WO2016140330A1 - 層状無機化合物と有機化合物との複合体及びその製造方法、剥離化された層状無機化合物及びその製造方法、絶縁性樹脂組成物、樹脂シート、絶縁物、樹脂シート硬化物並びに放熱部材 - Google Patents
層状無機化合物と有機化合物との複合体及びその製造方法、剥離化された層状無機化合物及びその製造方法、絶縁性樹脂組成物、樹脂シート、絶縁物、樹脂シート硬化物並びに放熱部材 Download PDFInfo
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- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/42—Micas ; Interstratified clay-mica products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/20—Mica; Vermiculite
- C04B14/206—Mica or vermiculite modified by cation-exchange; chemically exfoliated vermiculate
- C04B14/208—Mica or vermiculite modified by cation-exchange; chemically exfoliated vermiculate delaminated mica or vermiculite platelets
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- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/107—Ceramic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/304—Insulating
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- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
Definitions
- the present invention relates to a composite of a layered inorganic compound and an organic compound and a manufacturing method thereof, a peeled layered inorganic compound and a manufacturing method thereof, an insulating resin composition, a resin sheet, an insulator, a cured resin sheet, and a heat dissipation member About.
- High-voltage equipment materials such as generators, rotating electrical machines, and power transmission / transformation equipment include a conductive member for flowing electricity and an insulating member for blocking between conductors or between a conductor and ground.
- An insulating resin material based on an epoxy resin is generally used for the insulating member of such a high voltage device from the viewpoint of insulation, chemical stability, mechanical strength, heat resistance, cost, and the like. ing.
- JP-A-2008-75069 discloses that an epoxy compound is filled with an inorganic compound such as silica, alumina, or a smectite clay compound.
- the insulating property of the composite material is obtained by dispersing a layered inorganic compound such as mica in a thermoplastic resin such as polypropylene or polyamide. Attempts have been made to improve various performances such as voltage resistance and heat resistance. In these prior arts, when the thermoplastic resin and the layered inorganic compound are dispersed, a method of melt kneading the layered inorganic compound into the thermoplastic resin is used.
- the method of melt-kneading a layered inorganic compound into a thermoplastic resin is to disperse the layered inorganic compound by applying heat to a thermoplastic resin such as polypropylene, and thus thermosetting epoxy resin or the like that is difficult to melt and knead by heat. It cannot be applied to a functional resin.
- layered inorganic compounds inherently contain alkali metals such as sodium and potassium, which have hydrophilicity between layers, and have hydroxyl groups on the crystal surface, and thus have affinity for polar solvents such as water, but organic Low affinity for organic substances such as solvents and epoxy resins. Therefore, in the kneading with the resin, the layered inorganic compound is agglomerated and voids accompanying the aggregation occur, making it difficult to uniformly disperse the layered inorganic compound in the resin, and insulating, voltage resistance, heat resistance There is a problem that various performances and the like are deteriorated.
- the insulating resin material is required to have high reliability, in order to improve various performances such as better insulation, high thermal conductivity, voltage resistance, etc., a certain amount or more of the layered inorganic compound is required. Filling is necessary. However, when the filling rate is increased, the resin does not enter the space around the layered inorganic compound, and voids are easily formed. In addition to the deterioration of various performances of the insulating resin material, there is a problem that the manufacturing cost increases. . In order to solve this problem, it is effective to increase the aspect ratio (aspect ratio) of the layered inorganic compound, that is, to increase the specific surface area.
- JP-A-9-87096 reports that the mechanical properties of a composite material of a smectite clay compound, which is a layered inorganic compound having an increased aspect ratio, and resin are improved.
- a layered inorganic compound Like the smectite clay compound, mica, a layered inorganic compound, is considered to have a higher effect of improving insulation, voltage resistance, heat resistance, etc. of the material combined with the resin as the aspect ratio is larger. Therefore, in order to realize these problems, development of a layered inorganic compound peeling technique (nanosheet forming technique) is required.
- the layers of the layered inorganic compound are formed by relatively weak bonds such as van der Waals force and electrostatic interaction.
- This van der Waals force can be generally expressed by the dispersion force of the Lennard-Jones potential shown in equation (1) (the sixth-order term in the equation), and is known to be inversely proportional to the sixth power of the distance r. ing.
- the electrostatic interaction can be expressed by the equation (2), and is known to be inversely proportional to the distance r.
- U (r) is the potential energy of an arbitrary pair of molecules
- ⁇ and ⁇ are the fitting parameters specific to the molecule
- q + and q ⁇ are the charge amount
- ⁇ r is the relative dielectric constant of the medium
- ⁇ 0 is the vacuum Dielectric constant
- r refers to distance.
- the present inventors have so far conducted extensive research on a method (intercalation) for intercalating an organic compound between layers of a layered inorganic compound. And a manufacturing method thereof (that is, organic treatment), a peeled layered inorganic compound, and a manufacturing method thereof.
- Intercalation is a phenomenon in which atoms, molecules, etc. enter between layers of a layered inorganic compound. Since there is no change in crystal structure before and after intercalation, it is used for clay compounds such as smectite as pretreatment for exfoliation of layered inorganic compounds and for improving the affinity between resin and layered inorganic compounds. Yes.
- the layered inorganic compound organically treated by intercalation shows affinity for a resin such as a nylon resin.
- a layered inorganic compound is uniformly dispersed in a resin by kneading and polymerizing the layered inorganic compound and an organic compound such as a monomer.
- Japanese Patent Application Laid-Open No. 2004-169030 an attempt is made to obtain a layered inorganic compound obtained by dispersing and treating an organically treated layered inorganic compound under strong conditions such as ultrasonic irradiation.
- JP 2009-191239 A describes that a resin composition with improved partial discharge resistance can be obtained.
- JP 2012-158622 A discloses that after laminating a layered inorganic compound with water or an aqueous mixed solvent, the layered inorganic compound functionalized with a silane coupling agent is kneaded with a resin. A method for producing a resin composition for high voltage equipment with improved insulation performance is described.
- International Publication No. 2006/22431 is an organic-inorganic composite obtained by treating non-swellable mica having a large primary particle size with a concentrated solution of a positively charged organic compound, and the organic-inorganic composite is well dispersed.
- the present invention relates to a polymer composite material.
- JP-A-63-215775 uses a polymerization reaction, it is necessary to consider the reaction method according to the type and amount of the monomer of the base resin and the organic compound to be intercalated, and the production cost is reduced. There is a problem that it increases.
- the method disclosed in Japanese Patent Application Laid-Open No. 2004-169030 has a problem in that the mica is pulverized, not peeled, by ultrasonic waves, and the length of the mica in the longitudinal direction (a-axis) is reduced, thereby reducing the aspect ratio. .
- the resin composition is produced by kneading with the resin as it is, a large amount of residual organic compound and various metal ions are present in the finally obtained resin composition. Therefore, it is considered that the insulating effect of the resin composition is small.
- JP 2009-191239 A describes that ammonium ions are usually used as the organic compound.
- the life of the resin composition may be shortened by moisture absorption by the amine.
- the resin sheet formed by molding the resin composition into a sheet may be hardened and hardened by the catalytic effect of the amine.
- the layered inorganic compound is exfoliated only in the complexing process with the polymer, that is, the kneading process. Therefore, the compounding method and compounding conditions for obtaining a sufficient effect are limited.
- JP 2009-191239 A, JP 2012-158622 A, and JP 2008-63408 A a layered inorganic compound is dispersed in a single resin. Therefore, the knowledge regarding the improvement of insulation performance by application of the layered inorganic compound to the insulating resin composition highly filled with inorganic fillers such as alumina contributing to high thermal conductivity has not been described so far.
- the present invention relates to a composite of a layered inorganic compound and an organic compound that expands a regular stack of non-swellable layered inorganic compounds by intercalation of organic compounds and improves affinity for resins, and a method for producing the same.
- the purpose is to provide.
- Another object of the present invention is to provide a peeled layered inorganic compound having a high aspect ratio by mechanical treatment and a method for producing the same.
- an object of the present invention is to provide an insulating resin composition, a resin sheet, an insulator, a cured resin sheet, and a heat radiating member having a high dielectric strength voltage.
- ⁇ 1> a step of heat-treating the non-swellable layered inorganic compound within a range of a thermal decomposition temperature of the non-swellable layered inorganic compound;
- An organic compound is intercalated in the non-swellable layered inorganic compound and dispersed between the non-swellable layered inorganic compound in a dispersion liquid in which the heat-treated nonswellable layered inorganic compound is dispersed in a medium.
- Inserting Have
- the non-swellable layered inorganic compound has a layered structure in which unit crystal layers are stacked on each other, and is heated in the c-axis direction in the range of 0.05 to 0.20 by heating for 1 hour at the upper limit of the thermal decomposition temperature.
- ⁇ 2> The method for producing a complex of a layered inorganic compound and an organic compound according to ⁇ 1>, wherein the non-swellable layered inorganic compound is mica.
- ⁇ 3> The ⁇ 1> or ⁇ 2>, wherein the organic compound is at least one cationic organic compound selected from the group consisting of amine salts, phosphonium salts, imidazolium salts, pyridinium salts, sulfonium salts, and iodonium salts.
- the organic compound is at least one cationic organic compound selected from the group consisting of amine salts, phosphonium salts, imidazolium salts, pyridinium salts, sulfonium salts, and iodonium salts.
- the concentration of the organic compound in the dispersion is 0.01 mol / L or more and not more than the solubility of the organic compound
- ⁇ 5> a step of heat-treating the non-swellable layered inorganic compound within a range of a thermal decomposition temperature of the non-swellable layered inorganic compound;
- An organic compound is intercalated in the non-swellable layered inorganic compound and dispersed between the non-swellable layered inorganic compound in a dispersion liquid in which the heat-treated nonswellable layered inorganic compound is dispersed in a medium.
- the non-swellable layered inorganic compound has a layered structure in which unit crystal layers are stacked on each other, and is heated in the c-axis direction in the range of 0.05 to 0.20 by heating for 1 hour at the upper limit of the thermal decomposition temperature.
- ⁇ 6> The method for producing a peeled layered inorganic compound according to ⁇ 5>, wherein an equilibrium filler density of the dispersion after applying a shearing force to the dispersion is 30% by volume or less.
- ⁇ 8> The method for producing a peeled layered inorganic compound according to any one of ⁇ 5> to ⁇ 7>, wherein a collision pressure of the dispersion during the mechanical treatment is 50 MPa to 250 MPa.
- An organic compound is intercalated into a non-swellable layered inorganic compound,
- the non-swellable layered inorganic compound has a layered structure in which unit crystal layers are stacked on each other, and is heated in the c-axis direction in the range of 0.05 to 0.20 by heating for 1 hour at the upper limit of the thermal decomposition temperature.
- the organic compound intercalated between layers of the non-swellable layered inorganic compound is 1% by mass to 40% by mass with respect to 100% by mass of the non-swellable layered inorganic compound.
- An insulating resin composition comprising a thermosetting resin and an inorganic filler, wherein at least a part of the inorganic filler is the exfoliated layered inorganic compound according to ⁇ 11> or ⁇ 12>.
- ⁇ 14> The insulating resin composition according to ⁇ 13>, wherein a ratio of the exfoliated layered inorganic compound to the inorganic filler is 0.5% by volume to 10% by volume.
- ⁇ 15> A resin sheet obtained by molding the insulating resin composition according to ⁇ 13> or ⁇ 14> into a sheet shape.
- a cured resin sheet which is a heat-treated product of the resin sheet according to ⁇ 15>.
- a composite of a layered inorganic compound and an organic compound that expands a regular stack of non-swellable layered inorganic compounds by intercalation of organic compounds and improves affinity for resins and a method for producing the same Is provided.
- a peeled layered inorganic compound having a high aspect ratio and a method for producing the same are provided by mechanical treatment.
- an insulating resin composition, a resin sheet, an insulator, a cured resin sheet, and a heat radiating member having a high withstand voltage there are provided.
- FIG. 3 is a graph showing the results of XRD measurement of the sample obtained in Example 1. It is the photograph which shows the state which left the dispersion liquid for 2 weeks, (a) shows the case of the dispersion liquid which did not implement peeling processing, (b) shows the case of the dispersion liquid which performed peeling processing.
- 6 is a graph showing the results of XRD measurement of a sample obtained in Comparative Example 2. 6 is a graph showing the results of XRD measurement of the sample obtained in Example 5. It is a photograph which shows the SEM image of the mica powder before peeling processing. 2 is a photograph showing an SEM image of the exfoliating compound refluxed for 96 hours in Example 5.
- the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range. Good. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
- the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. .
- the particle size of each component in the composition is such that when there are a plurality of types of particles corresponding to each component in the composition, unless otherwise specified, the mixture of the plurality of types of particles present in the composition. Mean value.
- the term “resin composition layer” includes not only a configuration of a shape formed on the entire surface but also a configuration of a shape formed on a part when observed as a plan view.
- the method for producing a complex of a layered inorganic compound and an organic compound is a method of thermally decomposing a non-swellable layered inorganic compound into the non-swellable layered inorganic compound.
- the specific composite of the present embodiment is formed by intercalating an organic compound into a non-swellable layered inorganic compound, and as a non-swellable layered inorganic compound, unit crystal layers are stacked to form a layered structure, When heated at the upper limit of the thermal decomposition temperature for 1 hour, it expands in the c-axis direction in the range of 0.05 to 0.20 mm, and when heated at the upper limit of the thermal decomposition temperature for 1 hour, the crystal structure of the unit crystal layer is The one that does not change is used.
