TW201942239A - Resin composition containing plate-shape alumina, and heat dissipation member - Google Patents

Abstract

A resin composition is provided which contains, as essential components, plate-shape alumina (A) containing silicon as atoms and/or inorganic compounds, and a resin (B). Further, a paint containing said resin composition, a molded body formed by molding said resin composition, and a heat dissipation member containing said molded body are provided. In this resin composition, it is favorably the case that the plate-shape alumina is characterized in that the silicon atoms and/or inorganic silicon compounds are unevenly distributed on the surface of the plate-shape alumina, and the ratio [Si]/[Al] of the silicon concentration to the aluminum concentration, measured with X-ray photoelectric spectroscopy (XPS), is 2.0-50.0%.

Description

Plate-shaped alumina-containing resin composition and heat radiation member

The present invention relates to a resin composition containing a plate-like alumina and a heat radiation member.

As for heat-resistant compounds containing heat-dissipating fillers (compounds) or heat-dissipating adhesive insulating sheets (both heat-dissipating fillers / resin compositions), it is expected that the demand for thermal measures such as electric vehicles will increase in the future. Among them, alumina having high crystallinity has been studied as a filler that can be produced at low cost and has heat dissipation properties.

Among them, a resin composition having both thermal conductivity and fluidity using an alumina filler having an amorphous shape or a spherical shape, that is, having no anisotropic shape has been studied, but there is a combination of excellent fluidity and thermal conductivity (heat dissipation). Still insufficient issues.
[Prior Art Literature]
[Patent Literature]

Japanese Patent Laid-Open No. 2002-146187

[Problems to be Solved by the Invention]
The main object of the present invention is to provide a resin composition capable of obtaining a molded article having more excellent fluidity and heat dissipation.
[Means for solving problems]

The present inventors have made intensive studies in view of the above-mentioned actual situation, focusing on the fact that plate-shaped alumina has superior thermal conductivity compared to alumina having no anisotropic shape, and have made various plate-shaped aluminas. As a result of research on the change of state, it was found that the use of plate-like alumina containing silicon in the form of atomic and / or inorganic compounds, especially plate-like alumina in which silicon is biased to exist on the surface is used as a component of the resin composition. The plate-shaped alumina, which does not contain silicon in the form of atoms and / or inorganic compounds, can specifically solve the problems, and completed the present invention.
[Effect of the invention]

In the present invention, since a plate-like alumina containing silicon in the form of atoms and / or inorganic compounds is used in the resin composition, it has excellent affinity with the resin and can obtain a molded article having excellent thermal conductivity. Extraordinarily significant technical effects.

Hereinafter, the form for implementing this invention is demonstrated in detail.

＜ Plate-shaped alumina (A) ＞
In the present invention, plate-shaped alumina particles containing silicon in the form of atoms and / or inorganic compounds are selectively used.

The plate-shaped alumina (A) of the present invention contains silicon in the form of an atom and / or an inorganic compound, and is a polygonal plate-shaped particle.

The "plate shape" in the present invention means that the aspect ratio obtained by dividing the average particle diameter by the thickness is 2 or more. In addition, in this specification, the "thickness of a plate-like alumina particle" shall be the value measured using the scanning electron microscope (SEM). The "particle diameter of plate-like alumina particles" refers to the arithmetic mean of the maximum length and the minimum length of the distance between two points on the contour line of the plate, and a scanning electron microscope (SEM) is used as the value. Measured value. The value of "average particle diameter" refers to a value measured and calculated from an image photograph (image) obtained by using a scanning electron microscope (SEM) with respect to the particle diameter of an arbitrary 100 plate-like alumina particles. .

In addition, the plate-shaped alumina (A) contains silicon atoms and / or inorganic silicon compounds on the surface of the plate-shaped alumina, and in particular, when the surface partially contains silicon atoms and / or inorganic silicon compounds, and the inside thereof As compared with the case where a silicon atom and / or an inorganic silicon compound is contained, the affinity with the resin (B) is effectively improved in a smaller amount as described above, and therefore, it is preferable. From this viewpoint, as a plate-like alumina, in the analysis by X-ray photoelectron spectroscopy (XPS), it is necessary to detect silicon atoms and / or inorganic silicon compounds. In this XPS measurement, the plate-like alumina surface as a sample is irradiated with X-rays, and the kinetic energy of photoelectrons released from the sample surface is measured, whereby the composition and chemical bonding of elements constituting the sample surface can be measured. Status analysis.

Whether or not silicon atoms and / or inorganic silicon compounds are locally contained on the surface can be confirmed by comparing the results of the XPS surface analysis with the results of elemental analysis of the entire particles by fluorescent X-ray analysis.

As the plate-like alumina (A) of the present invention, it is preferable that the surface thereof contains silicon atoms and / or an inorganic silicon compound locally, but the ratio of the silicon concentration to the aluminum concentration measured by the XPS measurement The plate-shaped alumina with [Si] / [Al] of 2.0% to 50.0% can have a better affinity with the resin (B). The ratio of the silicon concentration to the aluminum concentration obtained by the XPS measurement [Si] The plate-shaped alumina whose [/ Al] is 5.0% to 40.0% can further improve the affinity with the resin (B). The ratio of the silicon concentration to the aluminum concentration obtained by the XPS measurement [Si] / [Al The plate-like alumina having a content of 10% to 30.0% can maximize the affinity with the resin (B). For example, by improving the fluidity of the resin composition containing the plate-like alumina, not only the moldability can be improved, but also the moldability can be improved. It is more preferable to reduce the interface thermal resistance between the resin and the plate-like alumina.

From the same technical viewpoint as above, the plate-shaped alumina (A) is preferably a plate-shaped alumina having a contact angle with water of 30 degrees (°) to 80 degrees.

The plate-like alumina (A) particles preferably have a thickness of 0.01 μm to 5 μm, an average particle diameter of 0.1 μm to 500 μm, and a ratio of the particle diameter to the thickness, that is, an aspect ratio of 2 to 500. The reason is that if the aspect ratio of the plate-like alumina particles is 2 or more, it can have a two-dimensional alignment characteristic, so it is preferable. If the aspect ratio of the plate-like alumina particles is 500 or less, it is obtained by the present invention. The molded body is excellent in mechanical strength. More preferably, the thickness is 0.03 μm to 3 μm, the average particle diameter is 0.5 μm to 100 μm, and the ratio of the particle diameter to the thickness, that is, the aspect ratio is 10 to 300. When the aspect ratio is 10 to 300, the resin composition is preferred because it has high thermal conductivity.

The thickness, average particle size, aspect ratio, and the like of the plate-like alumina (A) of the present invention can be controlled by appropriately selecting the following items: an existing board that does not contain silicon in the form of atoms and / or inorganic compounds as a raw material What kind of particles are selected as the alumina particles; what kind of methods are selected as a means for including silicon in the form of atoms and / or inorganic compounds.

The plate-like alumina (A) of the present invention can be obtained by any manufacturing method as long as it contains silicon in the form of an atom and / or an inorganic compound in the particles. However, when an existing alumina is used and an anisotropic shape having a plate-like shape and containing silicon atoms and / or inorganic silicon compounds is obtained by post-treatment, the production step is deteriorated due to multiple steps in the production process. And poor. For example, from the viewpoint of productivity, it is also preferable to use an existing alumina raw material, to selectively form a plate shape as a shape, and to easily contain silicon atoms and / or inorganic silicon compounds in the oxidation. A method for producing alumina that serves two purposes in aluminum.

