WO2024101192A1 - Composition de résine composite, son procédé de production, complexe de résine isolante et appareil électrique utilisant celui-ci - Google Patents

Composition de résine composite, son procédé de production, complexe de résine isolante et appareil électrique utilisant celui-ci Download PDF

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WO2024101192A1
WO2024101192A1 PCT/JP2023/038968 JP2023038968W WO2024101192A1 WO 2024101192 A1 WO2024101192 A1 WO 2024101192A1 JP 2023038968 W JP2023038968 W JP 2023038968W WO 2024101192 A1 WO2024101192 A1 WO 2024101192A1
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composite
resin composition
monomer
resin
vegetable
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純 布重
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株式会社日立製作所
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  • the present invention relates to a composite resin composition, an insulating resin composite, and electric power equipment using the same, in particular a composite resin composition and an insulating resin composite that are applied to high-voltage and high-temperature electric power systems.
  • insulating structures e.g., parts requiring insulation
  • voltage equipment high-voltage equipment, etc.
  • switching devices such as circuit breakers and disconnectors inside the housing (e.g., when directly exposed to the outdoors).
  • polymer products that use, as the main component of the polymer material, for example, heat-resistant epoxy resins with a glass transition temperature (hereafter referred to as Tg) of 100°C or higher or bisphenol A-type epoxy resins with relatively high mechanical properties (strength, etc.) are known, but in consideration of the disposal of the above-mentioned polymer products (for example, disposal due to end of life, breakdown, etc.), attempts have been made to develop polymer products made from biodegradable polymer materials (for example, Patent Document 1).
  • polymer products made using heat-resistant epoxy resins with a glass transition temperature (hereafter referred to as Tg) of 100°C or higher as the main component of the polymer material are hard and brittle, and may be prone to cracking when used in environments with rapid temperature changes. For this reason, attempts have been made to improve crack resistance, for example by using solid epoxy resins (for example, those with a crack resistance test result of -30°C or lower using a metal conductor) as the main component of the polymer material, or by adding a large amount of filler to the polymer material.
  • the viscosity of the polymer material becomes significantly high, and there is a risk that a sufficient pot life (the minimum time required for industrial work) cannot be ensured during, for example, casting work, and workability may deteriorate.
  • the present invention has been made in consideration of these circumstances, and its purpose is to provide an insulating polymer material composition that has a high biomass content, excellent insulating performance and mechanical strength, and has little adverse effect on the global environment when discarded.
  • the present invention focuses on modifying the molecular structure and particle surface of vegetable phenolic polymers, and by incorporating a dispersant, the reaction with thermosetting resin and increased entanglement improves the interfacial adhesion with the thermosetting resin, suppresses the occurrence of cracks, and achieves high filling of the vegetable phenolic polymer, thereby achieving the above-mentioned purpose.
  • a composite resin composition containing a vegetable phenol polymer obtained by curing a mixture containing a thermosetting resin monomer, a vegetable phenol polymer, a polymerization accelerator, and a curing agent with or without a polymerization accelerator, the mixture further containing a dispersant, and the vegetable phenol polymer contains a surface treatment functional group that shows reactivity with the thermosetting resin monomer.
  • the invention described in 1 above further comprises a composite resin composition, characterized in that the content of the dispersant contained in the mixture is higher in an area containing the vegetable phenol polymer than in an area containing only a resin not containing the vegetable phenol polymer.
  • the invention described in 1 or 2 above is a composite resin composition, characterized in that the vegetable phenol polymer is lignin. 4.
  • the invention described in any one of 1 to 3 above is a composite resin composition, characterized in that the thermosetting monomer includes at least one of an epoxy monomer and a polyfunctional vinyl monomer. 5.
  • the invention described in any one of 1 to 4 above is a composite resin composition, characterized in that the curing agent contains an acid anhydride. 6.
  • the invention described in any one of 1 to 5 above is a composite resin composition, characterized in that the thermosetting monomer further contains a monomer derived from a biomass-derived epoxy resin. 7.
  • the invention described in any one of 1 to 6 above is a composite resin composition, characterized in that the surface treatment functional group reactive with the thermosetting monomer treated on the surface of the vegetable phenol polymer includes one or more of an epoxy group, an amino group, and an alkyl group.
  • the dispersant includes one or more of a phosphonic acid amine salt, a long-chain fatty acid salt, an alkylbenzene sulfonate, an alkyl ether sulfate ester salt, a polyglycerin fatty acid ester, and an alkylamine.
  • An insulating resin composite characterized in that it has a structure in which silica particles are dispersed in a matrix of the composite resin composition according to any one of 1 to 8 above. 10.
  • a laminate comprising the insulating resin composite according to 9 or 10 above and a polyamideimide resin layer.
