WO2024038900A1 - Sol de silice contenant un composé de silicone, et composition de résine - Google Patents

Sol de silice contenant un composé de silicone, et composition de résine Download PDF

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Publication number
WO2024038900A1
WO2024038900A1 PCT/JP2023/029749 JP2023029749W WO2024038900A1 WO 2024038900 A1 WO2024038900 A1 WO 2024038900A1 JP 2023029749 W JP2023029749 W JP 2023029749W WO 2024038900 A1 WO2024038900 A1 WO 2024038900A1
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group
silicone compound
silica sol
formula
organic solvent
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PCT/JP2023/029749
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Japanese (ja)
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和也 黒岩
智也 前田
尚彦 末村
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日産化学株式会社
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Publication of WO2024038900A1 publication Critical patent/WO2024038900A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/145—Preparation of hydroorganosols, organosols or dispersions in an organic medium
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • 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
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes

Definitions

  • the present invention relates to a silica sol and a resin composition containing a silicone compound, particularly an insulating resin composition.
  • Insulating resin compositions containing silica particles and polyimide resin are used.
  • a polyimide composition is prepared by mixing 1 to 70 parts by mass of alkoxysilane per 100 parts by mass of polyamic acid and water in an organic polar solvent, followed by dehydration and ring closure.
  • a manufacturing method is disclosed (see Patent Document 1).
  • a modified polyimide precursor solution in which all components are completely dissolved which is made by dissolving tetraalkoxysilane and pure water in a polyimide precursor solution, fine silica particles are generated in the polyimide resin.
  • a finely dispersed silica polyimide enameled wire is disclosed.
  • the present invention is aimed at improving the film-forming properties of an inorganic insulating film when producing a composition that is an insulating resin (hereinafter also referred to as a composition or an insulating resin composition) using a resin composition containing silica particles.
  • the present invention aims to provide a silica particle-containing resin composition containing a silicone compound, and an insulating resin composition using the same. That is, the present invention is an organic solvent silica sol containing a silicone compound, and provides an insulating resin composition and an insulating coated conductive wire using the organic solvent silica sol.
  • the formula (1) or formula (2) [In formula (1), R 1 , R 2 , R 3 , and R 4 each represent a methyl group or an ethyl group, and n1 represents a repeating unit.
  • R 5 represents a methyl group or a phenyl group
  • R 7 and R 8 each represent a methyl group or an ethyl group
  • R 6 represents a methyl group, an ethyl group, or a formula (3):
  • R 9 represents a methyl group or a phenyl group
  • R 10 represents a methyl group, ethyl group, or a silicone compound
  • R 11 represents a methyl group or an ethyl group
  • n3 represents a repeating unit.
  • * indicates a bonding site with an oxygen atom
  • n2 indicates a repeating unit.
  • the silicone compound-containing organic solvent silica sol according to the first aspect which contains a silicone compound represented by (representing a repeating unit);
  • the silicone compound represented by R 10 in the above formula (3) is the formula (3-1), the formula (3-1) and the formula (3-2), or the formula (3-1) to the formula ( 3-3):
  • R 31 represents a methyl group or a phenyl group
  • R 32 represents a methyl group, ethyl group, or a group represented by formula (3-2)
  • R 33 represents a methyl group or an ethyl group.
  • R 34 represents a methyl group or a phenyl group
  • R 35 represents a methyl group, an ethyl group, or a group represented by the formula (3-3)
  • R 36 represents a methyl group.
  • group or ethyl group in formula (3-3)
  • R 37 represents a methyl group or phenyl group
  • R 38 represents a methyl group or ethyl group
  • R 39 represents a methyl group or ethyl group, n13
  • the silicone compound-containing organic solvent silica sol according to the first aspect which contains the silicone compound shown in (n14 and n15 represent repeating units, * represents a bonding site with an oxygen atom).
  • the silicone compound according to the first aspect or the second aspect wherein n1 of the silicone compound of formula (1) or (n11+n12) of the silicone compound of formula (4) has 4 to 15 repeating units.
  • Containing organic solvent silica sol As a fifth aspect, the above repeating unit n2, (n2+n3), n13, n14 or n15 is represented by formula (2), or formula (3), formula (3-1), formula (3-2) and formula (3).
  • the silicone compound-containing organic solvent according to the first or third aspect which is a repeating unit that meets the conditions of exhibiting a kinematic viscosity of 3 to 300 mm 2 /s at 25° C.
  • silicone compound of formula (2) containing -3) silica sol As a sixth aspect, the silicone compound-containing organic solvent silica sol according to any one of the first to fifth aspects, wherein the content ratio of the silicone compound to SiO 2 in the organic solvent silica sol is 1 to 100% by mass. As a seventh aspect, the silicone compound-containing organic solvent according to any one of the first to fifth aspects, wherein the content ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol is 1 to 100% by mass.
  • R 21 is an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, respectively.
  • R22 each represents an alkoxy group, an acyloxy group, or a halogen group
  • a represents an integer of 1 to 3
  • R 23 and R 25 are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms, and are bonded to a silicon atom through a Si-C bond
  • R 24 and R 26 each represent an alkoxy group, an acyloxy group, or a halogen group
  • Y represents an alkylene group, an NH group, or an oxygen atom
  • b is an integer from 1 to 3
  • c is an integer of 0 or 1
  • d is an integer of 1 to 3.
  • the silicone compound-containing organic solvent silica sol according to any one of the first to seventh aspects which contains at least one silane compound selected from the group consisting of compounds represented by As a ninth aspect, the number of silicon atoms in the silane compounds of the above formulas (5) to (7) is coated on the surface of the silica particles from 0.3 atoms/nm 2 to 5.0 atoms/nm 2 .