That is, when the plate-shaped alumina (A) used in the present invention is obtained, it is preferable to use a combination of molybdenum and a shape control agent in terms of higher aspect ratio, more excellent dispersibility, and more excellent productivity. Obtained by calcining an aluminum compound in the presence. That is, after molybdenum and aluminum compounds react at high temperature to form aluminum molybdate, the aluminum molybdate is further decomposed into alumina and molybdenum oxide at a higher temperature. At this time, molybdenum is introduced into the plate-shaped alumina particles, and This makes it easier to obtain plate-like alumina particles. Molybdenum oxide will sublime, and it can also be recycled and reused. Hereinafter, this manufacturing method is referred to as a flux method. This flux method will be described in detail later.

The shape control agent plays an important role in the growth of plate-like crystals. In the conventional molybdenum oxide flux method, molybdenum oxide selectively adsorbs to the [113] plane of the α crystal of alumina, and it becomes difficult to supply crystal components to the [113] plane, and the [001] plane can be completely suppressed Appearance of polyhedron particles, thus forming a hexagonal two-hammer type base. In the manufacturing method, a shape control agent is used to suppress the selective adsorption of molybdenum oxide as a flux to the [113] plane, thereby forming a densely packed hexagonal crystal with the [001] plane expansion that is the most thermodynamically stable. Plate-like morphology of lattice crystal structure. By using molybdenum as a flux, it is possible to more easily form plate-like alumina particles containing molybdenum having a high α crystallinity and an α crystallinity of 90% or more.

With this mechanism, and by effectively using molybdenum oxide, silicon as an additive can be selectively biased to exist on the surface of alumina.

By utilizing molybdenum effectively, the plate-like alumina particles have high α crystallinity and self-shape, so that excellent dispersibility, mechanical strength, and high thermal conductivity can be achieved.

In addition, since the plate-like alumina obtained by the above-mentioned production method contains molybdenum in the particles, the isoelectric point of the sundial potential is shifted to the acid side compared to ordinary alumina, and therefore, it is excellent in dispersibility. In addition, due to the characteristics of molybdenum contained in the plate-shaped alumina particles, it is suitable for use in oxidation reaction catalysts and optical materials.

[Alumina]
"Alumina" is an aluminum oxide and is not particularly limited. For example, it can be transition alumina of various crystal forms such as γ, δ, θ, and κ, or it can also include alumina hydrate in the transition alumina. From the viewpoint of more excellent mechanical strength or thermal conductivity, the α-crystal form is preferred.

[molybdenum]
Molybdenum has a catalyst function and an optical function. In addition, by effectively using molybdenum, plate-like alumina particles having a high aspect ratio and excellent dispersibility can be produced in a production method described later. Furthermore, by effectively using molybdenum, silicon as an additive can be selectively biased on the surface of alumina.

The molybdenum is not particularly limited, and may include not only molybdenum metal, but also molybdenum oxide or partially reduced molybdenum oxide, and molybdenum compounds.

The form of the molybdenum content is not particularly limited, and may be included in the form attached to the surface of the plate-shaped alumina particles, or may be included instead of the form of a part of the aluminum in the crystal structure of alumina, or a combination of these .

The molybdenum content of the plate-shaped alumina particles in the plate-shaped alumina (A) containing a silicon atom and / or an inorganic silicon compound is preferably 10% by mass or less in terms of molybdenum trioxide. The calcination temperature, calcination time, and molybdenum The sublimation speed is adjusted to be 0.001% to 8% by mass, and more preferably 0.01% to 5% by mass. When the content of molybdenum is 10% by mass or less, the α single crystal quality of alumina is improved, so it is preferable.

<Manufacturing method of plate-shaped alumina (A) particle>
The method for producing the plate-like alumina (A) particles is not particularly limited, and a known technique can be suitably applied. From the viewpoint of better control of alumina having a high α crystallinity at a relatively low temperature, it is preferable. It is a manufacturing method applicable by the flux method using molybdenum.

More specifically, a preferred method for producing plate-shaped alumina particles includes a step of firing an aluminum compound in the presence of molybdenum and a shape control agent.

[Calcination step]
The calcination step is a step of calcining an aluminum compound in the presence of molybdenum and a shape control agent.

(Aluminum compound)
The aluminum compound is a raw material of plate-shaped alumina (A) particles, and is not particularly limited as long as it is formed into alumina by heat treatment. For example, aluminum chloride, aluminum sulfate, basic aluminum acetate, aluminum hydroxide, and aluminum hydroxide can be used. Boehmite, boehmite, transition alumina (γ-alumina, δ-alumina, θ-alumina, etc.), α-alumina, mixed alumina with two or more crystalline phases, etc. The physical form such as the shape, particle size, and specific surface area of the aluminum compound as the precursor is not particularly limited.

According to the flux method described in detail below, the shape of the plate-like alumina (A) particles hardly reflects the shape of the aluminum compound as a raw material. Therefore, for example, spherical, amorphous, and Any of vertical and horizontal structures (threads, fibers, tapes, tubes, etc.) and sheets.

Similarly, the particle size of the aluminum compound is hardly reflected in the plate-shaped alumina (A) particles by the flux method described in detail below. Therefore, it is preferable to use a particle size of several nm to several hundred μm. Aluminum compound solid.

The specific surface area of the aluminum compound is also not particularly limited. In order for molybdenum to effectively function, a large specific surface area is preferred. However, by adjusting the calcination conditions or the amount of molybdenum used, it can be used as a raw material at any specific surface area.

(Shape Control Agent)
In order to form the plate-like alumina particles of the present invention, a shape control agent must be used. The shape control agent plays an important role in the plate-like crystal growth of alumina by calcining an alumina compound in the presence of molybdenum.

The shape control agent is not particularly limited as long as it can be brought into contact with the aluminum compound. For example, a composite of a shape control agent with an aluminum compound and a physical mixture, a shape control agent that exists uniformly or locally on the surface or inside of the aluminum compound, and the like can be preferably used.

The shape control agent may be added to the aluminum compound, or may be contained in the aluminum compound as an impurity.

The type of the shape control agent is not particularly limited as long as it can suppress the selective adsorption of molybdenum oxide to the [113] plane of α-alumina and form a plate-like morphology in the presence of molybdenum during high-temperature calcination. It is preferable to use a metal compound other than a molybdenum compound and an aluminum compound in terms of higher aspect ratio, more excellent dispersibility, and more excellent productivity. In the present invention, plate-shaped alumina (A) containing silicon containing atomic and / or inorganic compound forms is the largest feature. Therefore, it is more preferable to use silicon after selectively forming alumina into a plate-like shape. Silicon atoms and / or silicon compounds that also function as the shape control agent when biased on the surface of the alumina in the form of atoms and / or inorganic compounds. As the silicon compound, even if an organic silicon compound is used, during the firing process, the organic component will disappear and become a silicon atom and / or an inorganic silicon compound.

The silicon atom or silicon compound is not particularly limited, and a known one can be used. Specific examples include synthetic silicon compounds such as metallic silicon, organic silane compounds, silicone resins, silicon oxide fine particles, silica gel, mesoporous silica, SiC, and mullite; natural materials such as biosilica Silicon compounds, etc. Among these, it is preferable to use an organic silane compound, a silicone resin, and a silicon oxide fine particle from a viewpoint of compounding and mixing with an aluminum compound more uniformly. Furthermore, the silicon atom or silicon compound may be used alone, or two or more of them may be used in combination.

The shape of silicon or a compound containing a silicon atom is not particularly limited, and for example, a spherical, amorphous, structure (thread, fiber, tape, tube, etc.) having a vertical and horizontal shape, and a sheet can be preferably used.

The use amount of the silicon atom or the silicon compound is not particularly limited, and is preferably 0.0001 mol to 1 mol, and more preferably 0.001 mol to 0.5 mol relative to 1 mol of the aluminum metal in the aluminum compound. When the usage amount of the silicon atom or the silicon compound is within the above range, plate-shaped alumina particles having a high aspect ratio and excellent dispersibility are easily obtained, which is preferable.