  • An electric power device having the insulating resin composite according to 9 or 10 or the laminate according to 11 in a structural part or an insulating part. 13.
  • a method for producing a composite resin composition containing a vegetable phenol polymer comprising: a mixture containing a thermosetting resin monomer, a vegetable phenol polymer containing a surface treatment functional group reactive with the thermosetting resin monomer, a polymerization accelerator, and a curing agent that may or may not be contained, and curing the monomer to obtain a composite resin composition containing a vegetable phenol polymer; and before curing the monomer, a dispersant is added to the mixture and a heat dispersion treatment is performed so that the content of the dispersant contained in the mixture after the monomer curing is higher in a region containing the vegetable phenol polymer than in a region containing only the resin that does not contain the vegetable phenol polymer.
  • the present invention provides a resin composition obtained by compounding a high concentration of a plant-based phenolic polymer derived from heat-resistant biomass into a thermosetting resin as a polymer matrix, which enables high bending strength while maintaining the properties of the thermosetting resin, such as strength, heat resistance (Tg), viscosity before curing, and insulating properties.
  • a resin composition obtained by compounding a high concentration of a plant-based phenolic polymer derived from heat-resistant biomass into a thermosetting resin as a polymer matrix, which enables high bending strength while maintaining the properties of the thermosetting resin, such as strength, heat resistance (Tg), viscosity before curing, and insulating properties.
  • Tg heat resistance
  • insulating resin composite and resin composition shown in the present invention it is possible to provide an insulating material that is excellent in insulating performance and mechanical strength, and that can reduce the impact on the global environment even when discarded.
  • FIG. 1 shows SEM images, taken by a scanning electron microscope, of cross sections of cured products obtained from the composition in Example 5 and the composition in Example 2 of the present invention.
  • 1 shows EDX images of cross sections of cured products obtained from the composition in Example 5 and the composition in Example 2 of the present invention.
  • FIG. 2 is a schematic diagram of sample preparation in a thermal shock test according to the present invention.
  • 1 is a schematic cross-sectional view of a cast coil for a model transformer manufactured using the resin composite of the present invention.
  • Epoxy resin raw materials that can meet almost all the characteristics required for industrial materials are derived from fossil fuels such as petroleum.
  • biomass-derived raw materials are effective in replacing epoxy resin raw materials and reducing the amount of them used. Even if incinerated, they are carbon neutral and are not considered to generate new carbon dioxide.
  • thermosetting resin monomer examples include an epoxy resin monomer, a biomass-derived epoxy resin monomer, and a polyfunctional vinyl monomer.
  • the amount of the thermosetting resin monomer used is preferably 10 to 50 parts by weight, more preferably 20 to 40 parts by weight, and even more preferably 25 to 30 parts by weight.
  • the epoxy resin used in the present invention is preferably a bisphenol A type or bisphenol F type epoxy resin. More preferably, the epoxy resin has an epoxy equivalent of 200 g/eq or less, from the viewpoint of reducing the viscosity of the varnish.
  • EPICLON 840 (epoxy equivalent 180-190g/eq, viscosity 9000-11000mP ⁇ s/25°C)
  • EPICLON 850 (epoxy equivalent 183-193g/eq, viscosity 11000-15000mP ⁇ s/25°C)
  • EPICLON 830 (epoxy equivalent 165-177g/eq, viscosity 3000-4000mP ⁇ s/25°C)
  • jER827 (epoxy equivalent 180-190g/eq, viscosity 9000-11000mP ⁇ s/25°C) manufactured by DIC Corporation.
  • Examples include bisphenol A epoxy resins, bisphenol F epoxy resins, and bisphenol B epoxy resins.
  • bisphenol A epoxy resins From the viewpoint of heat resistance, it is preferable to use bisphenol A epoxy resins, and from the viewpoint of low viscosity, it is preferable to use bisphenol F epoxy resins. In order to balance the two properties, one or more of these epoxy resins may be selected and used.
  • the biomass-derived epoxy resin used in the present invention is preferably an epoxy resin with a plant-based raw material as the parent structure. More preferred epoxy resins have an epoxy equivalent of 200 g/eq or less, from the viewpoint of reducing the viscosity of the varnish.
