aggregate comprising 100 parts by weight of alumina particles having an average primary particle diameter of 2 μm and 2 parts by weight of a polyurethane resin, having an average particle diameter of 20 μm and an average compressive force of 0.5 mN. ) The easily deformable aggregate (D) according to claim 1 , containing 20 to 90% by volume, 10 to 80% by volume of the binder resin (E), and a solvent (F) for dissolving the binder resin (E). The heat conductive resin composition (G) characterized by the above-mentioned. The heat conductive resin composition (G) according to claim 2 , wherein the organic binder (B) does not dissolve in the solvent (F). The thermally conductive resin composition (G) according to claim 2 or 3, wherein the organic binder (B) is a water-soluble resin and the binder resin (E) is a water-insoluble resin. It claims 2 to 4 or 1 thermal conductivity formed by removing the solvent (F) is a thermally conductive resin composition according (G) in Section member (H).   A heat conductive member (I) obtained by pressurizing the heat conductive member (H) according to claim 5.   The heat conductive adhesive sheet which comprises a peeling film and the heat conductive member (H) of Claim 5, or the heat conductive member (I) of Claim 6.