(Molybdenum compound)
As described later, the molybdenum compound functions as a flux for α crystal growth of alumina at a relatively low temperature. The molybdenum compound is not particularly limited, and examples thereof include molybdenum oxide and a compound containing an acid anion (MoO _x ^n- ) containing a bond between a molybdenum metal and oxygen.

The compound containing an acid anion (MoO _x ^n- ) is not particularly limited, and examples thereof include molybdic acid, sodium molybdate, potassium molybdate, lithium molybdate, H ₃ PMo ₁₂ O ₄₀ , H ₃ SiMo ₁₂ O ₄₀ , NH ₄ Mo ₇ O ₁₂ , molybdenum disulfide, etc.

The molybdenum compound may contain silicon atoms and / or silicon compounds. In this case, the molybdenum compound containing silicon atoms and / or silicon compounds functions as both a flux and a shape control agent.

Among the molybdenum compounds, molybdenum oxide is preferably used from the viewpoint of cost. The molybdenum compounds may be used alone or in combination of two or more.

The use amount of the molybdenum compound is not particularly limited, and is preferably 0.005 to 3.0 mol, and more preferably 0.01 to 0.7 mol relative to 1 mol of the aluminum metal in the aluminum compound. When the use amount of molybdenum is within the above range, plate-shaped alumina particles having a high aspect ratio and excellent dispersibility are easily obtained, which is preferable.

(Calcined)
As described above, the plate-like alumina (A) particles are preferably obtained by calcining an aluminum compound in the presence of molybdenum and silicon atoms and / or silicon compounds that function as shape control agents. As mentioned above, this manufacturing method is called a co-solvent method. If the aluminum compound is calcined in the presence of molybdenum, the molybdenum and the aluminum compound react at high temperature to form aluminum molybdate, and the aluminum molybdate is further decomposed into alumina and molybdenum oxide at a higher temperature, and the shape The plate-like crystals of α-alumina are grown in the presence of the control agent, whereby plate-like alumina particles having silicon atoms and / or silicon compounds on the surface can be easily obtained. The obtained plate-like alumina particles contained molybdenum in the particles, and the shape of the particles was polygonal plate-like, the thickness was 0.01 μm to 5 μm, the average particle diameter was 0.1 μm to 500 μm, and the ratio of the particle diameter to the thickness was the aspect ratio. It is 2 to 500.

The method of firing is not particularly limited, and it can be performed by a known and commonly used method. If the calcination temperature exceeds 700 ° C, the aluminum compound reacts with molybdenum to form aluminum molybdate. Furthermore, when the calcination temperature is 900 ° C or higher, aluminum molybdate is decomposed, and plate-shaped alumina particles are formed by the action of a shape control agent. In addition, when aluminum molybdate is decomposed into alumina and molybdenum oxide, a molybdenum compound is introduced into alumina particles, and silicon derived from the additive is biased to exist on the surface of the alumina, thereby obtaining plate-like oxidation. Aluminum particles.

In addition, the states of the aluminum compound, the shape control agent, and the molybdenum compound are not particularly limited at the time of firing, as long as the molybdenum compound and the shape control agent are close to the state where they can act on the aluminum compound. Specifically, the molybdenum compound can be simply mixed with a powder of a shape control agent and an aluminum compound; mechanically mixed using a pulverizer or the like; mixed using a mortar or the like, or in a dry state or a wet state the mix of.

The conditions of the calcination temperature are not particularly limited, and can be appropriately determined according to the average particle diameter, aspect ratio, dispersibility, and the like of the plate-like alumina particles of the present invention as the object. In general, the firing temperature is only required to be 900 ° C or higher as the decomposition temperature of aluminum molybdate (Al ₂ (MoO ₄ ) ₃ ).

In general, if the shape of the α-alumina obtained after calcination is to be controlled, high-temperature calcination at about 2000 ° C. or higher, which is close to the melting point of the α-alumina, is required, but the burden on the calciner or In terms of fuel cost, there is a large problem for industrial use.

In the above-mentioned manufacturing method, it can be carried out even at a high temperature exceeding 2000 ° C, and even at a temperature far below the melting point of α-alumina below 1600 ° C, α crystallinity can be formed regardless of the shape of the precursor. Α-alumina having a high plate-like shape having a high aspect ratio is preferred.

According to the above-mentioned preferred manufacturing method for calcination in the presence of molybdenum and a shape control agent, even under conditions of a maximum calcination temperature of 900 ° C to 1600 ° C, high aspect ratio and α crystallinity can be efficiently and cost-effectively performed. It is 90% or more of plate-like alumina particles, more preferably, calcination at a maximum temperature of 920 ° C to 1500 ° C, and most preferably calcination at a maximum temperature of 950 ° C to 1400 ° C.

The firing time is preferably performed by setting the temperature rise time to a predetermined maximum temperature in the range of 15 minutes to 10 hours, and the retention time at the maximum firing temperature in the range of 5 minutes to 30 hours. In order to efficiently form the plate-shaped alumina particles, the calcination holding time is more preferably about 10 minutes to 15 hours.

The calcination environment is not particularly limited as long as the desired effect can be obtained. For example, an oxygen-containing environment such as air or oxygen, or an inert environment such as nitrogen or argon is preferred. In consideration of cost, it is more preferred. Air environment.

The apparatus for calcining is not necessarily limited, and a so-called calcining furnace can be used. The calcining furnace is preferably made of a material that does not react with the sublimed molybdenum oxide, and it is more preferable to use a calcining furnace with high airtightness so as to efficiently use the molybdenum oxide.

[Molybdenum removal step]
As a preferred manufacturing method for sintering the plate-shaped alumina (A) particles in the presence of molybdenum and a shape control agent, the calcination step may further include a molybdenum removal step to remove at least a portion of the molybdenum, if necessary.

As described above, the sublimation of molybdenum is accompanied during the calcination. Therefore, the molybdenum content contained in the plate-shaped alumina (A) particles can be controlled by controlling the calcination time, the calcination temperature, and the like.

Molybdenum can adhere to the surface of the plate-shaped alumina particles. Therefore, when manufacturing a plate-like alumina containing silicon in the form of atomic and / or inorganic compounds, in the case of employing the preferred manufacturing method, as long as the molybdenum is not fully sublimated, the plate-like alumina (A) becomes on the surface Plate-shaped alumina (A) containing a silicon atom and / or an inorganic silicon compound and a molybdenum atom and / or an inorganic molybdenum compound. With this, when molybdenum is detected from the surface of an unknown plate-shaped alumina, it can be concluded that the plate-shaped alumina is produced by a flux method using molybdenum oxide as an inorganic molybdenum compound as a flux. If the molybdenum on the surface of alumina is useless, the molybdenum can be removed by washing with water, an aqueous ammonia solution, an aqueous sodium hydroxide solution, and an acidic aqueous solution.

At this time, the content of molybdenum can be controlled by appropriately changing the concentration, usage amount, washing position, washing time, and the like of the water, ammonia solution, sodium hydroxide solution, and acidic aqueous solution used.

[Organic Compound Layer Formation Step]
In one embodiment, the method for producing plate-shaped alumina (A) particles may further include an organic compound layer forming step. The organic compound layer formation step is performed at a temperature at which the organic compound does not decompose, and is usually performed after the calcination step or after the molybdenum removal step.

The method for forming the organic compound layer is not particularly limited, and a known method can be suitably used. For example, the method of contacting the solution or dispersion liquid containing an organic compound with this plate-shaped alumina particle, and drying is mentioned.

Examples of the organic compound that can be used in the formation of the organic compound layer include an organic silane compound.

Furthermore, by forming an organic compound layer, a well-known and conventional effect which improves the adhesiveness of the interface of a filler and a resin can also be obtained by this invention. Therefore, the mechanical strength (tensile strength, bending strength, etc.), the elasticity coefficient, and the Young's coefficient of a molded object can be improved.