  • Denacol EX612 (epoxy equivalent 160-170g/eq, viscosity 11,000mP ⁇ s/25°C), Denacol EX614 (epoxy equivalent 160-170g/eq, viscosity 22,000mP ⁇ s/25°C), Denacol EX614B (epoxy equivalent 170-180g/eq, viscosity 5,000mP ⁇ s/25°C), and Denacol EX622 (epoxy equivalent 170-180g/eq, viscosity 5,000 mP ⁇ s/25°C), Denacol EX313 (epoxy equivalent 140-150g/eq, viscosity 150mP ⁇ s/25°C), Denacol EX321 (epoxy equivalent 140-150g/eq, viscosity 130mP ⁇ s/25°C), Denacol EX421 (epoxy equivalent 150-160g/eq, viscosity 650mP ⁇ s/
  • a compound having multiple unsaturated double bonds in the molecule such as acrylate groups, methacrylate groups, styrene groups, and allyl groups, can be used. Among these, it is preferable to use a compound that is liquid at room temperature.
  • Examples include hexanediol diacrylate (Miramer M200, viscosity 15 mPa ⁇ s/25°C), hexanediol EO-modified diacrylate (Miramer M202, viscosity 30 mPa ⁇ s/25°C), tripropylene glycol diacrylate (Miramer M220, viscosity 20 mPa ⁇ s/25°C), trimethylolpropane triacrylate (Miramer M300, viscosity 120 mPa ⁇ s/25°C), and trimethylolpropane EO-modified triacrylate (Miramer M3130, viscosity 65 mPa ⁇ s), all manufactured by Toyo Chemicals Co., Ltd.
  • the composite resin composition of the present invention preferably contains the aforementioned epoxy resin, and more preferably contains a biomass-derived epoxy resin in addition to the aforementioned bisphenol A epoxy resin and an acid anhydride that serves as a curing agent.
  • Plant-based phenolic polymer a plant-derived phenol polymer, which is a raw material derived from biomass, is blended in order to increase the heat resistance and strength of the composite resin composition.
  • the polymer or aggregate include lignins and natural polyphenols.
  • polyphenol components examples include flavonoids (anthocyanidin, anthocyanin (anthocyanidin glycoside), flavanone, naringenin, flavan, catechin, flavone, flavonol, quercetin, isoflavonoid, isoflavone, isoflavan, isoflavandiol, neoflavonoid, biflavonoid, aurone), phenolic acid (chlorogenic acid), ellagic acid, lignan, curcumin, coumarin, etc.
  • flavonoids antagonisthocyanidin, anthocyanin (anthocyanidin glycoside)
  • flavanone naringenin
  • flavan catechin
  • flavone flavonol
  • quercetin quercetin
  • isoflavonoid isoflavone
  • isoflavan isoflavandiol
  • neoflavonoid biflavonoid, aurone
  • phenolic acid chlorogenic
  • the amount of vegetable phenol polymer used is preferably 20 to 50 parts by weight, more preferably 20 to 40 parts by weight, and even more preferably 25 to 30 parts by weight.
  • Lignin is particularly preferred as the vegetable phenol polymer.
  • Lignin is a natural polymer with phenylpropane as a structural unit, which is contained in plants along with cellulose and semicellulose, and its terminal phenol group is reactive with epoxy groups and silanol groups, but in the present invention, lignin recovered from plants, which is the lignin raw material, is used as it is as a hardener or filler.
  • the lignin raw material is produced, for example, from plant raw materials of plants.
  • Lignin recovery methods include, for example, the Kraft method, saccharification method using acid and oxygen, steaming and explosion method, and solvent method, and the molecular structure of the recovered lignin varies depending on the processing conditions such as additive type, temperature, and time.
  • the vegetable phenol polymer is surface-treated and its surface is modified with reactive functional groups to impart reactivity with thermosetting resins. This treatment modifies the molecular chains near the surface, rather than the entire surface, leaving behind agglomerated particles.
  • the surface treatment functional group that is treated on the surface of the vegetable phenol polymer and exhibits reactivity with the thermosetting monomer may be one or more types selected from an epoxy group, an amino group, and an alkyl group.
  • the alkyl group is preferably an alkyl group having 3 or more carbon atoms, such as a propyl group, a butyl group, an isobutyl group, a hexyl group, a decyl group, an octyl group, a heptyl group, etc.
  • Methods for surface treatment of vegetable phenolic polymers include condensation reactions using reactive terminal groups that react with phenolic hydroxyl groups, such as dehalogenation condensation reactions and dehydration condensation reactions. There are no particular limitations to the method, so long as it is possible to modify the phenolic hydroxyl groups through a condensation reaction. Among these, methods that use coupling treatment agents allow for easy and convenient purification of by-products.
  • silane and titanate coupling agents can be used.
  • silane coupling agents include epoxy silanes such as KBM-402 and KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd., amino silanes such as KBM-573, KBM-575, KBM-602, KBM-603, and KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd., vinyl silanes such as KBM-502 and KBM-504 manufactured by Shin-Etsu Chemical Co., Ltd., and alkyl silanes such as KBE-3083 manufactured by Shin-Etsu Chemical Co., Ltd.
