JP6127765B2 - Thermally conductive easily deformable aggregate, thermally conductive resin composition, thermally conductive member, and thermally conductive adhesive sheet - Google Patents

Description

  The present invention relates to a thermally conductive easily 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. In addition to high insulation reliability and downsizing to increase the density of electronic circuits, there is a strong demand for improved heat dissipation to prevent deterioration of electronic devices due to heat generated by higher output of electronic devices. Yes.
In the electronics field, a polymer material is suitably used as an insulating material. Therefore, 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.

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 the fusion integration, huge hard particles are formed.

  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 agglomerated particles obtained by isotropically agglomerating primary particles of scaly boron nitride.
Specifically, after calcining scaly boron nitride at around 1800 ° C., granules formed from pulverized primary particles are fired at 2000 ° C., the porosity is 50% or less, and the average pore diameter is 0. A method for obtaining a secondary aggregate of 0.05 to 3 μm has been 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.

  Patent Document 10 discloses the use of a thermally conductive composite material in which boron nitride particles and carbon fibers are combined.

However, as the demand for heat dissipation increases, conventional thermal conductive particles and granulated bodies thereof cannot sufficiently meet the demand.
Therefore, there has been a demand for a material for imparting thermal conductivity, which can provide the same level of thermal conductivity as before with a smaller amount of use, or can provide higher thermal conductivity with the amount of use as conventional. It was.

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 Special Table 2002-535469

  An object of the present invention is to provide a thermal conductivity-imparting material that can impart the same level of thermal conductivity as before with a smaller amount of use, or that can impart higher thermal conductivity with the amount of level of conventional use. That is.

The present invention relates to an aggregate obtained by agglomerating spherical heat conductive particles and a non-spherical carbon material with an organic binder, which is easily deformed with respect to pressure but hardly collapses.
That is, the present invention relates to 100 parts by weight of spherical heat conductive particles (A) having an average primary particle size of 0.1 to 10 μm, a carbon material (J) other than a sphere, and an organic binder (B) 0. 1 to 30 parts by weight,
The present invention relates to an easily deformable aggregate (D) having an average particle diameter of 2 to 100 μm and an average compression force required for a compression deformation rate of 10% of 5 mN or less.
Moreover, this invention relates to the easily deformable aggregate (D) whose carbon material (J) other than a sphere is at least one of a fibrous carbon material and a plate-shaped carbon material.
The present invention also relates to a heat conduction comprising 20-90% by volume of the easily deformable aggregate (D), 10-80% by volume of the binder resin (E), and a solvent (F) that dissolves the binder resin (E). A functional resin composition comprising:
The easily deformable aggregate (D) is composed of 100 parts by weight of spherical heat conductive particles (A) having an average primary particle size of 0.1 to 10 μm, a carbon material (J) other than a sphere, and an organic binder. (B) It is related with the heat conductive resin composition (G) which is 0.1-30 weight part and whose average particle diameter is 2-100 micrometers and whose average compressive force required for 10% of a compressive deformation rate is 5 mN or less.
Moreover, this invention relates to the heat conductive resin composition (G) characterized by the organic binder (B) not melt | dissolving in the said solvent (F).
The present invention also relates to a heat conductive resin composition (G), wherein the organic binder (B) is a water-soluble resin and the binder resin (E) is a water-insoluble resin.
Moreover, this invention relates to the heat conductive member (H) containing the heat conductive layer by which a solvent (F) is removed from a heat conductive resin composition (G).
Moreover, this invention relates to the heat conductive member (I) formed by pressurizing a heat conductive member (H).
Moreover, this invention consists of a heat conductive member (H) or a heat conductive member (I),
The present invention relates to a thermally conductive adhesive sheet having a release film on at least one surface.
The present invention also relates to a method for producing the easily deformable aggregate (D),
100 parts by mass of thermally conductive particles (A) having an average primary particle size of 0.1 to 10 μm, carbon material (J) other than spherical, 0.1 to 30 parts by mass of organic binder (B), and organic Obtaining a slurry containing a solvent (C) for dissolving the binder (B);

And a step of removing the solvent (C) from the slurry.

The present invention also includes a step of applying a heat conductive resin composition (G) on a substrate to form a coating film,
Removing the solvent (F) from the coating film to form a heat conductive layer;
It is related with the manufacturing method of heat conductive member (I) which has the process of pressurizing the said heat conductive layer.

The easily deformable agglomerates of the present invention impart the same thermal conductivity to the heat conductive member with a smaller amount of use, or provide a higher thermal conductivity with the same amount of the conventional heat conductivity. It can be applied to the sex member. A material for imparting thermal conductivity can be provided.
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 size of 1 μm, thermally conductive particles (A) having an average primary particle size of 10 μm, thermally conductive particles (A) having an average primary particle size of 1 μm, and other than spherical 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 which aggregated the carbon material (J) with the organic binder (B). The SEM photograph of the heat conductive particle (A) whose average primary particle diameter is 1 micrometer. 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 and a carbon material (J) other than a sphere with an organic binder (B). SEM photograph. The SEM photograph of the plane of the thermosetting sheet | seat containing the easily deformable aggregate with an average particle diameter of 10 micrometers which aggregated the heat conductive particle (A) with an average primary particle diameter of 1 micrometer with the organic binder (B). 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.

  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 diameter of 0.1 to 10 μm, a carbon material (J) other than a sphere, and an organic bond. It includes 0.1 to 30 parts by weight of the adhesive (B), has an average particle diameter of 2 to 100 μm, and an 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 compression 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 plane SEM photograph of a thermosetting sheet which is a kind of heat conductive member containing easily deformable aggregates, and FIG. 3b is a plane SEM of a cured product obtained by thermosetting the heat conductive member under pressure. FIG. 3c is a SEM photograph of a cross section of the cured product. 3a, b, and c, it can be confirmed that they are “easy deformable” aggregates.