- the specific complex of the present embodiment can be easily obtained by the above-described production method.
- the inventors of the present invention have made extensive studies in order to solve the above-described problems when an organic compound is intercalated into a non-swellable layered inorganic compound.
- the non-swellable layered inorganic compound is heat-treated within the range of the thermal decomposition temperature of the non-swellable layered inorganic compound, and the non-swellable layered inorganic compound is easily expanded between the layers by expanding in the c-axis direction. It was found that a specific complex can be formed by intercalation with the present invention, and the present invention has been made based on this finding.
- the specific composite of the present embodiment is useful as a substance in the previous stage when exfoliating the layered inorganic compound.
- non-swellable layered inorganic compound used in the present embodiment examples include mica, kaolinite, and pyrophyllite. Among these, mica having excellent insulating properties is preferable.
- non-swellable mica examples include muscovite, biotite, paragonite, margarite, clintonite, anandite, chlorite, phlogopite, lepidrite, mascobite, biotite, teniolite, and tetrasilicic mica.
- the non-swellable layered inorganic compound used in the present embodiment expands in the c-axis direction in the range of 0.05 to 0.20 by heating at the upper limit of the thermal decomposition temperature for 1 hour, and the thermal decomposition temperature. It is necessary that the crystal structure of the unit crystal layer does not change by heating at the upper limit of 1 hour.
- the type of mica is not particularly limited, and may be a natural product, such as hydrothermal synthesis, melting method, solid phase method, etc. It may be a composite.
- the non-swellable layered inorganic compound is a compound in which unit crystal layers are stacked to form a layered structure.
- the degree of expansion of the non-swellable layered inorganic compound in the c-axis direction can be measured with an X-ray diffraction apparatus (X-Ray Diffraction, XRD).
- X-Ray Diffraction X-Ray Diffraction
- Whether or not the crystal structure of the unit crystal layer of the non-swellable layered inorganic compound has been changed by heating for 1 hour at the upper limit of the thermal decomposition temperature is determined by measuring the non-swellable layered inorganic compound before and after heating by XRD. Analysis can be confirmed by measuring changes in the crystal structure.
- the specific complex of the present embodiment can be obtained by intercalating an organic compound between layers of a layered inorganic compound.
- the intercalating substance is an organic compound.
- the organic compound used in the present embodiment is not particularly limited in its kind, and is at least one cationic organic compound selected from the group consisting of amine salts, phosphonium salts, imidazolium salts, pyridinium salts, sulfonium salts, and iodonium salts. Is mentioned.
- Examples of amine salts that can be used in the present embodiment include primary to quaternary amine hydrochlorides such as dodecylamine hydrochloride and octadecylamine hydrochloride.
- Examples of phosphonium salts that can be used in the present embodiment include trihexyl phosphonium salts.
- Examples of the imidazolium salt that can be used in the present embodiment include 1-ethyl-3-methylimidazolium salt.
- Examples of pyridinium salts that can be used in the present embodiment include N-alkylpyridinium salts.
- Examples of the sulfonium salt that can be used in the present embodiment include triarylsulfonium salts.
- Examples of iodonium salts that can be used in this embodiment include N-alkyl iodonium salts.
- the interlayer distance can be increased and the interlayer can be made oleophilic, so that the affinity of the exfoliated layered inorganic compound prepared from the specific composite to the resin is improved. It is possible to disperse the layered inorganic compound that has been more uniformly peeled in the resin.
- the non-swellable layered inorganic compound is heated within the range of the thermal decomposition temperature of the non-swellable layered inorganic compound.
- the heating temperature exceeds the upper limit of the thermal decomposition temperature of the non-swellable layered inorganic compound, the structural water (hydroxyl group in the crystal structure) of the non-swellable layered inorganic compound is removed, and the crystals of the non-swellable layered inorganic compound are crystallized.
- the structure tends to change, and the non-swellable layered inorganic compound itself is undesirably altered.
- the heat treatment temperature of the non-swellable layered inorganic compound is set within the range of the thermal decomposition temperature of the non-swellable layered inorganic compound.
- the thermal decomposition temperature of the non-swellable layered inorganic compound means a temperature range having an upper limit value and a lower limit value.
- details of the method for confirming the thermal decomposition temperature of the non-swellable layered inorganic compound are as follows.
- the thermal decomposition temperature can be measured by using thermogravimetry (Thermo Gravimetry, TG) and differential thermal analysis (Differential Thermal Analysis, DTA). It is possible to heat a non-swellable layered inorganic compound at 500 ° C.
- the thermal decomposition temperature from the peak shape of endothermic reaction and exothermic reaction of DTA, the peak temperature of endothermic reaction and exothermic reaction, etc. .
- the reaction for intercalating the organic compound between the layers of the non-swellable layered inorganic compound (that is, the step of inserting the organic compound between the layers of the non-swellable layered inorganic compound)
- the organic compound is added as a guest compound to the dispersion in which the heat-treated non-swellable layered inorganic compound is dispersed in the medium, and heated and stirred. It may be done by
- the concentration of the organic compound in the dispersion is preferably higher at a concentration of 0.01 mol / L or more in order to increase the number of contact between the non-swellable layered inorganic compound and the organic compound. However, when the concentration of the organic compound exceeds a certain level, the viscosity of the dispersion liquid may increase remarkably. Therefore, the concentration of the organic compound in the dispersion liquid is preferably adjusted to be equal to or lower than the solubility of the organic compound.
- the content of the non-swellable layered inorganic compound in the dispersion is preferably in the range of 0.5 volume% to 50 volume%. If it is 50 volume% or less, since the viscosity of a dispersion liquid does not become high too much, it exists in the tendency for the fall of stirring efficiency to be suppressed. If it is 0.5 volume% or more, it exists in the tendency which can ensure the quantity of the grade which can be industrially implemented as the quantity of the specific complex produced
- the medium for dispersing the heat-treated non-swellable layered inorganic compound is not particularly limited as long as it is a solvent capable of dissolving the intercalating organic compound. Specifically, water, organic solvents, such as alcohol, etc. are mentioned.
- a heat-treated non-swellable layered inorganic compound may be dispersed in a medium containing an organic compound to be intercalated.
- reaction rate increases as the temperature during the intercalation reaction increases, room temperature (25 ° C.) or higher is preferable.
- the organic compound intercalated between the layers of the non-swellable layered inorganic compound is preferably 1% by weight to 40% by weight, more preferably 1% by weight to 30% by weight with respect to 100% by weight of the non-swellable layered inorganic compound. More preferably, it is 1% by mass to 25% by mass. Suitable for efficient mechanical peeling treatment of non-swellable layered inorganic compound by the amount of intercalated organic compound being 1% by weight to 40% by weight with respect to 100% by weight of non-swellable layered inorganic compound It is.
- the amount of the organic compound to be intercalated is 1% by mass or more, it becomes possible to expand the layer of the non-swellable layered inorganic compound to a range suitable for exfoliation and effectively peel off the non-swellable layered inorganic compound. And tend to be nanosheets.
- the intercalated specific complex may be redispersed in the medium.
- the method for removing the unreacted organic compound include a washing method in which the intercalated specific complex is dispersed in water or an organic solvent and recovered by filtration, filter press, centrifugation, or the like.
- the solvent used for washing a solvent having high solubility of the intercalated organic compound is preferable.
- the amount of the organic compound intercalated between the layers can be measured by methods such as thermogravimetry (TG) and differential thermal analysis (DTA). By measuring the mass decreased in the range of 150 ° C. to 800 ° C., it is possible to measure the amount of the organic compound intercalated into the non-swellable layered inorganic compound.
- TG thermogravimetry
- DTA differential thermal analysis
- the production method of the exfoliated layered inorganic compound of the present embodiment includes the non-swellable layered inorganic compound in the range of the thermal decomposition temperature of the non-swellable layered inorganic compound.
- a non-swelling step by intercalating the non-swellable layered inorganic compound with an organic compound in a dispersion obtained by dispersing the heat-treated non-swellable layered inorganic compound in a medium.
- the non-swellable layered inorganic compound unit crystal layers are stacked on each other to form a layered structure, and heated at the upper limit of the thermal decomposition temperature for 1 hour, the c-axis is in the range of 0.05 to 0.20%. Expands toward the crystal structure of the unit crystal layers by heating 1 hour at the upper limit of the pyrolysis temperature is a method using one that does not change.
- the exfoliating compound of this embodiment is an exfoliated layered inorganic compound having an average particle thickness in the c-axis direction of 1 nm to 80 nm.
- the exfoliating compound of this embodiment can be easily obtained by the above-described production method.
- the inventors of the present invention have made extensive studies in order to solve the problem that the aspect ratio during the peeling treatment after the organic compound is intercalated into the non-swellable layered inorganic compound.
- a specific composite in which an organic compound is intercalated with a non-swellable layered inorganic compound is formed, and then high pressure and high shear stress are mechanically applied to the specific composite, thereby preventing non-swelling with a high aspect ratio.
- the present inventors have found that a peeled product of a layered inorganic compound can be produced, and have reached the present invention based on this finding.
- any method may be used as long as shear is imparted in the dispersion of the non-swellable layered inorganic compound.
- a wet jet mill a high-pressure homogenizer, or the like, which is a device that applies a shear flow.
- a planetary homogenizer, a high-speed stirrer, a three-roll mill, and the like can be given.
- any method may be used as long as the specific composite dispersed in the liquid is sheared.
- an organic layer is formed between the step of heat-treating the non-swellable layered inorganic compound within the range of the thermal decomposition temperature of the non-swellable layered inorganic compound and the layer of the non-swellable layered inorganic compound.
- the step of inserting a compound is the same as in the case of the method for producing the specific complex of the present embodiment described above, and the same materials and processing conditions can be applied. According to the production method of the exfoliating compound of this embodiment, for example, it is possible to exfoliate the layered inorganic compound to a range where the average particle thickness in the c-axis direction is 1 nm to 80 nm.
- the specific exfoliation method is not limited to a wet jet mill or the like.
- the specific composite tends to be pulverized without being peeled and become fine particles. It is difficult to be performed. Therefore, it is preferable to carry out a peeling process by mechanical treatment using a device capable of shearing at high speed in a dispersion such as a wet jet mill. Thereby, it becomes possible to exfoliate, without grind
- the collision pressure of the dispersion during the mechanical treatment in the exfoliating step is preferably 50 MPa to 250 MPa, more preferably 100 MPa to 200 MPa, and further preferably 150 MPa to 200 MPa.
- the shear rate is preferably 100 m / s to 400 m / s, more preferably 180 m / s to 300 m / s, and still more preferably 200 m / s to 300 m / s. If this method is used, a release compound having a high aspect ratio can be obtained with high productivity.
- the average particle diameter of the specific composite before the mechanical treatment used in the exfoliation step is preferably 0.01 ⁇ m to 100 ⁇ m. If the average particle size of the specific composite before the mechanical treatment is 0.01 ⁇ m or more, the aspect ratio of the specific composite before the mechanical treatment is not too small, and the exfoliation by the mechanical treatment can be incorporated into the dispersion. By doing so, a shearing force is likely to be applied, and peeling tends to be facilitated.
- the average particle size of the specific composite before mechanical treatment is 100 ⁇ m or less, the specific composite before mechanical treatment is easily dispersed in the dispersion, and peeling is promoted by applying a shearing force. It tends to be easier.
- the average particle diameter of particles such as a specific complex can be measured by using a laser diffraction / scattering particle size distribution measuring apparatus. After putting the measurement object into the dispersion, it is dispersed with a stirrer or the like. By measuring the particle size distribution of the dispersion, the particle size distribution of the measurement object is measured. Based on the particle size distribution, the average particle size is determined as a particle size corresponding to 50% volume accumulation from the small diameter side.
- the average particle size of the exfoliated non-swellable layered inorganic compound after applying shear force to the dispersion is the intercalated non-swelling property before applying shear force to the dispersion
- the average particle diameter of the layered inorganic compound is preferably 50% to 100%, more preferably 70% to 100%, still more preferably 90% to 100%. If the average particle size of the exfoliating compound is 50% to 100% of the average particle size of the specific composite, the influence of peeling in the thickness direction (c-axis) is greater than the fracture in the longitudinal direction (a-axis), and the aspect There is an advantage that a reduction in the ratio can be suppressed.
- the average particle thickness in the c-axis direction of the exfoliating compound of the present embodiment can be measured by a scanning electron microscope (Scanning Electron Microscope, SEM) by the following method.
- a release compound and a dispersion medium are mixed to prepare a dispersion slurry.
- the prepared dispersion slurry is poured into a mold to obtain a disk-shaped exfoliated compound molded body.
- the exfoliated particles are laminated in the thickness direction because the aspect ratio is large.
- a thickness distribution chart can be created by randomly measuring the thickness of the exfoliating compound at 200 or more and performing image analysis.
- the 50% cumulative thickness (T 50 ) in the thickness distribution is defined as the average particle thickness in the c-axis direction.
- the thickness of the exfoliating compound after the mechanical treatment can be defined by measuring the equilibrium filler density in addition to the thickness distribution using a scanning electron microscope (SEM).
- the equilibrium filler density refers to the bulk density in the dispersion of the exfoliating compound when the equilibrium is reached in the dispersion. This is an index that expresses, by volume percentage, how much the exfoliating compound after dispersion stabilization exists in a dispersion in a certain volume.
- the settling thickness increases due to exfoliation of the specific composite that is a laminate, and the density of the exfoliating compound decreases.
- the equilibrium filler density is preferably lower. In the present embodiment, it is preferable that the content be 30% by volume or less. If the equilibrium filler density is 30% by volume or less, it can be said that peeling is proceeding efficiently.