  • titanate coupling agents include S-151, S-152, and S-181 manufactured by Nippon Soda Co., Ltd.
  • the treatment with the coupling agent only decomposes the surface of the plant-based phenolic polymer, so the molecular chains on the surface do not penetrate sufficiently. Therefore, in the present invention, it is more preferable to mix a dispersant and heat the mixture.
  • the dispersant When the dispersant is heated to its melting point, it softens and penetrates, and it adheres uniformly to the surface of the plant-based phenolic polymer particles and is concentrated.
  • the stirring operation With the stirring operation, the surface of the plant-based phenolic polymer particles is softened, and the molecular chains on the surface are defibrated, and the free chains at the ends are increased, the free movement area is expanded, and the entanglement with the thermosetting resin is further improved.
  • the dispersant is concentrated on the surface of the plant-based phenolic polymer, and the concentration of the dispersant on the surface of the plant-based phenolic polymer is significantly different from the area where the plant-based phenolic polymer does not exist (only the resin).
  • the dispersant used in the present invention may be a surfactant, and a low-viscosity dispersion medium such as a low-viscosity acrylate monomer or a low-viscosity liquid epoxy resin may be used as necessary.
  • a low-viscosity dispersion medium such as a low-viscosity acrylate monomer or a low-viscosity liquid epoxy resin may be used as necessary.
  • Specific examples include long-chain fatty acid salts such as phosphonic acid amine salts, sodium laurate, and triethanolamine myristate salt, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, alkyl ether sulfate ester salts such as sodium polyoxyethylene lauryl ether sulfate, polyglycerin fatty acid esters such as glycerin monostearate, and alkylamines such as octadecylamine acetate.
  • phosphonic acid amine salts and various nonionic surfactants are preferred, and examples of such surfactants include SN Dispersant 2060 manufactured by San Nopco, and BYK-W903, BYK-W980, BYK-W996, and BYKW9010 manufactured by BYK Japan Co., Ltd.
  • an acid anhydride can be used as a curing agent.
  • the acid anhydride in addition to general-purpose acid anhydrides such as phthalic anhydride and maleic anhydride, it is preferable to use an acid anhydride that is liquid at room temperature.
  • Examples of the acid anhydride include HN-2000 (acid anhydride equivalent 166 g/eq, viscosity 30 to 50 mPa ⁇ s/25°C), HN-5500 (acid anhydride equivalent 168 g/eq, viscosity 50 to 80 mPa ⁇ s/25°C), MHAC-P (acid anhydride equivalent 178 g/eq, viscosity 150 to 300 mPa ⁇ s/25°C), and EPICLON B-570H (acid anhydride equivalent 166 g/eq, viscosity 40 mPa ⁇ s/25°C) manufactured by Hitachi Chemical Co., Ltd. One or more of these may be selected and used.
  • maleic anhydride has high copolymerizability with the polyfunctional vinyl monomer, making it a preferred component of epoxy-vinyl copolymer insulating compositions.
  • ⁇ Curing accelerator> examples of the curing accelerator used in the resin composition include organic oxides, amines, imidazoles, and the like.
  • imidazoles such as ethyl-4-ethylimidazole, 1-butylimidazole, 1-propyl-2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-azine-2-methylimidazole, and 1-azine-2-undecyl imidazoles; triethylammonium tetraphenylborate, 2-ethyl-4-methyltetraphenylborate, and 1,8-diaza-bicyclo(5,4,0)-undecene.
  • amine tetraphenylborate examples include amine tetraphenylborate such as 1,8-diaza-bicyclo(5,4,0)-undecene-7, tetramethylbutylguanidine, metal salts of amines with zinc octanoate or cobalt, triphenylphosphine, triphenylphosphonium tetraphenylborate, aluminum trialkylacetoacetate, aluminum trisacetylacetoacetate, aluminum alcoholate, aluminum acylate, sodium alcoholate, etc.
  • amine tetraphenylborate such as 1,8-diaza-bicyclo(5,4,0)-undecene-7, tetramethylbutylguanidine, metal salts of amines with zinc octanoate or cobalt
  • triphenylphosphine triphenylphosphonium tetraphenylborate
  • aluminum trialkylacetoacetate aluminum trisacetylace
  • the amount of the curing catalyst added is preferably in the range of 0.1 parts by weight or more and 3.0 parts by weight or less per 100 parts by weight of epoxy resin, and particularly when the purpose is to suppress the thickening of the varnish during the casting process, the amount of the curing catalyst added is preferably in the range of 0.1 parts by weight or more and 2 parts by weight or less. Within this range, the gelation time at 100°C and the glass transition temperature of the cured product, which is an epoxy-vinyl copolymer insulating material, can be adjusted.
