WO2022162805A1 - 絶縁樹脂組成物、硬化物、回転機用コイル、および回転機 - Google Patents

絶縁樹脂組成物、硬化物、回転機用コイル、および回転機 Download PDF

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Publication number
WO2022162805A1
WO2022162805A1 PCT/JP2021/002915 JP2021002915W WO2022162805A1 WO 2022162805 A1 WO2022162805 A1 WO 2022162805A1 JP 2021002915 W JP2021002915 W JP 2021002915W WO 2022162805 A1 WO2022162805 A1 WO 2022162805A1
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Prior art keywords
resin composition
insulating resin
curing
coil
liquid paraffin
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PCT/JP2021/002915
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English (en)
French (fr)
Japanese (ja)
Inventor
あずさ 大澤
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Mitsubishi Electric Corp
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Mitsubishi Electric Corp
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Filing date
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Priority to JP2022577895A priority Critical patent/JP7537525B2/ja
Priority to PCT/JP2021/002915 priority patent/WO2022162805A1/ja
Priority to CN202180086498.6A priority patent/CN116648479B/zh
Publication of WO2022162805A1 publication Critical patent/WO2022162805A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04C—ROTARY-PISTON, OR OSCILLATING-PISTON, POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; ROTARY-PISTON, OR OSCILLATING-PISTON, POSITIVE-DISPLACEMENT PUMPS
    • F04C29/00—Component parts, details or accessories of pumps or pumping installations, not provided for in groups F04C18/00 - F04C28/00
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02K—DYNAMO-ELECTRIC MACHINES
    • H02K15/00—Processes or apparatus specially adapted for manufacturing, assembling, maintaining or repairing of dynamo-electric machines
    • H02K15/12—Impregnating, moulding insulation, heating or drying of windings, stators, rotors or machines
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02K—DYNAMO-ELECTRIC MACHINES
    • H02K3/00—Details of windings
    • H02K3/30—Windings characterised by the insulating material

Definitions

  • the present disclosure relates to insulating resin compositions, cured products, coils for rotating machines, and rotating machines.
  • Patent Document 1 discloses an example of a solventless varnish composition.
  • the solvent-free varnish composition includes a thermosetting resin having two or more meth(acryloyl) groups in one molecule, and a thermosetting resin having both an epoxy group and a meth(acryloyl) group in one molecule. , and a monofunctional vinyl monomer.
  • Solvent-free varnish compositions are used to maintain insulation and mechanical strength in coils of rotating machines.
  • the solvent-free varnish composition is immersed in the coil by, for example, an immersion method in which the coil is immersed in an impregnation tank containing the solvent-free varnish composition.
  • a monofunctional vinyl-based monomer is used as a reactive diluent that lowers the viscosity of the insulating resin composition in order to improve impregnation of the coil.
  • the insulating resin composition with which the coil is impregnated is heated in a curing furnace to be cured to form a cured product.
  • part of the monofunctional vinyl monomer may volatilize during heating in the curing furnace.
  • the volatilized monofunctional vinyl-based monomer that fills the curing oven may redeposit on the surface of the cured product. As a result, stickiness may remain on the surface of the cured product.
  • the present disclosure relates to solving such problems.
  • the present disclosure provides an insulating resin composition and a cured product thereof, which can further enhance surface touchability of a cured product, a coil for a rotating machine with good surface touchability, and a rotating machine using the same.
  • the insulating resin composition according to the present disclosure is an insulating resin composition that cures at a curing heating temperature, a thermosetting resin having both an epoxy group and a meth (acryloyl) group in one molecule, and the curing heating temperature It contains a varnish component containing a monofunctional vinyl-based monomer that volatilizes as described above, a curing agent and a reaction initiator, and liquid paraffin.
  • the cured product according to the present disclosure is obtained by curing the above insulating resin composition.
  • a coil for a rotating machine according to the present disclosure is impregnated with the insulating resin composition.
  • a rotating machine according to the present disclosure is a rotating machine used for a hoist that drives a car of a rope elevator, and includes a stator that uses the rotating machine coil described above.
  • the touchability of the surface of the cured product is further enhanced.
  • the tactile feel of the surface of the rotating machine coil is further enhanced.
  • FIG. 2 is a conceptual diagram showing an example of a state in which the insulating resin composition according to Embodiment 1 is cured; 1 is a cross-sectional view of a hoist according to Embodiment 1; FIG.
  • Embodiment 1 modes for implementing the subject of the present disclosure will be described. It should be noted that the subject of the present disclosure is not limited to the following embodiments, and modifications of any constituent elements of the embodiments, or modifications of any constituent elements of the embodiments, within the scope of the present disclosure. It can be omitted. In addition, the embodiments and examples in the present disclosure are illustrative in all respects and should not be construed as restrictive.