  The reason why the aggregate (D) of the present invention is excellent in thermal conductivity because it is “easy to deform” and the reason why it is excellent in thermal conductivity because it contains a carbon material other than spherical 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 materials such as carbon black.
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. Of these, aluminum oxide, aluminum nitride, and boron nitride are more preferable from the viewpoint of thermal conductivity. 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”. This circularity is an arbitrary number of particles selected from a photograph of particles taken with an SEM or the like. Can be expressed as (circularity) = 4πS / L2, where S is the circumference and L is the perimeter. 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.

<Carbon material other than spherical (J)>
The carbon material (J) other than the spherical shape has a function of assisting heat conduction between the heat conductive particles (A). By using the thermally conductive particles (A) with a smaller particle diameter in combination with the spherical thermally conductive particles (A), the voids in the aggregate can be reduced, but a carbon material other than the spherical shape is also used in combination. The thermal conductivity is further improved by assisting the thermal conduction between the thermally conductive particles (A).

  The non-spherical carbon material (J) is not particularly limited as long as it is a non-spherical carbon material having thermal conductivity, but plate-like graphite and carbon black, fibrous carbon (carbon fiber, graphite fiber, Vapor growth carbon fiber, carbon nanofiber, and carbon nanotube), graphene, or the like can be used alone or in combination of two or more.

Fibrous and plate-like carbon materials are preferable because a heat conduction path can be efficiently formed between the heat conductive particles (A).
The fibrous carbon material preferably has an average fiber diameter of 5 to 30 nm and an average fiber length of 0.1 to 20 μm.
The plate-like carbon material preferably has an average aspect ratio of 10 to 1000 and an average thickness of 0.1 to 500 nm.

  The easily deformable aggregate (D) of the present invention preferably contains 0.5 to 10 parts by weight of a non-spherical carbon material (J) with respect to 100 parts by weight of the heat conductive particles (A). It is more preferable to contain ~ 5 parts by weight. This is because the heat conduction path can be formed while maintaining the insulating property within the above range.

<Organic binder (B)>
The organic binder (B) in the present invention plays a role of “tethering” for binding the heat conductive particles (A) and the carbon material (J) other than the spherical shape.
The organic binder (B) is not particularly limited, and for example, the molecular weight is not limited as long as it can play the role of “tethering”.
Surfactant, polyether resin, polyurethane resin, (unsaturated) polyester resin, alkyd resin, butyral resin, acetal resin, polyamide resin, (meth) acrylic resin, styrene / (meth) acrylic resin, polystyrene resin, nitrocellulose, Benzylcellulose, cellulose (tri) acetate, casein, shellac, gelatin, gilsonite, rosin, rosin ester, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, Carboxymethylcellulose, carboxymethylethylcellulose, carboxymethylnitrocell , Ethylene / vinyl alcohol resin, 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 Resin, vinyl chloride / vinyl acetate / maleic acid resin, fluorine resin, silicone resin, epoxy resin, phenoxy resin, phenol resin, maleic acid resin, urea resin, melamine resin, benzoguanamine resin, ketone resin, petroleum resin, chlorinated polyolefin resin , Modified chlorinated polyolefin resin, chlorinated polyurethane resin and the like, but are not limited thereto.
An organic binder (B) may be used individually by 1 type, or may be used in mixture of 2 or more types.

The organic binder (B) is preferably insoluble in the solvent (F). The term “insoluble” as used herein means that precipitation is visually confirmed when 1 g of the organic binder (B) is put in 100 g of the solvent (F) and stirred at 25 ° C. for 24 hours.
Since the organic binder (B) plays a role of “bonding” for binding the heat conductive particles, if the organic binder (B) is insoluble in the solvent (F), it is easily deformable in the heat conductive resin composition. This is because the aggregate (D) can maintain the aggregation state.

The organic binder (B) 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 starch, agar, gelatin, polyethylene oxide, polyvinyl alcohol, and polyvinyl pyrrolidone.

Moreover, since the said organic binder (B) also affects the deformability of the easily deformable aggregate (D) obtained, it is preferable that it is non-hardening.
Non-curable means that the organic binder (B) does not self-crosslink at 25 ° C.
In addition, it is preferable not to use the component which functions as a hardening | curing agent with respect to an organic binder (B).

  The easily deformable aggregate (D) of the present invention contains 0.1 to 30 parts by weight of the organic binder (B) with respect to 100 parts by weight of the heat conductive particles (A). It is preferable to contain -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 heat conductive particles (A) and the carbon material (J) other than the sphere is increased, but the heat conductive particles (A) and the carbon material other than the sphere (carbon material ( J) is not preferable because the binder may enter more than necessary in the meantime and may impair the thermal conductivity.

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.).

<Method for producing easily deformable aggregate (D)>
Such an easily deformable aggregate (D) of the present invention includes, for example, 100 parts by weight of spherical heat conductive particles (A) having an average primary particle diameter of 0.1 to 10 μm, and a carbon material other than spherical (J ), 0.1 to 30 parts by weight of the organic binder (B) and the solvent (C) for dissolving the organic binder (B), and then the solvent (C ) Can be obtained.
Alternatively, it can be obtained by mixing 100 parts by weight of the heat conductive particles (A), a carbon material (J) other than a sphere, and 0.1 to 30 parts by weight of the organic binder (B), or heat conductive particles. (A) 0.1 to 30 parts by weight of an organic binder (B) and a solvent (C) for dissolving the organic binder (B) in 100 parts by weight and a carbon material (J) other than a sphere It can also be obtained by removing the solvent (C) after spraying the organic binder solution contained or while spraying.
In order to obtain an easily deformable aggregate (D) having a uniform composition, the thermally conductive particles (A), the carbon material (J) other than the sphere and the organic binder (B) are mixed in the solvent (C). It is preferable that the solvent (C) is removed after passing through a step of mixing in advance to form a slurry.

<Solvent (C)>
The solvent (C) is for dispersing the heat conductive particles (A) and the carbon material (J) other than the spherical shape and dissolving the organic binder (B).
The solvent (C) is not particularly limited as long as it can dissolve the organic binder (B), and can be appropriately selected depending on the type of the organic binder (B). 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 can be appropriately changed according to the solubility of the organic binder (B) and the drying apparatus. .