  • a radical polymerization catalyst whose one-hour half-life temperature exceeds at least 100°C.
  • examples of such compounds include t-butylperoxymaleic acid (half-life temperature 119°C, Perbutyl MA manufactured by NOF Corp.), n-butyl-4,4-bis(t-butylperoxy)valerate (half-life temperature 126.5°C, Perhexa V manufactured by NOF Corp.), 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 (half-life temperature 149.9°C, Perhexyne 25B manufactured by NOF Corp.), and dicumyl peroxyside (half-life temperature 175.2°C, Percumyl D manufactured by NOF Corp.).
  • the amount of the compound added is preferably in the range of 0.1 parts by weight or more and 2 parts by weight or less per 100 parts by weight of the total amount of maleic anhydride and polyfunctional vinyl monomer, from the viewpoint of adjusting the gelation time.
  • the curing catalyst in an amount of 0.1 parts by weight or more and 1 part by weight or less.
  • the amount of curing accelerator added is set, for example, at 0.2 to 2 parts by weight (phr) per 100 parts by weight (phr) of the epoxy resin.
  • the curing temperature is set, for example, at 150 to 170°C, and the curing time is set at 10 to 20 hours.
  • the heat treatment is performed in two stages, for example, by heating for several hours at 150°C or less (specifically, around 100°C) and then heating for several hours at 150°C.
  • the resin composite of the present invention can be obtained by mixing the composite resin composition of the present invention with inorganic fibers, rubber, etc. Since the plant-derived phenolic polymer (lignin) itself is amphiphilic, the affinity with resins such as inorganic fibers and rubber is improved by high dispersion, the biomass content in the thermosetting resin (petroleum-derived) is increased, and the performance of the composite is improved.
  • Inorganic fibers that can be blended into the composite resin composition of the present invention include crushed crystalline silica, scaly fillers, rubber particles, etc.
  • Fractured crystalline silica is preferred as the main component of the composite because it has low thermal expansion, high thermal conductivity, and is inexpensive. Its preferred average particle size is 5 ⁇ m or more and 50 ⁇ m or less, and more preferably has a wide particle size distribution of about 0.1 ⁇ m to 100 ⁇ m. If it is in this range, the increase in varnish viscosity can be suppressed even when the crushed crystalline silica is highly loaded.
  • the content of crushed crystalline silica in the insulating resin composite is in the range of 60 to 80%.
  • the incorporation of scaly filler not only suppresses cure shrinkage and increases the strength of the cured product, but also contributes to improved crack resistance and heat resistance through its composite action with the rubber particle components.
  • the size of the scaly filler is preferably an average particle size of 5 ⁇ m or more and 200 ⁇ m or less to suppress an increase in the viscosity of the varnish.
  • the content of the scaly filler in the insulating resin composite is in the range of 0 to 5%.
  • rubber particle components gives the cured product flexibility and stress relaxation properties, contributing to improved crack resistance and heat resistance.
  • rubber particles include carboxylic acid-modified radiation-crosslinked acrylonitrile butadiene rubber particles (average particle size 50-100 nm) and core-shell rubber particles (Staphyloid AC3355, manufactured by Ganz Chemical Co., Ltd., average particle size 100-500 nm).
  • crosslinked acrylonitrile butadiene rubber particles having a particle size of 10 nm or more and 100 nm or less in combination with core-shell rubber particles having a particle size of 100 nm or more and 2000 nm or less.
  • the small rubber particles suppress the growth of fine cracks, and the large rubber particles further relieve the stress that cannot be fully relieved by the small rubber particles, thereby minimizing the progression of cracks.
  • the present invention by using rubber particles of a different particle size in combination, a significant increase in the varnish viscosity is suppressed while improving the crack resistance. It is preferable to use core-shell rubber particles with improved dispersibility in epoxy resin as the large rubber particles.
  • the content of rubber particles in the insulating resin composite is in the range of 1 to 7%.
  • a polyamide-imide resin layer may be applied to the surface of the insulating resin composite layer, with a thickness of preferably 10 to 50 ⁇ m.
  • the method for producing a resin composite of the present invention includes the steps of: (1) dispersing and contacting a surface-modified vegetable phenolic polymer and a dispersant in a small amount of medium (phthalic anhydride: also used as a monomer) to prepare a mixture in which the dispersant is dispersed and adsorbed at a high concentration on the surface of the polymer; (2) adding the remaining resin monomer to the mixture obtained in step (1) to dilute the mixture to prepare a mixture in which a polymer of a phenolic compound containing a high concentration of dispersant is dispersed; and (3) curing the mixture under conditions of, for example, a curing temperature of 200°C and a curing time of 1 hour.