  • Embodiment 1 the curable insulating resin composition (X) and its cured product (Y) will be described.
  • a rotating machine coil using the insulating resin composition (X) and a rotating machine using this as a stator will also be described.
  • the insulating resin composition (X) of Embodiment 1 contains a varnish component (Z), a curing agent and a reaction initiator (C), and liquid paraffin (D).
  • the varnish component (Z) contains a thermosetting resin (A) having both an epoxy group and a meth(acryloyl) group, and a monofunctional vinyl-based monomer (B) that volatilizes at a curing heating temperature or higher.
  • a meth(acryloyl) group represents an acryloyl group or a methacryloyl group.
  • a numerical range expressed using “x to y” in the present disclosure represents a numerical range including a lower limit value x and an upper limit value y.
  • the insulating resin composition (X) is used, for example, to maintain insulation and mechanical strength in coils.
  • Devices to which the coil is applied are not limited to specific devices.
  • the coil is applied to, for example, an electric motor such as a motor, or a rotating machine such as a generator.
  • the coil is applied to, for example, an elevator hoist or an electric compressor.
  • the insulating resin composition (X) is immersed in the coil by, for example, an immersion method in which the coil is immersed in an impregnation bath containing the insulating resin composition (X).
  • the insulating resin composition (X) with which the coil is impregnated is heated and cured in a curing furnace to form a cured product (Y).
  • FIG. 1 is a conceptual diagram showing an example of a state in which the insulating resin composition (X) according to Embodiment 1 is cured.
  • FIG. 1 an example of an insulating resin composition 2 cured on the surface of a coil 1 is shown.
  • the liquid paraffin forms a thin film 3 on the surface of the insulating resin composition 2 that is curing.
  • reattachment of the monofunctional vinyl-based monomer 4 which has volatilized and filled the curing furnace, to the cured product is suppressed.
  • the coil when the coil is impregnated with the insulating resin composition in the impregnation tank, the coil pulled up from the impregnation tank, the iron core of the coil, and other constituent members are covered with excess insulating resin composition. . If excess insulating resin composition remains adhered during the curing process, the excess insulating resin composition may cure as it is to form a hardened mass on the lower portion of the coil and other components. In addition, excess insulating resin composition may drip into the curing furnace due to a decrease in viscosity during heating for curing. The dripped insulating resin composition forms a hardened mass in the hardening furnace.
  • a hardened mass formed on a component such as a coil may damage the enameled wire of the coil and other members due to thermal stress such as curing shrinkage, resulting in a decrease in insulation.
  • the hardened lumps formed on the constituent members interfere with the work of assembling the coil or the like into the housing or the fixing member, it is necessary to remove the hardened lumps formed on the constituent members.
  • periodic cleaning is required periodically to remove lumps of hardened material that have formed in the curing oven.
  • the insulating resin composition (X) according to Embodiment 1 drain well from the coil so as not to adhere excessively to the coil pulled up from the impregnation tank.
  • the overall viscosity of the insulating resin composition (X) is from 10 mPa ⁇ s to 200 mPa ⁇ s from the viewpoint of improving the drainage of the insulating resin composition (X) from the coil or the like and suppressing the formation of excessive lump-shaped cured products. s, preferably 10 mPa ⁇ s to 100 mPa ⁇ s, more preferably 15 mPa ⁇ s to 50 mPa ⁇ s.
  • thermosetting resin (A) The thermosetting resin (A) is not limited to a specific resin as long as it has both one or more epoxy groups and one or more meta(acryloyl) groups in one molecule as reactive groups.
  • the thermosetting resin (A) uses a meta(acryloyl) group as a reactive group and undergoes both an addition reaction via a free radical generated from an organic peroxide and a ring-opening polymerization using an epoxy group as a reactive group. dimension cross-linking reaction is promoted. This can accelerate the curing reaction and enhance the heat resistance and mechanical strength of the cured product (Y).
  • the thermosetting resin (A) may be a single resin containing both an epoxy group and a meta(acryloyl) group as reactive groups.
  • the thermosetting resin (A) may be used in combination with other resins having either or both of an epoxy group and a meth(acryloyl) group.
  • Other resins used in combination may contain both epoxy groups and meth(acryloyl) groups in one molecule.
  • Other resins used in combination may contain only either one of an epoxy group or a meth(acryloyl) group in one molecule.
