WO2016043146A1 - 熱伝導性組成物及びその製造方法 - Google Patents
熱伝導性組成物及びその製造方法 Download PDFInfo
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Definitions
- the present invention relates to a thermally conductive composition and a method for producing the same. Specifically, the present invention relates to a thermally conductive composition that can control anisotropy, has high transparency, and has high flexibility, and is useful as a sheet, film, coating, and the like, and a method for producing the same.
- thermal conductive materials and heat dissipation materials are one of the important material / technical fields in industry as thermal conductive materials and heat dissipation materials.
- These heat conductive films and sheets generally contain a large amount of a high heat conductive material in order to exhibit a high function.
- the high thermal conductivity material include metallic silicon, alumina, magnesium oxide, aluminum hydroxide, boron nitride, aluminum nitride, and silicon carbide.
- the characteristics as a polymer material such as flexibility and lightness are sacrificed.
- Non-Patent Document 1 In recent years, attempts to utilize cellulose nanofibers as thermally conductive materials have begun (Non-Patent Document 1). It has been reported that high thermal conductivity and transparency can be obtained when a film is composed of cellulose nanofibers and boron nitride (Non-patent Document 2). However, this uses boron nitride particles much larger than cellulose nanofibers, and thermal conductivity is still not sufficient. Some of the present inventors have proposed the production of cellulose nanofibers efficiently (Patent Document 1) and a conductive film made of a water-dispersible polymer in which the cellulose nanofibers are dispersed in a conductive polymer. (Patent Document 2). Although cellulose nanofibers are electrically insulating, it has been proposed that when used in combination with a conductive polymer, the conductivity of the composition is improved.
- the present invention makes use of cellulose nanofibers and inorganic powders having a nanoscale size and thermal conductivity, greatly improving thermal conductivity, and further imparting characteristics such as anisotropy and transparency.
- a thermally conductive composition that can be used and a method for manufacturing the same are provided.
- the thermally conductive composition of the present invention is a thermally conductive composition comprising cellulose nanofibers and fine particles, (A) cellulose nanofibers, and (B) a metal oxide having an average particle diameter of 50 nm or less, and It contains at least one kind of inorganic powder selected from diamond.
- the method for producing a thermally conductive composition of the present invention includes (A) cellulose nanofibers, and (B) at least one inorganic powder selected from metal oxides and diamonds having an average particle size of 50 nm or less, Water or a water / hydrophilic solvent dispersion is added to this to obtain a dispersion, and the heat conductive composition is produced by removing water or water / hydrophilic solvent from the dispersion.
- the composition of the present invention comprises (A) cellulose nanofibers, and (B) at least one inorganic powder selected from metal oxides having a mean particle size of 50 nm or less and diamond, (B) It has high thermal conductivity that cannot be achieved by the component alone. That is, since cellulose nanofibers adsorb component (B) efficiently, even a composition containing only a small amount of fine particles exhibits high thermal conductivity. Furthermore, it can be set as the composition which also contains the polymer matrix of (E) component, and much more excellent thermal conductivity can be exhibited. Furthermore, these compositions can be imparted with properties such as anisotropic thermal conductivity and transparency. Therefore, it can be applied as a heat conductive film or sheet, a coating material laminated on a base material, or the like.
- FIG. 1 shows a photograph (50,000 times) of the composition according to one embodiment of the present invention observed with a scanning electron microscope.
- FIG. 2 shows a photograph (50,000 times) of the composition according to another example of the present invention observed with a scanning electron microscope.
- the fiber diameter of the cellulose nanofiber is several tens of nanometers.
- at least one kind of inorganic powder selected from materials having a fiber diameter close to that of cellulose nanofiber, for example, metal oxide and diamond having an average particle size of component (B) of 50 nm or less unprecedented characteristics I got the idea that there is a high possibility that a material will be made.
- the cellulose nanofiber of component (A) used in the present invention is a fibrillated cellulose fiber.
- the cellulose fiber include plant-derived fibers, fibers separated from animal fibers, and bacterial cellulose. Among these, cellulose fibers separated from plant fibers are preferable.
- Cellulose nanofibers can be obtained by chemically or physically purifying and defibrating such cellulose fibers.
- the average fiber diameter of the cellulose nanofiber is preferably 10 to 500 nm, more preferably 10 to 100 nm, and more preferably 10 to 50 nm.
- the length of the cellulose nanofiber is indefinite, and it looks like a continuous fiber with high branching when viewed with a potential microscope.
- “defibration” refers to making a lump of fibers into discrete fibers, and means dispersing in a liquid. Since cellulose nanofibers adsorb component (B) efficiently, even a composition containing only a small amount of thermally conductive microparticles exhibits high thermal conductivity.
- the method for producing cellulose nanofiber includes a physical production method and a chemical production method.
- the physical production method is a method of defibrating cellulose fibers by performing physical treatment on a raw material containing cellulose fibers.
- the chemical production method is a method for defibrating cellulose fibers by performing a physical treatment after performing chemical treatment (oxidation or the like) on the cellulose raw material to facilitate defibration.
- the physical production method is to defibrate a dispersion of cellulose raw material dispersed in water or the like by applying high shear. Examples of means for applying high shear include a bead mill, a blender type disperser, a high-speed rotation homogenizer, a high-pressure homogenizer, a high-pressure jet treatment, and an ultrasonic disperser.
- the dispersion medium of the dispersion is generally water, but an aqueous organic solvent or a mixed solvent of water and a water-soluble organic solvent can also be used.
