WO2014091594A1

WO2014091594A1 - Layered clay mineral, varnish and organic-inorganic composite material including same, and electrical device, semiconductor device, and rotary machine coil using said organic-inorganic composite material

Info

Publication number: WO2014091594A1
Application number: PCT/JP2012/082340
Authority: WO
Inventors: 智和棚瀬
Original assignee: 株式会社日立製作所
Priority date: 2012-12-13
Filing date: 2012-12-13
Publication date: 2014-06-19
Also published as: JP5945335B2; JPWO2014091594A1

Abstract

The present invention addresses the problem of providing: an interlayer-modified layered clay mineral including a silicon-containing oligomer having excellent electrical insulation properties; a varnish and an organic-inorganic composite material including same; and an electrical device, a semiconductor device, and a rotary machine coil using said organic-inorganic composite material. Said problem is solved by: a layered clay mineral being interlayer-modified by an appropriate cationic compound and having an expanded clay interlayer distance as a result of the insertion of a silicon oligomer generated by the hydrolysis reaction of an alkoxysilane; and an organic-inorganic composite material having said layered clay mineral added to a resin and having the electrical insulation properties thereof greatly improved.

Description

Layered clay mineral, varnish containing the same, organic-inorganic composite material, electric device using the organic-inorganic composite material, semiconductor device and rotary coil

The present invention relates to an interlayer modified layered clay mineral containing a silicon-containing oligomer excellent in electrical insulation, a varnish containing the same, an organic-inorganic composite material, an electric device using the organic-inorganic composite material, a semiconductor device, It relates to a rotating machine coil.

The power density of electric and electronic devices is increasing year by year, and the operating environment of inverters and generators is getting higher in temperature and higher in electric field. In connection with it, high heat resistance-ization and high voltage-resistance-ization become a subject about the insulation resin material which comprises these.

Layered clay minerals (clays) represented by montmorillonite and smectite are excellent in electrical insulation, and combined with various resin materials such as polyolefin, nylon, polystyrene, epoxy resin, etc. to reduce flame resistance, lower dielectric constant, and improve insulation life It is known that excellent properties such as high strength and low thermal expansion can be imparted.

For example, Patent Document 1 describes that when the clay organically treated with ammonium ion and the polyolefin are complexed, the flame retardancy is improved. Patent Document 2 describes that the insulation life of an epoxy resin containing a layered clay mineral modified with a quaternary ammonium ion is improved. Non-Patent Document 1 describes that an epoxy resin with montmorillonite interlayer-modified with phosphonium ion has improved low thermal expansion. Non-Patent Document 2 describes that montmorillonite obtained by interlayer modification of 1,2-aminolauric acid improves the strength of nylon.

JP, 2006-265507, A JP 2005-251543 A

However, in the clay dispersion technology by the conventional interlayer modification method, it is necessary to select an appropriate interlayer modifier according to the type of resin to be combined, and there is a problem that the combination of resins and types of resins that can be manufactured are limited. The In addition, the clay obtained by the conventional method is insufficient in peeling, and as a result, there is a problem that the function required of the clay, such as electrical insulation and material strength, is not sufficiently exhibited. Therefore, the present invention provides an interlayer-modified layered clay mineral containing a silicon-containing oligomer which can be highly dispersed in the resin regardless of the type of resin to be combined, and a varnish and an organic-inorganic composite material using the layered clay mineral, An object of the present invention is to provide an electrical device, a semiconductor device and a rotating machine coil using the organic-inorganic composite material.

The present inventor has intensively studied to solve the above-mentioned problems. Then, when the layered clay mineral is modified between layers with a suitable cationic compound and a silicon-based oligomer formed by the hydrolysis reaction of an alkoxysilane is inserted, the interlayer distance of the layered clay mineral is expanded, and the layered clay mineral is It has been found that addition to a resin gives an organic-inorganic composite material in which the electrical insulation property is greatly improved, and the present invention has been completed.

That is, the present invention is as follows.

(1) An interlayer modified layered clay mineral comprising a silicon-containing oligomer, wherein the layered clay mineral is at least one selected from the group consisting of smectite group, mica group, vermiculite group and mica group And the interlayer modified layered clay mineral. Preferably, the particle size of the silicon-containing oligomer is 0.1 μm to 100 nm. In addition, preferably, the thickness of the layered clay mineral is 0.05 μm to 10 μm.

(2) The interlayer-modified layered clay according to (1), wherein the layered clay mineral is contained at 0.1 wt% to 10 wt% and the silicon-containing oligomer is contained at 0.1 wt% to 30 wt%. It is a mineral.

(3) In the interlayer-modified layered clay mineral according to (1) or (2): (1,10 phenanthroline) copper complex is ion-exchanged between layers of the interlayer-modified layered clay mineral, and silicon The contained oligomer contains a benzene ring; or the cationized aliphatic amine is ion-exchanged between the layers of the interlayer-modified layered clay mineral, and the silicon-containing oligomer contains a long chain alkyl group; An interlayer modified layered clay mineral.

(4) A varnish comprising the interlayer modified layered clay mineral according to any one of (1) to (3) and a monomer.

(5) In the varnish described in (4), the monomer is a bisphenol A type epoxy prepolymer, 4,4′-ethylidene diphenyl dicyanate, 3,3′-4,4′-biphenyl tetracarboxylic acid dianhydride, It is a varnish which is at least one or more selected from the group consisting of p-phenylenediamines.