  • the thermosetting resin (A) preferably has a number average molecular weight (Mn) of 15,000 or less, preferably 1,000 to 10,000, and a viscosity of 10,000 mPa ⁇ s or less at 60°C, for ease of viscosity adjustment.
  • Mn number average molecular weight
  • the epoxy equivalent of the thermosetting resin (A) mixed in the insulating resin composition (X) is preferably 500-5000, more preferably 1000-4000. By controlling the epoxy equivalent within the above range, it is possible to improve the curing rate without impairing the pot life of the insulating resin composition (X), and further improve the crosslink density of the cured product (Y). can.
  • Monofunctional vinyl monomer (B) The monofunctional vinyl-based monomer (B) is used mainly for adjusting the viscosity of the insulating resin composition (X) in addition to adjusting the crosslinked structure.
  • the monofunctional vinyl-based monomer (B) is desirably a monofunctional one having one functional group per molecule in order to maintain the pot life of the insulating resin composition (X).
  • a low-viscosity one having an ether bond or an ester bond is used as the monofunctional vinyl-based monomer (B).
  • the monofunctional vinyl-based monomer (B) preferably used in the insulating resin composition (X) is a hydroxyalkyl, alkyl, alicyclic, aromatic monomer having a vinyl group, an allyl group, a methacryloyl group, or an acryloyl group. of the family, or of the ether class.
  • a low-viscosity methacrylic monomer or acrylic monomer having a viscosity of 20 mPa ⁇ s or less at room temperature (25° C.) is preferable in order to adjust the viscosity.
  • monofunctional vinyl-based monomers having one methacryloyl group or one acryloyl group are more preferable from the viewpoint of achieving both high reactivity during curing and pot life.
  • monofunctional vinyl monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, lauryl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, 4-hydroxybutyl ( meth)acrylate, n-octyl acrylate and the like.
  • these monofunctional vinyl monomers may be used singly or in combination of multiple types.
  • the amount of the monofunctional vinyl-based monomer (B) to be blended is preferably as large as possible, from the viewpoint of improving the drainage of the insulating resin composition (X) from the coil or the like and suppressing the formation of excessive lump-like cured products. .
  • the monofunctional vinyl-based monomer (B) contributes to increase the number of cross-linking points, it does not contribute to the curing reaction because it is a low-molecular monomer and partly volatilizes when heated for curing. Therefore, if the amount of the monofunctional vinyl monomer (B) is too large, the mechanical strength of the cured product (Y) may decrease.
  • the amount of the monofunctional vinyl-based monomer (B) to be blended must be adjusted within a range that achieves the two functions required for both suppression of excessive cured lumps and mechanical strength.
  • the amount of the monofunctional vinyl monomer (B) is 45 wt% or more, preferably 50 wt% or more, more preferably 55 wt% or more of the total amount of the varnish component (Z). It is desirable to On the other hand, from the viewpoint of mechanical strength, the amount of the monofunctional vinyl monomer (B) is 85 wt% or less, preferably 75 wt% or less, more preferably 70 wt% or less of the total amount of the varnish component (Z). desirable.
  • the amount of the monofunctional vinyl monomer (B) is desirably 45 wt% to 85 wt%, preferably 50 wt% of the total amount of the varnish component (Z). ⁇ 75 wt%, more preferably between 55 wt% and 70 wt%.
  • a polyfunctional vinyl having two or more meta(acryloyl) groups or allyl groups in one molecule A system monomer may be blended.
  • the polyfunctional vinyl-based monomer as a reactive diluent, makes it possible to lower the viscosity of the insulating resin composition (X).
  • the polyfunctional vinyl monomer contains a plurality of meth (acryloyl) groups or allyl groups, which are reactive groups, in one molecule, so that the insulating resin composition (X) contributes to polymerization in the curing reaction of , and generally reacts completely.
  • polyfunctional vinyl-based monomers volatilize less during curing. This suppresses redeposition due to volatile matter. Furthermore, the addition of the polyfunctional vinyl-based monomer has the effect of promoting three-dimensional cross-linking of the cured product (Y) and increasing the heat resistance and mechanical strength of the cured product (Y).
  • the blending amount of the polyfunctional vinyl monomer may be within a range that can guarantee the blending amount of the monofunctional vinyl monomer (B), and from the viewpoint of mechanical strength and heat resistance, It is desirable to be within the range of 2 wt % to 20 wt %.
  • Curing agent and initiator (C) A curing agent and a reaction initiator (C) are used to cure the thermosetting resin (A) and the monofunctional vinyl monomer (B).
  • the curing agent and reaction initiator (C) an organic peroxide that mainly acts on meth(acryloyl) groups and a curing agent for epoxy groups are used in combination.