- An acid or alkali, an ionic or nonionic dispersant, a surfactant, an inorganic salt, or the like may be added to the dispersion medium.
- a chemical method for defibration includes oxidation treatment.
- An oxidation treatment performed using an N-oxyl compound and an oxidizing agent is preferable.
- the cellulose nanofiber of component (A) is preferably used in the present invention as a dispersion dispersed in water, an aqueous organic solvent, or a mixed solvent of water and a water-soluble organic solvent.
- the concentration of cellulose nanofibers in the dispersion is preferably 0.1 to 10% by mass. If the cellulose nanofiber concentration is lower than this, it is not preferable because it takes time to remove the aqueous solvent when producing the composition of the present invention. If the cellulose nanofiber concentration is higher than this, the viscosity is so high that it is difficult to produce the composition of the present invention, or it tends to be a non-uniform composition, which is not preferable.
- the component (B) used in the present invention is at least one inorganic powder selected from a metal oxide having an average particle size of 50 nm or less and diamond.
- the preferable average particle diameter of a component is 2 nm or more and 50 nm or less.
- Examples of the (B) component metal oxide used in the present invention include aluminum oxide, zinc oxide, zirconium oxide, silicon oxide, iron oxide, titanium oxide and the like. An oxide in which a plurality of metals are mixed may be used. These metal oxides are required to have an average particle size of 50 nm or less. If the average particle size is larger than this, a synergistic effect with the component (A) cannot be exhibited.
- Alumina having an average particle size of 50 nm or less includes ⁇ -alumina and ⁇ -alumina, both of which can be used effectively.
- Silica having an average particle size of 50 nm or less is generally amorphous, and dry silica obtained by oxidizing silicon tetrachloride with an oxyhydrogen flame and wet silica obtained by neutralizing water glass are used. is there. Regardless of the production method, any silica having an average particle size of 50 nm or less can be used in the present invention.
- the diamond of component (B) used in the present invention is required to have an average particle size of 50 nm or less, and such diamond is generally produced by a detonation method (detonation method).
- the metal oxide or diamond used as the component (B) having an average particle diameter of 50 nm or less may be subjected to surface treatment or surface functional group substitution. Even if such surface treatment or surface functional group substitution is carried out, it can be used as the component (B) of the present invention, but in order to exert a synergistic effect with the component (A), it is hydrophilic. It is preferable that it can be dispersed in water.
- the composition of the component (A) and the component (B) is not particularly limited, but the component (A) in the total mass of the component (A) and the component (B) is 5 to 98% by mass, and the component (B) is 2 ⁇ 95% by mass is preferred.
- the mass of the component (B) in the total mass of the component (A) and the component (B) is more preferably 5% by mass to 90% by mass, and the mass of the component (B) is 10% by mass to 80% by mass. It is particularly preferred that When the component (B) is less than 2% by mass or exceeds 95% by mass, the effect of improving the thermal conductivity is hardly exhibited.
- This invention is a composition which has (A) component and (B) component as a main component.
- the “main component” means a component that cannot exhibit the effect of the present invention (thermal conductivity in the present invention) unless the component is contained, and when the composition is 100% by mass, (A) The sum total of a component and (B) component says 5 mass% or more.
- a reducing agent as the component (C).
- the reducing agent include hydrazine and pyrogallol, but other reducing agents can also be used.
- the amount of the reducing agent is not particularly limited, it is preferably used in an amount of 1 to 50% by mass with respect to component (B). The use of a reducing agent is particularly preferable when using the polymer described later.
- the composition of the present invention preferably contains an anionic dispersant as the component (D).
- the anionic dispersant used as component (D) is preferably selected from the group consisting of a carboxyl group, a sulfo group, a phosphate group, or a salt thereof (carboxylate group, sulfonate group, or phosphate group). It is preferable to have at least one kind of group.
- anionic dispersants include pyrophosphoric acid, polyphosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, metaphosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid, hexametaphosphoric acid, polyacrylic acid, polymethacrylic acid, and polyitacon.
- the component (D) used in the present invention includes a polyaniline derivative treated with sulfonic acid or the like. As such a polyaniline derivative, a polymer polymerized after synthesizing the aniline derivative at the monomer stage can also be used.
- the amount of component (D) used is not particularly limited, but it is preferably about 0.05 to 1 times that of component (A).
- a polymer can be used as the component (E).
- the component (E) By using the component (E), it is possible to obtain effects such as improving the flexibility and mechanical strength of the composition, improving the transparency, and improving the adhesion with other materials that come into contact.
- the polymer of component (E) include polyolefins such as polyethylene and polypropylene, chlorinated polyolefins, fluorinated polyolefins, polystyrenes, polyesters, polyamides, polyacetals, polycarbonates, polyethylene glycols, polyethylene oxides, polyacrylic acid, and polyacrylic esters. , Polymethacrylic acid ester, polyvinyl alcohol and the like.
- an epoxy resin a urethane resin, an acrylic resin, a silicone resin, and a precursor thereof that are cured by heating or ultraviolet irradiation after applying and drying the composition of the present invention can also be used.
- These curable polymers can be used either in the form of a resin that finally becomes resinous or in the form of an elastomer.
- (A) component is hydrophilic and (B) component is also often hydrophilic. Therefore, water-soluble polymers and water-dispersible polyamides, polyethylene glycols, polyacrylic acid copolymers, polymethacrylic acid copolymers, polyacrylic acid ester copolymers, polymethacrylic acid ester copolymers, Polyester copolymers, polyvinyl alcohol, and the like are preferable for finely dispersing each component.