  • medium phthalic anhydride: also used as a monomer
  • the curing temperature of the present invention is preferably 150 to 230°C, more preferably 180 to 220°C, and the curing time is preferably 0.5 to 2.0 hours, more preferably 1.0 to 1.5 hours.
  • the coupling treatment temperature of the present invention is preferably 90 to 120°C, more preferably 95 to 110°C, and the heat treatment time is preferably 30 to 120 minutes, more preferably 45 to 90 minutes.
  • the heat dispersion processing temperature of the present invention is preferably 40 to 90°C, more preferably 50 to 80°C, and the heat dispersion processing time is preferably 15 to 60 minutes, more preferably 20 to 40 minutes.
  • the method for producing a resin composite of the present invention is characterized by including a mixing step for increasing the dispersant concentration on the surface of the vegetable phenolic polymer, i.e., a mixing step for dispersing and heating the vegetable phenolic polymer in advance to adhere the dispersant to its surface.
  • a mixing step for increasing the dispersant concentration on the surface of the vegetable phenolic polymer i.e., a mixing step for dispersing and heating the vegetable phenolic polymer in advance to adhere the dispersant to its surface.
  • lignin is a polymeric polyphenol, some of this is due to electrostatic repulsion, and the aggregated hydrophobic groups can be defibrated simply by adding a small amount of dispersant and heating. In other words, surface defibration is possible by adding a smaller amount than with normal polymer materials (surface concentration only). It is sufficient to add a small amount of dispersant; for example, the dispersant content in the insulating resin composite is in the range of 0.1 to 1 mass%.
  • composition of the resin composition and the selection of the curing temperature conditions are merely controls to approximate physical properties suited to the purpose, and the product cured under different temperature and time conditions does not exhibit completely different physical properties, and combinations of curing, temperature and time different from those of the present invention also fall within the technical scope of the present invention.
  • reaction accelerators, inhibitors, etc. used as additives to improve workability and productivity, increase reactivity, and make the product safer, also fall within the technical scope of the invention as long as they do not significantly change the physical properties of the resulting cured product.
  • the resin composite and resin composition of the present invention are applicable to high-voltage equipment in general: insulating parts, resin molds, insulating layers, resin insulators, cast coils for transformers, cast molds for transformers, transformer insulating layers, cast molds for circuit breakers, circuit breaker insulating layers, etc.
  • Table 1 shows the material composition ratios and properties of the resin composition according to the comparative example based on the conventional technology and the resin composition according to the example of the present invention.
  • the material composition ratios in Table 1 are weight ratios.
  • the glass transition temperature, volume resistivity (based on JIS-K6911), and bending strength (based on JIS-K7203) were measured as the properties. The bending strength was measured at room temperature.
  • the reagents used in the examples and comparative examples are as follows: Lignin: Lignin (de-alkalized) manufactured by Tokyo Chemical Industry Co., Ltd. Bisphenol A type epoxy resin: jER828 manufactured by Mitsubishi Chemical Corporation Biomass-derived epoxy resin: EX-614B manufactured by Nagase ChemteX Corporation Phthalic anhydride: MHAC-P manufactured by Showa Denko Materials Co., Ltd. N-benzyl-2-methylimidazole: 1B2MZ manufactured by Shikoku Kasei Corporation Coupling treatment agent (epoxy group terminal): KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.
  • the glass transition temperature of this comparative composition was 100° C.
  • the volume resistivity was 7 ⁇ 10 14 ⁇ cm, and the bending strength was 50 MPa.
  • the lignin was immersed in a 2% by weight isopropanol solution of a coupling agent (epoxy group terminal) for 1 hour, and the filtered recovered material was heated at 100°C for 1 hour to obtain a lignin containing an epoxy surface treatment functional group.
  • the composition was prepared and cured under the same conditions as in the comparative example.
  • the composition of this example had a glass transition temperature of 130° C., a volume resistivity of 10 ⁇ 10 14 ⁇ cm, and a flexural strength of 90 MPa.
  • the lignin was immersed in an isopropanol solution of 2% by weight of a coupling agent (epoxy group terminal) for 1 hour, and the filtered recovered material was heated at 100°C for 1 hour to obtain lignin containing epoxy surface treatment functional groups.
  • the lignin was then added to a mixture of 1 part by weight of phosphonic acid amine salt and phthalic anhydride (half the amount added) as a dispersant and dispersed at 60°C for 30 minutes. After that, bisphenol A type epoxy resin, biomass-derived epoxy resin, the remaining phthalic anhydride, and N-benzyl-2-methylimidazole were mixed and cured under the same conditions as in the comparative example.