(6) An organic-inorganic composite material comprising the interlayer-modified layered clay mineral and resin according to any one of (1) to (3), or the varnish according to (4) or (5).

(7) The organic-inorganic composite material according to (6), wherein the resin is at least one selected from the group consisting of an epoxy resin, a cyanate ester resin, and a polyimide resin.

(8) A semiconductor device including a semiconductor element and a sealing material, wherein the sealing material includes the organic-inorganic composite material according to (6) or (7), and the semiconductor element is sealed with the sealing material. Semiconductor device.

(9) A wire containing a conductor and an insulating material, wherein the conductor is coated with the varnish described in (4) or (5) or the insulating material containing the organic-inorganic composite material described in (6) or (7). And the electric wire.

(10) A rotating machine coil including a conductor and an insulating material, wherein the conductor wound with the insulating material is the varnish according to (4) or (5) or the organic-according to (6) or (7) It is the said rotary machine coil impregnated with the inorganic composite material.

The interlayer-modified layered clay mineral containing the silicon-containing oligomer of the present invention has a high dielectric breakdown strength and can be highly dispersed in the resin regardless of the type of resin to be combined. It can be applied to materials and electrical devices.

FIG. 1 is a schematic explanatory view of a method for introducing a copper complex into a layered clay mineral. FIG. 2 is a schematic explanatory view of a method of expanding the layers of the layered clay mineral by utilizing the hydrolysis reaction of alkoxysilane. FIG. 3 is a schematic cross-sectional view of a power semiconductor device to which the organic-inorganic composite material of the present invention is applied. FIG. 4 is a schematic cross-sectional view of an insulated wire manufactured using a varnish containing a layered clay mineral and a resin material according to the present invention. FIG. 5 is a schematic cross-sectional view showing the configuration of a rotary machine coil to which the organic-inorganic composite material of the present invention is applied. FIG. 6 is a schematic view of a dielectric breakdown voltage measuring apparatus. FIG. 7 shows the results of XRD measurement and X-ray fluorescence measurement of an untreated layered clay mineral. FIG. 8 shows the results of XRD measurement and X-ray fluorescence measurement of the layered clay mineral to which the copper complex obtained in Examples 1 to 11 is introduced. FIG. 9 is a graph showing the results of XRD measurement of a layered clay mineral in which the interlayer is expanded using the hydrolysis reaction of the alkoxysilane obtained in Example 4. FIG. 10 is a graph showing the results of XRD measurement of the organic-inorganic composite material obtained in Example 4. FIG. 11 is a cross-sectional SEM photograph of the organic-inorganic composite material obtained in Example 4 and a result of elemental analysis.

The present invention relates to a layered clay mineral having an interlayer distance extended with a silicon-based oligomer further formed by hydrolysis reaction of an alkoxysilane with respect to a layered clay mineral interlayer modified with a suitable cationic compound, and an organic containing the layered clay mineral -An inorganic composite material, an electric device using the organic-inorganic composite material, a semiconductor device, and a rotating machine coil are provided. Hereinafter, the present invention will be described in detail.

(1) Interlayer-modified layered clay mineral containing the silicon-containing oligomer of the present invention The interlayer-modified layered clay mineral containing the silicon-containing oligomer of the present invention comprises the silicon-containing oligomer intercalated between layers of the layered clay mineral It is characterized in that the layers are expanded.

<Layered clay mineral>
A layered clay mineral is a fine-grained natural product that exhibits viscosity and plasticity when it contains an appropriate amount of water, and is a mineral that has an ordered layered structure. The chemical components mainly include, but are not limited to, iron (Fe), magnesium (Mg), calcium (Ca), sodium (Na), potassium (K) and the like in addition to silicic acid, alumina and water. The main minerals are layered clay layered silicate minerals (phylosilicate minerals), but minerals such as calcite, dolomite, feldspars, quartz, and zeolites (zeolites) can also be mentioned.

The layered clay mineral of the present invention includes, for example, at least one selected from the mineral group consisting of smectite group, mica group, vermiculite group and mica group. Layered clay minerals belonging to the smectite group include montmorillonite, hectorite, saponite, sauconite, beidellite, stevensite, nontronite and the like, but are not limited thereto. Layered clay minerals belonging to the mica group include, but are not limited to, chlorite, phlogopite, lepidolite, muscovite, biotite, paragonite, margarite, teniolight, tetrasilicic mica, and the like. Layered clay minerals belonging to the vermiculite group include, but are not limited to, trioctahedral vermiculite, dioctahedral vermiculite, and the like. Layered clay minerals belonging to the mica group include, but are not limited to, muscovite, biotite, paragonite, levitrite, margarite, clintonite, anandite and the like. The layered clay mineral of the present invention may be a natural product or a synthetic product, and the above-mentioned minerals can be used alone or in combination of two or more.

<Layered clay mineral intercalated with cationic compound>
The layered clay mineral according to the present invention may be interlayer modified with a cationic compound. The layered clay mineral modified with the cationic compound of the present invention refers to a mineral in which the cationic compound is ionically bonded to the interlayer and / or the surface of the layered clay mineral. In the layered clay mineral, inorganic cations such as alkali metal ions such as sodium ions and alkaline earth metal ions are usually supported between layers. Various substances can be supported between the layers of layered clay mineral by replacing this inorganic cation with other ions by ion exchange reaction or the like. This is called interlayer modification.