- composition of the present invention is not limited depending on whether the component (E) is hydrophilic or hydrophobic.
- One of the features of the present invention is that even a hydrophobic polymer can be used in the composition of the present invention.
- the amount of component (E) used is not limited as long as the effect of the composition of the present invention is maintained. Rather, the amount of component (E) used depends on the purpose of use of the composition of the present invention.
- the refractive index of the component (E) is 1.45 to 1.60, which improves the transparency of the composition of the present invention. Is preferable.
- the composition of the present invention removes water / hydrophilic solvent from a dispersion of water / hydrophilic solvent to which components (A) and (B), and if necessary, components (C) to (E) are added. Can be molded.
- the means for removing the water / hydrophilic solvent there is no limitation on the means for removing the water / hydrophilic solvent. Specific examples of the means include volatilization, filtration, and centrifugation.
- the molded composition is preferably heated at 80 to 200 ° C. to completely remove the water / hydrophilic solvent.
- the shape can be adjusted by pressurizing simultaneously with heating.
- This heat treatment when containing the component (C), has the effect of improving the thermal conductivity of the composition, and is more preferable.
- the composition of the present invention is a dispersion of water / hydrophilic solvent to which the components (A) and (B), and (C) to (D), if necessary, are added. From the liquid, a preform can be prepared by the above-described method, and then the (E) component can be impregnated into the preform. In the impregnation, it is effective to reduce the system pressure.
- component (E) is a thermosetting polymer
- a prepolymer composition in which a crosslinking agent or a curing catalyst is blended with component (E) can be prepared, and the preform can be impregnated with the prepolymer composition. .
- the composition impregnated with the component (E) can be finally molded by heat treatment or hot pressing to produce the composition of the present invention.
- composition of the present invention reinforcing filler, filler for weight increase, other thermally conductive filler and thermally conductive compound, other thermally conductive filler, polymer and plasticizer for adjusting physical properties, heat resistance as necessary
- additives that improve UV resistance, light resistance, oxidation resistance, flame retardancy, and the like can be used as long as the original purpose of the composition of the present invention is not impaired.
- the thermal conductive composition of the present invention preferably has anisotropic thermal conductivity having a higher thermal conductivity in the plane direction than in the thickness direction.
- the anisotropic thermal conductivity is preferably such that the thermal conductivity in the thickness direction is 0.4 W / m ⁇ K or more and the thermal conductivity in the plane direction is 1.0 W / m ⁇ K or more.
- At least one inorganic powder selected from graphene, graphene oxide, and derivatives thereof may be added.
- a thermally conductive and conductive composition can be obtained.
- the graphene is preferably thin-layer graphite, and includes not only single-layer graphite but also two or more layers of cleaved graphite.
- Graphene oxide is produced by oxidizing graphite, and includes not only single-layer graphite oxide but also two or more layers of cleaved graphite oxide. Such graphene and graphene oxide derivatives can also be used. Derivatives are generally obtained by chemically modifying the surface of graphene or graphene oxide.
- Such graphene or graphene oxide is a thin layer having a thickness of several nm.
- the size in the surface direction of graphene and graphene oxide can be measured as an average particle diameter by a light scattering method.
- graphene, graphene oxide, or a derivative thereof having an average particle size of 2 ⁇ m or more and 50 ⁇ m or less is preferable in order to obtain high conductivity.
- ⁇ Measurement method of average particle diameter The average particle size of graphene oxide was measured by a light scattering method using a zeta potential / particle size measurement analyzer ELS-Z manufactured by Otsuka Electronics Co., Ltd.
- the average particle size of nano alumina and nano diamond is the value described by the manufacturer in the technical data.
- Example 1 Cellulose nanofiber aqueous dispersion, manufactured by Sugino Machine Co., Ltd., trade name “Vinfis Wma-1202” (solid content 2%), trade name “Nano Alumina” manufactured by TECNAN (average particle size 10-20 nm: BET surface area measurement by manufacturer Calculated value), polyvinyl alcohol, manufactured by Kuraray Co., Ltd., trade name “PVA-505”, diluted with water to adjust the solid content concentration to 5%, and subjected to ultrasonic dispersion treatment for 30 minutes. After preparing the aqueous dispersion, the mixed aqueous dispersion was prepared by centrifugal defoaming. The composition ratio is shown in Table 1.
- surface shows the mass part per 1 mass part of polyvinyl alcohol.
- the film was coated on a polyethylene terephthalate (PET) film, allowed to stand until the water was volatilized and the sample was solidified, and then heat-treated in an oven at 100 ° C. for 30 minutes to obtain a translucent and smooth coating film.
- PET polyethylene terephthalate
- the mixed water dispersion is poured into a silicone rubber mold and left to stand until the water evaporates and the sample is solidified, and then heat-treated in an oven at 100 ° C. for 30 minutes. A transparent and smooth film was obtained.
- Each film thickness is shown in Table 1.
- the thermal characteristics in the surface direction and thickness direction of the film prepared with the silicone mold of Example 4 were measured with a product name “Thermo Wave Analyzer TA-3” manufactured by Bethel.
- the thermal conductivity in the thickness direction and in the plane direction is 0.6 W / mK and 1.4 W / mK, respectively, and even in the case of a film just poured into a silicone mold, the anisotropic thermal conductivity is high in the plane direction. showed that.