- the equilibrium filler density can be measured by the following method. A certain amount of the exfoliating compound slurry after the mechanical treatment is added to a test tube, and left at room temperature (25 ° C.) for 2 weeks. By measuring the sedimentation height of the exfoliating compound after standing for 2 weeks, the equilibrium filler density can be calculated by equation (3).
- Equilibrium filler density (%) concentration of exfoliating compound in slurry / ⁇ (precipitation height of exfoliating compound) / (slurry height) ⁇ (3)
- the exfoliating compound obtained through the exfoliating step may be dried to obtain a powder sample, or may be obtained as a slurry sample in the liquid. Moreover, you may preserve
- the exfoliating compound without reducing the length in the longitudinal direction (a-axis). Therefore, the aspect ratio of the release compound increases.
- a thermoplastic resin or a thermosetting resin with a release compound having a high aspect ratio, the insulation, voltage resistance, heat resistance, etc. of the non-swellable layered inorganic compound can be effectively expressed. it can.
- the exfoliating compound of the present embodiment can be provided in either a slurry state or a powder state, and can be easily incorporated into various nanocomposite manufacturing processes.
- a composite with a thermosetting resin such as an epoxy resin leads to the development of an insulating resin material excellent in insulation, voltage resistance, heat resistance, and the like.
- the insulating resin composition of the present embodiment contains a thermosetting resin and an inorganic filler, and at least a part of the inorganic filler is the release compound of the present embodiment.
- an insulating resin composition containing rounded alumina or the like that has a small anisotropy and contributes to an improvement in thermal conductivity has a short dielectric breakdown path, and the dielectric breakdown voltage of the resin composition decreases.
- scaly fillers had to be added.
- inorganic nanoparticles include layered inorganic compounds such as nano-sized BN and mica.
- BN since there are few surface functional groups, the affinity with the resin is poor, voids are likely to be generated inside the resin composition, and the insulation may be lowered.
- an insulating resin composition having high insulation reliability by using a layered inorganic compound separated into a specific thickness (the exfoliating compound of this embodiment) It has been found that it is possible to produce a product. This has led to the realization of a resin composition, a resin sheet, an insulator, a cured resin sheet, and a heat radiating member using the same, which have a high withstand voltage, in a more versatile and simple process.
- the exfoliating compound of this embodiment is excellent not only in electrical insulation but also in heat resistance, chemical resistance, etc., and further in cost performance.
- the insulating resin composition of the present embodiment contains at least one thermosetting resin.
- the thermosetting resin include epoxy resin, oxazine resin, bismaleimide resin, phenol resin, unsaturated polyester resin, and silicone resin. From the viewpoint of electrical insulation, an epoxy resin is preferable.
- the epoxy resin used in the present embodiment is not particularly limited. Examples thereof include bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthalene type epoxy resin and cycloaliphatic epoxy resin. Among these, from the viewpoint of increasing the thermal conductivity, it is preferable to use an epoxy resin having a mesogenic skeleton in the molecule, which is a structure that is easily self-aligned such as a biphenyl group. An epoxy resin having such a mesogenic skeleton in the molecule is disclosed, for example, in JP-A-2005-206814.
- epoxy resin examples include, for example, 1- ⁇ (3-methyl-4-oxiranylmethoxy) phenyl ⁇ -4- (4-oxiranylmethoxyphenyl) -1-cyclohexene, 1- ⁇ (2-methyl -4-oxiranylmethoxy) phenyl ⁇ -4- (4-oxiranylmethoxyphenyl) -1-cyclohexene and 1- ⁇ (3-ethyl-4-oxiranylmethoxy) phenyl ⁇ -4- (4- And oxiranylmethoxyphenyl) -1-cyclohexene.
- the content of the thermosetting resin in the insulating resin composition of the present embodiment is not particularly limited.
- the solid content of the insulating resin composition can be 1% by mass to 50% by mass, and preferably 1% by mass to 10% by mass. Adhesiveness and heat conductivity can be improved more because the content rate of a thermosetting resin is the said range.
- the solid content of the insulating resin composition means a residue obtained by removing volatile components from the insulating resin composition.
- the insulating resin composition of this embodiment contains an inorganic filler.
- at least a part of the inorganic filler is the release compound of the present embodiment.
- the proportion of the exfoliating compound in the inorganic filler is preferably in the range of 0.5 volume% to 10 volume%.
- the content rate of a peeling compound is 0.5 volume% or more, it exists in the tendency for the insulation of an insulating resin composition to improve more.
- the content rate of a peeling compound is 10 volume% or less, it exists in the tendency for the heat conductivity of an insulating resin composition to improve more.
- the inorganic filler other than the exfoliating compound when used, is not particularly limited, and compounds well known in the art can be used. Examples thereof include aluminum oxide (alumina), magnesium oxide, aluminum nitride, boron nitride, silicon nitride, silicon dioxide, aluminum hydroxide, and barium sulfate.
- the inorganic filler other than the exfoliating compound when using an inorganic filler other than the exfoliating compound, may be used alone or in combination of two or more.
- inorganic fillers having different particle diameters may be used in combination.
- the inorganic filler with a small particle diameter enters between the gaps between the inorganic fillers with a large particle diameter, and it is easy to increase the filling of the inorganic filler, and the high thermal conductivity efficiently. Since it is thought that rate improvement is realizable, it is preferable.
- the average particle diameter (D50) of the inorganic filler is preferably 0.1 ⁇ m to 100 ⁇ m, more preferably 0.1 ⁇ m to 70 ⁇ m from the viewpoint of thermal conductivity.
- the method for measuring the average particle size of the inorganic filler is the same as that for particles of a specific composite or the like.
- the content of the entire inorganic filler in the insulating resin composition is not particularly limited. Among them, it is preferably 30% by volume to 95% by volume in the total solid content volume of the insulating resin composition, and more preferably 45% by volume to 90% by volume from the viewpoint of improving thermal conductivity. From the viewpoint of improving the thermal conductivity, it is more preferably 70 to 90% by volume.
- the thermal conductivity of the insulating resin composition tends to be higher.
- the total solid content volume of the insulating resin composition means the total volume of non-volatile components among the components constituting the insulating resin composition.
- the insulating resin composition preferably contains at least one curing agent.
- curing agent there is no restriction
- the thermosetting resin is an epoxy resin
- the curing agent can be appropriately selected from curing agents usually used as a curing agent for epoxy resins. Specific examples include amine curing agents such as dicyandiamide and aromatic diamine, and phenolic curing agents such as phenol novolac resin, cresol novolac resin, and catechol resorcinol novolak resin.
- a phenolic curing agent is preferable, and a phenolic curing agent including a structural unit derived from a bifunctional phenolic compound such as catechol, resorcinol and p-hydroquinone is more preferable.
- the content of the curing agent in the insulating resin composition is not particularly limited.
- the content of the curing agent can be 0.1 to 2.0 equivalents per 1 equivalent of epoxy resin, and 0.5 to 1.5 equivalents from the viewpoint of improving flexibility.
- the number is preferably 0.8, and more preferably 0.8 to 1.1 equivalents from the viewpoint of high thermal conductivity. It exists in the tendency which can improve a thermal conductivity more because content of a hardening
- curing agent is the above-mentioned range.
- the insulating resin composition preferably contains at least one curing catalyst.
- a curing catalyst there is no restriction
- the thermosetting resin is an epoxy resin
- specific examples of the curing catalyst include triphenylphosphine, 2-ethyl-4-methylimidazole, boron trifluoride amine complex, and 1-benzyl-2-methylimidazole. Can be mentioned. Among them, it is preferable to use triphenylphosphine from the viewpoint of achieving high thermal conductivity.
- the content of the curing catalyst in the insulating resin composition is not particularly limited.
- the content of the curing catalyst in the insulating resin composition can be, for example, 0.1% by mass to 2.0% by mass with respect to the epoxy resin, and is 0.5% by mass to 1.5% by mass. It is more preferable. It exists in the tendency which can improve a thermal conductivity more because the content rate of a curing catalyst is the above-mentioned range.
- the insulating resin composition preferably contains at least one coupling agent.
- the coupling agent can be contained for the purpose of, for example, surface treatment of inorganic filler.
- the coupling agent is not particularly limited, and can be appropriately selected from commonly used coupling agents. Specifically, for example, methyltrimethoxysilane (available from Shin-Etsu Chemical Co., Ltd., available as trade name “KBM-13”), 3-mercaptopropyltrimethoxysilane (available from Shin-Etsu Chemical Co., Ltd., trade name “KBM”).
- N-phenyl-3-Aminopropyltrimethoxysilane available from Shin-Etsu Chemical Co., Ltd., trade name “KBM-573”
- 3-aminopropyltrimethoxysilane made by Shin-Etsu Chemical Co., Ltd., trade name “KBM-903”
- 3-glycidyloxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd., trade name “ BM-403 "available as) and the like.
- N-phenyl-3-aminopropyltrimethoxysilane is preferable from the viewpoint of achieving high thermal conductivity.
- the content of the coupling agent in the insulating resin composition is not particularly limited.
- the content of the coupling agent in the insulating resin composition can be, for example, 0.05% by mass to 1.0% by mass with respect to the inorganic filler, and 0.1% by mass to 0.5% by mass. More preferably. It exists in the tendency which can improve heat conductivity more because the content rate of a coupling agent is the above-mentioned range.
- the insulating resin composition may contain at least one solvent.
- the solvent is not particularly limited as long as it does not inhibit the curing reaction of the resin composition, and can be appropriately selected from commonly used organic solvents. Specific examples include ketone solvents such as methyl ethyl ketone and cyclohexanone, and alcohol solvents such as cyclohexanol.
- the insulating resin composition contains a solvent, the content of the solvent in the insulating resin composition is not particularly limited, and can be appropriately selected according to the applicability of the resin composition.
- the insulating resin composition can further contain other additives other than the curing catalyst and the solvent as described above as necessary.
- additives include an elastomer that can improve the peelability and dispersibility of the release compound.
- various additives generally used for resin compositions such as antioxidants, anti-aging agents, stabilizers, flame retardants, and thickeners can be exemplified.
- the content of these additives is not particularly limited as long as the effects of the present invention are not impaired.
- the resin sheet of this embodiment is formed by molding the insulating resin composition of this embodiment into a sheet shape.
- the resin sheet of this embodiment is not particularly limited as long as the insulating resin composition of this embodiment is formed into a sheet shape.
- the resin sheet of the present embodiment is preferably a so-called B stage sheet that is further heat-treated until it is in a semi-cured state (B-suge state).
- B stage is defined by JIS K6900: 1994.
- the resin sheet can be manufactured as follows. After applying a varnish-like insulating resin composition to which a solvent such as methyl ethyl ketone or cyclohexanenon is added on a release film such as a PET (polyethylene terephthalate) film as necessary, the resin composition is dried as necessary. It can be obtained as a physical layer.
- coating can be implemented by a well-known method. Specific examples of the coating method include a comma coating method, a die coating method, a lip coating method, and a gravure coating method.
- a coating method for forming a resin composition layer with a predetermined thickness As a coating method for forming a resin composition layer with a predetermined thickness, a comma coating method for passing an object to be passed between gaps, a die coating method for applying a resin varnish with a flow rate adjusted from a nozzle, or the like is applied. Can do. For example, when the thickness of the resin composition layer before drying is 50 ⁇ m to 500 ⁇ m, it is preferable to use a comma coating method.
- the thickness of the resin sheet can be appropriately selected depending on the purpose, and can be, for example, 50 ⁇ m to 300 ⁇ m, and preferably 60 ⁇ m to 250 ⁇ m from the viewpoint of thermal conductivity and sheet flexibility.
- the resin sheet can also be produced by hot pressing while laminating two or more resin composition layers.
- the insulator of this embodiment is a cured product of the insulating resin composition of this embodiment.
- the insulator according to the present embodiment can be manufactured by the same manufacturing method as in the case of using a normal resin for casting insulator, in which the insulating resin composition according to the present embodiment is injected into a mold. .
- the insulating resin composition of the present embodiment it is possible to obtain an insulator having a higher withstand voltage as compared with an epoxy resin used as a conventional casting resin. Examples of such an insulator include an insulating spacer, an insulating rod, and a molded insulating part.
- the cured resin sheet of the present embodiment is a heat-treated product of the resin sheet of the present embodiment.
- the resin sheet cured product of the present embodiment may be obtained by heat-treating and curing the insulating resin composition of the present embodiment.
- the curing method for curing the insulating resin composition can be appropriately selected according to the configuration of the insulating resin composition, the purpose of the cured resin sheet, and the like.
- the curing method for curing the insulating resin composition is preferably a heat and pressure treatment.
- the conditions for the heat and pressure treatment are, for example, that the heating temperature is 80 ° C. to 250 ° C., the pressure is preferably 0.5 MPa to 8.0 MPa, the heating temperature is 130 ° C.
- the treatment time for the heat and pressure treatment can be appropriately selected according to the heating temperature and the like. For example, it can be 2 to 8 hours, and preferably 4 to 6 hours. Further, the heat and pressure treatment may be performed once, or may be performed twice or more by changing the heating temperature or the like.
- the heat radiating member of this embodiment has a metal work and the resin sheet of this embodiment arrange
- the “metal workpiece” means a molded product including a metal material that can function as a heat dissipation member, including a substrate, fins, and the like.
- the metal workpiece is preferably a substrate composed of various metals such as Al (aluminum) and Cu (copper).