  • the silicone compound-containing organic solvent silica sol according to any one of the first to eighth aspects As a tenth aspect, the silicone compound-containing organic solvent silica sol according to any one of the first to ninth aspects, wherein the silicone compound or silane compound contains a covalent bond with a silica particle;
  • the nitrogen-containing solvent is dimethylacetamide, dimethylformamide, N-methylpyrrolidone, or N-ethylpyrrolidone
  • the carbonyl group-containing oxygen-containing solvent is ⁇ -butyrolactone or cyclohexanone
  • the sulfur-containing solvent is dimethyl
  • the silicone compound-containing organic solvent silica sol according to any one of the first to twelfth aspects which is sulfoxide or dimethyl sulfone
  • organic solvent silica sol As a fifteenth aspect, a composition comprising a silicone compound-containing organic solvent silica sol and a nitrogen-containing polymer according to any one of the first to fourteenth aspects, As a 16th aspect, a composition that is an insulating resin containing a silicone compound-containing organic solvent silica sol and a nitrogen-containing polymer according to any one of the 1st to 14th aspects; As a 17th aspect, in the 15th or 16th aspect, the amount of silica particles contained in the silicone compound-containing organic solvent silica sol is 0.01 to 1 part by mass with respect to 1 part by mass of the nitrogen-containing polymer.
  • compositions described As an 18th aspect, the composition according to any one of the 15th to 17th aspects, wherein the nitrogen-containing polymer is polyimide, polyamide, polyamic acid, polyamideimide, polyetherimide, polyesterimide, or a mixture thereof.
  • An insulating layer of 35 ⁇ m was formed, and a voltage (AC) of 3.0 kV (frequency 50 Hz) was applied between a disk electrode (25 mm in diameter) in close contact with the copper plate side and a spherical electrode (20 mm in diameter) in close contact with the insulating layer side.
  • a composition having an insulation life of 85 minutes or more when measured at a temperature of 155°C As a 20th aspect, an insulated conductive wire in which the conductive wire is insulated and coated with the composition according to any one of the 15th to 19th aspects;
  • step (A) preparing an alcohol solvent silica sol having 1 to 5 carbon atoms containing silica particles having an average primary particle diameter of 5 to 100 nm;
  • step (B) A silane compound according to any one of formulas (5) to (7) is added to the silica sol obtained in step (A), and after the addition, at 20 to 100 ° C.
  • the process of maintaining (C) step a step of replacing the alcohol solvent of the silica sol obtained in step (B) with a nitrogen-containing solvent, a carbonyl group-containing oxygen-containing solvent, or a sulfur-containing solvent;
  • the method for producing a silicone compound-containing organic solvent silica sol according to the first to fourteenth aspects includes a step (D) of adding a secondary or tertiary amine at a desired stage from the start of the step (B) to the end of the step (C).
  • an alcohol solvent silica sol having 1 to 5 carbon atoms [organic solvent silica sol (i)] containing silica particles having an average primary particle diameter of 5 to 100 nm, and the above nitrogen-containing polymer [nitrogen-containing polymer (ii)] ] and the silicone compound [silicone compound (iii)] according to claim 1 or 2.
  • step (E) is a step (E-1) of adding a silicone compound (iii) to the organic solvent silica sol (i) and further adding a nitrogen-containing polymer (ii); Step (E-2) of adding the nitrogen-containing polymer (ii) to the organic solvent silica sol (i) and further adding the silicone compound (iii), or adding the silicone compound (iii) to the nitrogen-containing polymer (ii),
  • a method for producing a composition according to the 23rd aspect which is a step (E-3) of further adding an organic solvent silica sol (i)
  • a method for producing the composition according to the twenty-fourth aspect including a step (F) of removing the organic solvent at a desired stage from the start of the (E) step to the end of the (E) step, and the twenty-sixth aspect.
  • the present invention relates to an organic solvent silica sol containing a silicone compound, and an insulating resin composition and an insulated conductor using the same.
  • insulating resin compositions that contain resins such as polyimide and polyamic acid and silica particles.
  • the silica particles are added to the resin as an organic solvent silica sol, and after the organic solvent is removed, they are cured by heating or the like to form an insulating film in which the silica particles are dispersed in the resin.
  • a silica insulating film is formed when the resin is eroded by the occurrence of electric discharge, and exhibits insulation properties.In the insulating film, the silica particles are close to each other, but since the silica particles exist alone, the silica Due to the deterioration of the film-forming properties of the insulating film, the gaps between the silica particles become paths for discharge phenomena, which may reach the surface of the base material and cause dielectric breakdown.
  • the present invention uses an organic solvent silica sol containing a silicone oligomer to form an insulating resin composition and coats a base material to form an insulating film. It was found that the film-forming properties of the film were improved. Moreover, since silicone itself has high heat resistance and high insulation properties, it was found that the silica particles themselves and the gaps between the silica particles also have high insulation properties. In addition, in the present invention, the silica particles themselves are made hydrophobic by the silane compound, leading to improved dispersibility in organic solvents and improved compatibility with resins, so that they stably exist in the insulating resin composition, and can be applied to substrates. When this is done, film forming properties can be improved.
  • the present invention is an organic solvent silica sol containing a silicone compound, which contains a silicone compound represented by formula (1) or formula (2) in an organic solvent silica sol containing silica particles having an average primary particle diameter of 5 to 100 nm.
  • the above average primary particle diameter can be measured by the BET method (nitrogen gas adsorption method).
  • R 1 , R 2 , R 3 and R 4 each represent a methyl group or an ethyl group, and n1 represents a repeating unit.