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, the easily deformable aggregate (D) which is relatively round and has a uniform particle diameter can be obtained with high productivity, and the easily deformable aggregate (D) which is faster in drying rate and more easily deformable can be obtained. Spray drying can be preferably used.
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), thermal conductive member (H), (I)>
The thermally conductive resin composition (G) of the present invention comprises 20 to 90% by volume of the easily deformable aggregate (D) of the present invention, 10 to 80% by volume of a binder resin (E), and a binder resin (E It is preferable to contain the solvent (F) which melt | dissolves.

A thermally conductive resin composition (G) is applied onto a substrate to form a coating film, and the solvent (F) is removed from the coating film to form a thermally conductive layer. H) can be obtained.
Furthermore, the heat conductivity which improved the heat conductivity of the heat conductive member (H) by applying a pressure to the heat conductive member (H), and deforming the easily deformable aggregate (D) contained. A member (thermally conductive member) (I) can be obtained.
For example, using the thermally conductive resin composition (G) to obtain a thermally conductive sheet as the thermally conductive member (H), and applying pressure by sandwiching the thermally conductive sheet between the object to be radiated and the heat radiating member Thus, a thermally conductive sheet with improved thermal conductivity can be obtained as the thermally conductive member (I). This heat conductive sheet can efficiently transmit the heat of the object to be radiated to the heat radiating member.
As the heat conductive member (H), a heat conductive sheet having adhesiveness or tackiness can be obtained. In this case, the article to be radiated and the radiating member can be bonded together at the time of pressurization.

By applying pressure and heat to the thermally conductive resin composition (G) and deforming the easily deformable aggregate (D) contained therein, the sheet-like thermally conductive member (I) can be obtained directly. it can.

The heat conductive member (I) can also be obtained directly by applying pressure to the easily deformable aggregate (D) itself to deform the easily deformable aggregate (D). In this case, the organic binder (B) constituting the easily deformable aggregate (D) also serves as the binder resin (E).
For example, by sandwiching the easily deformable aggregate (D) between the heat dissipation target article and the heat dissipation member and applying pressure to deform the easily deformable aggregate (D), the heat of the heat dissipation target article is efficiently increased. It can be transmitted well to the heat dissipation member.

  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, the heat conductive particles (A) are aggregated. Therefore, since the distance between the particles is close and the heat conduction path is formed in advance, heat conduction can be performed efficiently. Furthermore, carbon materials other than the spherical shape are also disposed in the slightly formed voids, and heat can be transferred with higher efficiency.
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 a thermosetting containing an easily deformable aggregate having an average particle diameter of 10 μm 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). 3B and 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 aggregates are more closely adhered to each other, and more of the thermally conductive particles (A) are present on the surface of the cured product. It can be confirmed that it follows the shape.
Here, although it demonstrated using the thermosetting sheet | seat (FIG. 3 a, b, c) using the easily deformable aggregate which does not contain carbon materials (J) other than a spherical shape, as FIG. 1 and an Example show. When the easily deformable aggregate (D) of the present invention further containing a carbon material (J) other than the spherical shape is used, the same effect can be obtained.
On the other hand, non-aggregated thermally conductive particles (A) as shown in FIG. 4 having the same size as the easily deformable aggregate shown in FIG. Since it does not have, the above changes can hardly be confirmed before and after pressing the thermosetting sheet.
Thus, since the easily deformable aggregate (D) of the present invention is “easy to deform”, it has excellent thermal conductivity. That is, the easily deformable aggregate (D) of the present invention imparts the same thermal conductivity to the heat conductive member with a smaller amount of use, or higher heat with the same amount of the conventional one. Conductivity can be imparted to the thermally conductive member.

The thermal conductivity (W / m · K) of the present invention is the thermal diffusivity (mm ² / s) representing the rate at which heat is conducted in the sample, and the specific heat capacity (J / (g · K)) of the measurement sample. It can be obtained by the following formula multiplied by the density (g / cm ³ ).

Thermal conductivity (W / m · K) = thermal diffusivity (mm ² / s) × specific heat capacity (J / (g · K)) × density (g / cm ³ )

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).

<Binder resin (E)>
As binder resin (E) used when obtaining a heat conductive resin composition, for example,
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, from the viewpoint of flexibility, an epoxy resin is preferably used from the viewpoints of urethane resin and insulation and heat resistance when used as an electronic component.
In addition, it is preferable that the organic binder (B) 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.

A heat conductive resin composition (G) contains an easily deformable aggregate (D), binder resin (E), and a solvent (F). The solvent (F) used is used for uniformly dispersing the easily deformable aggregate (D) and the binder resin (E) in the heat conductive resin composition (G).
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 carbon materials (J) other than the spherical shape may be used in combination with different types and amounts of the carbon material (J) and different organic binders (B).

<Solvent (F)>
The solvent (F) used can dissolve the binder resin (E) and can appropriately select a solvent that does not dissolve the organic binder (B) constituting the easily deformable aggregate (D). is important. When the heat conductive resin composition (G) is obtained, if the solvent (F) that dissolves the organic binder (B) is used, the aggregation state of the easily deformable aggregate (D) cannot be maintained.
For example, when a water-soluble resin such as polyvinyl alcohol or polyvinylpyrrolidone is selected as the organic binder (B), toluene, xylene, or the like is used as the solvent (F) when obtaining the heat conductive resin composition (G). The non-aqueous solvent may be selected.
When a water-insoluble resin such as phenoxy resin or petroleum resin is selected as the organic binder (B), the solvent (F) for obtaining the heat conductive resin composition (G) may be water or alcohol. An aqueous solvent may be selected.
As used herein, “insoluble” means that 1 g of the organic binder (B) is added to 100 g of the solvent (F), stirred at 25 ° C. for 24 hours, and precipitation is confirmed visually.