A silicon-containing oligomer is inserted into the layered viscosity mineral to expand the layers of the layered viscosity mineral. The silicon-containing oligomer has a substituent that is compatible with the cationic compound. Therefore, silicon-containing oligomers can be inserted between the layers by modifying the cationic compound in advance between the layers of the layered viscosity mineral. That is, the layered viscosity mineral of the present invention is preferably modified between layers with a cationic compound.

The cationic compound used in the present invention is a compound having a high affinity to a silicon-containing oligomer containing a phenyl group for extending the interlayer distance of a layered viscosity mineral, an alkoxysilane having an amino group, an alkylamine, and an arylamine Organic cationic compounds such as quaternary ammonium compounds and tertiary amine compounds such as dimethyldodecylamine; inorganic ions such as aluminum, copper, zinc, potassium and calcium; methylene blue, rhodamine B, phthalocyanines, and amine-modified Examples include, but are not limited to, heparin, proteins, and DNA molecules. Preferably, organic cationic compounds such as dimethyldodecylamine, diethylenetriamine, triethyltetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiverazine, mensene diamine, isophorone diamine, m-xylene diamine, meta-phenylene Diamine, diaminodiphenylmethane, diaminodiphenyl sulfone, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) Organic cation compounds obtained by cationizing 3-aminopropylmethyldimethoxysilane, 3- (N-phenyl) aminopropyltrimethoxysilane, etc. with strong acid such as hydrochloric acid, metal with an amine as a ligand It is a copper complex having ethylenediamine, diaminopropane, diethylenetriamine, triethyltetramine, tetraethylenepentamine, 1,10 phenanthroline as a ligand, and more preferably a copper complex having 1,10 phenanthroline as a ligand. is there. In the present invention, the above cationic compounds can be used alone or in combination of two or more.

The method of interlayer modification with the cationic compound of the present invention is a method of adsorbing and / or binding the cationic compound to the interlayer and / or the surface of the layered clay mineral by a physical or chemical method. For example, when layer clay mineral and hydrochloric acid cationized dimethyldodecylamine are mixed and stirred while heating, sodium ions are separated from the layer by ion exchange reaction, and cationized dimethyldodecylamine is supported on the layer or the surface A layered clay mineral is obtained. In addition, when an aqueous solution of a metal complex having an amine as a ligand and a layered clay mineral are mixed and stirred, an ion exchange reaction similarly occurs to obtain a layered clay mineral in which a cationic metal complex is supported between layers (FIG. 1) ).

<Silicon containing oligomers>
The present invention is characterized in that a silicon-based oligomer is precipitated on a layered clay mineral which is interlayer-modified with the cationic compound thus obtained, to obtain a layered clay mineral having an expanded interlayer (FIG. 2). . The silicon-containing oligomer can be produced by hydrolyzing an alkoxysilane. Specifically, the layered clay mineral and an appropriate alkoxysilane are mixed and stirred in an organic solvent, and then a hydrolysis reaction is performed in the presence of an alkali catalyst or an acid catalyst to precipitate a silicon-based oligomer in the layered clay mineral. Here, the molar volume of the silicon-based oligomer is several tens to several hundreds times that of the raw material alkoxysilane as the molecular weight of the silicon-based oligomer is increased, and the layer of the layered clay mineral is expanded as the hydrolysis reaction progresses. The Thus, the silicon-containing oligomers of the present invention function as so-called spacers, which extend the interlayer distance of layered clay minerals.

Examples of the alkoxysilane that is a raw material of silicon-based oligomers include tetraethoxysilane, tetramethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, mercaptopropyltrimethoxysilane, aminopropyltrimethoxysilane, methyltriethoxysilane and methyltrimethoxy Examples include, but are not limited to, silane, hexyl ethoxysilane, hexyltrimethoxysilane, p-styryltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and the like. Among them, from the viewpoint of affinity with layered clay minerals, alkoxy having a benzene ring such as phenyltriethoxysilane, phenyltrimethoxysilane, p-styryltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and the like Alkoxysilanes having alkyl groups such as silanes or ethyltrimethoxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, etc. preferable. These alkoxides can be used alone or as a mixture of two or more. In addition to the above alkoxysilane, an alkoxide containing a metal element other than silicon such as titanium tetraethoxide, titanium tetraisopropoxide, aluminum propoxide, zirconium butoxide, etc. may be included.

As an interlayer modified layered clay mineral containing a preferred silicon-containing oligomer of the present invention, a (1, 10 phenanthroline) copper complex is ion-exchanged between layers of the layered clay mineral, and the silicon-containing oligomer has a benzene ring Or a layered clay mineral in which cationized aliphatic amines are ion-exchanged between layers of the layered clay mineral, and a silicon-containing oligomer includes a long chain alkyl group, Not limited to these.

The particle size of the silicon-containing oligomer used in the present invention can be designed to be any size as long as it allows the interlayer to be expanded, preferably 0.1 nm to 100 nm, more preferably 1.61 nm to 2 .02 nm.

The layers can be measured by a known method, for example, using a high resolution X-ray diffractometer. In the measurement method, for example, the X-ray source is set to Cu, the X-ray output is set to 50 kV-250 mA, and the scanning range is set to 0.5 ≦ 2θ ≦ 60 deg, and the XRD pattern is measured. The obtained XRD pattern is represented by Bragg's equation 2d sin .theta. = N.lambda.
(Here, d represents the layer spacing, θ represents the diffraction angle, n represents the reflection order, and λ represents the X-ray wavelength = 0.154 nm)
The layer spacing can be calculated by using

The interlayer modified layered clay mineral containing the silicon-containing oligomer of the present invention can be designed to any thickness that exhibits excellent dielectric breakdown strength and dielectric breakdown voltage. Preferably, the thickness is 0.05 to 10 μm. The thickness can be measured by a known method. For example, the layer clay mineral can be embedded in a resin or the like, fixed, and polished to expose the cross section of the layer clay mineral, and can be measured by a direct measurement with an electron microscope .