- Examples 5 to 12 Cellulose nanofiber aqueous dispersion, manufactured by Sugino Machine Co., Ltd., trade name “Vinfis Wma-1202” (solid content 2%) 10 g, and TECNAN, trade name “Nanoalumina” (average particle size 10-20 nm, depending on manufacturer) (Calculated value from BET surface area measurement value), or CARBODEN nano-diamond aqueous dispersion (trade name “Andante”, primary particle size 4.2 nm, solid content 5%) and mixed with a centrifugal mixer, Next, 8 g of methanol (in the case of Example 8, 4 g of methanol) was added and further mixed with a centrifugal mixer to prepare a dispersion.
- methanol in the case of Example 8, 4 g of methanol
- the composition is shown in Table 2.
- a 1.7 mm thick paper frame was placed on the PET film, and the dispersion was poured. After air drying at room temperature for 2 hours, it was dried in a 70 ° C. oven for 20 minutes, and then in a 100 ° C. oven for 10 minutes.
- the obtained film was cut out 10 ⁇ 10 mm in width and press-molded at a temperature of 120 ° C. and a pressure of 30 kgf / cm 2 for 5 minutes to obtain smooth films (Examples 5 to 8).
- the composition of the film is shown in Table 2.
- a polymer-containing composition film impregnated with was obtained. This was heated at 150 ° C. for 20 minutes to obtain cured silicone-containing compositions (Examples 9 to 12).
- the thicknesses of the sheets of Examples 5 to 12 were measured, and the surface electrical resistance was measured by applying an electrode to the surface.
- the surface electrical resistance in Table 2 was measured by applying an electrode to the sheet surface. As shown in Table 2, Examples 5 to 8 had a resistance value of 50 M ⁇ or more, and were confirmed to be at a level that can be used as an electrical insulating material.
- the composition composed of nano-alumina and cellulose nanofibers was highly transparent, and the transparency became even higher when impregnated with silicone. Even a composition composed of nanodiamonds and cellulose nanofibers was observed to be slightly transparent.
- Example 13 The same cellulose nanofiber aqueous dispersion and nanoalumina as in Examples 5-12 were used. To 25 g of the cellulose nanofiber aqueous dispersion, 0.9 g of nanoalumina and 75 g of methanol were added and mixed with a centrifugal mixer for 30 seconds to prepare a composition dispersion. Using 10 g of this composition dispersion, a liquid component was separated under reduced pressure using a membrane filter having an aperture of 0.8 ⁇ m. The composition film was peeled from the membrane filter, and press-molded at a temperature of 80 ° C. and a pressure of 30 kgf / cm 2 for 5 minutes to obtain a smooth film.
- Example 14 Momentive's addition-cured silicone, trade names “X32-1679-2” and “XC32-1679-2” were mixed at a mass ratio of 10/1.
- the film obtained in Example 13 was immersed in this silicone mixed solution, and vacuum impregnation was performed for 20 minutes under vacuum.
- the taken out film was sandwiched between PET films, and further sandwiched between cardboards and press cured at a temperature of 70 ° C. for 20 minutes to obtain a smooth and highly transparent silicone-impregnated cellulose nanofiber / nanoalumina composition film.
- Example 15 The same cellulose nanofiber aqueous dispersion and nanoalumina as in Example 13 were used. 45 g of cellulose nanofiber aqueous dispersion, 2.7 g of nanoalumina, and 135 g of methanol were added and mixed for 5 minutes with a homogenizer (15000 rpm) to prepare a composition dispersion. Using 10 g of this composition dispersion, a liquid component was separated under reduced pressure using a membrane filter having an aperture of 0.8 ⁇ m. The composition film was peeled off from the membrane filter, and sandwiched between cardboards and dried at 100 ° C. for 15 minutes while applying a pressure of 1 kg to obtain a smooth film.
- Example 16 A smooth and transparent silicone impregnated cellulose nanofiber / nanoalumina composition film having the same transparency as that of Example 14 except that the film obtained in Example 15 was used and the vacuum impregnation time was 45 minutes. Obtained.
- Example 17 To 25 g of the same cellulose nanofiber aqueous dispersion as in Examples 5 to 12, 10 g of the same nanodiamond aqueous dispersion and 65 g of methanol as in Example 8 were added, and mixed for 30 seconds with a centrifugal mixer to prepare a composition dispersion. Using 10 g of this composition dispersion, a liquid component was separated under reduced pressure using a membrane filter having an aperture of 0.8 ⁇ m. The composition film was peeled off from the membrane filter, and a smooth film was obtained by press molding at a temperature of 80 ° C. and a pressure of 30 kgf / cm 2 for 5 minutes.
- Example 18 A smooth and slightly transparent silicone impregnated cellulose nanofiber / nanodiamond composition film was obtained in the same manner as in Example 14 except that the film obtained in Example 17 was used.
- Example 19 To 25 g of the same cellulose nanofiber aqueous dispersion as in Example 17, 10 g of the same nanodiamond aqueous dispersion as in Example 17 and 65 g of water (Pure water for industrial use manufactured by Yamaei Co., Ltd.) are added and mixed for 30 seconds with a centrifugal mixer. A composition dispersion was prepared. Using 10 g of this composition dispersion, a liquid component was separated under reduced pressure using a membrane filter having an aperture of 0.8 ⁇ m. The composition film was peeled from the membrane filter and press-molded at a temperature of 70 ° C. and a pressure of 30 kgf / cm 2 for 20 minutes to obtain a smooth film.