  • Organic peroxides are mainly used as reaction initiators for meth(acryloyl) groups, and those known in the art are used.
  • the organic peroxide is not particularly limited as long as it has a 10-hour half-life temperature of 40° C. or higher. 170° C. is preferred.
  • Examples of these organic peroxides include ketone peroxide-based, peroxyketal-based, hydroperoxide-based, dialkyl peroxide-based, diacyl peroxide-based, peroxyester-based, and peroxydicarbonate-based peroxides. etc. can be used. These organic peroxides may be used alone or in combination of two or more.
  • organic peroxides having such a 10-hour half-life temperature include 1,1-di(t-butylperoxy)cyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, 1, 1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-butylperoxy)-2-methylcyclohexane, 2,2-di(4,4-di- (Butylperoxy)cyclohexyl)propane, n-butyl 4,4-di-(t-butylperoxy)valerate, 2,2-di-(t-butylperoxy)butane, t-hexylperoxyisopropyl monocarbonate , t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoic acid, t-butylperoxylauric acid, t-
  • the amount of the organic peroxide compounded in the insulating resin composition (X) is not particularly limited. Preferably, it is 0.5 parts by mass to 5 parts by mass. If the amount of the organic peroxide is less than 0.1 part by mass, the crosslink density will be low and the mechanical strength required for the cured product will not be obtained. On the other hand, if the amount of the organic peroxide is more than 10 parts by mass, the pot life of the insulating resin composition (X) tends to be significantly shortened.
  • Curing Agent for Epoxy Group those known in the art are used. , quaternary phosphonium salts, amine complexes, imidazole compounds, compounds containing transition metals such as titanium and cobalt, acid anhydrides, imidazole compounds, polymercaptan compounds, phenols, Lewis acid compounds, isocyanate compounds, etc. is mentioned. These may be used alone or in combination of two or more.
  • amine curing agents include tertiary amines and tertiary amine salts.
  • tertiary amine salts include carboxylates, sulfonates, and inorganic acid salts of the tertiary amines described above.
  • carboxylates include salts of carboxylic acids (especially salts of fatty acids) having 1 to 30 carbon atoms (especially 1 to 10 carbon atoms) such as octylate.
  • Sulfonates include p-toluenesulfonate, benzenesulfonate, methanesulfonate, ethanesulfonate, and the like.
  • tertiary amine salts include salts of 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) (eg, p-toluenesulfonate, octylate), and the like. mentioned. However, these are merely examples. The use of amine-based curing agents other than these does not depart from the gist of the present disclosure.
  • DBU 1,8-diazabicyclo[5.4.0]undecene-7
  • borate esters examples include trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, and cyclic borate ester compounds. However, these are merely examples. The use of borate esters other than these does not depart from the spirit of the present disclosure.
  • organometallic compounds include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and aluminum acetylacetone complexes. However, these are merely examples. The use of organometallic compounds other than these does not depart from the spirit of the present disclosure.
  • organic phosphorus compounds examples include tetraphenylphosphonium/tetraphenylborate and triphenylphosphine. However, these are merely examples. The use of organophosphorus compounds other than these does not depart from the gist of the present disclosure.
  • quaternary ammonium salts include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrabutylammonium chloride, tetrabutyl bromide.
  • quaternary phosphonium salts include tetrabutylphosphonium chloride, tetrabutylphosphonium iodide, tetrabutylphosphonium acetate, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, ethyltriphenylphosphonium chloride, bromine ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, ethyltriphenylphosphonium phosphate, propyltriphenylphosphonium chloride, propyltriphenylphosphonium bromide, propyltriphenylphosphonium iodide, butyltriphenyl chloride phosphonium, butyltriphenylphosphonium bromide, butyltri
  • amine complexes include boron halide-amine complexes, which are complexes of boron halides such as boron trifluoride, boron trichloride and boron tribromide, and amine compounds.
  • examples of amine compounds include aliphatic tertiary amines such as trimethylamine, tri-n-propylamine, N,N-dimethyloctylamine and N,N-dimethylbenzylamine, and N,N-dimethylaniline.
  • heterocyclic tertiary amines such as substituted or unsubstituted imidazole or pyridine alkylated at the 1-position, aliphatic primary amines such as monoethylamine and n-hexylamine, benzylamine, etc. aliphatic primary amines containing an aromatic ring, aromatic primary amines such as aniline, secondary amines such as piperidine, and the like.