  • R 1 , R 2 , R 3 and R 4 in formula (1) are all ethyl groups, it is called ethyl silicate.
  • These silicates undergo hydrolysis and polycondensation with water in the presence of an acid or basic catalyst to form siloxane polymers, which function as a binder.
  • silica particles act as a catalyst to cause hydrolysis and polycondensation of ethyl silicate, and can form graft bonds on the surface of the silica particles, coat the surfaces of the silica particles, or exist in the vicinity of the silica particles.
  • R 1 , R 2 , R 3 , and R 4 each represent a methyl group or an ethyl group, and a mixture of methyl silicate oligomer and ethyl silicate oligomer can be used as formula (4).
  • R 111 , R 112 , R 113 , and R 114 each represent an ethyl group
  • R 115 , R 116 , R 117 , and R 118 each represent a methyl group
  • n11 and n12 each represent a repeating group. Indicates the unit.
  • silicone compound of formula (1) or formula (4) a silicone compound in which the repeating unit n1 or (n11+n12) is an integer of 5 to 10 can be used. These are oligomers, and the integer of 4 to 15 or 5 to 10 is the average value of the degree of polymerization of these silicone compounds, and can be used, for example, as an average pentamer or an average decamer.
  • the viscosity of the silicone compound of formula (1) or formula (4), measured at 25° C., is, for example, in the range of 2 to 4 mPa ⁇ s for a pentameric compound and 13 to 24 mPa ⁇ s for a decameric compound. These are available as silicone compounds manufactured by Colcoat Co., Ltd.
  • the silicone compound of formula (2) is a silicone compound obtained by hydrolysis and polycondensation of a silane compound having three hydrolyzable groups in one molecule.
  • R 5 represents a methyl group or a phenyl group
  • R 7 and R 8 each represent a methyl group or an ethyl group
  • R 6 represents a methyl group, an ethyl group, or the formula (3).
  • R 9 represents a methyl group or a phenyl group
  • R 10 represents a methyl group, an ethyl group, or the formula (3-1)
  • R 11 represents a methyl group or an ethyl group.
  • R 6 is the formula (3) and R 10 is the formula (3-1)
  • the side chain extends from the silicone main chain, and the side chain becomes the silicone main chain, and the side chain further extends from the main chain. It can have a multi-branched structure. For example, this corresponds to the case where R 32 in formula (3-1) is formula (3-2) and R 35 is formula (3-3).
  • n2, (n2+n3), n13, n14 in the silicone compound of formula (2) or formula (3) containing formula (3-1), formula (3-2) and formula (3-3) or the integer of the repeating unit n15 is the above repeating unit in a range that exhibits a kinematic viscosity (25°C) of 3 to 300 mm 2 /s as a silicone compound of formula (2) or formula (2) containing formula (3) It can be expressed as an integer.
  • These can be obtained by purchasing silicone compounds manufactured by Shin-Etsu Chemical Co., Ltd.
  • the above-mentioned kinematic viscosity can be measured, for example, with a simple kinematic viscometer manufactured by STM Co., Ltd. under the trade name ASTM D7279.
  • the silicone compounds of the above formulas (1), (2), and (4) can be used alone or in combination.
  • the above-mentioned silicone compound can include at least a bond via a covalent bond with a silica particle.
  • the ratio of the silicone compound to SiO 2 in the organic solvent silica sol can be in the range of 1 to 100% by mass, 1 to 70% by mass, 1 to 60% by mass, or 2 to 60% by mass.
  • the ratio of the silicone compound to SiO 2 in the organic solvent silica sol containing the silicone compound is 1 to 100% by mass, 1 to 70% by mass, 1 to 60% by mass, 1 to 50% by mass, or 2 to 50% by mass. It can be contained within the range of.
  • the silica particles can contain at least one silane compound selected from the group consisting of formulas (5) to (7).
  • R 21 is an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group.
  • R22 each represents an alkoxy group, an acyloxy group, or a halogen group, and a represents an integer of 1 to 3;
  • R 23 and R 25 are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms, and are bonded to a silicon atom through a Si-C bond.
  • R 24 and R 26 each represent an alkoxy group, an acyloxy group, or a halogen group
  • Y represents an alkylene group, an NH group, or an oxygen atom
  • b is an integer from 1 to 3
  • c is an integer of 0 or 1
  • d is an integer of 1 to 3.
  • the above alkyl group is an alkyl group having 1 to 18 carbon atoms, such as methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group.
  • These include, but are not limited to:
  • the alkylene group can be an alkylene group derived from the above-mentioned alkyl group.
  • the above aryl group is an aryl group having 6 to 30 carbon atoms, and examples thereof include phenyl group, naphthyl group, anthracene group, and pyrene group.
  • the alkenyl group is an alkenyl group having 2 to 10 carbon atoms, such as ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group.
  • alkoxy group examples include alkoxy groups having 1 to 10 carbon atoms, such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t -butoxy group, n-pentyloxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2 -dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, etc., but are not limited to these.
  • the above acyloxy group has 2 to 10 carbon atoms, for example, methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, i-propylcarbonyloxy group, n-butylcarbonyloxy group, i-butyloxy group.
  • halogen group examples include fluorine, chlorine, bromine, and iodine.
  • organic group having an epoxy group examples include 2-(3,4-epoxycyclohexyl)ethyl group and 3-glycidoxypropyl group.
  • the above (meth)acryloyl group represents both an acryloyl group and a methacryloyl group.
  • the organic group having a (meth)acryloyl group include a 3-methacryloxypropyl group and a 3-acryloxypropyl group.
  • An example of the organic group having a mercapto group is a 3-mercaptopropyl group.