- the thermal characteristics in the surface direction and thickness direction of the cellulose nanofiber nanofiller composition film and the silicone-impregnated cellulose nanofiber nanofiller composition film obtained in Example 13 to Example 19 were manufactured by Bethel and trade name “Thermo”. Measurement was performed with a wave analyzer TA-3 ". The results are shown in Table 4.
- composition film containing cellulose nanofibers and nanofillers has higher thermal conductivity in the plane direction than in the thickness direction, that is, has anisotropic thermal conductivity.
- composition dispersion (Comparative Example 1) The same cellulose nanofiber aqueous dispersion as in Examples 5 to 12 was used. 75 g of methanol was added to 25 g of the cellulose nanofiber aqueous dispersion and mixed with a centrifugal mixer for 30 seconds to prepare a composition dispersion. Using 10 g of this composition dispersion, a liquid component was separated under reduced pressure using a membrane filter having an aperture of 0.8 ⁇ m. The composition film was peeled from the membrane filter, and press-molded at a temperature of 80 ° C. and a pressure of 30 kgf / cm 2 for 5 minutes to obtain a smooth film.
- Example 20 has the same composition as Example 13
- Example 21 has the same composition as Example 15
- Example 22 has the same composition as Example 17
- Example 23 has the same composition as Example 19.
- the thermal conductivity of the composition when it is assumed that there is no void is calculated using the Bruggman equation.
- Bruggman's formula ⁇ ( ⁇ c - ⁇ f ) / ( ⁇ m - ⁇ f ) ⁇ ( ⁇ m / ⁇ c ) 1/3
- ⁇ m is the thermal conductivity of the composition
- ⁇ f is the thermal conductivity of the air phase
- ⁇ c is the thermal conductivity of the composite
- ⁇ is the porosity
- ⁇ m is the thermal conductivity when there is no void.
- the composition film containing cellulose nanofibers and nanofillers has a higher solid component thermal conductivity than the composition film containing only cellulose nanofibers (Comparative Example 1), that is, the nanofillers coexist.
- Example 24 Cellulose nanofiber aqueous dispersion, manufactured by Sugino Machine Co., Ltd., trade name “Vinfis Wma-1202” diluted with water to a solid content concentration of 0.02%, 1 g of aqueous dispersion, trade name “Nano” manufactured by CARBODEN Diamond “Water Dispersion (Andante) was diluted with water to add 0.2 g of an aqueous dispersion having a solid content of 0.02%, and the mixture was subjected to dispersion treatment with ultrasonic waves for 30 minutes to give cellulose nanofibers and nanodiamond water. A dispersion was prepared.
- FIG. 1 photograph
- the photograph in FIG. 1 is 50,000 times, and the mark below the center is 200 nm.
- nanodiamond particles of about 5 nm existing on the surface of the cellulose nanofiber were observed. It is considered that nanodiamonds are adsorbed on the surface of cellulose nanofibers, and it is considered that this adsorbing structure provides excellent thermal conductivity even in a composition containing only a small amount of fine particles.
- Example 25 Cellulose nanofiber aqueous dispersion, manufactured by Sugino Machine Co., Ltd., trade name “Vinfis Wma-1202” diluted with water to a solid content concentration of 0.02%, and 1 g of an anionic dispersant Mitsubishi A sulfonated polyaniline aqueous dispersion manufactured by Rayon Co., Ltd., trade name “aquaPASS” (solid content 5%) was diluted with water to add 0.25 g of an aqueous dispersion having a solid content concentration of 0.02%.
- the product name “Nanodiamond” aqueous dispersion (Andante) was diluted with water to add 0.2 g of an aqueous dispersion with a solid content concentration of 0.02%, and dispersed with ultrasonic waves for 30 minutes. An aqueous dispersion of nanodiamond was prepared. The precipitate was removed from this aqueous dispersion by centrifugation, and the supernatant was dropped onto a copper foil tape and allowed to dry naturally. The result of observing this sample with a scanning electron microscope is shown in FIG. 2 (photograph). The photograph in FIG. 2 is 100,000 times, and the mark at the center is 200 nm.
- composition of the present invention can be applied to various uses such as a film, a sheet, a coating material laminated on a substrate, a paint, and an ink.