  At this time, although content of easily deformable aggregate (D) can be suitably selected according to target heat conductivity and a use, in order to obtain high heat conductivity, heat conductive resin composition ( It is preferable that it is 20-90 volume% on the basis of solid content of 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 the content exceeds 90% by volume, the content of the binder resin (E) is relatively reduced, and the formed heat conductive member (H) or the heat conductive member (I) becomes 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 heat conductive particles (A) with respect to the solid content in the heat conductive resin composition (G), carbon material other than spherical (J), organic binder (B), binder resin ( The theoretical value calculated based on the weight ratio and specific gravity of E) is shown.

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 thermally conductive particles that can be used in combination include those exemplified as thermally conductive particles (A) and carbon materials (J) other than spherical.

Moreover, you may add other fillers, such as a flame retardant, to a heat conductive resin composition (G) further as needed.
Although it does not specifically limit as a flame retardant, For example, aluminum hydroxide, magnesium hydroxide, etc. are mentioned.

  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 increasing the insulation reliability at the time of moisture absorption, and a leveling agent. These may use 1 type and can also use multiple types together.

<The manufacturing method of a heat conductive resin composition (G), a heat conductive member (H), (I)>
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, scandex, paint conditioner, sand mill, rake machine, medialess disperser, three rolls, bead mill, etc. Can do.

  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.

The manufacturing method of the heat conductive member (H) of the present invention is:
Applying a thermally conductive resin composition (G) on a substrate to form a coating film;
Removing the solvent (F) from the coating film to form a heat conductive layer.

The method for producing the heat conductive member (I) of the present invention comprises:
Preparing a thermally conductive member (H);
And pressurizing the heat conductive layer.

As the heat conductive members (H) and (I), a heat conductive sheet or the like can be manufactured. A heat conductive sheet may be called a heat conductive film.

Examples of the substrate include plastic films such as polyester film, polyethylene film, polypropylene film, and polyimide film;
and,
A film obtained by releasing the plastic film (hereinafter referred to as a release film);
Examples thereof include metal bodies or metal foils such as aluminum, copper, stainless steel, and beryllium copper.

Examples of the method for applying the thermally conductive resin composition (G) to the substrate include knife coating, die coating, lip coating, roll coating, curtain coating, bar coating, gravure coating, flexographic coating, dip coating, spray coating, and Examples include spin coating.

The thickness of the heat conductive layer can be appropriately determined according to the application.
In applications such as a heat conductive sheet, which is disposed between a heat source and a heat sink and used to release heat, the thickness of the heat conductive layer is usually 10 to 200 μm from the viewpoint of heat conductivity and various physical properties, The thickness is preferably 30 to 150 μm. In addition, in applications such as a housing such as a package in which heat from a heat source is not trapped, the thickness of the heat conductive layer can be set to 200 μm or more, and in some cases, about 1 mm in view of strength and the like. .

After the heat conductive layer (H) is manufactured by forming a heat conductive layer on an arbitrary base material, another arbitrary base material is stacked, and press-pressed under heating, and the heat conductive member (I) is Can be obtained.
At least one of the two substrates can be a release film. In this case, the release film can be peeled off.
When two base materials are used as release films, the two release films are peeled off to isolate the heat conductive layer, which can be used as 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.

  The pressure at the time of pressing can be appropriately selected as long as a pressure capable of deforming the easily deformable aggregate (D) can be applied, but it is preferably 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 “%” represent “parts by weight” and “wt%”, “vol%” represents “volume%”, 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 / The 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.

<Shape of non-spherical carbon material (J)>
The average fiber diameter and average fiber length were obtained by extracting 30 fibrous carbons from an enlarged image (for example, 20,000 times to 100,000 times) of a field emission scanning electron microscope, and measuring the line segments measured as follows: The average value of length was defined as the average fiber diameter, and the average value of fiber length was defined as the average fiber length. Here, the length of the line segment is the normal line of one of the two curves drawn by the contour in the length direction of the image of the fibrous carbon for each of the 30 fibrous carbons. The length of a line segment cut out by a curve.

The average aspect ratio is defined as a value indicating a relationship of average thickness t and Z = X / t, where X is the average particle diameter. The diluted dispersion is applied to a flat substrate (for example, cleaved surface of mica mineral), the solvent is dried, 30 samples are extracted from the enlarged image of the atomic force microscope, and the measured average value is the average particle diameter X (Average length in the longitudinal direction), the average value measured with the height profile was defined as the average thickness t.

<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. The average particle diameter was 80% or more of the average particle diameter.

<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 parts by weight of toluene, and reacted at 90 ° C for 3 hours in a nitrogen atmosphere Then, 300 parts of toluene was added thereto to obtain a urethane prepolymer solution having an isocyanate group. 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 a 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, Mw = 54,000, acid value = 8 mgKOH / g of polyurethane polyurea resin solution E-1 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 solution of carboxyl group-containing modified ester resin E-2 with 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 a solution of acrylic resin E-3 having Mw = 84000 was obtained.

Example 1
100 parts by weight of alumina particles (“AO-502” manufactured by Admatechs Co., Ltd., average primary particle size: about 1 μm, average circularity: 0.99), 4 wt% aqueous solution of polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd. GOHSENOL NL-05 "): 125 parts by weight (solid content: 5 parts by weight), carbon nanotube dispersion (" LB200 "manufactured by Cano Technology, average fiber diameter 11 nm, average fiber length 10 µm): 100 parts by weight (solid content: 5 Parts by weight) and ion-exchanged water: 25 parts by weight were dispersed with an ultrasonic homogenizer 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 7 mN and an average particle diameter after the shaking test of 98% was obtained.

(Example 2)
100 parts by weight of alumina particles (“CB-P02” manufactured by Showa Denko KK, average primary particle size: about 2 μm, average circularity: 0.98), 4 wt% aqueous solution of polyvinyl alcohol: 50 parts by weight (solid content: 2 Parts by weight), carbon nanotube dispersion (“LB200” manufactured by Cano Technology): 40 parts by weight (solid content: 2 parts by weight), and ion-exchanged water: 100 parts by weight. An easily deformable aggregate D-2 having an average particle size of about 20 μm, an average compression force required for a compression deformation rate of 10%: about 0.6 mN, and an average particle size maintenance rate after shaking test of 94% was obtained.