  • organic groups having an amino group include 2-aminoethyl group, 3-aminopropyl group, N-2-(aminoethyl)-3-aminopropyl group, and N-(1,3-dimethyl-butylidene)aminopropyl group.
  • N-phenyl-3-aminopropyl group N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl group, and the like.
  • An example of the organic group having a ureido group is a 3-ureidopropyl group.
  • An example of the organic group having a cyano group is a 3-cyanopropyl group.
  • the above formulas (2) and (3) are preferably compounds that can form a trimethylsilyl group on the surface of the silica particles.
  • R 12 is an alkoxy group, such as a methoxy group or an ethoxy group.
  • silane compound a silane compound manufactured by Shin-Etsu Chemical Co., Ltd. can be used.
  • the reaction temperature can be from 20°C to the boiling point of the dispersion medium, for example from 20°C to 100°C.
  • the reaction time can be about 0.1 to 6 hours.
  • the number of silicon atoms in the silane compound is 0.3/nm 2 to 5.0/nm 2 or 0.6/nm 2 to 5.0 as the amount of coverage of the silica particle surface of the silane compound.
  • the surface of the silica particles can be coated by containing a silane compound in the silica sol in a coating amount of 0.6/nm 2 or 0.6/nm 2 to 3.0/nm 2 .
  • Water is required for hydrolysis of the above-mentioned silane compound, and if the sol is an aqueous solvent, such an aqueous solvent can be used. Water remaining in the solvent when the aqueous medium is replaced with an organic solvent such as methanol or ethanol can be used. For example, water present at 0.01 to 1% by weight can be used.
  • hydrolysis can be carried out with or without a catalyst. When carrying out without a catalyst, the silica particle surface is present on the acidic side, and when using a catalyst, examples of the hydrolysis catalyst include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.
  • Examples of the metal chelate compound as a hydrolysis catalyst include triethoxy mono(acetylacetonato) titanium and triethoxy mono(acetylacetonato) zirconium.
  • Examples of organic acids as hydrolysis catalysts include acetic acid and oxalic acid.
  • Examples of inorganic acids as hydrolysis catalysts include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.
  • Examples of organic bases used as hydrolysis catalysts include pyridine, pyrrole, piperazine, and quaternary ammonium salts.
  • Examples of the inorganic base as a hydrolysis catalyst include ammonia, sodium hydroxide, and potassium hydroxide.
  • the above-mentioned silane compound contains at least one bond via a covalent bond with the silica particle.
  • the silica particles have aluminum atoms on the surface of the silica particles in an amount of 0.001 to 2.0 mass%/SiO 2 in terms of Al 2 O 3 , or 0.001 to 1.0 mass %/SiO 2 , or The silica particles can be bonded at a ratio of 0.001 to 0.5% by mass/SiO 2 or 0.001 to 0.3% by mass/SiO 2 .
  • the amount of negative charge present on the silica particle surface increases, and is measured at, for example, 0.25 to 0.40 ⁇ eq/m 2 .
  • a nitrogen-containing solvent, a carbonyl group-containing oxygen-containing solvent, or a sulfur-containing solvent can be used as the organic solvent.
  • nitrogen-containing solvents include dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, tetramethylurea, hexamethylphosphoric triamide, dimethylacrylamide, acryloylmorpholine, and hydroxyl.
  • Ethylacrylamide isopropylacrylamide, diethylacrylamide, dimethylaminopropylacrylamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, dimethylaminopropylacrylamide methyl chloride quaternary salt, dimethylamino Examples include ethyl acrylate benzyl chloride quaternary salt.
  • the nitrogen-containing solvent can be dimethylacetamide, dimethylformamide, N-methylpyrrolidone, or N-ethylpyrrolidone.
  • Examples of carbonyl group-containing oxygen-containing solvents include ketones and esters.
  • the ketone is a linear or cyclic aliphatic ketone having 3 to 30 carbon atoms, such as methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, and the like.
  • Esters are linear or cyclic esters having 2 to 30 carbon atoms, such as ethyl acetate, n-butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, n-propyl acetate, isopropyl acetate, ethyl lactate, lactic acid.
  • Examples include butyl, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, phenyl acetate, phenyl lactate, phenyl propionate, and the like.
  • the carbonyl group-containing oxygen-containing solvent is preferably ⁇ -butyrolactone or cyclohexanone.
  • sulfur-containing solvents include dimethyl sulfoxide and dimethyl sulfone.
  • amines can be added.
  • examples of amines include secondary amines and tertiary amines having a total number of carbon atoms of 5 to 35.
  • examples of the secondary amines include ethyl-n-propylamine, ethylisopropylamine, dipropylamine, diisopropylamine, ethylbutylamine, n-propylbutylamine, dibutylamine, ethylpentylamine, n-propylpentylamine, and isopropylpentylamine.
  • tertiary amines include triethylamine, ethyldi-n-propylamine, diethyl-n-propylamine, tri-n-propylamine, triisopropylamine, ethyldibutylamine, diethylbutylamine, isopropyldibutylamine, diisopropylethylamine, diisopropyl
  • examples include butylamine, tributylamine, ethyldipentylamine, diethylpentylamine, tripentylamine, methyldioctylamine, dimethyloctylamine, ethyldioctylamine, diethyloctylamine, trioctylamine,
  • secondary amines and tertiary amines having an alkyl group having a total number of carbon atoms of 6 to 35 are preferred, such as diisopropylamine, tripentylamine, triisopropylamine, dimethyloctylamine, trioctylamine, etc. Can be mentioned. Furthermore, quaternary ammonium can be added.
  • the quaternary ammonium hydroxide is preferably a tetraalkylammonium hydroxide having a total number of carbon atoms of 4 to 40.
  • Examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-i-propylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, and the like.
  • the present invention includes a composition containing the above-mentioned silicone compound-containing organic solvent silica sol and a nitrogen-containing polymer.
  • the above composition can be exemplified as an insulating composition.
  • the nitrogen-containing polymer used in the present invention can be polyimide, polyamide, polyamic acid, polyamideimide, polyetherimide, polyesterimide, or a mixture thereof.
  • Polyimide is a polymer obtained by imidizing aromatic diamine and aromatic tetracarboxylic dianhydride via polyamic acid.
  • Polyamic acid can also be used as a polymer component of an insulating resin composition and converted into polyimide by heating during coating on a substrate.
  • Polyamideimide, polyetherimide, and polyesterimide can be selected by selecting aromatic diamine and aromatic tetracarboxylic dianhydride.
  • aromatic diamines that can be used as raw materials for the nitrogen-containing polymer include m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, o-tolidine, o-dianidine, Examples include 1,5-diaminonaphthalene, 4,4'-diaminodiphenylsulfide, and 4,4'-diaminodiphenylsulfone.
  • aromatic tetracarboxylic dianhydride used as a raw material for the nitrogen-containing polymer examples include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenone)propane dianhydride, bis (3,4-dicarboxyphenyl)ether dianhydride, ethylenetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, Examples include 4,4'-oxydiphthalic dianhydride.
  • Preferred solvents in the reaction include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, tetramethylenesulfone, dimethylsulfone, pyridine, diethylene glycol dimethyl ether, and the like.
  • the solvents can be used alone or in combination, or in combination with benzene, toluene, xylene, dioxane, butyrolactone, cyclohexane, and the like.
  • Examples of dehydrating agents include aliphatic and aromatic carboxylic acid anhydrides such as acetic acid, propionic acid, isobutyric acid, benzoic acid, and propylbenzoic acid.
  • Examples of imidization catalysts include tertiary amines such as pyridine, isoquinoline, 4-methylpyridine, and 3-methylpyridine.
  • the organic solvent silica sol containing a silicone compound can have an average particle diameter of 5 to 100 nm as measured by dynamic light scattering (DLS). In the insulating resin composition, the amount of silica particles contained in the silicone compound-containing organic solvent silica sol can be 0.01 to 1 part by mass per 1 part by mass of the nitrogen-containing polymer.
  • an insulated conductive wire is obtained in which a conductive wire is insulated and coated with the above-mentioned insulating resin composition.
  • an insulating layer of the above insulating resin composition containing 7 to 30% by mass of silica was formed on a 0.5 mm thick copper plate to a thickness of 30 to 35 ⁇ m, and a disk electrode was placed in close contact with the copper plate. (diameter: 25 mm), insulation life is 85 minutes or more when measured under conditions of applied voltage (AC) of 3.0 kV, frequency of 50 Hz, and temperature of 155°C for a spherical electrode (diameter of 20 mm) that is in close contact with the insulating layer side.
  • AC applied voltage
  • the organic solvent silica sol of this case is manufactured by the following steps (A) to (C): (A) Step: preparing an alcohol solvent silica sol having 1 to 5 carbon atoms containing silica particles having an average primary particle diameter of 5 to 100 nm; (B) Step: A silane compound according to any one of formulas (5) to (7) is added to the silica sol obtained in step (A) at 20 to 100°C for 0.1 to 48 hours, or a step of carrying out a reaction for 0.1 to 6 hours; (C) Step: Production can include a step of replacing the silica sol obtained in Step (B) with a nitrogen-containing solvent, a carbonyl group-containing oxygen-containing solvent, or a sulfur-containing solvent.
  • step (A) examples include methanol, ethanol, n-propanol, i-propanol, n-butanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and the like.
  • a step (D) of adding a secondary or tertiary amine can be added at any stage from the start of the step (B) to the end of the step (C).
  • the insulating resin composition of the present invention comprises the alcohol solvent silica sol [organic solvent silica sol (i)], the nitrogen-containing polymer [nitrogen-containing polymer (ii)], and the above formula (1), formula (2), or It can be manufactured by including the step (E) of adding and mixing the silicone compound (iii) of formula (4).
  • the order of addition of the organic solvent silica sol (i), the nitrogen-containing polymer (ii), and the silicone compound (iii) of the formula (1), formula (2), or formula (4) is at least three. Any order is possible as long as they are mixed.
  • step (E) is a step (E-1) of adding a silicone compound (iii) to an organic solvent silica sol (i) and further adding a nitrogen-containing polymer (ii);
  • the above-mentioned insulating resin composition can contain the organic solvent contained in the organic solvent silica sol, it is preferable to increase the solid content in the composition and improve the silica concentration in the coating film.
  • E) It may include the step (F) of removing an organic solvent such as an alcohol, a nitrogen-containing solvent, a carbonyl group-containing oxygen-containing solvent, or a sulfur-containing solvent at any stage from the start of the process to the end of the (E) process. preferable.
  • the organic solvent silica sol (i) may or may not contain at least one silane compound selected from the group consisting of formulas (5) to (7), and may or may not contain at least one silane compound selected from the group consisting of formulas (5) to (7).
  • Step 1 1000 g of water-dispersed silica sol (average primary particle size 12 nm, pH 2.5, silica concentration 20% by mass, Al2O3 concentration 0.42% by mass/ SiO2 , manufactured by Nissan Chemical Co., Ltd.) was placed in a stirrer, A glass reactor with an internal volume of 2 L equipped with a condenser, a thermometer, and two injection ports is charged, and while the sol in the reactor is kept boiling, methanol vapor generated in another boiler is poured into the reactor. Water was replaced by methanol while the liquid level was gradually raised by continuously blowing into the silica sol in the tank.