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Abstract
Description
酸化グラフェンの平均粒子径は、大塚電子(株)製ゼータ電位・粒径測定アナライザELS-Zにより、光散乱法で測定した。ナノアルミナとナノダイヤモンドの平均粒子径は、製造メーカーが技術資料に記載した値である。
セルロースナノファイバー水分散液、スギノマシン社製、商品名"ビンフィスWma-10002"(固形分2%)、TECNAN社製の商品名"ナノアルミナ"(平均粒径10~20nm:メーカーによるBET表面積測定値からの計算値)、ポリビニルアルコール、クラレ社製、商品名"PVA-505"を加え、水で希釈して固形分濃度5%に調整し、超音波分散処理を30分間行って組成物の水分散液を調製した後、遠心脱泡を行うことによって混合水分散液を調製した。組成比は表1に示す。表中の質量比は、ポリビニルアルコール1質量部当たりの質量部を示す。ポリエチレンテレフタレート(PET)フィルム上にコーティングし、水が揮発して試料が固まるまで静置してから、100℃のオーブンで30分間熱処理することにより、半透明で平滑なコーティング膜を得た。また、混合水分散液をシリコーンゴム型に流し込み、水が揮発して試料が固まるまで静置してから、100℃のオーブンで30分間熱処理し、生成した皮膜をシリコーンゴム型から剥離して半透明で平滑なフィルムを得た。それぞれの膜厚を表1に示す。
セルロースナノファイバー水分散液、スギノマシン社製、商品名"ビンフィスWma-10002"(固形分2%)10g、及び、TECNAN社製、商品名"ナノアルミナ"(平均粒径10~20nm:メーカーによるBET表面積測定値からの計算値)、又はCARBODEN社製のナノダイヤモンド水分散液(商品名"Andante"、1次粒子径4.2nm、固形分5%)を加えて遠心式ミキサーで混合し、ついでメタノール8g(実施例8の場合はメタノール4g)を加えてさらに遠心式ミキサーで混合して分散液を調整した。組成は表2に示す。PETフィルム上に厚さ1.7mmの紙枠を置き、分散液を注ぎ込んだ。室温で2時間風乾した後、70℃オーブンで20分間、続いて100℃オーブンで10分間乾燥した。得られたフィルムを縦10×横10mmに切り抜き、温度120℃、圧力30kgf/cm2で5分プレス成型することによって、平滑なフィルムを得た(実施例5~8)。フィルムの組成を表2に示す。
実施例5~12と同じと同じセルロースナノファイバー水分散液とナノアルミナを使用した。セルロースナノファイバー水分散液25gにナノアルミナ0.9gとメタノール75gを加え、遠心ミキサーで30秒混合して組成物分散液を調製した。この組成物分散液10gを、開孔0.8μmのメンブレンフィルターを使用して、減圧で液状成分を分離した。組成物フィルムをメンブレンフィルターから剥がし、温度80℃、圧力30kgf/cm2で5分プレス成型することによって、平滑なフィルムを得た。
モメンティブ社製付加硬化シリコーン、商品名"X32-1679-2"と"XC32-1679-2"を10/1の質量比で混合した。このシリコーン混合液に実施例13で得られたフィルムを浸漬して、真空下で20分間真空含浸を行った。取り出したフィルムをPETフィルムで挟み、さらに厚紙で挟んで温度70℃で20分間プレス硬化させることにより、平滑で透明性が高いシリコーン含浸のセルロースナノファイバー・ナノアルミナ組成物フィルムを得た。
実施例13と同じセルロースナノファイバー水分散液とナノアルミナを使用した。セルロースナノファイバー水分散液45gとナノアルミナ2.7gとメタノール135gを加え、ホモジナイザー(15000rpm)で5分間混合して組成物分散液を調製した。この組成物分散液10gを、開孔0.8μmのメンブレンフィルターを使用して、減圧で液状成分を分離した。組成物フィルムをメンブレンフィルターから剥がし、厚紙で挟んで1kgの圧力をかけながら100℃で15分間乾燥して、平滑なフィルムを得た。
実施例15で得られたフィルムを使用し、真空含浸時間を45分としたほかは実施例14と同様の方法で、平滑で透明性を有するシリコーン含浸のセルロースナノファイバー・ナノアルミナ組成物フィルムを得た。
実施例5~12と同じセルロースナノファイバー水分散液25gに、実施例8と同じナノダイヤモンド水分散液10gとメタノール65gを加え、遠心ミキサーで30秒間混合して組成物分散液を調製した。この組成物分散液10gを、開孔0.8μmのメンブレンフィルターを使用して、減圧で液状成分を分離した。組成物フィルムをメンブレンフィルターから剥がし、温度80℃、圧力30kgf/cm2で5分間プレス成型することによって平滑なフィルムを得た。
実施例17で得られたフィルムを使用したほかは実施例14と同様の方法で、平滑でわずかに透明性を有するシリコーン含浸のセルロースナノファイバー・ナノダイヤモンド組成物フィルムを得た。
実施例17と同じセルロースナノファイバー水分散液25gに、実施例17と同じナノダイヤモンド水分散液10gと水(株式会社山栄製工業用精製水)65gを加え、遠心ミキサーで30秒間混合して組成物分散液を調製した。この組成物分散液10gを、開孔0.8μmのメンブレンフィルターを使用して、減圧で液状成分を分離した。組成物フィルムをメンブレンフィルターから剥がし、温度70℃、圧力30kgf/cm2で20分間プレス成型することによって平滑なフィルムを得た。
実施例5~12と同じセルロースナノファイバー水分散液を使用した。セルロースナノファイバー水分散液25gにメタノール75gを加え、遠心ミキサーで30秒混合して組成物分散液を調製した。この組成物分散液10gを、開孔0.8μmのメンブレンフィルターを使用して、減圧で液状成分を分離した。組成物フィルムをメンブレンフィルターから剥がし、温度80℃、圧力30kgf/cm2で5分プレス成型することによって、平滑なフィルムを得た。
実施例20は実施例13、実施例21は実施例15、実施例22は実施例17、実施例23は実施例19と同じ組成物である。
Bruggmanの式 φ=(λc -λf)/(λm -λf)×(λm /λc)1/3
但し、λm:組成物の熱伝導率
λf:空気相の熱伝導率
λc:コンポジットの熱伝導率
φ:空隙率
前記において、λmは空隙がないと仮定した場合の熱伝導率であり、これは本発明のコンポジットをたとえば高温・高湿・高圧などの条件で圧縮することによって近づけることができる空隙率が低い材料の熱伝導率(固体成分熱伝導率)ということになる。
表5で見るように、セルロースナノファイバーとナノフィラーを含有する組成物フィルムは、セルロースナノファイバーのみの組成物フィルム(比較例1)よりも固体成分熱伝導率が高い、すなわちナノフィラーを共存させると空隙率は高くなるが、空隙がないか又は空隙率が低い材料の熱伝導率を高くすることができる。