Among the interlayer-modified layered clay minerals including the silicon-containing oligomer of the present invention, the silicon-containing oligomer and the interlayer-modified layered clay mineral may be present in any ratio as long as the interlayer is expanded. For example, 0.1 wt% to 10 wt% of the interlayer modified layered clay mineral and 0.1 wt% to 30 wt% of the silicon-containing oligomer.

(2) Varnish of the Present Invention The varnish of the present invention contains an interlayer-modified layered clay mineral containing the above-mentioned silicon-containing oligomer and a monomer, and refers to the state before curing reaction of these substances.

Specific examples of the monomer used for the varnish of the present invention include bisphenol A epoxy prepolymer, bisphenol F epoxy prepolymer, ortho-cresol novolac epoxy prepolymer, methylhymic anhydride, 2-ethyl- 4-Methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 4,4'-ethylidene diphenyl dicyanate, 4,4'-dicyanatobiphenyl, 3,3 ', 5,5'-tetra Methyl-4,4'-dicyanatobiphenyl, 3,3'-3,4'-biphenyltetracarboxylic dianhydride, p-phenylenediamine, pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, Phenolic compounds, formaldehyde, urea, polyols, diisocyanates , Methyl methacrylate, styrene, but is at least one or more selected from the group consisting of terephthalic acid and ethylene glycol, and the like.

The varnish of the present invention can be prepared by mixing an interlayer modified layered clay mineral containing a silicon-containing oligomer with a resin raw material and sufficiently stirring, and any known method may be used. Examples of resin raw materials include, but are not limited to, monomers, curing agents, curing catalysts and the like. Furthermore, an organic solvent may be added for the purpose of lowering the viscosity of the resin raw material. As a stirring method, a method of applying mechanical shearing such as a planetary ball mill or a bead mill may be used.

The varnish of the present invention can be used to provide an insulated wire exhibiting a high breakdown voltage.

(3) Organic-Inorganic Composite Material of the Present Invention The organic-inorganic composite material of the present invention comprises an interlayer-modified layered clay mineral and a resin comprising the above-mentioned silicon-containing oligomer of the present invention. As described above, when a layered clay mineral excellent in electrical insulation is used in combination with a resin material, the resin is characterized by flame retardancy, low dielectric constant, improvement in insulation life, high strength, low thermal expansion, etc. It can be granted. Here, when a layered viscosity mineral having an increased interlayer distance is mixed with a resin, the layered viscosity mineral is highly dispersed in the resin. As a result, the above-mentioned characteristics of the resin can be enhanced. In the present invention, the above-mentioned silicon-containing oligomer is inserted between the layers described in “(1) Interlayer-modified layered clay mineral containing the silicon-containing oligomer of the present invention”, and the layered clay mineral in which the layers are expanded is mixed with the resin. Thus, the present invention provides an organic-inorganic composite material excellent in withstand voltage characteristics.

<Resin>
The resin raw material of the present invention includes glycidyl ether compounds such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, ortho cresol novolac type epoxy resin, phenol resin, unsaturated polyester resin, polyimide resin, polyamide resin, polyamide imide resin, Although cyanate ester resin etc. are mention | raise | lifted, it is not limited to these. These can be used alone or as a mixture of two or more.

<Method of producing organic-inorganic composite material>
The organic-inorganic composite material of the present invention can be produced using any known method. For example, the varnish described in the above-mentioned "(2) varnish of the present invention" is injected into a mold made of aluminum or the like together with other substances such as a catalyst, and heat-cured in an electric furnace to obtain an organic-inorganic composite material. Can.

(4) Semiconductor Device of the Present Invention The semiconductor device of the present invention is a semiconductor device including a semiconductor element and a sealing material, and the sealing material is the above-mentioned “(3) Organic-inorganic composite material of the present invention”. The semiconductor element is sealed with the sealing material, including the organic-inorganic composite material of the present invention described above.

The semiconductor device of the present invention includes any known semiconductor device.

The semiconductor element of the present invention means an element of the functional central portion of the electronic component or the electronic component in the semiconductor, and is incorporated in an electric product / electronic device such as a television receiver, a cellular phone, or a computer. It is incorporated in the form of a computer etc. Semiconductor devices according to the present invention include, but are not limited to, transistors, integrated circuits (IC · LSI), resistors, capacitors, and the like.

The sealing material of the present invention is one of the materials constituting the semiconductor package, and is a resin containing the organic-inorganic composite material of the present invention among resins used for preventing air oxidation and mixing of impurities.

FIG. 3 shows a schematic cross-sectional view of a power semiconductor device which is an example of the semiconductor device of the present invention. In the power semiconductor device shown in FIG. 3, the back side electrode of power semiconductor element 401 is electrically connected to circuit wiring member 402 on insulating substrate 406 by bonding material 404, and the main electrode of power semiconductor element 401 is lead member 403. Are electrically connected by the wire 405. On the back side of the insulating substrate 406, a heat sink for dissipating heat generated by the power semiconductor element 401 to the outside is provided. Then, the periphery of the power semiconductor element 401 is sealed with a sealing resin (sealing material) 408 in a state where the circuit wiring member 402, the lead member 403, and a part of the heat dissipation plate 407 are exposed. The organic-inorganic composite material of the present invention can be applied to the sealing resin (sealing material) 408.