- FIG. 1 a heat radiating member using a resin sheet obtained by molding an insulating resin composition into a sheet shape is illustrated in FIG.
- a resin sheet 10 is located between a first metal workpiece 20 made of, for example, Al (aluminum) and a second metal workpiece 30 made of, for example, Cu (copper), and one side thereof. Is bonded to the surface of the metal workpiece 20, and the other surface is bonded to the surface of the metal workpiece 30. Since the resin sheet 10 has a high dielectric strength voltage, for example, even if a large potential difference is generated between the first metal workpiece 20 and the second metal workpiece 30, the first metal workpiece 20 and the second metal workpiece 20 are provided. It is possible to ensure insulation between the two.
- Example 1 As the non-swellable layered inorganic compound, Indian mascobite (SJ-005, manufactured by Yamaguchi Mica Co., Ltd., thermal decomposition temperature: 600 ° C. to 800 ° C.) was used. SJ-005 expands 0.09 mm in the c-axis direction when heated at 800 ° C. for 1 hour. Powder X-ray diffraction (RINT-2550, manufactured by Rigaku Corporation) measuring the result of, the basal spacing (d 002) value was 9.98A. Further, the particle size distribution was measured using a laser diffraction particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.). As a result, the average particle size was 5.38 ⁇ m.
- SJ-005 manufactured by Yamaguchi Mica Co., Ltd., thermal decomposition temperature: 600 ° C. to 800 ° C.
- SJ-005 expands 0.09 mm in the c-axis direction when heated at 800 ° C. for 1 hour
- Muscovite (0.2 g) and sodium carbonate (2 g) were melted at 950 ° C. for 30 minutes, treated with hydrogen fluoride (HF) to remove Si, and then the residue was 5 mL of 18% by mass hydrochloric acid and 15 mL of water. After heating and dissolving on a hot plate (125 ° C.), the volume was adjusted to about 100 g with water, diluted 10 times, and quantitative analysis was performed by ICP emission spectroscopic analysis (ICP-OES). As a result, the chemical composition of this sample was (K 0.97 Ca 0.01 ) (Al 1.75 Mg 0.11 Fe 3+ 0.11 ) (Si 3.21 Al 0.79 ) O 10 (OH) 2 .
- ICP-OES ICP emission spectroscopic analysis
- the mascovite powder was put in a crucible and heat-treated at 800 ° C. for 1 hour in an electric furnace (SB2025D, manufactured by Motoyama Co., Ltd.). 11.2 g of heat-treated mascobite powder was mixed in a 0.5 M aqueous solution obtained by dissolving dodecylamine hydrochloride (DDA-HCl, manufactured by Tokyo Chemical Industry Co., Ltd.) as an organic compound in 200 mL of distilled water. The mixture (dispersion) was stirred and then refluxed at 120 ° C. for 24 hours, and then washed with water and ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a specific complex. The content of the mascobite powder in the mixture (dispersion) was 2% by volume. The average particle size of the specific composite was 4.50 ⁇ m.
- thermogravimetric differential thermal analyzer (TG-8120, manufactured by Rigaku Corporation) was used. As a result of measuring the mass decrease from 150 ° C. to 800 ° C., the content of dodecylamine hydrochloride was 2.97% by mass.
- FIG. 3 (a) shows a state in which the dispersion liquid that was not subjected to the peeling treatment was allowed to stand for 2 weeks, and FIG.
- Example 1 A specific complex was prepared in the same manner as in Example 1 except that the heat treatment of mascovite was not performed. As a result of XRD measurement, a very strong 9.98 mm bottom reflection was observed, which revealed that dodecylamine hydrochloride was not intercalated between the layers of mascobite. Moreover, the content rate of dodecylamine hydrochloride is 0.95 mass%, and it is thought that it is the amount of organic substances adsorbed on the mica surface. Moreover, the equilibrium filler density after the peeling treatment was 5.90% by volume.
- Example 3 While stirring 600 mL of ethanol at 30 ° C., 200 g of octadecylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved by heating, 125 mL of concentrated hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, and reacted for 3 hours. After the solvent was distilled off with an evaporator, recrystallization was performed with ethanol. The crystals were collected and dried under reduced pressure to obtain octadecylamine hydrochloride (ODA-HCl).
- ODA-HCl octadecylamine hydrochloride
- a specific complex was prepared in the same manner as in Example 1 using the above octadecylamine hydrochloride, distilled water and mascobite powder as the organic compound.
- a decrease in the peak intensity of the 002 reflection was observed.
- Progress of intercalation was confirmed.
- the content of octadecylamine hydrochloride was 13.80% by mass.
- the equilibrium filler density after the peeling treatment was 2.53% by volume.
- Example 5 After refluxing for 24 hours in the same manner as in Example 1, the mascobite precipitated by centrifugation was collected and again mixed with the same amount of dodecylamine hydrochloride aqueous solution. Mixing, refluxing for 24 hours, and centrifugation were repeated, and the refluxing time was adjusted to 48 hours, 72 hours, and 96 hours in total to prepare a specific complex.
- the XRD results of the obtained sample are shown in FIG. Unlike 24 hours of Example 1 (curve (a)), as the reaction time increased to 48 hours (curve (b)), 72 hours (curve (c)), 96 hours (curve (d)), The peak of the intercalated layer shifted to the high angle side, and the peak became sharp.
- the content rate of the dodecylamine hydrochloride was 4.46 mass% (48 hours), 5.31 mass% (72 hours), 5.67 mass% (96 hours).
- the amount of intercalation increased by increasing the reaction time while replacing the solution.
- the equilibrium filler densities after the peeling treatment were 2.71 vol%, 2.53 vol% and 2.19 vol%, respectively. 5 is the curve (a), the second spectrum from the bottom is the curve (b), the second spectrum from the top is the curve (c), and the top spectrum.
- the spectrum is curve (d).
- Table 1 shows the composition of the specific composite prepared in Examples 1 to 5, Comparative Example 1 and Comparative Example 2, the organic compound content, and the equilibrium filler density.
- Example 1 when the dodecylamine hydrochloride content and the equilibrium filler density (Table 1) of Example 1 and Example 2 were compared, the amount of intercalation decreased at a concentration of 2.0M. This is because the viscosity of the solution (the viscosity at 60 ° C. is 1.7 mPa ⁇ s at 0.5 M, 12 mPa ⁇ s at 1.0 M, and 758 mPa ⁇ s at 2.0 M), and the stirring (contact) efficiency is lowered. This is because.
- Example 4 when the dodecylamine hydrochloride content and the equilibrium filler density (Table 1) of Example 1, Example 4 and Example 5 are compared, the dodecylamine hydrochloride content increases as the intercalation time increases. It was confirmed that the equilibrium filler density decreased. It was also shown that the efficiency of intercalation is improved by exchanging the reaction solution every 24 hours.
- Example 6 Using the specific composite (exfoliation compound) after the exfoliation treatment of Example 1 and Example 5 and the mica powder before the exfoliation treatment, the thickness in the c-axis direction was determined by the following method. First, the exfoliating compound was powdered by lyophilization. Next, the exfoliating compound and the mica powder before the exfoliation treatment were each mixed with water, and a dispersant was added to prepare a dispersion slurry. A silicon mold was placed on the gypsum, the slurry was poured, and after 15 minutes of fleshing, it was air-dried overnight to obtain a disk-shaped molded body.
- FIG. 8 is a graph showing the thickness distribution of the specific composite (peeling compound) after the peeling treatment obtained in Example 5 and the mica powder before the peeling treatment obtained in Example 1. Also in the thickness distribution, the mica powder before peeling treatment (FIG. 8a, T 50 is 109 nm), the peeling compound of Example 1 (FIG. 8b, T 50 is 52 nm), and 48 hours of Example 5 (FIG.
- T 50 is 41 nm
- 72 hours (FIG. 8d, T 50 is 36 nm)
- 96 hours (FIG. 8e, T 50 was observed to turn a release of 32 nm) is in progress. It was shown that exfoliation progressed as the amount of intercalation increased. Furthermore, when the average particle diameter of the exfoliating compound of Example 1 and Example 5 was measured with a laser diffraction scattering system particle size distribution measuring device, it was 3.57 ⁇ m (Example 1) and 4.00 ⁇ m (Examples 5 and 48), respectively. Time) and 4.26 ⁇ m (Example 5, 72 hours) and 4.35 ⁇ m (Example 5, 96 hours).
- Example 7 Synthesis of catechol resorcinol novolak (CRN) resin
- CRN catechol resorcinol novolak
- catechol resorcinol novolak resin was taken out.
- the resulting catechol resorcinol novolak resin had a number average molecular weight of 530 and a weight average molecular weight of 930.
- the hydroxyl equivalent of the catechol resorcinol novolak resin was 65 g / eq.
- the catechol resorcinol novolak resin obtained above was used in the following examples.
- the obtained resin sheet coating solution is applied to a release surface of a polyethylene terephthalate film (Fujimori Kogyo Co., Ltd., 75E-0010CTR-4, hereinafter abbreviated as PET film) to a thickness of about 300 ⁇ m. It was coated and allowed to stand for 15 minutes in a normal state, and then dried in a box oven at 100 ° C. for 30 minutes to form a resin composition layer on the PET film. Next, the upper surface of the resin composition layer that has been in contact with air is covered with a PET film, and flattened by hot pressing (upper hot plate 150 ° C., lower hot plate 80 ° C., pressure 1.5 MPa, treatment time 3 minutes). A B stage sheet was obtained as a resin sheet having a thickness of 200 ⁇ m.
- PET film polyethylene terephthalate film
- the PET film is peeled off from both sides of the resin sheet (B stage sheet) obtained by the above method, and both sides are sandwiched between 105 ⁇ m-thick copper foil (GTS foil, manufactured by Furukawa Electric Co., Ltd.) and vacuum hot press (upper hot plate 150 °C, lower heating plate 80 °C, vacuum degree 1 kPa or less, pressure 4 MPa, treatment time 7 minutes), then put in a box type oven for 2 hours at 140 °C, 2 hours at 165 °C, 2 hours at 190 °C Curing was performed by step cure. Copper was etched away from the obtained copper foil sandwich cured product using a sodium persulfate solution to obtain a cured product of an insulating resin sheet.
- GTS foil manufactured by Furukawa Electric Co., Ltd.
- vacuum hot press upper hot plate 150 °C, lower heating plate 80 °C, vacuum degree 1 kPa or less, pressure 4 MPa, treatment time 7 minutes
- the thermal conductivity was 8.3 W / (m ⁇ K). Further, when the insulation by a BDV (Break Down Voltage) method was measured as described later, the lowest value was 25.1 kV / mm and the average value was 25.9 kV / mm.
- the thermal diffusivity of the sheet was measured using a Nanoflash LFA447 Xe flash method thermal diffusivity measuring apparatus manufactured by NETZSCH.
- the thermal conductivity (W / (m ⁇ K)) was calculated by multiplying the numerical value of the obtained thermal diffusivity by the specific heat Cp (J / g ⁇ K) and the density d (g / cm 3 ). All measurements were performed at 25 ⁇ 1 ° C.
- the cured resin sheet obtained above was sandwiched between cylindrical electrodes having a diameter of 25 mm using a DAC-6032C dielectric breakdown tester manufactured by Soken Denki Co., Ltd., with a boosting speed of 500 V / s, an alternating current of 50 Hz, a step voltage of 0.50 kV, The voltage holding time was 60 s, measured at 25 ° C. in oil.
- Example 8 In a 100 cm 3 plastic bottle, 0.0960 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-573”) as a coupling agent, and the above as a curing agent 4.6680 parts by mass (solid content: 50% by mass) of the catechol resorcinol novolak resin dissolved in cyclohexanone synthesized in (1) was added in this order.
- KBM-573 N-phenyl-3-aminopropyltrimethoxysilane
- the obtained resin sheet coating solution is applied on the release surface of the PET film using an applicator so that the thickness is about 300 ⁇ m, and left for 15 minutes in a normal state, and then dried in a box oven at 100 ° C. for 30 minutes.
- the resin composition layer was formed on the PET film.
- the upper surface of the resin composition layer that has been in contact with air is covered with a PET film, and flattened by hot pressing (upper hot plate 150 ° C., lower hot plate 80 ° C., pressure 1.5 MPa, treatment time 3 minutes).
- a B stage sheet was obtained as a resin sheet having a thickness of 200 ⁇ m.
- the PET film is peeled off from both sides of the resin sheet (B stage sheet) obtained by the above method, and both sides are sandwiched between 105 ⁇ m-thick copper foil (GTS foil, manufactured by Furukawa Electric Co., Ltd.) and vacuum hot press (upper hot plate 150 °C, lower heating plate 80 °C, vacuum degree 1 kPa or less, pressure 4 MPa, treatment time 7 minutes), then put in a box type oven for 2 hours at 140 °C, 2 hours at 165 °C, 2 hours at 190 °C Curing was performed by step cure. Copper was etched away from the obtained copper foil sandwich cured product using a sodium persulfate solution to obtain a cured product of an insulating resin sheet.
- GTS foil manufactured by Furukawa Electric Co., Ltd.
- vacuum hot press upper hot plate 150 °C, lower heating plate 80 °C, vacuum degree 1 kPa or less, pressure 4 MPa, treatment time 7 minutes
- the thermal conductivity was 8.0 W / (m ⁇ K). Further, when the insulation property by the BDV method was measured, the lowest value was 25.6 kV / mm, and the average value was 28.4 kV / mm.