[Organic Silane Compound]
If the plate-shaped alumina used in the present invention contains silicon in the form of an atom and / or an inorganic compound, compared with the plate-shaped alumina which does not contain these, the above-mentioned performance improvement effect is obtained, but it can be further improved. It is a reactant of a plate-shaped alumina containing a silicon atom and / or an inorganic silicon compound and an organic silane compound. Compared with the plate-shaped alumina containing silicon atoms and / or inorganic silicon compounds, the plate-shaped alumina, which is a reaction product of the plate-shaped alumina and the organic silane compound, is based on the silicon atoms and The reaction between the inorganic silicon compound and the organic silane compound can improve the affinity with the resin (B). For example, the fluidity of the resin composition containing plate-shaped alumina is improved, thereby not only improving moldability, but also improving moldability. It is preferable to reduce the interface thermal resistance between the resin and the plate-like alumina.

Examples of the organic silane compound include methyltrimethoxysilane, dimethyldimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, Alkanes having 1 to 22 carbon atoms in alkyl groups such as n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, pentyltrimethoxysilane, and hexyltrimethoxysilane Trimethoxysilane or alkyltrichlorosilane; 3,3,3-trifluoropropyltrimethoxysilane, (tridecyl-1,1,2,2-tetrahydrooctyl) trichlorosilane ; Phenyltrimethoxysilane, phenyltriethoxysilane, p-chloromethylphenyltrimethoxysilane, p-chloromethylphenyltriethoxysilane, etc .; γ-glycidyloxypropyltrimethyl Epoxy silane such as oxysilane, γ-glycidyloxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; γ-aminopropyltriethyl Oxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-amine Propyltrimethoxysilane, γ- Aminosilanes such as propyltriethoxysilane; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane; p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy Vinyl ethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and other vinyl silanes; and epoxy-based, amine-based , Vinyl polymer type silane. The organic silane compound may be contained alone or in combination of two or more.

The organic silane compound may be connected to at least a part or all of the silicon atoms on the surface of the alumina and / or the inorganic silicon compound by a covalent bond by reaction, and it is not only a part of the alumina, but also the entire reactant. Wrapped. As a method for providing the alumina surface, dip coating or chemical vapor deposition (chemical vapor deposition (CVD)) can be used. Among them, the thermal CVD method does not require a vacuum device, and it is relatively easy to confirm a more effective performance improvement. Therefore, it is preferable.

The amount of the organic silane compound used is preferably 20% by mass or less, more preferably 10% by mass to 0.01% by mass based on the total amount of silicon atoms and inorganic silicon compounds contained on the surface of the plate-shaped alumina particles. %. When the usage-amount of an organosilane compound is 20 mass% or less, since the physical property derived from a plate-shaped alumina particle can be easily expressed, it is preferable.

The reaction of the plate-shaped alumina containing silicon atoms and / or inorganic silicon compounds with an organic silane compound can be performed by a known conventional surface modification method of a filler. For example, a spray method using a fluid nozzle, a Dry methods such as agitators, ball mills, and mixers, and wet methods such as aqueous or organic solvent systems. The treatment using a shearing force is desirably performed to such an extent that the plate-like alumina (A) used in the present invention is not damaged.

The temperature in the system of the dry method or the drying temperature after the wet method can be appropriately determined in a region where thermal decomposition does not occur depending on the type of the organic silane compound. For example, in the case of processing with the above-mentioned organosilane compound, a temperature of 80 ° C to 150 ° C is desirable.

The resin composition of the present invention can be prepared by mixing the plate-shaped alumina (A) and the resin (B) used in the present invention as described above.

＜ Resin (B) ＞
The resin (B) used in the present invention may be a polymer, an oligomer, or a monomer, and may be a thermosetting resin, an active energy ray-curable resin, or a thermoplastic resin.

<Thermosetting resin>
The thermosetting resin used in the present invention is a resin that has properties of being substantially insoluble and changeable to insolubility when it is hardened by means such as heating, radiation, and a catalyst. For example, it is a well-known and usual resin used for a molding material. Specific examples include: novolak-type phenol resins such as phenol novolac resins and cresol novolac resins; unmodified phenol resins that are not modified, soluble oils modified by tung oil, linseed oil, etc. Phenolic resins such as phenol resins such as phenol resins; phenol resins such as phenol resins; bisphenol epoxy resins such as bisphenol A epoxy resin and bisphenol F epoxy resins; bisphenol epoxy resins modified with fatty chains Novolac epoxy resins such as varnish epoxy resin, cresol novolac epoxy resin; epoxy resins such as biphenyl epoxy resin and polyalkylene glycol epoxy resin; urea (urea) resin, melamine resin, etc. Triazine ring resins; vinyl resins such as (meth) acrylic resins or vinyl ester resins; unsaturated polyester resins, bismaleimide resins, polyurethane resins, phthalic dienes A propyl resin, a silicone resin, a resin having a benzoxazine ring, a cyanate resin, or the like may be a polymer, an oligomer, or a monomer.

The thermosetting resin can be used together with a curing agent. The curing agent used in this case can be used in a known and customary combination with a thermosetting resin. For example, when the thermosetting resin is an epoxy resin, any compound commonly used as a curing agent may be used, and examples thereof include amine compounds, amidine compounds, acid anhydride compounds, and phenol compounds. Specific examples of the amine-based compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylphosphonium, isophoronediamine, imidazole, and BF3-amine complex Examples of guanidine derivatives include dicyandiamide, and polyamine resins synthesized from the dimer of linolenic acid and ethylenediamine. Examples of acid anhydride compounds include o-benzene. Dicarboxylic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyldic anhydride, hexahydrophthalic anhydride Phthalic anhydride, methylhexahydrophthalic anhydride, and the like. Examples of phenolic compounds include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, and dicyclopentadiene phenol. Molding resin, phenol aralkyl resin (xylok resin), resorcinol novolac resin represented by polyhydric phenol novolac resin synthesized from polyhydroxy compounds and formaldehyde, naphthol aralkyl resin, Hydroxymethylmethane resin, tetrahydroxyphenylethane resin Naphthol novolac resin, naphthol-phenol co-condensation novolac resin, naphthol-cresol co-condensation novolac resin, biphenyl modified phenol resin (polyphenol compound with phenolic core connected by bismethylene), Benzene modified naphthol resin (polynaphthol compound with phenolic core attached to bismethylene), aminotriazine modified phenol resin (polyphenol compound with phenolic core connected via melamine, benzoguanamine, etc.) or A polyphenol compound such as an alkoxy-containing aromatic ring modified novolac resin (a polyphenol compound in which a phenol core and an alkoxy-containing aromatic ring are linked by formaldehyde). These hardeners may be used alone or in combination of two or more.

The blending amount of the thermosetting resin and the curing agent in the resin composition of the present invention is not particularly limited. For example, when the curing resin is an epoxy resin, the obtained cured product has good characteristics. It is preferably used in an amount of 0.7 equivalents to 1.5 equivalents of the active group in the hardener, based on a total of 1 equivalent to the epoxy group of the epoxy resin.

Moreover, you may use a hardening accelerator together with the thermosetting resin in the resin composition of this invention suitably as needed. For example, when the curable resin is an epoxy resin, various types can be used as the hardening accelerator. Examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acid, and amines. Wrong salt, etc.

In addition, if necessary, a curing catalyst may be used in combination with the thermosetting resin of the present invention in a timely manner. Known and commonly used thermal polymerization initiators or active energy ray polymerization initiators may be mentioned.