Since the organic-inorganic composite material of the present invention has high dielectric breakdown strength, short circuit between the chip and the wiring due to partial discharge can be prevented, which can contribute to increase the life of the power semiconductor device. The structure of the power semiconductor device shown in FIG. 3 is an example, and it is possible to apply the organic-inorganic composite material of the present invention as a sealing resin that covers the periphery of the semiconductor element 401 even in semiconductor devices of other structures. Nor.

(5) Electric wire of the present invention The electric wire of the present invention is an electric wire containing a conductor and an insulating material, and the conductor is the varnish of the present invention described in the above-mentioned "(2) Varnish of the present invention" The organic-inorganic composite material according to the present invention "is coated with the insulating material containing the organic-inorganic composite material according to the present invention.

The electric wire of the present invention includes a linear conductor such as metal and is for conducting electricity between two points, and means a wire for insulation and protection. Also, high voltage distribution lines, high voltage drop lines, low voltage overhead lines, low voltage drop lines, electric power cables such as indoor wiring, electric equipment electric wires, communication electric wires, underground electric wires, indoor wiring, fire fighting equipment, control circuits, This includes, but is not limited to, cables for use in power equipment, ships, under carpet wiring, etc., and cords and the like used in connection with outlets of small electric products. Also, it includes electric wires of any shape such as single wires, twisted wires, twisted wire pairs, and shielded wires. The conductor contained in the electric wire of the present invention is a material having a high electric conductivity (conductivity) which contains movable electric charge and easily conducts electricity, and it is, for example, copper, silver, aluminum, an optical fiber or an alloy of these, etc. There is no limitation to these. As the insulating material, polyethylene, crosslinked polyethylene, polyvinyl chloride, Kapton, rubber-like polymer, oil-impregnated paper, Teflon (registered trademark), silicone, fluorine resin, etc. other than the varnish of the present invention or the organic-inorganic composite material A substance having the property of being difficult to pass through electricity or heat may be included.

In FIG. 4, sectional drawing of the insulated wire produced using the varnish of this invention which is one example of the electric wire of this invention is shown. The said insulated wire can be manufactured by, for example, forming the insulation coating 502 containing the varnish of this invention in the conductor 501, and baking it.

The film containing the varnish and the organic-inorganic composite material according to the present invention exhibits a high dielectric breakdown voltage, so that an insulated wire excellent in surge resistance can be obtained.

(6) The rotating machine coil of the present invention The rotating machine coil of the present invention includes a conductor and an insulating material, and the conductor wound with the insulating material is the book described in the above (2) the varnish of the present invention. It is impregnated with the insulating material containing the varnish of the invention or the organic-inorganic composite material of the present invention described in “(3) Organic-inorganic composite material of the present invention”.

The rotating machine coil of the present invention is an insulating coated conductor wound in a coil shape, and is used for a motor or a generator by combining with a magnet.

In FIG. 5, the structure of the rotary machine coil which is an example of the rotary machine coil of this invention is shown.

The rotary coil of the present invention is manufactured, for example, by winding an insulating tape around a conductor 601, heating and drying, and then vacuum impregnating the varnish of the present invention and then heating and curing to form an insulating coating 602. be able to.

Since the rotating machine coil of the present invention is coated with a resin having high insulating properties as described above, the heat resistant life is high.

Next, the present invention will be described by way of examples and comparative examples, but the present invention is not limited to the following.

(Examples 1 to 10)
5 g of Kunipia F (registered trademark) manufactured by Kunimine Kogyo Co., Ltd. as a layered clay mineral (hereinafter sometimes referred to as “clay”) was added to 400 ml of pure water and stirred for 2 hours while maintaining at 80 ° C. This gives a milky white dispersion in which Kunipia F is dispersed in water in a cloudy state. Separately, 3.25 g of a copper complex coordinated with 1,10-phenanthroline was dissolved in 400 ml of pure water, and the solution was poured into the clay dispersion obtained above. The mixture was further stirred at 80 ° C. for 2 hours, and sodium ions between the clay layers were ion-exchanged with each metal complex to obtain an interlayer modified clay in which each metal complex was substituted between the clay layers. The reaction mechanism is shown in FIG.

After the metal complex was supported between the clay layers by the above method, the clay was separated by vacuum filtration. At this time, it was confirmed that the filtrate had a blue, red or black color. The clay was again dispersed in pure water, and redispersion and filtration under reduced pressure were repeated until the color of the filtrate became clear, to completely remove unreacted copper complexes, sodium ions, chloride ions and the like in the dispersion.

The washed clay was vacuum dried at 75 ° C. for 12 hours to completely remove water. It was confirmed that the dried clay was blue, red or black depending on the type of copper complex supported. In addition, it was confirmed by fluorescent X-ray analysis that sodium and chlorine were removed from the dried clay.