- Example 9 In a 250 cm 3 plastic bottle, 4.1190 parts by mass (solid content 50% by mass) of the catechol resorcinol novolak resin synthesized above as a curing agent and 1- (3-methyl-4-hydroxyphenyl)- 1- ⁇ (3-methyl-4-oxiranylmethoxy) phenyl ⁇ -4- (4-oxiranylmethoxyphenyl) -1 synthesized from 4- (4-hydroxyphenyl) -1-cyclohexene and epichlorohydrin -6.6775 parts by mass of cyclohexene (epoxy resin), 0.0707 parts by mass of triphenylphosphine (manufactured by Wako Pure Chemical Industries, Ltd., curing catalyst), and 25.90 parts by mass of cyclohexanone (manufactured by Wako Pure Chemical Industries, Ltd.) And mixed.
- Example 5 Thereafter, 37.38 parts by mass of boron nitride particles (volume average particle diameter of 40 ⁇ m, manufactured by Mizushima Alloy Iron Co., Ltd., trade name “HP-40MF100”) as inorganic filler and exfoliation obtained in Example 5 (96 hours) 0.3188 parts by mass of a compound (c-axis direction thickness 32 nm, average particle size 4.35 ⁇ m) was added and further mixed to obtain a resin sheet coating solution as an insulating resin composition.
- boron nitride particles volume average particle diameter of 40 ⁇ m, manufactured by Mizushima Alloy Iron Co., Ltd., trade name “HP-40MF100”
- the obtained resin sheet coating solution is applied on the release surface of the PET film using an applicator so that the thickness is about 300 ⁇ m, and left standing for 10 minutes in a normal state, and then dried in a box oven at 100 ° C. for 10 minutes.
- the resin composition layer was formed on the PET film. After stacking two PET films on which the resin composition layer is formed so that the resin composition layers face each other, hot pressing (upper hot plate 150 ° C., lower hot plate 150 ° C., pressure 15 MPa, treatment time 4 minutes) ) To obtain a B stage sheet as a resin sheet having a thickness of 200 ⁇ m.
- the PET film is peeled off from both sides of the resin sheet (B stage sheet) obtained by the above-described method, and both sides are sandwiched between 105 ⁇ m thick copper foil (GTS foil, manufactured by Furukawa Electric Co., Ltd.) and vacuum hot press (upper hot plate 170 °C, lower heating plate 170 °C, vacuum degree 1 kPa or less, pressure 10 MPa, treatment time 7 minutes), then put into a box-type oven and cured by step cure at 160 °C for 30 minutes and 190 °C for 2 hours It was. Copper was etched away from the obtained copper foil sandwich cured product using a sodium persulfate solution to obtain a cured product of an insulating resin sheet.
- GTS foil manufactured by Furukawa Electric Co., Ltd.
- vacuum hot press upper hot plate 170 °C, lower heating plate 170 °C, vacuum degree 1 kPa or less, pressure 10 MPa, treatment time 7 minutes
- the thermal conductivity was 10.0 W / (m ⁇ K).
- the minimum value was 28.5 kV / mm and the average value was 30.4 kV / mm.
- Example 10 In a 100 cm 3 plastic bottle, 0.0960 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-573”) as a coupling agent, and the above as a curing agent 4.6680 parts by mass (solid content: 50% by mass) of the catechol resorcinol novolak resin dissolved in cyclohexanone synthesized in (1) was added in this order.
- KBM-573 N-phenyl-3-aminopropyltrimethoxysilane
- the obtained resin sheet coating solution is applied on the release surface of the PET film using an applicator so that the thickness is about 300 ⁇ m, and left for 15 minutes in a normal state, and then dried in a box oven at 100 ° C. for 30 minutes.
- the resin composition layer was formed on the PET film.
- the upper surface of the resin composition layer that has been in contact with air is covered with a PET film, and flattened by hot pressing (upper hot plate 150 ° C., lower hot plate 80 ° C., pressure 1.5 MPa, treatment time 3 minutes).
- a B stage sheet was obtained as a resin sheet having a thickness of 200 ⁇ m.
- the PET film is peeled off from both sides of the resin sheet (B stage sheet) obtained by the above method, and both sides are sandwiched between 105 ⁇ m-thick copper foil (GTS foil, manufactured by Furukawa Electric Co., Ltd.) and vacuum hot press (upper hot plate 150 °C, lower heating plate 80 °C, vacuum degree 1 kPa or less, pressure 4 MPa, treatment time 7 minutes), then put in a box type oven for 2 hours at 140 °C, 2 hours at 165 °C, 2 hours at 190 °C Curing was performed by step cure. Copper was etched away from the obtained copper foil sandwich cured product using a sodium persulfate solution to obtain a cured product of an insulating resin sheet.
- GTS foil manufactured by Furukawa Electric Co., Ltd.
- vacuum hot press upper hot plate 150 °C, lower heating plate 80 °C, vacuum degree 1 kPa or less, pressure 4 MPa, treatment time 7 minutes
- the thermal conductivity was 1.4 W / (m ⁇ K).
- the lowest value was 18.5 kV / mm and the average value was 20.5 kV / mm.
- the obtained resin sheet coating solution is applied on the release surface of the PET film using an applicator so that the thickness is about 300 ⁇ m, and left for 15 minutes in a normal state, and then dried in a box oven at 100 ° C. for 30 minutes.
- the resin composition layer was formed on the PET film.
- the upper surface of the resin composition layer that has been in contact with air is covered with a PET film, and flattened by hot pressing (upper hot plate 150 ° C., lower hot plate 80 ° C., pressure 1.5 MPa, treatment time 3 minutes).
- a B stage sheet was obtained as a resin sheet having a thickness of 200 ⁇ m.
- the PET film is peeled off from both sides of the resin sheet (B stage sheet) obtained by the above method, and both sides are sandwiched between 105 ⁇ m-thick copper foil (GTS foil, manufactured by Furukawa Electric Co., Ltd.) and vacuum hot press (upper hot plate 150 °C, lower heating plate 80 °C, vacuum degree 1 kPa or less, pressure 4 MPa, treatment time 7 minutes), then put in a box type oven for 2 hours at 140 °C, 2 hours at 165 °C, 2 hours at 190 °C Curing was performed by step cure. Copper was etched away from the obtained copper foil sandwich cured product using a sodium persulfate solution to obtain a cured product of an insulating resin sheet.
- GTS foil manufactured by Furukawa Electric Co., Ltd.
- vacuum hot press upper hot plate 150 °C, lower heating plate 80 °C, vacuum degree 1 kPa or less, pressure 4 MPa, treatment time 7 minutes
- the thermal conductivity was 8.9 W / (m ⁇ K).
- the lowest value was 19.5 kV / mm, and the average value was 25.4 kV / mm.
- the obtained resin sheet coating solution is applied on the release surface of the PET film using an applicator so that the thickness is about 300 ⁇ m, and left standing for 10 minutes in a normal state, and then dried in a box oven at 100 ° C. for 10 minutes.
- the resin composition layer was formed on the PET film. After stacking two PET films on which the resin composition layer is formed so that the resin composition layers face each other, hot pressing (upper hot plate 150 ° C., lower hot plate 150 ° C., pressure 15 MPa, treatment time 4 minutes) ) To obtain a B stage sheet as a resin sheet having a thickness of 200 ⁇ m.
- the PET film is peeled off from both sides of the resin sheet (B stage sheet) obtained by the above-described method, and both sides are sandwiched between 105 ⁇ m thick copper foil (GTS foil, manufactured by Furukawa Electric Co., Ltd.) and vacuum hot press (upper hot plate 170 °C, lower heating plate 170 °C, vacuum degree 1 kPa or less, pressure 10 MPa, treatment time 7 minutes), then put into a box-type oven and cured by step cure at 160 °C for 30 minutes and 190 °C for 2 hours It was. Copper was etched away from the obtained copper foil sandwich cured product using a sodium persulfate solution to obtain a cured product of an insulating resin sheet.
- GTS foil manufactured by Furukawa Electric Co., Ltd.
- vacuum hot press upper hot plate 170 °C, lower heating plate 170 °C, vacuum degree 1 kPa or less, pressure 10 MPa, treatment time 7 minutes
- the thermal conductivity was 10.1 W / (m ⁇ K).
- the minimum value was 25.6 kV / mm and the average value was 30.0 kV / mm.
- the obtained resin sheet coating solution is applied on the release surface of the PET film using an applicator so that the thickness is about 300 ⁇ m, and left for 15 minutes in a normal state, and then dried in a box oven at 100 ° C. for 30 minutes.
- the resin composition layer was formed on the PET film.
- the upper surface of the resin composition layer that has been in contact with air is covered with a PET film, and flattened by hot pressing (upper hot plate 150 ° C., lower hot plate 80 ° C., pressure 1.5 MPa, treatment time 3 minutes).
- a B stage sheet was obtained as a resin sheet having a thickness of 200 ⁇ m.
- the PET film is peeled off from both sides of the resin sheet (B stage sheet) obtained by the above method, and both sides are sandwiched between 105 ⁇ m-thick copper foil (GTS foil, manufactured by Furukawa Electric Co., Ltd.) and vacuum hot press (upper hot plate 150 °C, lower heating plate 80 °C, vacuum degree 1 kPa or less, pressure 4 MPa, treatment time 7 minutes), then put in a box type oven for 2 hours at 140 °C, 2 hours at 165 °C, 2 hours at 190 °C Curing was performed by step cure. Copper was etched away from the obtained copper foil sandwich cured product using a sodium persulfate solution to obtain a cured product of an insulating resin sheet.
- GTS foil manufactured by Furukawa Electric Co., Ltd.
- vacuum hot press upper hot plate 150 °C, lower heating plate 80 °C, vacuum degree 1 kPa or less, pressure 4 MPa, treatment time 7 minutes
- the thermal conductivity was 1.5 W / (m ⁇ K).
- the minimum value was 15.1 kV / mm and the average value was 20.0 kV / mm.
- Table 2 summarizes the results of examination of the thermal conductivity and BDV of the thermally conductive insulating sheets produced in Examples 7 to 10 and Comparative Examples 3 to 5.
- the resin sheet composed of the insulating resin composition of the present invention is excellent in insulating properties by the addition of the release compound of the present invention.