  • boron trifluoride amine complexes include boron trifluoride monoethylamine complex, boron trifluoride diethylamine complex, boron trifluoride isopropylamine complex, boron trifluoride chlorophenylamine complex, boron trifluoride- triallylamine complex, boron trifluoride benzylamine complex, boron trifluoride aniline complex, boron trichloride monoethylamine complex, boron trichloride phenol complex, boron trichloride piperidine complex, boron trichloride dimethyl sulfide complex, boron trichloride N, N-dimethyloctylamine complex, boron trichloride N,N-dimethyldodecylamine complex, boron trichloride N,N-diethyldioctylamine complex and the like. However, these are merely
  • imidazole compounds include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl- 4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole , 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 2,4-diamino-6 (2′-methylimidazole (1′))ethyl-s-triazine, 2,4-diamino-6 ( 2'-undecylimidazole (1'))ethyl-s-triazine
  • acid anhydride curing agents include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methylnadic anhydride. However, these are merely examples. The use of acid anhydride curing agents other than these does not depart from the gist of the present disclosure.
  • the blending amount of the epoxy group curing agent can be appropriately adjusted according to the type of the thermosetting resin (A), the type of the curing agent, and the like.
  • the blending amount of the curing agent is preferably about 0.5 equivalent or more and 2 equivalent or less with respect to the epoxy equivalent of the thermosetting resin (A). If the amount of the curing agent is less than 0.5 equivalents, curing of the thermosetting resin (A) may not progress sufficiently. If the blending amount of the curing agent exceeds 2 equivalents, the heat resistance, mechanical properties, etc. of the cured product may deteriorate.
  • a curing accelerator may be used in combination to accelerate or control the curing reaction.
  • Curing accelerators include, for example, tertiary amines and salts thereof, quaternary ammonium compounds, imidazoles, alkali metal alkoxides and the like. However, these are merely examples. The use of curing accelerators other than these does not depart from the gist of the present disclosure.
  • the amount of the curing accelerator is preferably about 0.01% by mass or more and 30% by mass or less (more preferably about 0.05% by mass or more and 20% by mass or less) relative to the mass of the thermosetting resin (A). is. If the blending amount is less than 0.01% by mass, the promotion effect may be small. If the blending amount exceeds 30% by mass, the storage stability of the insulating resin composition (X) and the moldability of the cured product (Y) may deteriorate.
  • liquid paraffin (D) The liquid paraffin (D) forms a thin film on the surface of the cured product (Y) during the curing reaction of the insulating resin composition (X), volatilizes, and fills the curing furnace with the monofunctional vinyl monomer (B). is added to exhibit the effect of preventing adhesion to the surface of the cured product (Y).
  • Liquid paraffin (D) is not particularly limited as long as it is liquid at room temperature.
  • Liquid paraffin (D) consists of a chain saturated hydrocarbon compound represented by, for example, C n H 2n+2 where n is an integer. The integer n is, for example, 20 or more.
  • the melting point of liquid paraffin (D) is, for example, 30° C. or lower.
  • Liquid paraffin (D) does not completely volatilize even at the boiling point of monofunctional vinyl monomer (B). That is, the liquid paraffin (D) remains to the extent that a thin film can be formed on the surface of the insulating resin composition (X) and its cured product (Y) even at the boiling point of the monofunctional vinyl monomer (B). I wish I had.
  • the boiling point of liquid paraffin (D) is higher than the boiling point of monofunctional vinyl monomer (B).
  • Examples of liquid paraffin (D) include liquid paraffin, mineral oil, liquid paraffin, white mineral oil, and the like.
  • the liquid paraffin (D) may be directly added to the mixture of the thermosetting resin (A) and the monofunctional vinyl monomer (B). is preferably dispersed in advance as a dispersion medium and then mixed.
  • the liquid paraffin (D) preferably has a viscosity of 10 mPa ⁇ s to 200 mPa ⁇ s at room temperature of 25°C.
  • the content of liquid paraffin (D) is 5 wt% or less, preferably 3 wt% or less, more preferably 0.01 wt% to 1 wt% of the total amount of varnish component (Z). If the blending amount is less than 0.01 wt %, it is difficult to form a sufficient coating film to prevent re-adhesion of the monofunctional vinyl monomer (B). On the other hand, if the blending amount exceeds 5 wt %, the mechanical strength and heat resistance of the cured product (Y) are affected.
  • Insulating resin composition (X) can be produced by the following production method.
  • the blending amounts of (A) to (D) are the amounts described in Examples and Comparative Examples.
  • the mixing method is not particularly limited as long as it can utilize a method known in the art and can be uniformly mixed.
  • Liquid paraffin (D) is added to the whole amount or a fractionated portion of monofunctional vinyl monomer (B) and uniformly dispersed by ultrasonic waves.