  • the composition of this example had a glass transition temperature of 132° C., a volume resistivity of 12 ⁇ 10 14 ⁇ cm, and a flexural strength of 110 MPa.
  • the coupling agent (epoxy group-terminated) shown in Example 2 was changed to a coupling agent (amino group-terminated), and a composition was prepared using the method shown in Example 2.
  • the composition of this example had a glass transition temperature of 134° C., a volume resistivity of 12 ⁇ 10 14 ⁇ cm, and a flexural strength of 105 MPa.
  • the coupling agent (epoxy end) shown in Example 2 was changed to a coupling agent (octyl end), and the composition was prepared by the method shown in Example 2.
  • the composition of this example had a glass transition temperature of 129° C., a volume resistivity of 11 ⁇ 10 14 ⁇ cm, and a flexural strength of 105 MPa.
  • composition was prepared under the conditions of Example 1, and 1 part by weight of phosphonic acid amine salt was added as a dispersant, and then cured under conditions of a curing temperature of 200°C and a curing time of 1 hour to obtain a composition.
  • Example 3 Based on the conditions of Example 3, the amounts of lignin, bisphenol A epoxy resin, and biomass-derived epoxy resin were changed to prepare a cured product.
  • Example 3 Based on the conditions of Example 3, the amounts of lignin, bisphenol A epoxy resin, and biomass-derived epoxy resin were changed to prepare a cured product.
  • Example 3 Based on the conditions of Example 3, the amounts of lignin, bisphenol A epoxy resin, and biomass-derived epoxy resin were changed to prepare a cured product.
  • FIG. 1 also shows a comparison of SEM images taken by a scanning electron microscope of the cross section of the cured product obtained from the composition in Example 5 of the present invention and the composition in Example 2. Although there are no significant differences between the images, elemental mapping of phosphorus by energy dispersive X-ray analysis suggests that phosphorus is present at a high concentration on the surface of the lignin in Example 2. If the phosphorus component ratio contained in the dispersant is estimated to be around 30%, then based on the contents of the lignin, acid anhydride, and dispersant, the amount of dispersant present on the lignin surface was estimated to be at least 2%.
  • the detection limit of EDX is said to be about 0.1 to 0.5%, and since there is no high concentration of phosphorus on the surface as shown in the EDX image of Example 5, the content of dispersant only in the non-lignin resin region was estimated to be 1% or less.
  • Example 5 is an example in which the dispersant was not heat-treated, as compared to Example 2.
  • the glass point transition temperature, volume resistivity, and bending strength values of Example 5 were equivalent to those of Example 1. It is therefore believed that in Example 2, the dispersant was concentrated on the lignin surface by heating, which improved the adhesion at the interface between the lignin and the epoxy resin. The reason for this is believed to be that by concentrating the dispersant on the lignin surface, the molecular chains near the interface with the lignin are loosened when the epoxy resin is mixed, and they easily become entangled with the epoxy resin during hardening, improving the adhesion at the interface.
  • the material composition ratios and characteristics of the insulating resin composite are shown in Table 2.
  • the material composition ratios in Table 2 are weight ratios.
  • the composite resin composition used was that shown in Example 3.
  • Other reagents and evaluation methods are shown below.
  • Test sample XJ-7 Crystalline crushed silica manufactured by Tatsumori Co., Ltd., particle size about 6.3 ⁇ m, crushed crystalline silica SJ-005: Mica powder manufactured by Yamaguchi Mica Co., Ltd., average particle size 5 ⁇ m, scale-like filler S-151: Titanium stearate manufactured by Nippon Soda Co., Ltd.
  • KBM-403 3-glycidoxypropyltrimethoxysilane carboxylic acid modified radiation crosslinked acrylonitrile butadiene rubber particles manufactured by Shin-Etsu Chemical Co., Ltd.: average particle size 50 to 100 nm Core-shell rubber particles: Staphyloid AC3355 manufactured by Ganz Chemical Co., Ltd., average particle size 100 to 500 nm Dispersant: BYK-W9010 manufactured by BYK Japan Co., Ltd.
  • the thickness of the heat-resistant resin layer made of polyamideimide was 10 to 50 ⁇ m.
  • the bending strength of five samples was observed for each resin plate sample, and the average value was calculated as the initial strength A.
  • each resin plate sample was thermally aged in air at 250°C for 100 hours, 500 hours, and 1000 hours.
  • the bending strength of five resin plate samples after each thermal aging was measured, and the average value B was calculated.
  • the strength reduction rate C% was calculated for each condition using the following formula.
  • Strength reduction rate C (%) (B - A) / A x 100
  • Example 9 is an example in which a heat-resistant resin layer was provided.