Examples of additional specific examples of the thermosetting resin include a radical polymerizable resin, an anionic polymerizable resin, and a cation polymerizable resin without using a hardener. Examples of the radical polymerizable resin include:
Radical polymerizable resin; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, ( Second butyl methacrylate, n-pentyl (meth) acrylate, second pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (formyl) Base) isodecyl acrylate, tridecyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearin (meth) acrylate Ester, benzyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, benzene (meth) acrylate Oxyethyl ester, tetrahydrofurfuryl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, α-hydroxymethyl methacrylate, α-hydroxymethyl methacrylate, α-hydroxymethacrylic acid third butyl ester, α-hydroxymethacrylic acid third pentyl ester, etc., and 1,4-dioxaspiro [4,5] dec-2-ylmethacrylic acid, (methyl ) Acrylomethylmorpholine, tetrahydrofurfuryl acrylate, 4- ( (Meth) acryloxymethyl-2-methyl-2-ethyl-1,3-dioxane, 4- (meth) acryloxymethyl-2-methyl-2- Isobutyl-1,3-dioxane, 4- (meth) propenyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxane, 4- ( (Meth) acryloxymethyl-2,2-dimethyl-1,3-dioxane monomer, oligomer, or polymer having a (meth) acrylate-based skeleton; or epoxy Acrylate resin, resin having an oxetane cyclic skeleton, and the like.

＜ Thermoplastic resin ＞
The thermoplastic resin used in the present invention is a known and commonly used resin used in molding materials and the like. Specific examples include polyethylene resins, polypropylene resins, polymethyl methacrylate resins, polyvinyl acetate resins, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, polyvinyl chloride resins, and polyethylene Styrene resin, polyacrylonitrile resin, polyamide resin, polycarbonate resin, polyacetal resin, polyethylene phthalate resin, polyphenylene ether resin, polyphenylene sulfide resin, polyfluorene resin, Ether resin, polyether ether ketone resin, polyallyl resin, thermoplastic polyimide resin, thermoplastic urethane resin, polyamine bismaleimide resin, polyimide resin , Polyether fluorene imine resin, bismaleimide imimine triazine resin, polymethylpentene resin, fluororesin, liquid crystal polymer, olefin-vinyl alcohol copolymer, ionomer resin, polyarylate resin, Acrylonitrile-ethylene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, phenoxy resin, and the like. At least one kind of thermoplastic resin may be selected, and two or more kinds of thermoplastic resins may be used in combination according to the purpose.

When the resin (B) is used in combination with the plate-shaped alumina (A) used in the present invention to form a resin composition, a thermoplastic resin (B) is preferably used. In a molding method such as extrusion molding or injection molding in which a resin component is melted to form a desired shape and cooled to manufacture a member, the affinity with alumina can be further improved, the fluidity improving effect is excellent, and excellent thermal conductivity can also be obtained. Sex.

The resin (B) is more preferably a polyarylene sulfide resin in terms of excellent dimensional stability or heat resistance of a molded article such as a member. Among them, as the resin (B), polyphenylene sulfide resin, which is more difficult to form and has poor affinity with alumina, has excellent fluidity-improving effects due to the affinity of the resin composition at the time of molding, and also has excellent thermal conductivity. So it's best.

The resin composition of the present invention may also contain other formulations as required, and external lubricants, internal lubricants, antioxidants, flame retardants, light stabilizers, ultraviolet absorbers, Glass fiber, carbon fiber and other reinforcing materials, fillers, various coloring agents, etc. In addition, butadiene-based copolymers such as silicone oil, liquid rubber, rubber powder, methyl acrylate-butadiene-styrene copolymer, and methyl methacrylate-butadiene-styrene copolymer can also be used. Low stress reducing agents (stress relievers) such as rubber or silicone compounds.

The resin composition of the present invention can be obtained by mixing plate-shaped alumina (A) with resin (B) and other formulations as necessary. The mixing method is not particularly limited, and the mixing can be performed by a known method.

As a general method when the resin (B) is a thermosetting resin, a predetermined amount of the thermosetting resin is mixed with a plate-shaped alumina (A) used in the present invention by a mixer or the like, if necessary. After the other components are sufficiently mixed, they are kneaded by three rolls or the like to form a liquid composition having fluidity, or a predetermined amount of thermosetting resin is mixed with a plater used in the present invention by a mixer or the like. After the alumina (A) and other components as necessary are sufficiently mixed, they are melt-kneaded with a mixing roll, an extruder, and the like, and then cooled to obtain a solid composition. Regarding the mixing state, when a hardener or a catalyst is prepared, it is sufficient that the hardening resin and these preparations can be sufficiently and uniformly mixed. The plate-shaped alumina (A ) A uniformly dispersed mixture is also obtained.

As a general method when the resin (B) is a thermoplastic resin, for example, various types of mixers such as a tumbler or a Henschel mixer are used to oxidize the thermoplastic resin and the plate-like shape used in the present invention. Aluminium (A) and other components, if necessary, are pre-mixed, using a Banbury mixer, rolls, Brabender, single-shaft kneading extruder, and twin-shaft A method for melt-kneading by a mixer such as a kneading extruder, a kneader, and a mixing roll. The temperature of the melt-kneading is not particularly limited, but is usually in the range of 240 ° C to 320 ° C.

The mixing ratio of the plate-shaped alumina (A) used in the present invention and the non-volatile component of the resin (B) used in the preparation of the resin composition of the present invention is not particularly limited. It is preferably 100 parts by mass, and is preferably selected from the range of 66.7 parts to 900 parts. Of course, when preparing the resin composition of the present invention, it is of course not limited to platy alumina (A), but a needle-shaped, spherical, polyhedral alumina may be used in combination, or it may not contain atoms and / or inorganic compounds. Well-known and commonly used alumina such as silicon plate alumina.

In addition, the content of the plate-shaped alumina (A) in the resin composition of the present invention in the case where only the plate-shaped alumina (A) is used is not particularly limited, and may be determined according to the degree of thermal conductivity required for each application. The content of the plate-shaped alumina (A) used in the present invention is preferably 15 to 90 parts by volume in 100 parts by volume of the resin composition.

When the content of the plate-like alumina (A) used in the present invention is less than 15 parts by volume, the resin cured product or the resin molded product has insufficient thermal conductivity and is therefore not satisfactory. On the other hand, if the content of the plate-like alumina (A) used in the present invention exceeds 90 parts by volume, for example, when a resin composition is used for adhesion between substrates such as a metal, the cured product or the molded product and the The substrate has insufficient adhesive force, warping of electronic parts becomes large, cracks or peeling of electronic parts may occur under cold and heat cycles, or peeling occurs at the adhesion interface, which is not satisfactory. In addition, if the content of the plate-shaped alumina (A) used in the present invention exceeds 90 parts by volume, the viscosity of the resin composition becomes high and the coatability, workability, and the like may decrease, which is not preferable. In order to effectively express the function of the plate-shaped alumina (A) used in the present invention as a thermally conductive filler and obtain high thermal conductivity, it is preferably highly filled with the plate-shaped alumina (A) used in the present invention, and more preferably Use 20 volume parts to 90 volume parts. In the case of a curable resin composition, considering the fluidity, it is more preferable to use 20 to 85 parts by volume.

As the plate-shaped alumina (A) used in the present invention, when preparing a resin composition, it is preferred to use two or more particles having different particle sizes in combination, or use a mixture obtained by mixing these particles in advance to obtain large particles. The plate-shaped alumina (A) used in the present invention packs the plate-shaped alumina (A) used in the present invention with a small particle diameter in the space of the plate-shaped alumina (A). The plate-shaped alumina (A) used is more densely packed than the plate-shaped alumina (A), and thus exhibits a higher thermal conductivity. For example, a plate-shaped alumina (A) used in the present invention having an average particle diameter of 5 μm to 20 μm (large particle diameter) and an average particle diameter of 0.4 μm to 1.0 μm (small particle diameter) used in combination The case of plate-shaped alumina (A) is preferred for the reasons described above. More specifically, the plate-shaped alumina (A) used in the present invention has an average particle diameter of 5 μm to 20 μm (large particle diameter). The plate-shaped alumina (A) used in the present invention having a capacity of 45% to 75% by volume and an average particle diameter of 0.4 μm to 1.0 μm (small particle diameter) is used in a proportion ranging from 25% to 55% by volume. Effects such as a decrease in temperature dependence of thermal conductivity can be obtained.