  • the polyfunctional vinyl-based monomer is, for example, a thermosetting resin together with the liquid paraffin solution in (b) above. (A) is mixed.
  • the cured product (Y) is a cured product of the insulating resin composition (X).
  • the cured product (Y) is typically produced by heating the insulating resin composition (X).
  • the cured product (Y) is used in various forms and shapes depending on the application.
  • the cured product (Y) can be molded into a desired shape by various molding methods such as impregnation, coating, casting, or sheet molding.
  • the cured product (Y) has excellent insulation performance and heat resistance. Therefore, the cured product (Y) is suitable for applications requiring at least one of insulation performance and heat resistance.
  • the cured product (Y) is suitable, for example, as an insulating member for heavy electrical equipment such as rotary machines and power transmission and transformation equipment. Examples of the insulating member include varnish, insulating paint, cable coating material, insulating sheet, and sealing material.
  • the step of impregnating the coil with the insulating resin composition (X) adjusted in the adjusting step is carried out.
  • the impregnation method in the impregnation step is not particularly limited, but a preheating step and an air cooling step are carried out before the impregnation step. Further, after the impregnation process, the heat-curing process is performed through the drip removal process.
  • the preheating process is a process of performing annealing treatment for the purpose of improving the crazing resistance of coil windings such as enameled wires.
  • the coil is heated to a predetermined temperature.
  • the heating temperature in the preheating step is not particularly limited as long as it can improve the crazing property, but the treatment is performed at, for example, 150°C.
  • the air cooling step is a step of cooling the coil to a predetermined temperature in order to suppress the temperature rise of the insulating resin composition (X).
  • the temperature after cooling is not particularly limited as long as it is within a temperature range that does not affect the pot life of the insulating resin composition (X).
  • the coil is impregnated with the insulating resin composition (X) by a treatment method known in the art, such as immersion, dripping, pressure impregnation, and vacuum impregnation.
  • a treatment method known in the art such as immersion, dripping, pressure impregnation, and vacuum impregnation.
  • immersion or pressure/vacuum impregnation is generally performed in order to impregnate the inside of the coil with the insulating resin composition (X).
  • immersion impregnation is performed, the coil is gently immersed in an impregnation tank filled with the insulating resin composition (X).
  • the immersion time is not particularly limited, but since the air adhering between the wound enameled wires and in the constituent members rises to the surface as bubbles during immersion, the immersion should be continued until these bubbles disappear. is desirable.
  • the immersion time is preferably about 10 to 60 minutes, and about 15 to 45 minutes from the viewpoint of improving the efficiency of the manufacturing process, that is, shortening the time. This is because if the immersion time is less than 10 minutes, the resin does not permeate the entire coil, and even if the immersion exceeds 60 minutes at which air bubbles converge, the amount of the insulating resin composition (X) permeating into the coil does not increase. be.
  • the impregnation temperature that is, the temperature of the insulating resin composition (X) in the impregnation bath, is not particularly limited as long as it does not start thickening due to curing, and is generally set at room temperature of 25°C to 60°C. Since the insulating resin composition (X) according to Embodiment 1 has a low viscosity, impregnation at room temperature of 25° C. is also possible.
  • the coil is brought into a state in which the insulating resin composition (X) enters between windings.
  • the insulating resin composition (X) impregnated in the coil in the impregnation step is heated and cured in a curing furnace to form a cured product (Y).
  • the curing heating temperature in the heat curing step is not particularly limited as long as it is equal to or higher than the reaction initiation temperature (half-life temperature) of the reaction initiator added to the insulating resin composition (X), and is generally 130° C. to 180° C., preferably. is between 140°C and 170°C.
  • the curing heating time required in the heat-curing step varies depending on the curing speed of the resin, the amount of resin adhered to the coil, the raw material composition, and the like.
  • the curing heating time required for curing depends on the temperature, and generally the higher the temperature, the shorter the time until curing. Therefore, the curing heating temperature and the curing heating time are set to the temperature and time necessary for complete curing according to the composition of the insulating resin composition (X).
  • the insulating resin composition (X) may not be completely cured and an uncured portion may occur. At this time, various properties such as electrical properties and mechanical properties may deteriorate.
  • the curing heating temperature or the curing heating time is excessive, the balance of the cross-linking reaction due to the curing heating may be lost, which may cause cracks in the cured product (Y).
  • Curing heating temperature and curing heating time are set within a range that does not cause these problems.
  • the insulating resin composition (X) according to Embodiment 1 is completely cured when the curing heating temperature is 130° C. to 180° C. and the curing heating time is 30 minutes to 8 hours. If the curing heating time is less than 30 minutes, the insulating resin composition (X) will not be completely cured.