  • DMAC dimethylacetamide
  • DMAC-dispersed silica sol 1A (silica concentration 30.5% by mass, pH 4.6, viscosity (20°C) 5 mPa ⁇ s, water 0.1% by mass, methanol 0.1% by mass, dynamic light scattering particle size 18 nm) ) was obtained.
  • step (c) of Reference Example 1 DMAC-dispersed silica sol 2A (silica concentration 30.5% by mass, pH 4.4, viscosity (20°C) 5 mPa ⁇ s, moisture 0.1% by mass, methanol 0.1% by mass, dynamic light scattering particle size 21nm)
  • DMAC dimethylacetamide
  • DMAC-dispersed silica sol 3A sica concentration 20.8% by mass, pH 4.0, viscosity (20°C) 2 mPa ⁇ s
  • 0.2% by mass of water 0.4% by mass of methanol, and a dynamic light scattering particle size of 21 nm.
  • Step (b) of Reference Example 1 and A methanol-dispersed silica sol (silica concentration: 30.5% by mass, pH: 4.2, moisture: 0.5% by mass, viscosity: 2 mPa ⁇ s) was obtained by replacing the solvent in a similar manner.
  • 1,000 g of the above methanol sol was placed in a 2L eggplant flask, and DMAC (dimethylacetamide) was supplied while the solvent was evaporated off using a rotary evaporator at a reduced pressure of 450 to 110 Torr and a bath temperature of 85 to 125°C.
  • DMAC-dispersed silica sol 4A (silica concentration 20.5% by mass, pH 4.9, viscosity (20°C) 3 mPa ⁇ s, water 0.2% by mass, methanol 0.6% by mass, dynamic light A particle size of 18 nm by scattering method was obtained.
  • Example 1 To 100 g of DMAC-dispersed silica sol 1A obtained in Reference Example 1, ethyl silicate oligomer (manufactured by Colcoat Co., Ltd., trade name ethyl silicate 40, ethoxy group as the alkoxy group in general formula (1), average molecular weight 745) was added as a silicone compound component. , was a pentamer on average. Note that ethyl silicate 40 also includes SiO 2 ) 0.90 g was added. After shaking vigorously by hand about 10 times, the mixture was mixed for 1 hour at 23°C using a mix rotor (manufactured by As One Co., Ltd., trade name MR-5).
  • a mix rotor manufactured by As One Co., Ltd., trade name MR-5
  • a particle size of 22 nm and a SiO 2 concentration of 30.8% by mass were obtained.
  • the ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 2.8% by mass.
  • the ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 2.7% by mass.
  • the above sol was added to the polyamic acid obtained in Reference Example 5 and mixed in a glass bottle so that the resin/SiO 2 ratio was 80/20, and the mixture was mixed with a vacuum defoaming machine (manufactured by EME, trade name: V-mini 300). By defoaming and stirring for 20 minutes, a silica-containing polyamic acid (insulating resin composition) was obtained.
  • Example 2 The same procedure as in Example 1 was carried out except that the amount of ethyl silicate oligomer (manufactured by Colcoat Co., Ltd., trade name: ethyl silicate 40) was changed to 1.7 g. A particle size of 21 nm as determined by light scattering method and a SiO 2 concentration of 30.8% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 5.6% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 5.5% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
  • ethyl silicate oligomer manufactured by Colcoat Co., Ltd., trade name: ethyl silicate 40
  • Example 3 The same procedure as in Example 1 was carried out except that the amount of ethyl silicate oligomer (manufactured by Colcoat Co., Ltd., trade name: Ethyl silicate 40) was changed to 4.3 g. A particle size of 25 nm as determined by light scattering method and a SiO 2 concentration of 30.4% by mass) was obtained.
  • the ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 14.0% by mass.
  • the ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 13.5% by mass.
  • a silica-containing polyamic acid (insulating resin composition) was obtained.
  • Example 4 The same procedure as in Example 1 was carried out except that the amount of ethylsilicate oligomer (manufactured by Colcoat Co., Ltd., trade name: Ethylsilicate 40) was changed to 17.1 g. A particle size of 20 nm as determined by optical scattering method and a SiO 2 concentration of 31.4% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 56.0% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 46.5% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
  • ethylsilicate oligomer manufactured by Colcoat Co., Ltd., trade name: Ethylsilicate 40
  • Example 5 The silicone compound component of Example 1 was an ethyl silicate oligomer (manufactured by Colcoat Co., Ltd., trade name ethyl silicate 48, in the general formula (1), the alkoxy group was an ethoxy group, the average molecular weight was 1400, and the average was a decamer. ) Except that the amount was changed to 1.6 g, the same operation as in Example 1 was performed to obtain a silicone compound-containing organic solvent silica sol (dynamic light scattering particle size: 20 nm, SiO 2 concentration: 30.3% by mass). Next, in the same manner as in Example 1, the mixture was mixed with polyamic acid to obtain a silica-containing polyamic acid. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 5.3% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 5.3% by mass.
  • Example 6 The same procedure as in Example 1 was carried out except that the silicone compound component in Example 1 was changed to 3.3 g of ethyl silicate oligomer (manufactured by Colcoat Co., Ltd., trade name: Ethyl Silicate 48), and a silicone compound-containing organic solvent silica sol ( A dynamic light scattering method particle size of 20 nm and SiO 2 concentration of 30.3% by mass) were obtained.
  • the ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 10.7% by mass.
  • the ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 10.4% by mass.