  • Table 2 by providing a heat-resistant resin layer on the resin composite of the present invention, the 5 wt% weight loss temperature of the resin component in the cured product became 372°C, and the heat resistance index became 145°C.
  • the thermal crack resistance was shown to be -60°C or less. This makes it clear that providing a heat-resistant resin layer on the cured product of the epoxy resin composition raises the 5 wt% weight loss temperature of the resin component in the cured product of the epoxy resin composition, contributing to improved heat resistance.
  • Example 10 is an example in which rubber particles and scaly filler were used in combination. After 1000 hours of degradation at 250°C, the strength decreased by 5%. By incorporating scaly filler, the rate of strength loss due to thermal degradation was significantly reduced, and heat resistance was improved. Electric power equipment manufactured using the resin composition of the present invention has been found to have improved heat resistance in its structural and insulating materials.
  • Example 10 25 kg of the epoxy liquid resin composition in Example 10 was prepared. This liquid resin composition was heated to 90°C and degassed at 1 torr for about 20 minutes. The varnish viscosity at 90°C was about 7 Pa ⁇ s.
  • a mold for a model transformer casting coil was heated to 90°C, 25 kg of the degassed liquid resin composition was poured into it, and it was again vacuum degassed at 1 torr for 20 minutes. It was then cured in air under the conditions of 100°C/5 hours, 110°C/2 hours, 140°C/2 hours, and 170°C/15 hours. It was then cooled to 50°C over 8 hours, and the mold was removed to produce the model transformer casting coil shown in Figure 4.
  • polyamideimide varnish was spray-painted so that the film thickness after drying would be about 10 to 50 ⁇ m.
  • the drying conditions for the polyamideimide varnish were air, 105°C/60 minutes, 150°C/60 minutes, 180°C/60 minutes, and 220°C/60 minutes.
  • the present invention provides a composite resin composition and insulating resin composite that contain a vegetable phenolic polymer that has excellent insulating properties and mechanical strength, and has minimal adverse effects on the global environment when discarded.
  • the composite resin composition and insulating resin composite are particularly suitable for use in the insulating structures of circuit breakers and high-voltage equipment.

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Abstract

L'invention concerne : une composition de résine composite qui contient un polymère phénolique à base de plante, présente d'excellentes performances d'isolation et une excellente résistance mécanique, et a peu d'effets indésirables sur l'environnement si elle est jetée; son procédé de production; un complexe de résine isolante; et un appareil électrique utilisant celui-ci. La composition de résine composite est obtenue par durcissement, au moyen d'un monomère de résine thermodurcissable, d'un mélange contenant le monomère, un polymère phénolique à base de plante, un accélérateur de polymérisation et, éventuellement, un agent de durcissement, et est caractérisée en ce que le mélange contient en outre un agent de dispersion, et le polymère phénolique à base de plante comprend un groupe fonctionnel de traitement de surface qui présente une réactivité avec le monomère de résine thermodurcissable.
PCT/JP2023/038968 2022-11-11 2023-10-27 Composition de résine composite, son procédé de production, complexe de résine isolante et appareil électrique utilisant celui-ci WO2024101192A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009263549A (ja) * 2008-04-28 2009-11-12 Hitachi Ltd 植物由来のエポキシ樹脂組成物及びそれを用いた各種機器
JP2012224787A (ja) * 2011-04-21 2012-11-15 Hitachi Ltd エポキシ樹脂組成物およびエポキシ樹脂硬化剤、ならびにそれらを用いた各製品
JP2013035969A (ja) * 2011-08-09 2013-02-21 Kyoto Univ リグニン誘導体の製造方法、リグニン二次誘導体の製造方法および天然有機化合物の製造方法
JP2016517913A (ja) * 2013-05-17 2016-06-20 ユー ピー エム キュンメネ コーポレーション 繊維強化複合材料
JP2017178973A (ja) * 2014-08-18 2017-10-05 日立化成株式会社 樹脂組成物及び成形体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009263549A (ja) * 2008-04-28 2009-11-12 Hitachi Ltd 植物由来のエポキシ樹脂組成物及びそれを用いた各種機器
JP2012224787A (ja) * 2011-04-21 2012-11-15 Hitachi Ltd エポキシ樹脂組成物およびエポキシ樹脂硬化剤、ならびにそれらを用いた各製品
JP2013035969A (ja) * 2011-08-09 2013-02-21 Kyoto Univ リグニン誘導体の製造方法、リグニン二次誘導体の製造方法および天然有機化合物の製造方法
JP2016517913A (ja) * 2013-05-17 2016-06-20 ユー ピー エム キュンメネ コーポレーション 繊維強化複合材料
JP2017178973A (ja) * 2014-08-18 2017-10-05 日立化成株式会社 樹脂組成物及び成形体

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