  • the mechanical strength that is, the wire fixing strength, gradually develops and improves after curing, and tends to converge after a predetermined time, here 4 hours or later. Therefore, from the viewpoint of complete curing and convergence of mechanical strength, the curing heating time is preferably 1 to 4 hours, more preferably 1 to 2 hours.
  • FIG. 2 is a cross-sectional view of the hoist according to Embodiment 1.
  • the hoist 10 shown in FIG. 2 includes a rotating section 11, a brake section 12, and a motor section 13.
  • the rotating part 11 includes a sheave 14 , a rotor 15 , a brake disc 16 and a rotating shaft 17 .
  • the sheave 14 , rotor 15 and brake disc 16 are coaxially coupled by a rotating shaft 17 .
  • a main rope (not shown) is wound around the sheave 14 .
  • An elevator car, not shown, supported on the main ropes is driven by friction between the main ropes and sheaves 14 .
  • the brake part 12 has a movable brake shoe (not shown).
  • the brake portion 12 generates a force for braking the rotating portion 2 by friction generated by pressing the brake shoe against the brake disc 16 .
  • the motor section 13 includes a frame 18 and a stator 19.
  • the stator 19 is fixed to the frame 18 by press fitting or shrink fitting.
  • the stator 19 has an annular iron core 20 .
  • a winding 21 is wound around each tooth of the iron core 20 .
  • the winding 21 and the iron core 20 are insulated by the insulator 22 .
  • the winding 21 is fixed by an insulator 22 .
  • the windings 21 wound around each tooth are connected to each other in the order set, and generate magnetic flux when energized.
  • the stator 19 is manufactured, for example, by a method including the following procedures. First, prepare a wire that is insulated and coated with enamel.
  • the strand has electrical conductivity.
  • the material of the wire is, for example, copper, aluminum, silver, or the like.
  • the type of enamel is not particularly limited, but polyesterimide, polyamideimide, polyamide and the like are used in combination. These enamel insulating coating layers may contain an inorganic filler for improving dielectric strength.
  • These enameled wires commercially available ones for motor coils can be used.
  • the enameled wire coated with such insulation is wound around each tooth of the iron core 20 to form the winding 21 .
  • the wire 21 is impregnated with the insulating resin composition (X) by the method of the impregnation step described above, and the insulating resin composition (X) is cured by the heat curing step.
  • the low-molecular-weight monofunctional vinyl-based monomer (B) is used as a reactive diluent that lowers the viscosity in order to improve the impregnation of the insulating resin composition (X) into the coil, the coil length is long.
  • the insulating resin composition (X) is easily impregnated into even the coil of a large rotating machine having a large thickness.
  • the low viscosity of the insulating resin composition (X) suppresses the formation of excess lumpy cured product, and the thin film formed by the liquid paraffin (B) further enhances the surface texture of the cured product (Y). This improves the manufacturability of a large rotating machine.
  • thermosetting resin A thermosetting resin having both an epoxy group and a meta(acryloyl) group in one molecule and having a number average molecular weight of about 2000 and a viscosity of about 3900 mPa s at 60°C
  • Monofunctional vinyl-based monomer B) 2-hydroxyethyl methacrylate (2-HEMA) - Polyfunctional vinyl-based monomer Polyfunctional vinyl-based monomer having two or more meta(acryloyl) groups or allyl groups in one molecule (neopentyl glycol dimethacrylate having a viscosity of 5 mPa s at 25°C) ⁇ Curing agent and initiator
  • Curing agent zinc octylate Reaction initiator: 2,5-dimethyl-2,5-di(t-butylperoxy)hexane Liquid paraffin (D) Liquid paraffin, solid paraffin (comparative example)
  • Table 1 shows the compounding amounts of Examples 1 to 26.
  • the weight percentages (wt%) of the liquid paraffin (D) and the reaction initiator are the thermosetting resin (A), the monofunctional vinyl monomer (B), and the polyfunctional vinyl monomer varnish. Represents the weight ratio of component (Z) as a whole.
  • 1 phr represents the blending amount of 1 part by mass of curing agent per 100 parts by mass of thermosetting resin (A) and monofunctional vinyl-based monomer (B).
  • thermosetting resin (A), monofunctional vinyl monomer (B), polyfunctional vinyl monomer, curing agent and reaction initiator (C) were weighed according to the blending amounts shown in Table 1.
  • the blending amount of the curing agent was 1 phr, and the blending amount of the reaction initiator was 0.4 wt %.