  • a silica-containing polyamic acid insulating resin composition
  • Example 7 The silicone compound component of Example 1 was converted into a silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-213, having a methoxy group as an alkoxy group and a phenyl group and a methyl group as organic functional groups in the general formula (2), The operation was carried out in the same manner as in Example 1, except that the kinematic viscosity (25° C.) was changed to 16 mm 2 /s ) 17.2 g. .1% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 56.5% by mass.
  • the ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 48.8% by mass.
  • a silica-containing polyamic acid (insulating resin composition) was obtained.
  • Example 8 The silicone compound component of Example 1 was a silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KC-89S, having a methoxy group as an alkoxy group and a methyl group as an organic functional group in the general formula (2), and having a kinematic viscosity ( 25°C) 5 mm 2 /s) 16.1 g, the same operation as in Example 1 was carried out, and a silicone compound-containing organic solvent silica sol (dynamic light scattering particle size 21 nm, SiO 2 concentration 33.0 mass) %) was obtained.
  • the ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 52.7% by mass.
  • the ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 42.0% by mass.
  • a silica-containing polyamic acid (insulating resin composition) was obtained.
  • Example 9 The silicone compound component of Example 1 was a silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-515, having a methoxy group as an alkoxy group and a methyl group as an organic functional group in the general formula (2), and having a kinematic viscosity ( 25° C.) 7 mm 2 /s) 2.1 g, the same operation was carried out as in Example 1, and a silicone compound-containing organic solvent silica sol (dynamic light scattering particle size 21 nm, SiO 2 concentration 30.1 mass) %) was obtained.
  • the ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 6.8% by mass.
  • the ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 6.7% by mass.
  • a silica-containing polyamic acid (insulating resin composition) was obtained.
  • Example 10 The same procedure as in Example 1 was carried out except that the silicone compound component in Example 1 was changed to 5.2 g of silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-515), and a silicone compound-containing organic solvent silica sol was prepared. (Dynamic light scattering particle size: 21 nm, SiO 2 concentration: 32.1% by mass). The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 1A was 17.0% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 15.3% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
  • silicone oligomer manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-515
  • Example 11 By adding 2.1 g of silicone oligomer (trade name KR-515, manufactured by Shin-Etsu Chemical Co., Ltd.) to 100 g of DMAC-dispersed silica sol 2A obtained in Reference Example 2, and performing the same operation as in Example 1, A silicone compound-containing organic solvent silica sol (dynamic light scattering particle size: 22 nm, SiO 2 concentration: 30.9% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 2A was 6.8% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 6.6% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
  • silicone oligomer trade name KR-515, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Example 12 By adding 5.2 g of silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-515) to 100 g of DMAC-dispersed silica sol 2A obtained in Reference Example 2, and performing the same operation as in Example 1, A silicone compound-containing organic solvent silica sol (dynamic light scattering particle size: 21 nm, SiO 2 concentration: 32.3% by mass) was obtained. Next, in the same manner as in Example 1, the mixture was mixed with polyamic acid to obtain a silica-containing polyamic acid. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 2A was 17.0% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 15.2% by mass.
  • silicone oligomer manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-515
  • Example 13 By adding 10.8 g of silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KC-89S) to 100 g of DMAC-dispersed silica sol 3A obtained in Reference Example 3, and performing the same operation as in Example 1, A silicone compound-containing organic solvent silica sol (dynamic light scattering particle size 20 nm, SiO 2 concentration 24.0% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 3A was 52.7% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 40.6% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
  • silicone oligomer manufactured by Shin-Etsu Chemical Co., Ltd., trade name KC-89S
  • Example 14 By adding 1.4 g of silicone oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-515) to 100 g of DMAC-dispersed silica sol 4A obtained in Reference Example 4, and performing the same operation as in Example 1, A silicone compound-containing organic solvent silica sol (dynamic light scattering particle size: 21 nm, SiO 2 concentration: 21.1% by mass) was obtained. The ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 4A was 6.8% by mass. The ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 6.5% by mass. Next, by mixing with polyamic acid in the same manner as in Example 1, a silica-containing polyamic acid (insulating resin composition) was obtained.
  • silicone oligomer manufactured by Shin-Etsu Chemical Co., Ltd., trade name KR-515
  • Example 1 A silica-containing polyamic acid was obtained by performing the same operation as in Example 1 without adding the silicone compound component to the DMAC-dispersed silica sol 2A obtained in Reference Example 2.
  • the ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 2A was 0% by mass.
  • the ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 0% by mass.
  • Example 2 A silica-blended polyamic acid (insulating resin composition) was obtained by performing the same operation as in Example 1 without adding a silicone compound component to DMAC-dispersed silica sol 3A obtained in Reference Example 3.
  • the ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 3A was 0% by mass.
  • the ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 0% by mass.
  • Example 3 A silica-blended polyamic acid (insulating resin composition) was obtained by performing the same operation as in Example 1 without adding the silicone compound component to DMAC-dispersed silica sol 4A obtained in Reference Example 4.
  • the ratio of the silicone compound to SiO 2 in DMAC-dispersed silica sol 4A was 0% by mass.
  • the ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol was 0% by mass.
  • Example 4 Polyamic acid (insulating resin composition) was obtained without adding silica sol, silane compound, and silicone compound.
  • (silicone) is the type of silicone compound used in the examples and corresponds to a silicone compound selected from formula (1), formula (2), and formula (3) shown in the general formula. It was something to do.
  • (Silicone content A) indicates the content ratio of the silicone compound to SiO 2 in the organic solvent silica sol (before addition of the silicone compound of formula (1) or formula (2)), and the unit is mass %.
  • (Silicone content B) indicates the ratio of the silicone compound to SiO 2 in the silicone compound-containing organic solvent silica sol (after addition of the silicone compound of formula (1) or formula (2)), and the unit is mass %.