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Abstract
Description
また、本発明は、機械的処理によって、高いアスペクト比を有する剥離化された層状無機化合物及びその製造方法を提供することを目的とする。
更に本発明は、高い絶縁耐電圧を備える絶縁性樹脂組成物、樹脂シート、絶縁物、樹脂シート硬化物及び放熱部材を提供することを目的とする。
加熱処理された前記非膨潤性層状無機化合物を媒体に分散させた分散液中で、前記非膨潤性層状無機化合物に有機化合物をインターカレートさせて前記非膨潤性層状無機化合物の層間に有機化合物を挿入する工程と、
を有し、
前記非膨潤性層状無機化合物は、単位結晶層が互いに積み重なって層状構造をなしており、熱分解温度の上限値で1時間加熱することによって0.05Å~0.20Åの範囲でc軸方向に膨張し、熱分解温度の上限値で1時間加熱することによって前記単位結晶層の結晶構造が変化しないものである層状無機化合物と有機化合物との複合体の製造方法。
前記分散液中における前記非膨潤性層状無機化合物の含有率が0.5体積%~50体積%である<1>~<3>のいずれか1項に記載の層状無機化合物と有機化合物との複合体の製造方法。
加熱処理された前記非膨潤性層状無機化合物を媒体に分散させた分散液中で、前記非膨潤性層状無機化合物に有機化合物をインターカレートさせて前記非膨潤性層状無機化合物の層間に有機化合物を挿入する工程と、
前記分散液に機械的処理にてせん断力を加えてインターカレートされた前記非膨潤性層状無機化合物を剥離化する工程と、
を有し、
前記非膨潤性層状無機化合物は、単位結晶層が互いに積み重なって層状構造をなしており、熱分解温度の上限値で1時間加熱することによって0.05Å~0.20Åの範囲でc軸方向に膨張し、熱分解温度の上限値で1時間加熱することによって前記単位結晶層の結晶構造が変化しないものである剥離化された層状無機化合物の製造方法。
前記非膨潤性層状無機化合物は、単位結晶層が互いに積み重なって層状構造をなしており、熱分解温度の上限値で1時間加熱することによって0.05Å~0.20Åの範囲でc軸方向に膨張し、熱分解温度の上限値で1時間加熱することによって前記単位結晶層の結晶構造が変化しないものである層状無機化合物と有機化合物との複合体。
また、本発明によれば、機械的処理によって、高いアスペクト比を有する剥離化された層状無機化合物及びその製造方法が提供される。
更に本発明によれば、高い絶縁耐電圧を備える絶縁性樹脂組成物、樹脂シート、絶縁物、樹脂シート硬化物及び放熱部材が提供される。
本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の目的が達成されれば、本用語に含まれる。
また「~」を用いて示された数値範囲は、「~」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。
本明細書中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
さらに、組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。
さらに、組成物中の各成分の粒子径は、組成物中に各成分に該当する粒子が複数種存在する場合、特に断らない限り、組成物中に存在する当該複数種の粒子の混合物についての値を意味する。
また、本明細書において「樹脂組成物層」との語は、平面図として観察したときに、全面に形成されている形状の構成に加え、一部に形成されている形状の構成も包含される。
本実施形態の層状無機化合物と有機化合物との複合体(以下、特定複合体と称することがある。)の製造方法は、非膨潤性層状無機化合物を、前記非膨潤性層状無機化合物の熱分解温度の範囲内で加熱処理する工程と、加熱処理された前記非膨潤性層状無機化合物を媒体に分散させた分散液中で、前記非膨潤性層状無機化合物に有機化合物をインターカレートさせて前記非膨潤性層状無機化合物の層間に有機化合物を挿入する工程と、を有し、前記非膨潤性層状無機化合物として、単位結晶層が互いに積み重なって層状構造をなしており、熱分解温度の上限値で1時間加熱することによって0.05Å~0.20Åの範囲でc軸方向に膨張し、熱分解温度の上限値で1時間加熱することによって前記単位結晶層の結晶構造が変化しないものを用いる方法である。
また、本実施形態の特定複合体は、非膨潤性層状無機化合物に有機化合物をインターカレートしてなり、非膨潤性層状無機化合物として、単位結晶層が互いに積み重なって層状構造をなしており、熱分解温度の上限値で1時間加熱することによって0.05Å~0.20Åの範囲でc軸方向に膨張し、熱分解温度の上限値で1時間加熱することによって単位結晶層の結晶構造が変化しないものを用いるものである。本実施形態の特定複合体は、上述の製造方法によって容易に得ることが可能である。
本実施形態の特定複合体は、層状無機化合物を剥離化する際の前段階の物質として有用である。
本実施形態において用いられる非膨潤性層状無機化合物としては、マイカ、カオリナイト、パイロフィライト等が挙げられる。これらの中でも、絶縁性に優れるマイカが好ましい。非膨潤性のマイカとしては、白雲母、黒雲母、パラゴナイト、マーガライト、クリントナイト、アナンダイト、クロライト、フロゴパイト、レピドライト、マスコバイト、バイオタイト、テニオライト、テトラシリシックマイカ等が挙げられる。ただし、本実施形態で用いられる非膨潤性層状無機化合物としては、熱分解温度の上限値で1時間加熱することによって0.05Å~0.20Åの範囲でc軸方向に膨張し、熱分解温度の上限値で1時間加熱することによって単位結晶層の結晶構造が変化しないことが必要である。本実施形態において、非膨潤性層状無機化合物としてマイカが用いられる場合、マイカの種類は特に限定されるものではなく、天然物であってもよく、水熱合成、溶融法、固相法等による合成物であってもよい。
なお、非膨潤性層状無機化合物は、単位結晶層が互いに積み重なって層状構造をなす化合物である。
本実施形態において使用可能なホスホニウム塩としては、トリヘキシルホスホニウム塩等が挙げられる。
本実施形態において使用可能なイミダゾリウム塩としては、1-エチル-3-メチルイミダゾリウム塩等が挙げられる。
本実施形態において使用可能なピリジニウム塩としては、N-アルキルピリジニウム塩等が挙げられる。
本実施形態において使用可能なスルホニウム塩としては、トリアリールスルホニウム塩等が挙げられる。
本実施形態において使用可能なヨードニウム塩としては、N-アルキルヨードニウム塩等が挙げられる。
なお、非膨潤性層状無機化合物の熱分解温度は、上限値と下限値とを有する温度範囲を意味する。
本実施形態において、非膨潤性層状無機化合物の熱分解温度の確認方法の詳細は、以下の通りである。熱分解温度は、熱重量測定(Thermo Gravimetry、TG)及び示差熱分析(Differential Thermal Analysis、DTA)を用いることで測定が可能である。非膨潤性層状無機化合物を500℃以上で加熱し、DTAの、吸熱反応及び発熱反応のピーク形状、吸熱反応及び発熱反応のピーク温度等から熱分解温度を簡易的に測定することが可能である。詳細な方法としては、加熱した非膨潤性層状無機化合物についての構造水のピーク波長、結晶構造の変化等を、赤外吸収又はX線回折装置を用いて観察することが好ましい。
未反応の有機化合物を除去する方法としては、例えば、インターカレートした特定複合体を水又は有機溶剤に分散し、ろ過、フィルタープレス、遠心分離等で回収する洗浄方法が挙げられる。洗浄に用いる溶剤としては、インターカレートした有機化合物の溶解度が高い溶剤が好ましい。
本実施形態の剥離化された層状無機化合物(以下、剥離化化合物と称することがある。)の製造方法は、非膨潤性層状無機化合物を、前記非膨潤性層状無機化合物の熱分解温度の範囲内で加熱処理する工程と、加熱処理された前記非膨潤性層状無機化合物を媒体に分散させた分散液中で、前記非膨潤性層状無機化合物に有機化合物をインターカレートさせて前記非膨潤性層状無機化合物の層間に有機化合物を挿入する工程と、前記分散液に機械的処理にてせん断力を加えてインターカレートされた前記非膨潤性層状無機化合物を剥離化する工程と、を有し、前記非膨潤性層状無機化合物として、単位結晶層が互いに積み重なって層状構造をなしており、熱分解温度の上限値で1時間加熱することによって0.05Å~0.20Åの範囲でc軸方向に膨張し、熱分解温度の上限値で1時間加熱することによって前記単位結晶層の結晶構造が変化しないものを用いる方法である。
また、本実施形態の剥離化化合物は、c軸方向の平均粒子厚さが1nm~80nmである剥離化された層状無機化合物である。本実施形態の剥離化化合物は、上述の製造方法によって容易に得ることが可能である。
本実施形態の剥離化化合物の製造方法において、非膨潤性層状無機化合物を、非膨潤性層状無機化合物の熱分解温度の範囲内で加熱処理する工程と、非膨潤性層状無機化合物の層間に有機化合物を挿入する工程とは、上述の本実施形態の特定複合体の製造方法の場合と同様であり、用いられる材料、処理条件等として同様のものを適用可能である。
本実施形態の剥離化化合物の製造方法によれば、例えば、層状無機化合物をc軸方向の平均粒子厚さが1nm~80nmの範囲まで剥離化することが可能となる。
機械的処理後の剥離化化合物スラリーを試験管に一定量加え、室温(25℃)で2週間静置する。2週間静置後の剥離化化合物の沈降高さを測定することで、式(3)により平衡フィラ密度の算出が可能である。
例えば、エポキシ樹脂等の熱硬化性樹脂との複合化によって、絶縁性、耐電圧性、耐熱性等に優れた絶縁樹脂材料の開発に繋がる。
本実施形態の絶縁性樹脂組成物は、熱硬化性樹脂と無機フィラとを含有し、無機フィラの少なくとも一部を本実施形態の剥離化化合物としたものである。
(熱硬化性樹脂)
本実施形態の絶縁性樹脂組成物は、熱硬化性樹脂の少なくとも一種を含有する。熱硬化性樹脂としては、例えば、エポキシ樹脂、オキサジン樹脂、ビスマレイミド樹脂、フェノール樹脂、不飽和ポリエステル樹脂及びシリコーン樹脂が挙げられる。電気絶縁性の観点から、エポキシ樹脂が好ましい。
本実施形態の絶縁性樹脂組成物は、無機フィラを含有する。本実施形態において無機フィラの少なくとも一部が本実施形態の剥離化化合物とされる。
剥離化化合物の無機フィラに占める割合は、0.5体積%~10体積%の範囲とすることが好ましい。剥離化化合物の含有率が0.5体積%以上の場合、絶縁性樹脂組成物の絶縁性がより向上する傾向にある。一方、剥離化化合物の含有率が10体積%以下の場合、絶縁性樹脂組成物の熱伝導率がより向上する傾向にある。
無機フィラの平均粒子径(D50)は、熱伝導性の観点から、0.1μm~100μmであることが好ましく、0.1μm~70μmであることがより好ましい。
本実施形態において、無機フィラの平均粒子径の測定方法は、特定複合体等の粒子の場合と同様である。
本実施形態の一実施形態では、無機フィラとしてアルミナを使用することが好ましく、互いに異なる粒子径を有するアルミナを組み合わせて使用することがより好ましい。
なお、絶縁性樹脂組成物の全固形分体積とは、絶縁性樹脂組成物を構成する成分のうち、非揮発性成分の総体積を意味する。
絶縁性樹脂組成物は、硬化剤の少なくとも1種を含むことが好ましい。硬化剤としては特に制限はなく、熱硬化性樹脂の種類に応じて適宜選択できる。特に熱硬化性樹脂がエポキシ樹脂である場合、硬化剤としてはエポキシ樹脂用硬化剤として通常用いられる硬化剤から適宜選択して用いることができる。具体的には、ジシアンジアミド、芳香族ジアミン等のアミン系硬化剤、フェノールノボラック樹脂、クレゾールノボラック樹脂、カテコールレゾルシノールノボラック樹脂等のフェノール系硬化剤などを挙げることができる。中でも熱伝導率向上の観点から、フェノール系硬化剤であることが好ましく、カテコール、レゾルシノール及びp-ハイドロキノンといった2官能フェノール性化合物由来の構造単位を含むフェノール系硬化剤であることがより好ましい。
硬化剤の含有量が上述の範囲であることで、熱伝導率をより向上することができる傾向にある。
絶縁性樹脂組成物は、硬化触媒の少なくとも1種を含むことが好ましい。硬化触媒としては特に制限はなく、熱硬化性樹脂の種類に応じて、通常用いられる硬化触媒から適宜選択して用いることができる。熱硬化性樹脂がエポキシ樹脂である場合、硬化触媒として具体的には、例えば、トリフェニルホスフィン、2-エチル-4-メチルイミダゾール、三フッ化ホウ素アミン錯体及び1-ベンジル-2-メチルイミダゾールを挙げることができる。中でも高熱伝導化の観点から、トリフェニルホスフィンを使用することが好ましい。
硬化触媒の含有率が上述の範囲であることで、熱伝導率をより向上することができる傾向にある。
絶縁性樹脂組成物は、カップリング剤の少なくとも1種を含むことが好ましい。カップリング剤は、例えば無機フィラの表面処理を目的に含有することができる。
カップリング剤としては特に制限されず、通常用いられるカップリング剤から適宜選択することができる。具体的には、例えば、メチルトリメトキシシラン(信越化学工業株式会社製、商品名「KBM-13」として入手可能)、3-メルカプトプロピルトリメトキシシラン(信越化学工業株式会社製、商品名「KBM-803」として入手可能)、3-トリエトキシシリル-N-(1,3-ジメチル-ブチリデン)プロピルアミン(信越化学工業株式会社製、商品名「KBE-9103」として入手可能)、N-フェニル-3-アミノプロピルトリメトキシシラン(信越化学工業株式会社製、商品名「KBM-573」として入手可能)、3-アミノプロピルトリメトキシシラン(信越化学工業株式会社製、商品名「KBM-903」として入手可能)及び3-グリシジルオキシプロピルトリメトキシシラン(信越化学工業株式会社製、商品名「KBM-403」として入手可能)が挙げられる。中でも、高熱伝導化の観点から、N-フェニル-3-アミノプロピルトリメトキシシランが好ましい。
カップリング剤の含有率が上述の範囲であることで、熱伝導率をより向上することができる傾向にある。
絶縁性樹脂組成物は、溶剤の少なくとも1種を含んでいてもよい。溶剤としては樹脂組成物の硬化反応を阻害しないものであれば特に制限はなく、通常用いられる有機溶剤から適宜選択して用いることができる。具体的には、メチルエチルケトン、シクロヘキサノン等のケトン溶剤、シクロヘキサノール等のアルコール溶剤などを挙げることができる。
絶縁性樹脂組成物が溶剤を含有する場合、絶縁性樹脂組成物における溶剤の含有量は特に制限されず、樹脂組成物の塗布性等に応じて適宜選択することができる。
絶縁性樹脂組成物は、上記に示したような硬化触媒及び溶剤以外のその他の添加剤を必要に応じて更に含むことができる。その他の添加剤としては、剥離化化合物の剥離性及び分散性を向上させることができるエラストマ等を挙げることができる。その他に、酸化防止剤、老化防止剤、安定剤、難燃剤、増粘剤等の樹脂組成物に一般に用いられる各種添加剤を挙げることができる。絶縁性樹脂組成物が添加剤を更に含有する場合、これらの添加剤の含有量は本発明の効果を損なわない範囲であれば特に制限されない。
本実施形態の樹脂シートは、本実施形態の絶縁性樹脂組成物をシート状に成形してなるものである。
なお、本明細書においてBステージとの用語は、JIS K6900:1994の定義による。