As the plate-shaped alumina (A) used in the present invention, as described above, not only a silicon atom and / or an inorganic silicon compound, but also a reactant obtained by reacting it with an organic silane compound can be used. In this case, if necessary, a plate-shaped alumina surface modified with a coupling agent different from the organosilane compound, such as a titanate-based and aluminate-based coupling agent, may be used in combination. As described above, the plate-shaped alumina used in the present invention is characterized by containing silicon in the form of atoms and / or inorganic compounds, and according to the findings of the present inventors, even when the organic silane compound as The plate-like alumina of silicon in the form of an inorganic compound is treated, but since there is no silicon atom and / or an inorganic silicon compound as a reaction point with an organic silane compound in the alumina itself, it lacks reactivity and cannot be expected. Degree of functionality. Because of this, the existing slab-like alumina surface lacks reactivity and is inert.

In order to further improve the fluidity of the resin composition or the thermal conductivity of its resin molded product or resin hardened product, the plate-shaped alumina (A) is preferably a plate-shaped alumina containing a silicon atom and / or an inorganic silicon compound and an organic silane compound. In some cases, the use of the plate-shaped alumina (A) used in the present invention, which has been surface-treated with a coupling agent other than the organosilane compound, may be favorable. Specifically, for example, by further surface treatment, the adhesion between the resin (B) in the resin molded article or the resin hardened product and the plate-shaped alumina (A) used in the present invention is further improved, and the resin (B) and In the case where the plate-like alumina (A) used in the present invention reduces the interface thermal resistance and improves the thermal conductivity.

As the plate-shaped alumina (A) used in the present invention, two or more kinds having different particle sizes are prepared as described above, and each is surface-treated with a coupling agent in advance as described above, and then these are used to prepare the present invention In this case, the resin composition is hardened or shaped, and in this case, the obtained hardened or shaped product becomes the one having the best thermal conductivity, and the temperature dependency thereof can be reduced, which is the best in terms of the above aspects.

In order to improve thermal conductivity, other thermally conductive fillers may be used in addition to the alumina (A) used in the present invention. As such a heat conductive filler, a well-known and commonly used metal-based filler, an inorganic compound filler, a carbon-based filler, etc. can be used. Specific examples include metal-based fillers such as silver, copper, aluminum, and iron; alumina, magnesia, beryllium oxide, silicon oxide, boron nitride, aluminum nitride, silicon carbide, boron carbide, and titanium carbide. And other inorganic fillers, carbon fillers such as diamond, black lead, graphite, and carbon fiber. It is also possible to use one or more thermally conductive fillers having different crystal shapes and particle sizes in combination. When heat dissipation is required in applications such as electronic equipment, electrical insulation is often required. Among these fillers, it is preferable to use alumina, magnesium oxide, zinc oxide, beryllium oxide, and oxide selected from the group having high volume resistivity. Thermally conductive fillers in silicon, boron nitride, aluminum nitride, and diamond. As these thermally conductive fillers, those having been surface-treated can also be used. For example, as the inorganic filler, a surface-modified by a silane-based and / or titanate-based coupling agent can be used.

＜ Painting ＞
The resin composition of the present invention can also be used as a coating material. Since the resin composition of the present invention is excellent in thermal conductivity, a coating material containing the resin composition can be preferably used as a heat radiation coating material.
As the coating material of the present invention, the resin composition of the present invention can be used directly as a coating material, or it can be used as a coating material by reducing the viscosity by a diluent, a solvent, or the like.

Examples of the solvent include organic solvents such as methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, toluene, dimethylformamide, methyl isobutyl ketone, methoxypropanol, Cyclohexanone, methyl cellosolve, ethyl diethylene glycol acetate, propylene glycol monomethyl ether acetate, and the like may be selected or appropriately used in accordance with the application.

As the diluent, a liquid organic polymer or a liquid monomer can be used.

The coating method of a coating material is not specifically limited, A well-known and usual method can be used. For example, in the case of directly coating the substrate, the coating method is not particularly limited, and examples thereof include a spray method, a spin coating method, a dipping method, a roll coating method, a doctor blade method, a doctor blade method, a doctor blade method, The curtain coating method, the slit coating method, the screen printing method, the inkjet method, and the like may be appropriately selected according to the application.

＜ Resin molded product ＞
By molding the resin composition of the present invention into a desired shape, a resin molded body suitable for use as a heat radiation member can be obtained. When obtaining a resin molded object, it can be performed by a well-known and usual method.

For example, in the case where the resin (B) of the present invention is a thermosetting resin, the method of curing the thermosetting resin composition such as a general epoxy resin composition may be used. For example, the resin (B) is an epoxy resin. The resin composition and the like can be hardened by heat, and the heating temperature conditions at this time may be appropriately selected according to the type or application of the hardener to be combined, and the heating may be performed at a temperature ranging from room temperature to 250 ° C. In the case of an active energy ray-curable resin, hardening molding can be performed by irradiating active energy rays such as ultraviolet rays or infrared rays.

Moreover, when the resin of this invention is a thermoplastic resin, a molded object can also be formed by a well-known and usual method. For example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, gas-assisted hollow molding method, molding method using adiabatic mold, molding method using rapid heating mold, foaming Forming (including supercritical fluid), injection molding, IMC (in mold coating) forming method, extrusion forming method, sheet forming method, rotary forming method, lamination forming method, press forming method, etc. In addition, a molding method using a hot runner method can also be used. The shape, pattern, color, size, and the like of the molded product are not limited, and may be arbitrarily set according to the use of the molded product.

The resin composition of the present invention can be used as a material for improving the thermal conductivity of the interface between substrates as a so-called thermal interface materials (TIM) that adheres the substrate to the substrate, or a resin hardened material or resin The shape of the molded article is used as a heat radiating member formed by molding itself into a desired shape.

For example, it can be used as an adhesive agent for adhering the heat-dissipating part of an electric or electronic device such as a power module to a heat-dissipating member (such as a metal plate or a heat sink) to exhibit good heat dissipation. The form of the resin composition to be used at this time is not particularly limited. When the resin composition is designed as a liquid or paste, the liquid or paste resin composition is injected into the interface of the adhesive surface to perform adhesion. Just harden it. As for a solid shape, a powder, wafer, or sheet may be placed on the interface of the adhesion surface, and then adhered and hardened.

In addition, the resin composition of the present invention can be used for a resin substrate such as a printed wiring board, and can also be effectively used as a resin heat-dissipating base material.
In addition, the resin composition of the present invention can be used as a heat-dissipating component such as a resin heat sink, and can be effectively used as a heat-dissipating member such as a light emitting diode (LED).
[Example]

Hereinafter, the present invention will be described more specifically with examples, but the present invention is not limited to these examples. In addition, unless otherwise specified, "%" means "mass%".

[Shape analysis of plate-like alumina particles by scanning electron microscope]
The sample was fixed to the sample support with a double-sided tape, and observed using a surface observation device VE-9800 manufactured by Keyence. A representative 100 independent plate-shaped alumina particles were extracted therefrom, the thicknesses and particle diameters thereof were estimated, and an average value was calculated to estimate the thickness, average particle size, and aspect ratio of the plate-shaped alumina particles.