  • (Silane functional group) indicates the type of organic functional group of the silane compound selected from formulas (5) to (7) represented by the general formula to be coated on the silica particles. And (none) indicates the case where the above-mentioned silane compound was not added.
  • (Resin content) indicates the ratio of silica particles contained in the organic solvent silica sol to 1 part by mass of the nitrogen-containing polymer (polyamic acid synthesized in Reference Example 5), and the unit is parts by mass. When it is zero, the case where no organic solvent silica sol is added is described.
  • (insulation life) is determined by forming insulating layers made of the insulating resin compositions of Examples 1 to 14 and Comparative Examples 1 to 4 to a film thickness of 30 to 35 ⁇ m on a 0.5 mm thick copper plate.
  • the insulation life was measured using a disk electrode (diameter 25 mm) closely attached to the copper plate side and a spherical electrode (diameter 20 mm diameter) closely attached to the insulating layer side at an applied voltage (AC) of 3.0 kV and a frequency of 50 Hz.
  • the unit is the length (minutes) until dielectric breakdown occurs.
  • the silica-containing polyamic acids (insulating resin compositions) obtained in Examples 1 to 14 improve the insulation life of cured films (insulating coatings) in which silica-containing polyimide is baked, compared to Comparative Examples 1 to 4. I was able to do that.
  • Preparation and evaluation of enameled wire 13 kg of the polyamic acid obtained in Reference Example 5 was placed in a 20 L plastic container, and while stirring with a mechanical stirrer, the silicone obtained by the same method as the silicone compound-containing organic solvent silica sol described in Example 2.
  • the above silica-containing polyamic acid was applied and baked onto a copper conductor (1.0 mm diameter), and an insulated wire having an insulating layer with a thickness of 34 ⁇ m was finally produced. Further, as Reference Example 6, the polyamic acid obtained in Reference Example 5 was coated and baked on a copper conductor (1.0 mm diameter) to produce an insulated wire having an insulating layer with a thickness of 36 ⁇ m.
  • the flexibility and insulation life (Vt test) of the insulated wire obtained above were evaluated. The evaluation method and conditions are shown below.
  • the flexibility test results show that the minimum winding diameter without cracking is the self-diameter (1d), the minimum winding diameter without cracking is twice the self-diameter (2d), and the minimum winding diameter without cracking is the self-diameter (2d). It is three times the diameter (3d), and it can be said that the smaller the minimum wrapping diameter d is, the better the flexibility is.
  • Example 6 has a composition containing only a polyamic acid insulating resin varnish. The insulated wire obtained in Example 2 was able to significantly increase the insulation life while maintaining mechanical properties compared to the wire coated with silica-free polyamic acid.
  • the present invention is an organic solvent silica sol containing a silicone compound, and provides an insulating resin composition and an insulated conductor using the same.

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Abstract

La présente invention a pour but de procurer : un sol de silice dispersé dans un solvant organique qui contient un composé de silicone ; une composition utilisant le sol de silice dispersé dans un solvant organique ; et un fil conducteur recouvert et isolé. La solution selon l'invention consiste en un sol de silice dispersé dans un solvant organique, qui contient des particules de silice ayant un diamètre moyen de 5 à 100 nm, pour contenir un composé de silicone de formule (1) ou de formule (2). (Dans la formule (1), chacun de R1, R2, R3 et R4 représente un groupe méthyle ou un groupe éthyle ; et n1 représente une unité de répétition. Dans la formule (2), R5 représente un groupe méthyle ou un groupe phényle ; R7 et R8 représentent chacun un groupe méthyle ou un groupe éthyle ; R6 représente un groupe méthyle, un groupe éthyle ou la formule (3) (où R9 représente un groupe méthyle ou un groupe phényle ; R10 représente un groupe méthyle, un groupe éthyle ou un composé de silicone ; R11 représente un groupe méthyle ou un groupe éthyle ; n3 représente une unité de répétition ; et * représente un site de liaison pour un atome d'oxygène) ; et n2 représente une unité de répétition).
PCT/JP2023/029749 2022-08-18 2023-08-17 Sol de silice contenant un composé de silicone, et composition de résine WO2024038900A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004269668A (ja) * 2003-03-07 2004-09-30 Mitsubishi Rayon Co Ltd シリカ系組成物、樹脂成形品及びその製造方法
JP2009059651A (ja) * 2007-09-03 2009-03-19 Osaka City シルセスキオキサン系絶縁材料
JP2018119073A (ja) * 2017-01-26 2018-08-02 石原ケミカル株式会社 親水性コーティング組成物
WO2019050008A1 (fr) * 2017-09-07 2019-03-14 日産化学株式会社 Composition isolante contenant de la silice
WO2022097694A1 (fr) * 2020-11-04 2022-05-12 日産化学株式会社 Sol de silice contenant de l'aluminium dispersé dans un solvant contenant de l'azote, et composition de résine

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004269668A (ja) * 2003-03-07 2004-09-30 Mitsubishi Rayon Co Ltd シリカ系組成物、樹脂成形品及びその製造方法
JP2009059651A (ja) * 2007-09-03 2009-03-19 Osaka City シルセスキオキサン系絶縁材料
JP2018119073A (ja) * 2017-01-26 2018-08-02 石原ケミカル株式会社 親水性コーティング組成物
WO2019050008A1 (fr) * 2017-09-07 2019-03-14 日産化学株式会社 Composition isolante contenant de la silice
WO2022097694A1 (fr) * 2020-11-04 2022-05-12 日産化学株式会社 Sol de silice contenant de l'aluminium dispersé dans un solvant contenant de l'azote, et composition de résine

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