0.4 g of clay was ultrasonically dispersed in 40 ml of hexane. Further, phenyltriethoxysilane and tetraethoxysilane were added, and left standing overnight. At this time, the addition amount of phenyltriethoxysilane and tetraethoxysilane was set to 1: 1, and four kinds of samples having different total addition amounts were manufactured to conduct an experiment. A mixed solution of 5 g of water, 3 g of 25% aqueous ammonia and 30 ml of ethanol was added to this dispersion, and the mixture was stirred at room temperature for 4 hours using a magnetic stirrer. After stirring, the solvent was removed at 80 ° C. using an aspirator, and ethanol washing and solvent removal were repeated three times. Finally, it was vacuum dried at 80 ° C. for 2 hours using a rotary pump. The weight of the obtained treated powder was weighed to determine the ratio of silicon-based oligomer to clay.

The above treated powder, Primaset LECy (compound name: 4,4'-ethylidene diphenyl dicyanate) manufactured by Lonza Co., Ltd. and 4-nonylphenol manufactured by Tokyo Chemical Industry Co., Ltd. are weighed, and put into an agate container made of agateball. And stirred with a ball mill for 2 hours. The addition amount of the treated powder was changed to 1 to 15 wt%. The rotation speed of the ball mill was set to 450 rpm, and the mode was set to reverse at intervals of 5 minutes. As mentioned above, the varnish in which the clay by which the metal complex was interlayer-modified was disperse | distributed in the resin raw material was obtained. The varnish was heated at 100 ° C. → 120 ° C. → 150 ° C. → 200 ° C. for 1 hour each and finally heated at 250 ° C. for 6 hours to obtain an organic-inorganic composite material.

(Example 11)
Treated powder prepared by the same method as in Example 2 and bisphenol A type epoxy resin (JER 828; Japan Epoxy), acid anhydride (MHAC-P; Hitachi Chemical) and imidazole curing catalyst (2EMZ-CN; Shikoku Kasei And the mixture was stirred by a ball mill for 2 hours. The rotation speed of the ball mill was set to 450 rpm, and the mode was set to reverse at intervals of 5 minutes. The resulting varnish was heated at 100 ° C. → 120 ° C. → 150 ° C. for 1 hour each, and finally heated at 180 ° C. for 2 hours to obtain an organic-inorganic composite material.

(Example 12)
The mixture was heated in 3,3'-4,4'-biphenyltetracarboxylic dianhydride and water, or in methanol or ethanol, to synthesize a tetracarboxylic acid or a carboxylic acid ester. After cooling, p-phenylenediamine was added and heated to synthesize a polyamic acid. The treated polyamic acid was dissolved in a solvent such as N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N 'dimethyl acetamide, N, N' dimethylformamide, etc. Mix and stir in a ball mill for 2 hours. The rotation speed of the ball mill was set to 450 rpm, and the mode was set to reverse at intervals of 5 minutes. The obtained varnish was heated at 100 ° C. for 1 hour, and then heated at 400 ° C. for 30 minutes to obtain an organic-inorganic composite material.

(Comparative example 1)
A cured resin was obtained in the same manner as in Example 1 except that the treated powder was not added.

(Production of Comparative Example 2)
A cured resin was obtained in the same manner as in Example 2 except that the treated powder was not added.

(Measurement and evaluation)
(1) XRD measurement (interlayer distance evaluation)
The distance between clay layers in the treated powder and the organic-inorganic composite material of Examples 1 to 11 and Comparative Examples 1 to 2 was measured using a high resolution X-ray diffractometer (manufactured by Rigaku Corporation, model: ATX-G) did. As the measurement conditions, the X-ray source is Cu, the X-ray output is 50 kV-250 mA, and the scanning range is 0.5 ≦ 2θ ≦ 60 deg. The layer spacing was calculated from the measured XRD pattern using Bragg's equation (2d sin θ = nλ, d: layer spacing, θ: diffraction angle, n: reflection order, λ: X-ray wavelength = 0.154 nm).

(2) Breakdown voltage measurement (breakdown strength evaluation)
The dielectric breakdown voltages of the organic-inorganic composites of Examples 1 to 12 and Comparative Examples 1 and 2 were measured as follows. For the measurement, a pressure measuring device (manufactured by Sasaki Denko Corporation) was used. FIG. 6 shows a schematic view of the measuring apparatus. As an electrode plate, using a 100 mm × 100 mm × 5 mmt aluminum plate 707 having a depression of 80 mm in diameter and 1 mm in depth formed on one side, 1 to 2 g of a resin material is poured into the depression and heated under the curing conditions described in each example. did. A spherical electrode 705 with a diameter of 5 mm is placed on the surface of the organic-inorganic composite material 704 on the aluminum plate 707, and the voltage of commercial frequency (50 Hz) is gradually boosted between the aluminum plate 707 and the spherical electrode 705 (boosting speed: 1 kV / sec ), And the voltage when the short circuit current flows is taken as the breakdown voltage V _TOP (kV). The measurement sample 704, the spherical electrode 705 and the aluminum plate 707 were immersed in an electrically insulating oil (Fluorinert (registered trademark) Sumitomo 3M Co., Ltd., FC-77) 702 filled in a polypropylene case 701.

The effective voltage _{V RMS} (breakdown _{voltage) = V TOP} / √2 calculated from V _{_TOP,} was split breakdown strength _{V RMS} in thickness (0.05 mm).

FIG. 7 shows the XRD measurement results and the fluorescent X-ray measurement results of the untreated layered clay mineral (Kunipia F (registered trademark)) used in Examples 1-12. From the XRD spectrum, a diffraction peak corresponding to the layer spacing of the layered clay mineral was observed at 2θ = 7.183 °. The layer spacing was 1.23 nm according to Bragg's equation. Moreover, sodium was contained in the layered clay mineral from the fluorescent X-ray measurement.