塗布は、公知の方法により実施することができる。塗布方法として、具体的には、コンマコート法、ダイコート法、リップコート法、グラビアコート法等の方法が挙げられる。所定の厚みに樹脂組成物層を形成するための塗布方法としては、ギャップ間に被塗工物を通過させるコンマコート法、ノズルから流量を調整した樹脂ワニスを塗布するダイコート法等を適用することができる。例えば、乾燥前の樹脂組成物層の厚みが50μm~500μmである場合、コンマコート法を用いることが好ましい。
本実施形態の絶縁物は、本実施形態の絶縁性樹脂組成物の硬化物である。本実施形態の絶縁物は、本実施形態の絶縁性樹脂組成物を金型に注入するような、通常の注型絶縁物用樹脂を使用した場合と同様の製造方法により、製造することができる。本実施形態の絶縁性樹脂組成物を用いることで、従来の注型樹脂として用いられているエポキシ樹脂に比べて、高い絶縁耐電圧を備える絶縁物を得ることができる。そのような絶縁物としては、絶縁スペーサ、絶縁ロッド、成形絶縁部品等が挙げられる。
本実施形態の樹脂シート硬化物は、本実施形態の樹脂シートの熱処理物である。
本実施形態の樹脂シート硬化物は、本実施形態の絶縁性樹脂組成物を加熱処理して硬化してなるものであってもよい。絶縁性樹脂組成物を硬化する硬化方法は、絶縁性樹脂組成物の構成、樹脂シート硬化物の目的等に応じて適宜選択することができる。絶縁性樹脂組成物を硬化する硬化方法は、中でも、加熱加圧処理であることが好ましい。加熱加圧処理の条件は例えば、加熱温度が80℃~250℃で、圧力が0.5MPa~8.0MPaであることが好ましく、加熱温度が130℃~230℃で、圧力が1.5MPa~5.0MPaであることがより好ましい。
加熱加圧処理する処理時間は、加熱温度等に応じて適宜選択できる。例えば2時間~8時間とすることができ、4時間~6時間であることが好ましい。
また加熱加圧処理は1回で行ってもよく、加熱温度等を変化させて2回以上行ってもよい。
本実施形態の放熱部材は、金属ワークと、前記金属ワーク上に配置された本実施形態の樹脂シート又は本実施形態の樹脂シート硬化物とを有する。
ここで「金属ワーク」とは、基板、フィン等を含む、放熱部材として機能することができる金属材料を含む成形品を意味する。本実施形態の一態様では、金属ワークはAl(アルミニウム)、Cu(銅)等の各種金属から構成される基板であることが好ましい。
図1において、樹脂シート10は、例えばAl(アルミニウム)から構成される第一の金属ワーク20と、例えばCu(銅)から構成される第二の金属ワーク30との間に位置し、その片面は金属ワーク20表面に接着し、他面は金属ワーク30表面に接着している。
樹脂シート10は高い絶縁耐電圧を備えるため、例えば、第一の金属ワーク20と第二の金属ワーク30との間に大きな電位差が生じても、第一の金属ワーク20と第二の金属ワーク30との間の絶縁性を確保できる。
非膨潤性層状無機化合物としては、インド産マスコバイト(SJ-005、株式会社ヤマグチマイカ製、熱分解温度600℃~800℃)を使用した。SJ-005は、800℃1時間加熱することによりc軸方向に0.09Å膨張するものである。粉末X線回折(RINT-2550、株式会社リガク製)測定を行った結果、底面間隔(d002)値は9.98Åであった。また、レーザー回折式粒度分布測定装置(LA-920、株式会社堀場製作所製)を用いて粒度分布を測定した結果、平均粒子径は5.38μmであった。マスコバイト(0.2g)と炭酸ナトリウム(2g)を950℃30分の条件で融解後、フッ化水素(HF)処理をしてSiを除いた後、残渣に18質量%塩酸5mL及び水15mLを加えてホットプレート(125℃)上で加熱及び溶解後、水で約100gに定容して、10倍に希釈後、ICP発光分光分析(ICP-OES)により定量分析を行った。その結果、本試料の化学組成は、(K0.97Ca0.01)(Al1.75Mg0.11Fe3+ 0.11)(Si3.21Al0.79)O10(OH)2であった。
混合液(分散液)中のマスコバイト粉末の含有率は2体積%であった。
特定複合体の平均粒子径は4.50μmであった。
なお、図2における一番下のスペクトルが曲線(a)であり、下から二番目のスペクトルが曲線(b)であり、一番上のスペクトルが曲線(c)である。
マスコバイトの加熱処理を行わない以外は実施例1と同様に特定複合体を調製した。XRD測定の結果、非常に強い9.98Åの底面反射が観察され、ドデシルアミン塩酸塩がマスコバイトの層間にインターカレートしていないことが明らかとなった。また、ドデシルアミン塩酸塩の含有率は、0.95質量%であり、マイカ表面に吸着している有機物量であると考えられる。また、剥離処理後の平衡フィラ密度は、5.90体積%であった。
マスコバイトの加熱処理温度を1000℃とした以外は実施例1と同様に特定複合体を調製した。XRD測定(図4)の結果、マスコバイト粉末(曲線(a))と比較して、加熱処理のみの場合でも、002反射のピーク強度の低下が観察された(曲線(b))。しかしながら、インターカレート前後において、ピーク強度の変化はほとんど観察されなかった(曲線(c))。また、ドデシルアミン塩酸塩の含有率は、0.68質量%であった。また、剥離処理後の平衡フィラ密度は、8.79体積%であった。
なお、図4における一番下のスペクトルが曲線(a)であり、下から二番目のスペクトルが曲線(b)であり、一番上のスペクトルが曲線(c)である。
ドデシルアミン塩酸塩の濃度を1.0M又は2.0Mにした以外は実施例1と同様にして特定複合体を調製した。XRD測定の結果、全ての濃度でピーク強度の低下した002反射と2θ=3°~2°にかけてのピークの上昇が観察され、インターカレートが進行していることが明らかとなった。また、ドデシルアミン塩酸塩の含有率は1.0Mで2.59質量%、2.0Mで1.02質量%であった。また、剥離処理後の平衡フィラ密度はそれぞれ3.44体積%、4.43体積%であった。
エタノール600mLを30℃で撹拌しながら、オクタデシルアミン(東京化成株式会社製)200gを加熱溶解させ、そこに濃塩酸(和光純薬工業株式会社製)125mLを加え、3時間反応させた。エバポレータで溶剤を留去した後、エタノールで再結晶させた。この結晶を回収し、減圧下で乾燥させ、オクタデシルアミン塩酸塩(ODA-HCl)を得た。
還流時間を96時間とした以外は実施例1と同様に特定複合体を調製した。XRD測定の結果、ピーク強度の低下した002反射と2θ=3°~2°にかけてのピークの上昇が観察された。また、ドデシルアミン塩酸塩の含有率は、3.18質量%であった。また、剥離処理後の平衡フィラ密度は、3.81体積%であった。
実施例1と同様の方法で、24時間還流した後、遠心分離で沈殿させたマスコバイトを回収し、再度、同量のドデシルアミン塩酸塩水溶液と混合した。混合、24時間還流及び遠心分離を繰り返し、還流時間が合計で48時間、72時間、96時間になるように調整し、特定複合体を調製した。得られた試料のXRDの結果を図5に示す。実施例1の24時間(曲線(a))とは異なり、反応時間が48時間(曲線(b))、72時間(曲線(c))、96時間(曲線(d))と増加するにつれ、インターカレートされた層のピークが高角側にシフトし、ピークがシャープになった。これは、非膨潤層がインターカレートされた層に移行していることを表している。また、ドデシルアミン塩酸塩の含有率は、4.46質量%(48時間)、5.31質量%(72時間)、5.67質量%(96時間)であった。溶液置換しながら反応時間を増加させることで、インターカレート量が増加した。また、剥離処理後の平衡フィラ密度は、それぞれ2.71体積%、2.53体積%、2.19体積%であった。
なお、図5における一番下のスペクトルが曲線(a)であり、下から二番目のスペクトルが曲線(b)であり、上から二番目のスペクトルが曲線(c)であり、一番上のスペクトルが曲線(d)である。
実施例1及び実施例5の剥離処理後の特定複合体(剥離化化合物)並びに剥離処理前のマイカ粉末を用いて、下記の方法によりc軸方向の厚さを求めた。まず、剥離化化合物を凍結乾燥により粉末状にした。次に、剥離化化合物及び剥離処理前のマイカ粉末を各々水と混合し、分散剤を加え、分散スラリーを調製した。石膏上にシリコン型を置き、スラリーを流し込み、15分間着肉後、一晩風乾することにより、ディスク状の成形体を得た。ディスク状の成形体を走査型電子顕微鏡(S-4300、株式会社日立製作所製)により観察し、厚さ分布を作成した。SEM観察の結果、剥離処理前のマイカ粉末(図6)に比べて、実施例5の96時間還流した剥離化化合物(図7)ではより厚さが薄くなっていることが観察された。図8は、実施例5で得られた剥離処理後の特定複合体(剥離化化合物)及び実施例1で得られた剥離処理前のマイカ粉末の厚さ分布を示すグラフである。厚さ分布においても、剥離処理前のマイカ粉末(図8a、T50は109nm)、実施例1の剥離化化合物(図8b、T50は52nm)、実施例5の48時間(図8c、T50は41nm)、72時間(図8d、T50は36nm)、96時間(図8e、T50は32nm)の順に剥離化が進行していることが観察された。インターカレート量が増加するにつれて、剥離化が進行することが示された。
更に、実施例1及び実施例5の剥離化化合物の平均粒子径をレーザー回折散乱方式粒度分布測定装置により測定したところ、各々3.57μm(実施例1)、4.00μm(実施例5、48時間)、4.26μm(実施例5、72時間)、4.35μm(実施例5、96時間)であった。
(カテコールレゾルシノールノボラック(CRN)樹脂の合成)
撹拌機、冷却器及び温度計を備えた3Lのセパラブルフラスコにレゾルシノール627g、カテコール33g、37質量%ホルマリン316.2g、シュウ酸15g、水300gを入れ、オイルバスで加温しながら100℃に昇温させ、この還流温度で4時間反応を続けた。その後、水を留去しながらフラスコ内の温度を170℃に昇温させ、170℃を保持しながら8時間反応を続けた。
更に、メチルエチルケトン14.33質量部とシクロヘキサノン2.44質量部を加えて混合した。混合した後に、1-(3-メチル-4-ヒドロキシフェニル)-4-(4-ヒドロキシフェニル)-1-シクロヘキセンとエピクロルヒドリンとから合成された1-{(3-メチル-4-オキシラニルメトキシ)フェニル}-4-(4-オキシラニルメトキシフェニル)-1-シクロヘキセン7.2170質量部(エポキシ樹脂)、及びトリフェニルホスフィン0.0760質量部(和光純薬工業株式会社製、硬化触媒)を加えて更に混合し、40時間~60時間にわたってボールミル粉砕を行い、絶縁性樹脂組成物として樹脂シート塗工液を得た。
得られた硬化物の熱伝導率を、以下のようにしてキセノンフラッシュ法により測定した結果、熱伝導率は8.3W/(m・K)であった。
またBDV(Break Down Voltage)法による絶縁性を、後述のようにして測定したところ、最低値は25.1kV/mm、平均値は25.9kV/mmであった。
NETZSCH社製のNanoflash LFA447型Xeフラッシュ法熱拡散率測定装置を用いてシートの熱拡散率を測定した。得られた熱拡散率の数値に比熱Cp(J/g・K)と密度d(g/cm3)を乗算することによって、熱伝導率(W/(m・K))を算出した。全ての測定は25±1℃で行った。
上記で得られた樹脂シート硬化物について、総研電気株式会社製DAC-6032C絶縁破壊試験装置を用いて、直径25mmの円筒電極ではさみ、昇圧速度500V/s、交流50Hz、ステップ電圧0.50kV、電圧保持時間60s、25℃、油中にて測定した。
100cm3のポリ瓶中に、カップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン0.0960質量部(信越化学工業株式会社製、商品名「KBM-573」)と、硬化剤として上記で合成したカテコールレゾルシノールノボラック樹脂のシクロヘキサノン溶解品4.6680質量部(固形分50質量%)をこの順序で加えた。
更に、メチルエチルケトン15.04質量部とシクロヘキサノン2.68質量部を加えて混合した。混合した後に、1-(3-メチル-4-ヒドロキシフェニル)-4-(4-ヒドロキシフェニル)-1-シクロヘキセンとエピクロルヒドリンとから合成された1-{(3-メチル-4-オキシラニルメトキシ)フェニル}-4-(4-オキシラニルメトキシフェニル)-1-シクロヘキセン7.2170質量部(エポキシ樹脂)、及びトリフェニルホスフィン0.0760質量部(和光純薬工業株式会社製、硬化触媒)を加えて更に混合し、40時間~60時間にわたってボールミル粉砕を行い、絶縁性樹脂組成物として樹脂シート塗工液を得た。
得られた硬化物の熱伝導率をキセノンフラッシュ法により測定した結果、熱伝導率は8.0W/(m・K)であった。
またBDV法による絶縁性を測定したところ、最低値は25.6kV/mm、平均値は28.4kV/mmであった。
250cm3のポリ瓶中に、硬化剤として上記で合成したカテコールレゾルシノールノボラック樹脂のシクロヘキサノン溶解品4.1190質量部(固形分50質量%)と、1-(3-メチル-4-ヒドロキシフェニル)-4-(4-ヒドロキシフェニル)-1-シクロヘキセンとエピクロルヒドリンとから合成された1-{(3-メチル-4-オキシラニルメトキシ)フェニル}-4-(4-オキシラニルメトキシフェニル)-1-シクロヘキセン6.6775質量部(エポキシ樹脂)と、トリフェニルホスフィン0.0707質量部(和光純薬工業株式会社製、硬化触媒)と、シクロヘキサノン25.90質量部(和光純薬工業株式会社製)とを加えて混合した。その後、無機フィラとして窒化ホウ素粒子37.38質量部(体積平均粒子径40μm、水島合金鉄株式会社製、商品名「HP-40MF100」)と、実施例5(96時間)で得られた剥離化化合物(c軸方向の厚さ32nm、平均粒子径4.35μm)0.3188質量部を加えて更に混合し、絶縁性樹脂組成物として樹脂シート塗工液を得た。
得られた硬化物の熱伝導率をキセノンフラッシュ法により測定した結果、熱伝導率は10.0W/(m・K)であった。
またBDV法による絶縁性を測定したところ、最低値は28.5kV/mm、平均値は30.4kV/mmであった。
100cm3のポリ瓶中に、カップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン0.0960質量部(信越化学工業株式会社製、商品名「KBM-573」)と、硬化剤として上記で合成したカテコールレゾルシノールノボラック樹脂のシクロヘキサノン溶解品4.6680質量部(固形分50質量%)をこの順序で加えた。
更に、メチルエチルケトン17.19質量部とシクロヘキサノン3.40質量部を加えて混合した。混合した後に、1-(3-メチル-4-ヒドロキシフェニル)-4-(4-ヒドロキシフェニル)-1-シクロヘキセンとエピクロルヒドリンとから合成された1-{(3-メチル-4-オキシラニルメトキシ)フェニル}-4-(4-オキシラニルメトキシフェニル)-1-シクロヘキセン7.2170質量部(エポキシ樹脂)、及びトリフェニルホスフィン0.0760質量部(和光純薬工業株式会社製、硬化触媒)を加えて更に混合し、40時間~60時間にわたってボールミル粉砕を行い、絶縁性樹脂組成物として樹脂シート塗工液を得た。
得られた硬化物の熱伝導率をキセノンフラッシュ法により測定した結果、熱伝導率は1.4W/(m・K)であった。
またBDV法による絶縁性を測定したところ、最低値は18.5kV/mm、平均値は20.5kV/mmであった。
100cm3のポリ瓶中に、カップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン0.0960質量部(信越化学工業株式会社製、商品名「KBM-573」)と、硬化剤として上記で合成したカテコールレゾルシノールノボラック樹脂のシクロヘキサノン溶解品4.6680質量部(固形分50質量%)をこの順序で加えた。