(Example 3)
Alumina particles (“AO-509” manufactured by Admatechs Co., Ltd., average primary particle size: about 10 μm, average circularity: 0.99) 100 parts, 40 wt% dispersant aqueous solution (“BYK-190” manufactured by Big Chemie Co., Ltd.): 1.25 parts by weight (solid content: 0.5 part by weight), carbon nanotube dispersion (“LB200” manufactured by Cano Technology): 10 parts by weight (solid content: 0.5 part by weight), and ion-exchanged water: 137. Except for using 5 parts by weight, in the same manner as in Example 1, an average particle size of about 50 μm, an average compression force required for a compression deformation rate of 10%: about 4.1 mN, an average particle size maintenance rate after a shaking test: 91% of easily deformable aggregate D-3 was obtained.

Example 4
70 parts by weight of alumina particles (“AO-502” manufactured by Admatechs Co., Ltd., average primary particle size: about 1 μm, average circularity: 0.99), alumina particles (“AO-509” manufactured by Admatechs Co., Ltd.), primary average Particle diameter: about 10 μm, average circularity: 0.99) 30 parts by weight, 4 wt% aqueous solution of polyvinyl alcohol: 50 parts by weight (solid content: 2 parts by weight), carbon nanotube dispersion (“LB200” manufactured by Cano Technology) : 40 parts by weight (solid content: 2 parts by weight) and ion-exchanged water: 100 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 1.1 mN, maintenance rate of average particle diameter after shaking test: 96% easily deformable aggregate D-4 was obtained.

(Example 5)
100 parts by weight of aluminum nitride (“H grade” manufactured by Tokuyama Corporation, average primary particle size: about 1 μm, average circularity: 0.97), 4 wt% aqueous solution of the polyvinyl alcohol: 50 parts by weight (solid content: 2 parts by weight) ), Carbon nanotube dispersion (“LB200” manufactured by Cano Technology): 100 parts by weight (solid content: 5 parts by weight) and ion-exchanged water: 100 parts by weight An easily deformable aggregate D-5 having a diameter of about 15 μm, an average compressive force required for a compressive deformation ratio of 10%: about 1.1 mN, and an average particle diameter maintenance ratio after a shaking test of 98% was obtained.

(Example 6)
100 parts by weight of alumina particles (“CB-P05” manufactured by Showa Denko KK, average primary particle size: about 5 μm, average circularity: 0.99), 20% by weight aqueous solution of polyvinylpyrrolidone (“K- manufactured by Nippon Shokubai Co., Ltd.”) 85W "): 25 parts by weight (solid content: 10 parts by weight), carbon nanotube dispersion (" LB200 "manufactured by Cano Technology): 100 parts by weight (solid content: 5 parts by weight), and ion-exchanged water: 125 parts by weight Except for use, in the same manner as in Example 1, an average particle size of about 40 μm, an average compression force required for a compression deformation rate of 10%: about 2.1 mN, an average particle size maintenance rate after a shaking test: 93% Deformable aggregate D-6 was obtained.

(Example 7)
The average particle diameter was about 20 μm, and the compressive deformation rate was 10 in the same manner as in Example 1 except that the 4 wt% aqueous solution of polyvinyl alcohol was 750 parts by weight (solid content: 30 parts by weight) and the ion exchange water was 150 parts by weight. Average compressive force required for%: about 0.8 mN, easily deformable aggregate D-7 having an average particle diameter maintenance rate after shaking test of 99% was obtained.

(Example 8)
100 parts by weight of alumina particles (“ASFP-20” manufactured by Denki Kagaku Kogyo Co., Ltd., average primary particle size: about 0.3 μm, average circularity: 0.99), 4 wt% aqueous solution of polyvinyl alcohol: 50 parts by weight (solid Min: 2 parts by weight), XG Sciences (scale-like graphene powder M grade, average aspect ratio 3000, average thickness 3 nm): 1 part by weight, and ion-exchanged water: 100 parts by weight Thus, an easily deformable aggregate D-8 having an average particle size of about 5 μm, an average compression force required for a compression deformation rate of 10%: about 0.3 mN, and an average particle size maintenance rate after a shaking test of 99% is obtained. It was.

Example 9
100 parts by weight of alumina particles (“AO-502” manufactured by Admatechs Co., Ltd., average primary particle size: about 1 μm, average circularity: 0.99), 20 wt% toluene of polyester resin (Toyobo Co., Ltd .: Byron 200) Solution: 10 parts by weight (solid content: 2 parts by weight), carbon nanotubes (“AMC” manufactured by Ube Industries, Ltd., average fiber diameter 11 nm, average fiber length 2 μm) 3 parts by weight, toluene: 200 parts by weight, spray drying Except that the temperature was changed from 125 ° C. to 140 ° C., the average particle size was about 20 μm, the average compression force required for a compression deformation rate of 10% was about 0.8 mN, and the average particle size after the shaking test was the same as in Example 1. Maintenance rate: 94% easily deformable aggregate D-9 was obtained.

(Comparative Example 1)
Instead of “CB-P02”, alumina particles (“CB-A20S” manufactured by Showa Denko KK, average primary particle size: about 20 μm, average circularity: 0.98, average compression force required for compression deformation rate of 10%: About 220 mN), a 4 wt% aqueous solution of polyvinyl alcohol was used for the alumina particles in the same manner as in Example 2 to obtain easily deformable aggregates. The unsuccessful product D′-10 was obtained.

(Comparative Example 2)
Although the polyvinyl alcohol was not used and ion-exchanged water was used in an amount of 150 parts by weight, an attempt was made to obtain an easily deformable aggregate in the same manner as in Example 1, but it was easy to disintegrate and formed an aggregate state. Product D'-11 was obtained.