FIG. 8 shows the XRD measurement results and the fluorescent X-ray measurement results of the layered clay mineral interlayer-modified with a copper complex in Examples 1 to 12. From the XRD spectrum, a diffraction peak corresponding to the layer spacing of the layered clay mineral was observed at 2θ = 5.646 °. According to Bragg's equation, the layer spacing is 1.56 nm, which is 0.33 nm wider than the untreated layer spacing. In this case, sodium was not detected in the layered clay mineral from fluorescent X-ray measurement, and copper was detected. From this, it is considered that the layer interval was expanded by the sodium ion exchange between the layers with the copper complex.

FIG. 9 shows the results of XRD measurement of a layered clay mineral dispersed with an alkoxysilane after ion exchange with a copper complex in Example 4. From the XRD spectrum, a diffraction peak corresponding to the layer spacing of the layered clay mineral was observed at 2θ = 5.264 °. The layer spacing was 1.68 nm according to Bragg's equation. From this, it was shown that the layer interval was expanded by 0.13 nm by the dispersion treatment with the alkoxysilane.

FIG. 10 shows the result of X-ray diffraction of the organic-inorganic composite prepared in Example 4. A diffraction peak corresponding to the layer spacing of the layered clay mineral was observed at 2θ = 5.187 °. The layer spacing was 1.70 nm according to Bragg's equation. Only an increase of 0.02 nm was observed as compared to the layered clay mineral processed in FIG.

Table 1 shows the layer spacing of the layered clay mineral dispersed under various conditions, and the spacing and dielectric breakdown strength of the layered clay mineral in the organic-inorganic composite material. The layer spacing of the layered clay mineral can be controlled from 1.61 nm to 2.02 nm by the blending amount of the alkoxysilane at the time of dispersion treatment. Also, the layer spacing in the organic-inorganic composite was controllable from 1.64 nm to 4.51 nm.

It was shown that the addition of 0.5 wt% to 30 wt% of the dispersed layered clay mineral significantly improves the dielectric breakdown strength of the organic-inorganic composite material as compared with the resin alone.

FIG. 11 shows a cross-sectional SEM photograph of the organic-inorganic composite produced in Example 4 and the result of elemental analysis. Elemental analysis showed that a peak of silicon was observed at the peak position of aluminum. On the other hand, it was shown that there are places where peaks of silicon and oxygen can be seen even in a part where aluminum does not exist. Since aluminum is a constituent element of a layered clay mineral, it was thought that in the resin, a portion in which the layered clay mineral and silicon oxide coexist and a portion in which only silicon oxide is present. Also, from the analysis of high-magnification SEM photographs, it is assumed that the particles of about 100 nm found in the resin are silicon oxide and that silicon oxide particles cover the periphery of layered clay minerals of about 0.1 to 3 μm. it was thought. The cause of this structure will be discussed below.

When the hydrolysis reaction of alkoxysilane is performed in the presence of an ammonia catalyst, the reaction solution becomes alkaline at about pH = 12, so the surface of the produced silicon oxide particles (isoelectric point pH = 2) forms a negative charge. It was thought that. Since a cationic copper complex is supported on the surface of the layered clay mineral, negatively charged silicon oxide particles are adsorbed on the surface of the layered clay mineral on which the copper complex is supported. Therefore, in Example 4, it was considered that excess silicon oxide particles deposited outside the layer of the layered clay mineral were adsorbed to the layered clay mineral by electrostatic action.

From the above, the reason why the dielectric breakdown strength of the organic-inorganic composite material is improved is that since the layered clay mineral is electrically neutralized by the adsorption of the layered clay mineral by the electrostatic interaction of the silicon oxide, the insulation The breakdown strength has been improved.

(Preparation of Example 13)
A power semiconductor device was manufactured using the organic-inorganic composite material of the present invention. First, 80 wt% of silica as a filler in the varnish of Example 4, 5 parts by weight of KBM 403 (Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, Hoechst Wax E (manufactured by Clariant Japan Co., Ltd.) as a release agent 2 parts by weight and 1 part by weight of carbon black as a colorant were added, and the mixture was melt-kneaded to prepare a sealing resin raw material. Separately, a module on which a power semiconductor element is mounted is manufactured, and the entire module is covered by a potting method using a sealing resin raw material, and 100 ° C. → 120 ° C. → 150 ° C. → 200 ° C. for one hour each It was heat cured for a while and sealed with a resin.

The schematic diagram of the produced power semiconductor device is shown in FIG. The back side electrode of the power semiconductor element 401 is electrically connected to the circuit wiring member 402 on the insulating substrate 406 by the bonding material 404, and the main electrode of the power semiconductor element 401 is electrically connected to the lead member 403 by the wire 405 There is. On the back side of the insulating substrate 406, a heat sink for dissipating heat generated by the power semiconductor element 401 to the outside is provided. The periphery of the power semiconductor element 401 is sealed with a sealing resin 408 in a state in which the circuit wiring member 402, the lead member 403, and a part of the heat dissipation plate 407 are exposed.

As Comparative Example 3, a power semiconductor device sealed with a resin containing no layered clay mineral was produced. The results of evaluating the cycle life of the power cycle (PC) test (ΔTc = 170 ° C., 20 ° C./190° C.) are shown in Table 2. In Table 2, α1 indicates the thermal expansion coefficient at a temperature equal to or lower than T _g , and α2 indicates the thermal expansion coefficient at a temperature higher than T _g . In Table 2, YDCN-750 is an o-cresol novolac epoxy resin, which is a trade name of Toto Kasei Co., Ltd.