更に、メチルエチルケトン14.33質量部とシクロヘキサノン2.44質量部を加えて混合した。混合した後に、1-(3-メチル-4-ヒドロキシフェニル)-4-(4-ヒドロキシフェニル)-1-シクロヘキセンとエピクロルヒドリンとから合成された1-{(3-メチル-4-オキシラニルメトキシ)フェニル}-4-(4-オキシラニルメトキシフェニル)-1-シクロヘキセン7.2170質量部(エポキシ樹脂)、及びトリフェニルホスフィン0.0760質量部(和光純薬工業株式会社製、硬化触媒)を加えて更に混合し、40時間~60時間にわたってボールミル粉砕を行い、絶縁性樹脂組成物として樹脂シート塗工液を得た。
得られた硬化物の熱伝導率を、キセノンフラッシュ法により測定した結果、熱伝導率は8.9W/(m・K)であった。
またBDV法による絶縁性を測定したところ、最低値は19.5kV/mm、平均値は25.4kV/mmであった。
250cm3のポリ瓶中に、硬化剤として上記で合成したカテコールレゾルシノールノボラック樹脂のシクロヘキサノン溶解品4.1190質量部(固形分50質量%)と、1-(3-メチル-4-ヒドロキシフェニル)-4-(4-ヒドロキシフェニル)-1-シクロヘキセンとエピクロルヒドリンとから合成された1-{(3-メチル-4-オキシラニルメトキシ)フェニル}-4-(4-オキシラニルメトキシフェニル)-1-シクロヘキセン6.6775質量部(エポキシ樹脂)と、トリフェニルホスフィン0.0707質量部(和光純薬工業株式会社製、硬化触媒)と、シクロヘキサノン25.90質量部(和光純薬工業株式会社製)とを加えて混合した。その後、無機フィラとして窒化ホウ素粒子37.38質量部(体積平均粒子径40μm、水島合金鉄株式会社製、商品名「HP-40MF100」)を加えて更に混合し、絶縁性樹脂組成物として樹脂シート塗工液を得た。
得られた硬化物の熱伝導率をキセノンフラッシュ法により測定した結果、熱伝導率は10.1W/(m・K)であった。
またBDV法による絶縁性を測定したところ、最低値は25.6kV/mm、平均値は30.0kV/mmであった。
100cm3のポリ瓶中に、カップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン0.0960質量部(信越化学工業株式会社製、商品名「KBM-573」)と、硬化剤として上記で合成したカテコールレゾルシノールノボラック樹脂のシクロヘキサノン溶解品4.6680質量部(固形分50質量%)をこの順序で加えた。
更に、メチルエチルケトン17.19質量部とシクロヘキサノン3.40質量部を加えて混合した。混合した後に、1-(3-メチル-4-ヒドロキシフェニル)-4-(4-ヒドロキシフェニル)-1-シクロヘキセンとエピクロルヒドリンとから合成された1-{(3-メチル-4-オキシラニルメトキシ)フェニル}-4-(4-オキシラニルメトキシフェニル)-1-シクロヘキセン7.2170質量部(エポキシ樹脂)、及びトリフェニルホスフィン0.0760質量部(和光純薬工業株式会社製、硬化触媒)を加えて更に混合し、40時間~60時間にわたってボールミル粉砕を行い、絶縁性樹脂組成物として樹脂シート塗工液を得た。
得られた硬化物の熱伝導率をキセノンフラッシュ法により測定した結果、熱伝導率は1.5W/(m・K)であった。
またBDV法による絶縁性を測定したところ、最低値は15.1kV/mm、平均値は20.0kV/mmであった。
本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (18)
- 非膨潤性層状無機化合物を、前記非膨潤性層状無機化合物の熱分解温度の範囲内で加熱処理する工程と、
加熱処理された前記非膨潤性層状無機化合物を媒体に分散させた分散液中で、前記非膨潤性層状無機化合物に有機化合物をインターカレートさせて前記非膨潤性層状無機化合物の層間に有機化合物を挿入する工程と、
を有し、
前記非膨潤性層状無機化合物は、単位結晶層が互いに積み重なって層状構造をなしており、熱分解温度の上限値で1時間加熱することによって0.05Å~0.20Åの範囲でc軸方向に膨張し、熱分解温度の上限値で1時間加熱することによって前記単位結晶層の結晶構造が変化しないものである層状無機化合物と有機化合物との複合体の製造方法。 - 前記非膨潤性層状無機化合物が、マイカである請求項1に記載の層状無機化合物と有機化合物との複合体の製造方法。
- 前記有機化合物が、アミン塩、ホスホニウム塩、イミダゾリウム塩、ピリジニウム塩、スルホニウム塩及びヨードニウム塩からなる群より選択される少なくとも一種のカチオン性有機化合物である請求項1又は請求項2に記載の層状無機化合物と有機化合物との複合体の製造方法。
- 前記分散液中における前記有機化合物の濃度が0.01mol/L以上かつ前記有機化合物の溶解度以下であり、
前記分散液中における前記非膨潤性層状無機化合物の含有率が0.5体積%~50体積%である請求項1~請求項3のいずれか1項に記載の層状無機化合物と有機化合物との複合体の製造方法。 - 非膨潤性層状無機化合物を、前記非膨潤性層状無機化合物の熱分解温度の範囲内で加熱処理する工程と、
加熱処理された前記非膨潤性層状無機化合物を媒体に分散させた分散液中で、前記非膨潤性層状無機化合物に有機化合物をインターカレートさせて前記非膨潤性層状無機化合物の層間に有機化合物を挿入する工程と、
前記分散液に機械的処理にてせん断力を加えてインターカレートされた前記非膨潤性層状無機化合物を剥離化する工程と、
を有し、
前記非膨潤性層状無機化合物は、単位結晶層が互いに積み重なって層状構造をなしており、熱分解温度の上限値で1時間加熱することによって0.05Å~0.20Åの範囲でc軸方向に膨張し、熱分解温度の上限値で1時間加熱することによって前記単位結晶層の結晶構造が変化しないものである剥離化された層状無機化合物の製造方法。 - 前記分散液にせん断力を加えた後における前記分散液の平衡フィラ密度が30体積%以下である請求項5に記載の剥離化された層状無機化合物の製造方法。
- 前記分散液にせん断力を加えた後の前記剥離化された非膨潤性層状無機化合物の平均粒子径が、前記分散液にせん断力を加える前のインターカレートされた前記非膨潤性層状無機化合物の平均粒子径の50%~100%である請求項5又は請求項6に記載の剥離化された層状無機化合物の製造方法。
- 前記機械的処理の際の前記分散液の衝突圧力が50MPa~250MPaである請求項5~請求項7のいずれか1項に記載の剥離化された層状無機化合物の製造方法。
- 非膨潤性層状無機化合物に有機化合物をインターカレートしてなり、
前記非膨潤性層状無機化合物は、単位結晶層が互いに積み重なって層状構造をなしており、熱分解温度の上限値で1時間加熱することによって0.05Å~0.20Åの範囲でc軸方向に膨張し、熱分解温度の上限値で1時間加熱することによって前記単位結晶層の結晶構造が変化しないものである層状無機化合物と有機化合物との複合体。 - 前記非膨潤性層状無機化合物の層間にインターカレートした前記有機化合物が、前記非膨潤性層状無機化合物100質量%に対して1質量%~40質量%である請求項9に記載の層状無機化合物と有機化合物との複合体。
- c軸方向の平均粒子厚さが1nm~80nmである剥離化された層状無機化合物。
- 平均粒子径が、インターカレートされた非膨潤性層状無機化合物の平均粒子径の50%~100%である請求項11に記載の剥離化された層状無機化合物。
- 熱硬化性樹脂と無機フィラとを含有し、前記無機フィラの少なくとも一部が請求項11又は請求項12に記載の剥離化された層状無機化合物である絶縁性樹脂組成物。
- 前記剥離化された層状無機化合物の前記無機フィラに占める割合が、0.5体積%~10体積%である請求項13に記載の絶縁性樹脂組成物。
- 請求項13又は請求項14に記載の絶縁性樹脂組成物をシート状に成形してなる樹脂シート。
- 請求項13又は請求項14に記載の絶縁性樹脂組成物の硬化物である絶縁物。
- 請求項15に記載の樹脂シートの熱処理物である樹脂シート硬化物。
- 金属ワークと、前記金属ワーク上に配置された請求項15に記載の樹脂シート又は請求項17に記載の樹脂シート硬化物とを有する放熱部材。
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JP2017503721A JP6664743B2 (ja) | 2015-03-05 | 2016-03-03 | 層状無機化合物と有機化合物との複合体及びその製造方法、剥離化された層状無機化合物及びその製造方法、絶縁性樹脂組成物、樹脂シート、絶縁物、樹脂シート硬化物並びに放熱部材 |
EP16759022.3A EP3266745A4 (en) | 2015-03-05 | 2016-03-03 | COMPLEX BETWEEN A LAMELLAR INORGANIC COMPOUND AND AN ORGANIC COMPOUND AND PRODUCTION METHOD THEREOF, EXFOLIATE LAMELLAR INORGANIC COMPOUND AND PROCESS FOR THE PRODUCTION THEREOF, INSULATING RESIN COMPOSITION, RESIN SHEET, INSULATION, CURED RESIN SHEET ARTICLE AND HEAT DISSIPATION ELEMENT |
CN201680013761.8A CN107406263A (zh) | 2015-03-05 | 2016-03-03 | 层状无机化合物与有机化合物的复合体及其制造方法、经剥离化的层状无机化合物及其制造方法、绝缘性树脂组合物、树脂片、绝缘物、树脂片固化物以及散热构件 |
US15/555,859 US20180044191A1 (en) | 2015-03-05 | 2016-03-03 | Complex of lamellar inorganic compound and organic compound and method of producing thereof, delaminated lamellar inorganic compound and method of producing thereof, insulating resin composition, resin sheet, insulator, resin sheet cured product, and heat dissipating member |
US16/817,894 US20200216324A1 (en) | 2015-03-05 | 2020-03-13 | Complex of lamellar inorganic compound and organic compound and method of producing thereof, delaminated lamellar inorganic compound and method of producing thereof, insulating resin composition, resin sheet, insulator, resin sheet cured product, and heat dissipating member |
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US16/817,894 Division US20200216324A1 (en) | 2015-03-05 | 2020-03-13 | Complex of lamellar inorganic compound and organic compound and method of producing thereof, delaminated lamellar inorganic compound and method of producing thereof, insulating resin composition, resin sheet, insulator, resin sheet cured product, and heat dissipating member |
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US (2) | US20180044191A1 (ja) |
EP (1) | EP3266745A4 (ja) |
JP (1) | JP6664743B2 (ja) |
CN (1) | CN107406263A (ja) |
TW (1) | TWI732751B (ja) |
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KR20210039370A (ko) * | 2018-07-30 | 2021-04-09 | 가부시키가이샤 아데카 | 복합 재료의 제조 방법 |
KR102243516B1 (ko) * | 2018-10-12 | 2021-04-23 | 주식회사 경동원 | 난연성이 우수한 열 경화성 발포폼의 제조방법 및 이를 이용한 열경화성 발포폼 |
CA3115812C (en) * | 2018-10-12 | 2023-08-01 | Ppg Industries Ohio, Inc. | Compositions containing thermally conductive fillers |
CN114956173B (zh) * | 2022-04-14 | 2023-12-29 | 辽宁大学 | 十二胺改性v2o5材料及其制备方法和作为超级电容器电极材料的应用 |
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- 2016-03-03 US US15/555,859 patent/US20180044191A1/en not_active Abandoned
- 2016-03-03 CN CN201680013761.8A patent/CN107406263A/zh active Pending
- 2016-03-03 WO PCT/JP2016/056670 patent/WO2016140330A1/ja active Application Filing
- 2016-03-03 EP EP16759022.3A patent/EP3266745A4/en not_active Withdrawn
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EP3266745A4 (en) | 2019-01-23 |
TWI732751B (zh) | 2021-07-11 |
EP3266745A1 (en) | 2018-01-10 |
JP6664743B2 (ja) | 2020-03-13 |
US20200216324A1 (en) | 2020-07-09 |
CN107406263A (zh) | 2017-11-28 |
US20180044191A1 (en) | 2018-02-15 |
JPWO2016140330A1 (ja) | 2018-02-08 |
TW201641614A (zh) | 2016-12-01 |
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