[Composition analysis of plate-like alumina particles by fluorescent X-ray]
About 100 mg of a sample was taken on a filter paper, covered with a polypropylene (PP) film, and subjected to fluorescent X-ray measurement (ZSX100e / Rigaku). Then, the ratio "[Si] / [Al]"% of the silicon (Si) concentration and aluminum (Al) contained in the filler was calculated.

[XPS surface analysis]
Regarding the surface element analysis of the plate-shaped alumina powder, the energy spectrum (Quantera) SXM manufactured by Ulvac-Phi was used. The monochromatic Al-Kα was used as the X-ray source, and the X-ray photoelectron spectrometry (XPS) was performed. : Xray Photoelectron Spectroscopy). By measuring the area with a measurement range of 1000 μm square, an average value of n = 3 measurements was obtained. Then, based on these values, the ratio "[Si] / [Al]"% of the silicon (Si) concentration and aluminum (Al) contained in the plate-shaped alumina was calculated.

[Evaluation of wettability of plate-like alumina]
The contact angle of the plate-shaped alumina with respect to water is measured by the following Washburn method.
On the inner bottom surface of the cylindrical unit with mesh-shaped holes at the bottom, a circular filter paper having an approximately the same inner diameter is provided, and a predetermined amount of plate-shaped alumina powder is filled therein, and then the plate-shaped alumina is filled. The same size filter paper is set on the surface to fix the plate-shaped alumina.
This cylindrical unit was set on a surface tensiometer K100 manufactured by KRUSS, and the permeation rate in n-hexane was measured, and the capillary coefficient was estimated based on the result. Next, the penetration rate of water was measured for the same unit, and the contact angle of the powder was estimated using the capillary coefficient.

[Evaluation of fluidity of resin composition]
The melt flow rate (MFR) of the resin composition was evaluated in accordance with the International Standardization Organization (ISO) 1133: 2005, and the results of the respective evaluations are described in Tables 2 and 4.

[Evaluation of Adhesiveness of Plate Alumina and Resin]
Various formed bodies were fractured, and SEM observation of the fractured surfaces was performed to evaluate "good" or "bad" adhesion. For those with good adhesion, it can be observed that the resin will be damaged by the material and the plate-like alumina surface will be exposed less, and the resin will adhere to the surface. On the other hand, if the adhesion is not good, the interface will be peeled off and the plate-like alumina will be peeled. The surface is exposed.

Synthesis example 1 <manufacturing of plate-like alumina particles>
100 parts by mass of aluminum hydroxide (manufactured by Nippon Light Metal Industries; average particle size 9.4 μm), 0.65 parts by mass of silicon oxide particles (manufactured by Kanto Chemical Co., Ltd.), and 3.44 parts by mass of molybdenum trioxide (TAIYO Mining Corporation Limited (Manufactured by the company) using a mortar to obtain a mixture. The obtained mixture was put into a crucible and calcined at 1100 ° C. for 10 hours using a ceramic electric furnace. After that, it was taken out from the crucible and crushed, and then immersed in a 0.5% ammonia aqueous solution at normal temperature for 30 minutes to perform washing. Then, the coarse particle component was removed by using a sieve with a pore size of 53 μ to obtain Light cyan powder (EF1).

Synthesis Example 2 to Synthesis Example 4 <Production of plate-like alumina particles>
According to the mass parts in Table 1 below, aluminum hydroxide (manufactured by Nippon Light Metal Industries; average particle diameter of 9.4 μm), silicon oxide particles (manufactured by Kanto Chemical Co., Ltd.), and molybdenum trioxide (manufactured by Sun Miner Co., Ltd.) Each light cyan powder (EF2 to EF4) of a plate-like alumina was obtained by mixing in a mortar and performing the same operation as in Synthesis Example 1. These characteristic values are collectively shown in Table 1. These plate-shaped aluminas are plate-shaped aluminas containing molybdenum and silicon oxide on the surface.

The plate-shaped alumina particles of these Synthesis Examples 1 to 4 have the shapes described in Table 1.

[Table 1]

Examples 1 to 4 and Comparative Example 1 <Production of Resin Composition and Molded Body>
As a thermoplastic resin, 7.29 parts by mass of DIC-PPS LR100G (polyphenylene sulfide resin manufactured by DIC Corporation), a plate-shaped alumina containing silicon oxide produced in Synthesis Examples 1 to 4, and As a comparative example, Serath 07070 (a plate-like alumina in which neither silicon atoms nor inorganic silicon compounds were detected) manufactured by Kinsei Matec Co., Ltd. The contact angle of the filler by the infiltration method is 19 °. CF1) 14.42 parts by mass of each of them is uniformly dry-mixed, and melt-kneading is performed at a mixing temperature of 300 ° C and a rotation speed of 100 rpm using a melt-kneading device MC15 manufactured by Xplore. 8.9 g of a polyphenylene sulfide resin composition having a filling rate of a thermally conductive filler of 40% by volume was obtained.
The injection molding machine IM12 manufactured by Xplore was used to obtain the composition obtained by the method at a composition temperature of 320 ° C, a mold temperature of 140 ° C, an injection pressure of 10 bar (bar), and a holding pressure of 11 bar. Each resin composition was injection-molded to obtain a dumbbell-shaped molded body.

[Measurement of thermal conductivity]
A 10 mm × 10 mm test piece (radiating member) was cut out of the manufactured dumbbell-shaped formed body, and a thermal conductivity measuring device (LFA467 HyperFlash, manufactured by NETZSCH) was used to perform a test at 25 ° C. Measurement of thermal diffusivity and specific heat. Next, the density of the heat radiating member was measured by the Archimedes method. The thermal conductivity of the heat radiating member is estimated from the product of the obtained thermal diffusivity, specific heat, and density.

[Table 2]

As can be seen from the comparison between Example 4 and Comparative Example 1, compared with a resin composition using a plate-shaped silicon oxide containing no silicon atoms and inorganic silicon compounds, a plate-shaped oxidation containing molybdenum and containing silicon oxide on the surface is used. The resin composition of aluminum is obviously excellent in affinity with the resin, and a molded article (radiating member) having excellent melt flow rate, thermal conductivity, and adhesion is obtained.

Surface treatment of plate-shaped alumina by thermal CVD method 40 parts by mass of plate-shaped alumina powder containing silicon oxide synthesized in Synthesis Examples 1 to 4 and γ-glycidoxypropyl group In a 5 ml glass container of 2 parts by mass of trimethoxysilane, 100 ml of teflon (Dupont (Dupont) was placed in a state where the plate-shaped alumina and γ-glycidoxypropyltrimethoxysilane were not in direct contact. ) Company's registered trademark) container, teflon (Dupont's registered trademark) container was capped, placed in a stainless steel high pressure reaction container, and heated in a dryer at 150 ° C for 16 hours Thus, surface-treated alumina particles (reaction products ESF1 to ESF4 of a plate-like alumina containing silicon oxide and an organic silane compound) to which a surface-treated layer containing a cured product containing the organic silane compound is uniformly adhered. These characteristic values are collectively shown in Table 3.

[table 3]

40 parts by mass of the plate-shaped alumina powder containing silicon oxide synthesized in Synthesis Example 1 to Synthesis Example 4 and a 5 ml glass container containing 2 parts by mass of γ-aminopropyltrimethoxysilane were placed in this plate. The alumina and γ-aminopropyltrimethoxysilane are not in direct contact with each other. They are placed in the same teflon (registered trademark of Dupont) container as above, and the teflon is teflon. (Dupont company registered trademark) After the container was capped, it was placed in a high-pressure stainless steel reaction container and heated in a dryer at 150 ° C for 16 hours, thereby obtaining a uniformly adhered organic silicon compound containing the organic silane compound. The surface-treated alumina particles of the surface-treated layer of the cured product (ESF5, a reaction product of a plate-like alumina containing silicon oxide and an organic silane compound). The Si concentration of ESF5 by XPS is 12.3%, and the contact angle of the filler is 72 degrees.