(Comparative Example 3)
The average particle diameter was about 20 μm and the compression deformation rate was 10 in the same manner as in Example 1 except that 1250 parts by weight (solid content: 50 parts by weight) of the 4 wt% aqueous solution of polyvinyl alcohol and 50 parts by weight of ion-exchanged water were used. Average compressive force required for%: about 0.8 mN, easily deformable aggregate D′-12 having an average particle diameter maintenance rate after shaking test of 97% was obtained.

(Comparative Example 4)
Instead of the 4 wt% aqueous solution of polyvinyl alcohol, a silane coupling agent ("KBM-04" manufactured by Shin-Etsu Chemical Co., Ltd.), tetramethoxysilane (10 wt% solution): 20 parts by weight (solid content: 2 parts by weight), A slurry is obtained in the same manner as in Example 1 except that the amount of ion-exchanged water is 130 parts by weight. The slurry is spray-dried and cured in an atmosphere of 125 ° C., and an average particle size of about 15 μm and a compression deformation rate of 10% are required. An easily deformable aggregate D′-13 having an average compressive force of about 42 mN and an average particle size retention rate after the shaking test of 75% was obtained.

(Comparative Example 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 aggregate D′-14 having a compressive force of about 200 mN and an average particle diameter retention rate after shaking test of 98% was obtained.

(Comparative Example 6)
A slurry similar to that of Example 3 was obtained, and the slurry was spray-dried in an atmosphere of 125 ° C., and then heated at 800 ° C. above the decomposition temperature of the organic binder to obtain an easily deformable aggregate. Product D′-15 which is easy to be formed and does not form an aggregate is obtained.

(Comparative Example 7)
Instead of “CB-P02”, a plate-like alumina (“Seraph 05025” manufactured by Kinsei Matec Co., Ltd., average circularity: 0.5) was used, and the polyvinyl particles were added to the alumina particles in the same manner as in Example 2. An easily deformable aggregate D ′ having an average particle diameter of about 30 μm, an average compression force required for a compression deformation ratio of 10%: about 15 mN, and an average particle diameter maintenance ratio after a shaking test of 50% using a 4 wt% aqueous solution of alcohol. -16 was obtained.

(Comparative Example 8)
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. '-17 was obtained.

As shown in Table 1, in order to produce an aggregate, the average primary particle diameter of the heat conductive particles (A) is 10 μm or less, and it is necessary to use an organic binder (B). 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. It turns out that it becomes scarce easily.

<Example 101>
37.1 parts by weight of easily deformable aggregate D-1 (average particle size 10 μm) obtained in Example 1 and 25% 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 bisphenol A type epoxy resin (“Epicoat 1001” manufactured by Japan Epoxy Resin Co., Ltd.), 6.5 parts by weight of isopropyl alcohol, toluene After adjusting the viscosity with 25.8 parts by weight, 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-1) having a thickness of 50 μm was obtained. The thermal conductivity obtained by the method described later was 5 (W / m · K).

<Example 102>
The release treatment sheet was stacked on the heat conductive layer of the heat conductive member (H-1) obtained in Example 101, and pressed at 150 ° C. and 2 MPa for 1 hour. The thickness of the heat conductive layer was 45 μm, easily deformable. The content of the aggregate D-1 was 50 vol%, and a thermal conductive member (I-2) having a thermal conductivity of 8.5 (W / m · K) was obtained.

<Example 103>
37.1 parts by weight of easily deformable aggregate D-2 (average particle size 20 μm) obtained in Example 2 and 25% toluene / 2-propanol of polyurethane polyurea resin E-1 obtained in Resin Synthesis Example 1 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 were dispersed with stirring, 6.5 parts by weight of isopropyl alcohol, 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 70 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, dried by heating at 100 ° C. for 2 minutes, and then the thermally conductive layer. The heat-treated member (I-3) having a heat-conductive layer thickness of 60 μm and a heat conductivity of 11 (W / m · K) is obtained. It was.

<Example 104>
32.4 parts by weight of easily deformable aggregate D-3 (average particle size 50 μm) obtained in Example 3 and 25% toluene / 2-propanol of 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 isopropyl alcohol, 25.8 parts by weight of toluene After adjusting the viscosity at the part, ultrasonic defoaming 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 103, and the heat conductive member (I-4) having a heat conductive layer thickness of 60 μm and a heat conductivity of 7 (W / m · K) was obtained. Obtained.

<Example 105>
25% toluene solution of 36.0 parts by weight of easily deformable aggregate D-4 (average particle size 30 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, and the viscosity is adjusted with 5.8 parts by weight of isopropyl alcohol and 23.2 parts by weight of toluene. Then, ultrasonic defoaming was performed to obtain a thermally conductive resin composition having a content of easily deformable aggregates of 50 vol%. In the same manner as in Example 103, the obtained thermally conductive resin composition was subjected to the thermal conductive member (I-5) having a thermal conductive layer thickness of 45 μm and a thermal conductivity of 8.5 (W / m · K). )

<Example 106>
36.0 parts by weight of easily deformable aggregate D-8 (average particle size 5 μm) obtained in Example 8 and 25% toluene / 2-propanol of polyurethane polyurea resin E-1 obtained in Resin Synthesis Example 1 36.0 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.) as a curing agent are dispersed and 6.5 parts by weight of isopropyl alcohol. After adjusting the viscosity with 25.8 parts by weight of toluene, ultrasonic degassing was performed to obtain a thermally conductive resin composition with a content of easily deformable aggregates of anomalous formation aggregates of 50 vol%. In the same manner as in Example 103, a conductive resin composition (I-6) having a thermal conductive layer thickness of 40 μm and a thermal conductivity of 7 (W / m · K) was obtained.