セルロースナノファイバー水分散液、スギノマシン社製、商品名"ビンフィスWma-10002"を水で希釈して固形分濃度を0.02%にした水分散液1gに、CARBODEN社製の商品名"ナノダイヤモンド"水分散液(Andante)を水で希釈して固形分濃度を0.02%にした水分散液0.2gを加え、超音波で30分間分散処理してセルロースナノファイバーとナノダイヤモンドの水分散液を調製した。この水分散液から遠心分離で沈殿物を除去し、上澄みを銅箔テープ上に滴下して自然乾燥させた。この試料を走査型電子顕微鏡で観察した結果を図1(写真)に示す。図1の写真は5万倍で、中央下のマークは200nmである。
セルロースナノファイバー水分散液、スギノマシン社製、商品名"ビンフィスWma-10002"を水で希釈して固形分濃度を0.02%にした水分散液1gに、陰イオン性分散剤である三菱レイヨン社製スルホン化ポリアニリン水分散液商品名"aquaPASS"(固形分5%)を水で希釈して固形分濃度を0.02%にした水分散液0.25gを加え、さらにCARBODEN社製の商品名"ナノダイヤモンド"水分散液(Andante)を水で希釈して固形分濃度を0.02%にした水分散液0.2gを加え、超音波で30分分散処理してセルロースナノファイバーとナノダイヤモンドの水分散液を調製した。この水分散液から遠心分離で沈殿物を除去し、上澄みを銅箔テープ上に滴下して自然乾燥させた。この試料を走査型電子顕微鏡で観察した結果を図2(写真)に示す。図2の写真は10万倍で、中央下のマークは200nmである。
Claims (11)
- セルロースナノファイバーと微小粒子を含む熱伝導性組成物であって、
(A)セルロースナノファイバー、及び、
(B)平均粒子径が50nm以下の金属酸化物及びダイヤモンドから選ばれる少なくとも一種類の無機粉体、
を含むことを特徴とする熱伝導性組成物。 - 前記(B)成分の金属酸化物がアルミナ及び/又はシリカである請求項1に記載の熱伝導性組成物。
- 前記(B)成分の平均粒子径が50nm以下の金属酸化物又はダイヤモンドが親水性である熱伝導性請求項1又は2に記載の組成物。
- 前記(A)成分と(B)成分の合計質量を100質量%としたとき、前記(A)成分は5~98質量%、前記(B)成分は2~95質量%である請求項1~3のいずれかに記載の熱伝導性組成物。
- 前記組成物に、さらに(D)成分として、陰イオン性分散剤を含有する請求項1~4のいずれかに記載の熱伝導性組成物。
- 前記組成物に、さらに(E)成分としてポリマーを含有する請求項1~5のいずれかに記載の熱伝導性組成物。
- 前記(E)成分のポリマーの屈折率が1.45~1.60である請求項6に記載の熱伝導性組成物。
- (A)セルロースナノファイバー、及び、
(B)平均粒子径が50nm以下の金属酸化物及びダイヤモンドから選ばれる少なくとも一種類の無機粉体、
を含み、これに水又は水・親水性溶媒分散液を加えて分散液とし、前記分散液から水又は水・親水性溶媒を除去して請求項1~7のいずれかに記載の熱伝導性組成物を製造することを特徴とする熱伝導性組成物の製造方法。 - 前記水・親水性溶媒分散液から水又は水・親水性溶媒を除去した後、80~200℃で熱処理することにより所定の形状に整える請求項8に記載の熱伝導性組成物の製造方法。
- 前記水又は水・親水性溶媒分散液から水又は水・親水性溶媒を除去した後、(E)成分を含浸する請求項8又は9に記載の熱伝導性組成物の製造方法。
- 前記(E)成分を含浸した後に前記(E)成分を硬化させる請求項10に記載の熱伝導性組成物の製造方法。
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WO2023243231A1 (ja) * | 2022-06-15 | 2023-12-21 | パナソニックIpマネジメント株式会社 | 導電性多孔質材料、それを用いた電極、および導電性多孔質材料の製造方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006035647A (ja) * | 2004-07-27 | 2006-02-09 | Kyoto Univ | 透明積層体 |
JP2008248033A (ja) * | 2007-03-29 | 2008-10-16 | Hitachi Ltd | 繊維強化複合樹脂組成物及びその製造方法 |
JP2012051991A (ja) * | 2010-08-31 | 2012-03-15 | Nagoya Univ | セルロースナノファイバー分散体及びその製造方法 |
WO2014049212A1 (en) * | 2012-09-28 | 2014-04-03 | Carbodeon Ltd Oy | Nanodiamonds containing thermoplastic thermal composites |
JP2015048358A (ja) * | 2013-08-29 | 2015-03-16 | 熊本県 | 熱伝導性複合粒子および樹脂成形体 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7071258B1 (en) | 2002-10-21 | 2006-07-04 | Nanotek Instruments, Inc. | Nano-scaled graphene plates |
DE102004016646A1 (de) * | 2004-03-31 | 2005-10-27 | Basf Ag | Verfahren zur Herstellung von Halbzeug und Formteilen |
US7745528B2 (en) | 2006-10-06 | 2010-06-29 | The Trustees Of Princeton University | Functional graphene-rubber nanocomposites |
KR101313768B1 (ko) * | 2010-02-12 | 2013-10-01 | 주식회사 네오엔비즈 | 나노 다이아몬드 분산액 및 그 제조 방법 |
CN103756347A (zh) | 2010-09-03 | 2014-04-30 | 积水化学工业株式会社 | 树脂复合材料及树脂复合材料的制造方法 |
DE102010043472A1 (de) | 2010-11-05 | 2012-05-10 | Evonik Goldschmidt Gmbh | Zusammensetzung aus Polymeren und elektrisch leitfähigem Kohlenstoff |