The production of the resin composition and the molded body containing the surface-treated plate-shaped alumina was performed in the same manner as described, and after the respective resin composition and the molded body were produced, various physical properties were evaluated, and the results obtained are shown in Table 4.

[Table 4]

<Example 11: Evaluation of physical properties of resin composition and molded article>
14.22 parts of ESF5 and 7.29 parts of resin were blended to prepare the same resin composition and molded body as in Examples 5 to 8. It was confirmed that the fluidity (melt flow rate) of the resin composition was 84 (g / min.), The thermal conductivity of the molded body was 1.7 W / mK, and the adhesiveness with the resin was good.

[Evaluation of the bending strength of the molded body]
The bending strength of the formed bodies produced in Examples 1 to 8 and 11 was measured by the following method.
Instron 5965 universal testing machine manufactured by Instron was used to support a 3-point bending test at a span of 32 mm and a test speed of 2 mm / min. Determination. The measurement results are shown in Table 5.

[table 5]

<Example 9, Example 10, and Comparative Example 2>
A thermosetting resin composition and a molded body are produced in the following procedure.

<Preparation of resin mixture>
Manufactured from 6.0 parts by mass of epoxy resin (DIC); EPICLON HP-4032D; EX-201 (resorcinol diglycidyl ether; Nagase Chemtex) , 1.3 parts by mass of epoxy equivalent 117 g / eq.) And 8.9 parts by mass of a phenoxy resin solution (fluorene-based phenoxy resin manufactured by Osaka Gas Chemical) were mixed to prepare a solid content amount 62% by mass of the resin mixture (R1).

Next, each filler used in Example 1 and Example 5, and Comparative Example 1 was prepared with the composition of Table 6 to produce a thermosetting resin composition. The mixing is performed by using a rotation-to-public conversion mixing device during deployment.

Next, the rod-shaped metal applicator was used to apply the thermosetting resin composition to a single side of a polyethylene terephthalate film having a thickness of 75 μm so that the thickness after drying became 100 μm. The surface of a release film that has been subjected to a release treatment with a silicone compound.

Next, the coated article was put into a dryer at 50 ° C. for 2 minutes, and then put into a dryer at 85 ° C. for 3 minutes to dry. Then, a 38 μm-thick polyparaphenylene was attached to the coated surface. A release film having one surface of an ethylene formate film subjected to a release treatment by a silicone compound.

Next, the pressure of the surface of the sticker was 0.2 MPa, and the sticker was passed between a heat roller heated to 90 ° C and a resin roller at a speed of 1.5 m per minute, thereby obtaining a thickness of 100. A laminated body in which a μm thermally conductive adhesive sheet is sandwiched by the two release films.

The thermally conductive adhesive sheet obtained by removing the release film was allowed to stand in a 200 ° C. environment for 90 minutes to thermally harden it. The obtained cured product was cut into 10 mm squares as a test sample, and a thermal conductivity measurement device (LFA467 HyperFlash, manufactured by NETZSCH) was used to measure the thermal conductivity at 25 ° C. .

The viscosity of the thermosetting resin as an evaluation item in Table 6 was measured using a viscometer TVB-10 manufactured by Toki Sangyo Co., Ltd. at a setting of a rotor M4 and a rotation speed of 100 rpm.

[TABLE 6]

<Each raw material used in the thermosetting resin composition>
DAW45: Alumina manufactured by Denka, with an average particle size of 45 μm
AA04: manufactured by Sumitomo Chemical, average particle size 0.4 μm
AH-154: Made by Ajinomoto Fine-Techno
2P4MHZ-PW: Shikoku Chemical Manufacturing
KBM-4803: Shin-Etsu Chemical Manufacturing

<Example 12 and Comparative Example 4>
A thermosetting resin composition and a molded body are produced in the following procedure.
Weighed 4.47 parts of the heat-dissipating filler EF1 obtained in Synthesis Example 1, 5.37 parts of DPEA-12 (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd., and 0.107 parts of Tokyo Chemical Industry Co., Ltd. reagent diphenyl (2,4,6-trimethylbenzyl) phosphine oxide, 0.054 parts of Perbutyl Z manufactured by Japan Oil Co., Ltd., and mixed to prepare a liquid thermosetting resin composition Thing. This composition was sandwiched in a glass plate and adjusted to a thickness of 200 μ, and then ultraviolet rays of 1,000 mJ / cm ² were irradiated from both surfaces using a UV irradiation device F-6100V manufactured by FUSION. Next, the sample was kept at a constant temperature of 150 ° C. for 1 hour to prepare a molded body of Example 12.
In Comparative Example 4, a hardened product was produced by the same method as in Example 12 and the number of parts prepared using a method other than Serase 07070 manufactured by Kinsei Matec Co., Ltd. in other methods.
The viscosity of the obtained thermosetting resin composition and the thermal conductivity of the molded body were evaluated by the same method as described above. The evaluation results are shown in Table 7.

[TABLE 7]

<Example 13 and Comparative Example 5>
The heat-dissipating liquid composition was produced in the following procedure.
0.79 parts of the heat-dissipating filler EF1 obtained in Synthesis Example 1 and 0.856 parts of silicone oil KF-54 manufactured by Shin-Etsu Chemical Co., Ltd. were weighed and mixed to prepare a liquid resin composition (Example 13) . In Comparative Example 5, a heat-dissipating liquid composition was prepared in the same manner as in Example 13 except that Serase 07070 manufactured by Kinsei Matec Co., Ltd. was used.
[Measurement of thermal conductivity]
The thermally conductive liquid composition of Example 13 and Comparative Example 5 was conducted by using a thermal conductivity measuring device TCM1000 manufactured by Rhesca Co., Ltd. and sandwiching the thermally conductive liquid composition between the copper blocks for evaluation. Determination of thermal conductivity. The viscosity of the heat-dissipating liquid composition was measured by the same method as described above. The above evaluation results are shown in Table 8.

[TABLE 8]

As can be seen from the comparison of Table 2, Table 4, and Table 6, it is obvious that the contact angle of the plate-shaped alumina obtained by using plate-shaped alumina with more silicon oxide content and reacting it with the organosilane compound is higher. As the affinity for the resin is improved, the thermal conductivity of the molded article (radiating member) is further improved.
[Industrial availability]

Since the resin composition of the present invention is excellent in fluidity and heat dissipation, it can be preferably used as a heat dissipation material. In particular, it can be preferably used as a heat radiation member such as a heat radiation paint or a heat radiation adhesive.

no

no

Claims (7)

A resin composition containing plate-shaped alumina (A) and resin (B) as essential components. The plate-shaped alumina (A) contains silicon in the form of an atom and / or an inorganic compound. A resin composition containing plate-shaped alumina (A) and resin (B) as essential components. The plate-shaped alumina (A) contains silicon atoms and / or inorganic silicon compounds, and molybdenum atoms and / or inorganic molybdenum compounds. . The resin composition according to item 1 or item 2 of the patent application scope, wherein the plate-shaped alumina (A) is characterized by the silicon atom and / or the inorganic silicon compound being biased to exist on the surface of the plate-shaped alumina, and is borrowed. Plate-shaped alumina having a ratio [Si] / [Al] of silicon concentration to aluminum concentration measured by X-ray photoelectron spectroscopy (XPS) of 2.0% to 50.0%. The resin composition according to any one of claims 1 to 3, wherein the plate-shaped alumina (A) is a plate-shaped alumina having a contact angle with water of 30 to 80 degrees. The resin composition according to any one of claims 1 to 4, in which the resin (B) is a thermoplastic resin. A formed article is formed by molding the resin composition according to any one of claims 1 to 5 of the scope of patent application. The formed body according to item 6 of the patent application scope, which is a heat dissipation member.