As a result of the cycle life evaluation, the power cycle life of the comparative example 3 was 4000 times while the power cycle life of the example 13 was 20000 times. From the above, it has been shown that the power cycle life is improved by using the organic-inorganic composite material of the present invention for a power semiconductor device. This is because when the organic-inorganic composite material of the present invention is used as the sealing material, the insulation deterioration due to the partial discharge voltage is suppressed.

(Preparation of Example 14 and Comparative Example 4)
As Example 14, an enameled wire was made on a trial basis by a process of applying a varnish containing the layered clay mineral of the present invention and a resin raw material to a wire and heating it. As a result of the accelerated life evaluation at 150 ° C., the reduction rate of the breakdown voltage at 500 h was 5% of the initial value.

As Comparative Example 4, an enameled wire was manufactured by using a commercially available insulating covering material. As a result of the accelerated life evaluation at 150 ° C., the reduction rate of the breakdown voltage at 500 h was 60% of the initial value. From the above, it was shown that an enameled wire excellent in voltage resistance can be obtained by using the organic-inorganic composite of the present invention as an enameled wire coating material.

(Preparation of Example 15 and Comparative Example 5)
As Example 15, after winding an insulating tape around a conductor, heating and drying, a varnish containing the layered clay mineral of the present invention and a resin raw material was vacuum impregnated and heat-cured to obtain a rotary machine coil. As a result of carrying out accelerated life evaluation of this rotary machine coil at 150 ° C., the decreasing rate of the breakdown voltage of 500 h was 10% of the initial value.

As a result of producing a rotating machine coil using a commercially available impregnated resin as Comparative Example 5, and carrying out accelerated life evaluation at 150 ° C., the decreasing rate of the breakdown voltage of 500 h was 60% of the initial value.

From the above, it has been shown that by using the organic-inorganic composite material of the present invention as the impregnated resin, it is possible to obtain a rotary machine coil having an excellent heat resistant life.

The organic-inorganic composite material containing the interlayer-modified layered clay mineral containing the silicon-containing oligomer of the present invention has a high dielectric breakdown strength, so that it is possible to prevent short circuit between the chip and the wiring due to partial discharge. Can contribute to the longevity of

A film using a varnish containing the interlayer-modified layered clay mineral of the present invention and a monomer exhibits a high dielectric breakdown voltage, and thus can provide an insulated wire excellent in surge resistance characteristics.

A rotary coil can be obtained by vacuum impregnation of the varnish of the present invention and heat curing to form an insulation coating. Since this rotating machine coil is coated with a highly insulating resin, it has a high heat resistant life and is useful.

DESCRIPTION OF SYMBOLS 401 Power semiconductor element 402 Circuit wiring member 403 Lead member 404 Bonding material 405 Wire 406 Insulating substrate 407 Heat dissipation plate 408 Sealing material 501 Conductor 502 Insulating coating 601 Conductor 602 Insulating coating 701 PP case 702 Electrical insulating oil 703 Organic-inorganic composite material 704 Spherical electrode 705 Counter electrode (made of aluminum)

Claims

An interlayer modified layered clay mineral comprising a silicon-containing oligomer, wherein the layered clay mineral is at least one or more selected from the group consisting of smectite group, mica group, vermiculite group and mica group. Modified layered clay mineral.
The interlayer modified layered clay mineral according to claim 1, wherein the layered clay mineral is contained at 0.1 wt% to 10 wt% and the silicon-containing oligomer is contained at 0.1 wt% to 30 wt%.
In the interlayer modified layered clay mineral according to claim 1 or 2,
(1,10 phenanthroline) copper complex is ion-exchanged between the layers of the interlayer modified layered clay mineral, and the silicon-containing oligomer contains a benzene ring, or
The cationized aliphatic amines are ion-exchanged between the layers of the interlayer-modified layered clay mineral, and the silicon-containing oligomer contains a long chain alkyl group.
Interlayer modified layered clay mineral.
A varnish comprising the interlayer modified layered clay mineral and monomer according to any one of claims 1 to 3.
5. The varnish according to claim 4, wherein the monomer is a bisphenol A epoxy prepolymer, 4,4′-ethylidene diphenyl dicyanate, 3,3′-4,4′-biphenyl tetracarboxylic dianhydride, p-phenylene A varnish which is at least one or more selected from the group consisting of diamines.
An organic-inorganic composite comprising the interlayer modified layered clay mineral and resin according to any one of claims 1 to 3 or the varnish according to claim 4 or 5.
The organic-inorganic composite material according to claim 6, wherein the resin is at least one selected from the group consisting of an epoxy resin, a cyanate ester resin, and a polyimide resin.
A semiconductor device comprising a semiconductor element and a sealing material, wherein the sealing material comprises the organic-inorganic composite material according to claim 6 or 7, and the semiconductor element is sealed with the sealing material. .
A wire comprising a conductor and an insulating material, wherein the conductor is coated with the varnish according to claim 4 or 5 or the organic-inorganic composite material according to claim 6 or 7.
A rotary coil comprising a conductor and an insulating material, wherein the conductor wound with the insulating material is impregnated with the varnish according to claim 4 or 5 or the organic-inorganic composite material according to claim 6 or 7 The said rotating machine coil.