JP2012236983A (ja) * | 2011-04-28 | 2012-12-06 | Nagoya Univ | 導電性組成物 |
JP2013216766A (ja) | 2012-04-06 | 2013-10-24 | Nagoya Univ | 導電性組成物 |
US9550871B2 (en) * | 2012-11-09 | 2017-01-24 | Wisconsin Alumni Research Foundation | Sustainable hybrid organic aerogels and methods and uses thereof |
CN104936895A (zh) * | 2013-01-24 | 2015-09-23 | 日本瑞翁株式会社 | 碳纳米管分散液及其制造方法、以及碳纳米管组合物及其制造方法 |
US9284193B2 (en) * | 2013-10-21 | 2016-03-15 | The Penn State Research Foundation | Method for preparing graphene oxide films and fibers |
-
2015
- 2015-09-14 US US15/108,961 patent/US20160319176A1/en not_active Abandoned
- 2015-09-14 US US15/108,994 patent/US9862840B2/en active Active
- 2015-09-14 JP JP2016548872A patent/JP6913307B2/ja active Active
- 2015-09-14 WO PCT/JP2015/075968 patent/WO2016043145A1/ja active Application Filing
- 2015-09-14 WO PCT/JP2015/075969 patent/WO2016043146A1/ja active Application Filing
- 2015-09-14 JP JP2016548873A patent/JP6748990B2/ja active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006035647A (ja) * | 2004-07-27 | 2006-02-09 | Kyoto Univ | 透明積層体 |
JP2008248033A (ja) * | 2007-03-29 | 2008-10-16 | Hitachi Ltd | 繊維強化複合樹脂組成物及びその製造方法 |
JP2012051991A (ja) * | 2010-08-31 | 2012-03-15 | Nagoya Univ | セルロースナノファイバー分散体及びその製造方法 |
WO2014049212A1 (en) * | 2012-09-28 | 2014-04-03 | Carbodeon Ltd Oy | Nanodiamonds containing thermoplastic thermal composites |
JP2015048358A (ja) * | 2013-08-29 | 2015-03-16 | 熊本県 | 熱伝導性複合粒子および樹脂成形体 |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109689760A (zh) * | 2016-08-29 | 2019-04-26 | 日本板硝子株式会社 | 树脂强化用填充材料和树脂组合物 |
JPWO2018043246A1 (ja) * | 2016-08-29 | 2018-09-13 | 日本板硝子株式会社 | 樹脂強化用充填材及び樹脂組成物 |
US11180638B2 (en) | 2016-08-29 | 2021-11-23 | Nippon Sheet Glass Company, Limited | Resin-reinforcing filler and resin composition |
WO2018043246A1 (ja) * | 2016-08-29 | 2018-03-08 | 日本板硝子株式会社 | 樹脂強化用充填材及び樹脂組成物 |
JP2018059057A (ja) * | 2016-10-03 | 2018-04-12 | 国立研究開発法人産業技術総合研究所 | 複合材料とその製造方法及び熱伝導性材料 |
JP2018154671A (ja) * | 2017-03-15 | 2018-10-04 | 東洋インキScホールディングス株式会社 | 樹脂組成物および成形体 |
JP2018154545A (ja) * | 2017-03-16 | 2018-10-04 | 太平洋セメント株式会社 | ナノ粒子集合体、ナノ粒子焼成物、及びこれらの製造方法 |
JP2019065086A (ja) * | 2017-09-28 | 2019-04-25 | 富士シリシア化学株式会社 | 複合スラリー、複合材料、及び複合スラリーの製造方法 |
JP7036336B2 (ja) | 2017-09-28 | 2022-03-15 | 富士シリシア化学株式会社 | 複合スラリーの製造方法 |
JP2019108440A (ja) * | 2017-12-16 | 2019-07-04 | 株式会社アマケンテック | ナノオーダー分散型水性遮断熱塗料及びナノオーダー分散型水性遮断熱塗料の製造方法 |
WO2020080319A1 (ja) * | 2018-10-18 | 2020-04-23 | 株式会社オートネットワーク技術研究所 | 熱伝導性材料 |
JP2021001292A (ja) * | 2019-06-24 | 2021-01-07 | 住友ゴム工業株式会社 | ナノセルロース・界面活性剤複合体 |
JP7322543B2 (ja) | 2019-06-24 | 2023-08-08 | 住友ゴム工業株式会社 | ナノセルロース・界面活性剤複合体 |
WO2021002194A1 (ja) * | 2019-07-03 | 2021-01-07 | 日本製紙株式会社 | 混合液 |
JP6887067B1 (ja) * | 2019-07-03 | 2021-06-16 | 日本製紙株式会社 | 混合液 |
TWI803758B (zh) * | 2019-07-03 | 2023-06-01 | 日商日本製紙股份有限公司 | 混合液 |
TWI817248B (zh) * | 2019-07-03 | 2023-10-01 | 日商日本製紙股份有限公司 | 混合液 |
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