<Example 107>
7.4 parts by weight of easily deformable aggregate D-1 (average particle size 10 μm) obtained in Example 1 and spherical alumina (CB-A20S manufactured by Showa Denko KK) having an average primary particle size of 20 μm 29. 7 parts by weight, 31.5 parts by weight of 25% toluene solution of carboxyl group-containing modified ester resin E-2 obtained in Resin Synthesis Example 2, and bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd.) as a curing agent Disperse stir with 3.2 parts by weight of 50% MEK solution of “Epicoat 1001), adjust viscosity with 0.4 parts by weight of isopropyl alcohol and 1.6 parts by weight of toluene, and then easily defoam by ultrasonic defoaming. A heat conductive resin composition having an agglomerate content of 55 vol% was obtained, and the obtained heat conductive resin composition was treated in the same manner as in Example 103. The thickness of the heat conductive layer was 40 μm and the heat conductivity was 8. 5 ( / M · K) thermal conductivity member (I-7) was obtained.

<Example 108>
19. 1 part by weight of easily deformable aggregate D-2 (average particle size 20 μm) obtained in Example 2 and spherical alumina having an average primary particle size of 10 μm (manufactured by Admatechs Co., Ltd., AO-509) 2 parts by weight, 26.1 parts by weight of a 25% toluene / 2-propanol solution of the polyurethane polyurea resin E-1 obtained in Resin Synthesis Example 1, and Chemite PZ (manufactured by Nippon Shokubai Co., Ltd.) 2 as a thermosetting aid 6 parts by weight of the mixture is disper stirred, and after adjusting the viscosity with 3.3 parts by weight of isopropyl alcohol and 13.2 parts by weight of toluene, ultrasonic degassing is performed to conduct heat conduction with an easily deformable aggregate content of 60 vol%. A functional resin composition was obtained. In the same manner as in Example 103, the obtained heat conductive resin composition was heat-conductive member (I-8) having a heat-conductive layer thickness of 40 μm and a heat conductivity of 8.5 (W / m · K). )

<Example 109>
34.0 parts by weight of the easily deformable aggregate D-2 (average particle size 20 μm) obtained in Example 2 and 64.0% of a 25% ethyl acetate solution of acrylic resin E-3 obtained in Resin Synthesis Example 3 Parts and 0.8 parts by weight of an epoxy curing agent Tetrad X (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a curing agent, and after adjusting the viscosity with 2.8 parts by weight of toluene, ultrasonic degassing A heat conductive resin composition having an easily deformable aggregate content of 35 vol% was obtained. The obtained heat conductive resin composition was uniformly coated on the peeled polyester film and dried to provide an adhesive layer. Next, another peeled polyester film is laminated on the pressure-sensitive adhesive layer side, and the thermal conductive member (H-9) having a thermal conductive layer thickness of 50 μm and a thermal conductivity of 4 (W / m · K). Got.

<Example 110>
56.5 parts by weight of easily deformable aggregate D-5 (average particle size 15 μm) obtained in Example 5 and 43.5 parts by weight of polystyrene resin PSJ polystyrene 679 (manufactured by PS Japan Co., Ltd.) as a thermoplastic resin. The mixture obtained by stirring and mixing was melt-kneaded with a twin-screw extruder set at 200 ° C. to prepare a thermally conductive resin composition having a content of easily deformable aggregates of 25 vol%, and then an injection molding machine (Toshiba Machine). The product was molded using IS-100F, and a heat conductive member (I-10) having a thickness of 1 mm and a heat conductivity of 12 (W / m · K) was obtained.

<Example 111>
61.6 parts by weight of easily deformable aggregate D-6 (average particle size 40 μm) obtained in Example 6 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. In the same manner as in Example 103, the obtained heat conductive resin composition was heat conductive member (I-11) having a heat conductive layer thickness of 100 μm and a heat conductivity of 8.5 (W / m · K). )

<Example 112>
94.0 parts by weight of easily deformable aggregate D-7 (average particle size 20 μm) obtained in Example 7 and 6.0 parts by weight of ethylene-methacrylic acid copolymer were mixed, put into a mold, and removed. After the gas was applied, a load of 3 MPa was applied and the mixture was pressed and hardened at 150 ° C. for 1 hour. The content of the easily deformable aggregate was 80 vol%, the thickness of the heat conductive layer was 500 μm, and the heat conductivity was 8 (W / m · K). A heat conductive member (I-12) was obtained.

<Example 113>
72.0 parts by weight of the easily deformable aggregate D-9 (average particle size 20 μm) obtained in Example 9 and 28.0 parts by weight of the high-density polyethylene resin Hizox 2100J (manufactured by Sumitomo Mitsui Polyolefin Co., Ltd.) were mixed. The mixture is heated and mixed with a kneader, cooled and pulverized, and then extruded with an extruder, and the pellet is thermally conductive with an easily deformable aggregate content of 40 vol% and a thermal conductivity of 7 (W / m · k). Sex member (I-13) was obtained.

<Comparative Example 101>
36.0 parts by weight of spherical aluminum oxide powder (manufactured by Admatechs Co., Ltd., AO-502) having an average primary particle diameter of 1 um, and polyurethane polyurea resin E obtained in Resin Synthesis Example 1
Dispersion of 36.0 parts by weight of 25% toluene / 2-propanol solution of -1 and 3.6 parts by weight of 50% MEK solution of bisphenol A type epoxy resin Epicoat 1001 (Japan Epoxy Resin Co., Ltd.) as a curing agent The mixture was stirred and the viscosity was adjusted with 5.7 parts by weight of isopropyl alcohol and 22.7 parts by weight of toluene, followed by ultrasonic defoaming to obtain a resin composition having an aluminum oxide content of 50 vol%. The obtained resin composition was applied to a release treatment sheet (a release treatment polyethylene terephthalate film having a thickness of 75 μm) using a comma coater, heated and dried at 100 ° C. for 2 minutes, and then the release treatment sheet was applied to the coating layer. The sheet was stacked 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).

<Comparative Example 102>
36.0 parts by weight of spherical aluminum oxide powder (CB-A20S, manufactured by Showa Denko KK) having an average primary particle size of 20 um, and 25% 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, 5.7 weights of isopropyl alcohol After adjusting the viscosity with 22.7 parts by weight of toluene, ultrasonic degassing was performed to obtain a resin composition with an aluminum oxide content of 50 vol%. A sheet having a thickness of 45 μm was obtained from the obtained resin composition in the same manner as in Comparative Example 101. The thermal conductivity of this sheet was as low as 0.7 (W / m · K).

<Comparative Example 103>
Aggregate D′-12 (average particle diameter 20 μm) 38.3 parts by weight obtained in Comparative Example 3 and polyurethane polyurea resin E-1 obtained in Resin Synthesis Example 1 in 25% toluene / 2-propanol solution 27 Disperse stirring 0.0 parts 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 isopropyl alcohol, toluene After adjusting the viscosity with 28.0 parts by weight, ultrasonic degassing was performed to obtain a resin composition having an aggregate content of 60 vol%. A sheet having a thickness of 50 μm was obtained using the obtained resin composition in the same manner as in Comparative Example 101. The thermal conductivity of this sheet was as low as 0.3 (W / m · K).

<Comparative Example 104>
Aggregate D′-13 (average particle size: 15 μm) 38.3 parts by weight obtained in Comparative Example 4 and polyurethane polyurea resin E-1 obtained in Resin Synthesis Example 1 in 25% toluene / 2-propanol solution 27 Disperse stirring 0.0 parts 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 isopropyl alcohol, toluene After adjusting the viscosity with 28.0 parts by weight, ultrasonic degassing was performed to obtain a resin composition having an aggregate content of 60 vol%. A sheet having a thickness of 50 μm was obtained using the obtained resin composition in the same manner as in Comparative Example 101. This sheet had many cracks due to the crushing of the particles, and the thermal conductivity was as low as 0.4 (W / m · K).

<Comparative Example 105>
Aggregate D′-14 (average particle size 15 μm) 38.3 parts by weight obtained in Comparative Example 5 and polyurethane polyurea resin E-1 obtained in Resin Synthesis Example 1 in 25% toluene / 2-propanol solution 27 Disperse stirring 0.0 parts 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 isopropyl alcohol, toluene After adjusting the viscosity with 28.0 parts by weight, ultrasonic degassing was performed to obtain a resin composition having an aggregate content of 60 vol%. A sheet having a thickness of 50 μm was obtained using the obtained resin composition in the same manner as in Comparative Example 101. The surface of this sheet had many irregularities derived from particles, and the thermal conductivity was as low as 0.5 (W / m · K).

<Comparative Example 106>
Aggregate D′-16 (average particle diameter 30 μm) 38.3 parts by weight obtained in Comparative Example 7 and polyurethane polyurea resin E-1 obtained in Resin Synthesis Example 1 in 25% toluene / 2-propanol solution 27 Disperse stirring 0.0 parts 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 isopropyl alcohol, toluene After adjusting the viscosity with 28.0 parts by weight, ultrasonic degassing was performed to obtain a resin composition having an aggregate content of 60 vol%. A sheet having a thickness of 50 μm was obtained using the obtained resin composition in the same manner as in Comparative Example 101. The thermal conductivity of this sheet was as low as 0.3 (W / m · K).

<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.

Only the solvent (F) in Table 2 was added.

As shown in Table 2, the aggregate (D) of the present invention is excellent in thermal conductivity. On the other hand, as shown in Comparative Example 103, since the easily deformable aggregate obtained in Comparative Example 3 contains a large amount of an organic binder having low thermal conductivity, the heat of the thermally conductive member (I) is increased. Low conductivity. Further, as shown in Comparative Examples 104 and 105, the aggregates obtained in Comparative Examples 4 and 5 are poorly deformable and thus have low thermal conductivity. Further, as shown in Comparative Example 106, the aggregate obtained in Comparative Example 7 using plate-like alumina has low thermal conductivity.

Claims (9)

100 parts by weight of spherical heat conductive particles (A) having an average primary particle size of 0.1 to 10 μm, a carbon material (J) other than a sphere, and 0.1 to 30 parts by weight of an organic binder (B) ,including,
An easily deformable aggregate (D) having an average particle diameter of 2 to 100 μm and an average compression force required for a compression deformation rate of 10% of 5 mN or less.   The easily deformable aggregate (D) according to claim 1, wherein the non-spherical carbon material (J) is at least one of a fibrous carbon material and a plate-like carbon material. It is a thermally conductive resin composition containing 20 to 90% by volume of easily deformable aggregate (D), 10 to 80% by volume of binder resin (E), and a solvent (F) for dissolving the binder resin (E). And
The easily deformable aggregate (D) is composed of 100 parts by weight of spherical heat conductive particles (A) having an average primary particle size of 0.1 to 10 μm, a carbon material (J) other than a sphere, and an organic binder. (B) and a 0.1 to 30 parts by weight, an average particle diameter of 2 to 100 m, an average compression force required for the compression deformation ratio of 10% is Ri der less 5 mN,
The dissolved organic binder (B) does not dissolve in the solvent (F),
Thermally conductive resin composition (G). The heat conductive resin composition (G) according to claim 3, wherein the organic binder (B) is a water-soluble resin and the binder resin (E) is a water-insoluble resin. The heat conductive member (H) containing the heat conductive layer by which a solvent (F) is removed from the heat conductive resin composition (G) of Claim 3 or 4 . The heat conductive member (I) formed by pressurizing the heat conductive member (H) according to claim 5 . The heat conductive member (H) according to claim 5 or the heat conductive member (I) according to claim 6 ,
A thermally conductive adhesive sheet having a release film on at least one surface. A method for producing the easily deformable aggregate (D) according to claim 1 or 2,
100 parts by mass of thermally conductive particles (A) having an average primary particle size of 0.1 to 10 μm, carbon material (J) other than spherical, 0.1 to 30 parts by mass of organic binder (B), and organic Obtaining a slurry containing a solvent (C) for dissolving the binder (B);
A process for removing the solvent (C) from the slurry, and a method for producing the easily deformable aggregate (D). Applying a thermally conductive resin composition (G) according to claim 3 or 4 on a substrate to form a coating film;
Removing the solvent (F) from the coating film to form a heat conductive layer;
A method for producing a thermally conductive member (I), comprising a step of pressurizing the thermally conductive layer.