  • the liquid paraffin (D) was weighed according to the compounding amount shown in Table 1 and dispersed in the monofunctional vinyl monomer (B) to prepare a liquid paraffin solution.
  • thermosetting resin (A), the polyfunctional vinyl-based monomer, the curing agent and the reaction initiator (C), and the prepared liquid paraffin solution are all mixed and uniformly stirred to form an insulating resin composition.
  • a product (X) was obtained.
  • Comparative example 1 Insulating resin compositions were prepared according to the blending amounts shown in Table 1 in the same manner as in Examples 1 to 26. As shown in Table 1, Comparative Example 1 is an example in which the blending of materials was the same as in Example 7, except that the liquid paraffin (D) was not included.
  • Comparative example 2 Insulating resin compositions were prepared according to the blending amounts shown in Table 1 in the same manner as in Examples 1 to 26. As shown in Table 1, Comparative Example 2 is an example in which the composition of materials was the same as in Example 7 except that 1 wt % of solid paraffin was included instead of liquid paraffin (D). As the solid paraffin, a paraffin that takes a solid form at a room temperature of 25° C., that is, has a melting point higher than 25° C. is used. In Comparative Example 2, pulverized solid paraffin was used in order to uniformly disperse it in the monofunctional vinyl monomer (B).
  • D liquid paraffin
  • Viscosity The viscosity of the insulating resin composition (X) was measured with an E-type viscometer. Table 1 shows the results of measurements at room temperature.
  • the curing heating time was 1 hour for Examples 1 to 21 and Comparative Examples 1 and 2, 25 minutes for Example 25, 30 minutes for Example 23, 120 minutes for Example 24, and 180 minutes for Example 25. minutes, and 240 minutes in Example 26.
  • the helical coil obtained by heat curing was subjected to a three-point bending test using an autograph (strength tester). The results of the evaluation are shown in the "Strength" column of Table 1. In Table 1, .DELTA.
  • Examples 1 to 26 have improved tactile properties compared to Comparative Examples 1 and 2. This is because the liquid paraffin (D) forms a thin film on the surface of the cured product (Y) and is distributed from the surface to the inside while having a concentration gradient, thereby filling the curing furnace with the monofunctional vinyl monomer (B ) is thought to be due to the suppression of re-adhesion.
  • Example 7 Based on the results of Example 7 and Comparative Example 1, the influence of the presence or absence of liquid paraffin (D) will be considered. Since Comparative Example 1 does not contain liquid paraffin (D), a thin film of liquid paraffin (D) is not formed on the surface of the cured product (Y), and the volatilized monofunctional vinyl monomer (B) is cured at the curing heating temperature. It is considered that the adhesion to the surface of the object was not suppressed. In addition, 2-HEMA used as the monofunctional vinyl-based monomer (B) in Example 7 and Comparative Example 1 has water absorbing properties.
  • Comparative Example 1 not only the reattachment of the volatilized 2-HEMA is not suppressed, but also the 2-HEMA reattached to the surface adsorbs the moisture in the air after cooling. is considered to have deteriorated.
  • the concentration of the paraffin solution of Comparative Example 2 is the same as that of the paraffin solution of Example 7, but in Comparative Example 2 solid paraffin that takes a solid form at room temperature of 25° C. is used.
  • pulverized solid paraffin is used, but unlike liquid paraffin (D), it is difficult to uniformly disperse it. For this reason, in Comparative Example 2, the formation of the paraffin thin film on the surface of the cured product became non-uniform, and the expected effect of improving touchability was not obtained.
  • Example 14 Based on the results of Examples 1 to 14, the influence of the compounding amount of the monofunctional vinyl monomer (B) will be discussed.
  • the amount of the monofunctional vinyl-based monomer (B) blended was less than 45 wt% of the total amount of the varnish component (Z) in Examples 1 to 3 and Example 13, Example 4, Example 5, and Example 10. 50 wt % to 75 wt % in Example 11, Example 12, and Example 14 is 84 wt % or more.
  • the mechanical strength was evaluated as excellent, but the thickness of the hardened block exceeded 10 mm.
  • Example 11, Example 12, and Example 14 the thickness of the block-like cured product was good at 2 mm or less, but the mechanical strength was lowered, resulting in a ⁇ evaluation.
  • the amount of the monofunctional vinyl monomer (B) should be 44 wt% to 84 wt% of the total amount of the varnish component (Z), preferably 51 wt%. % to 72 wt%, more preferably 58 wt% to 68 wt%.
  • the amount of liquid paraffin (D) is less than 0.01 wt% of the total amount of varnish component (Z) in Example 15, 1 wt% to 3 wt% in Examples 16 and 17, and 3 wt% in Examples 18 and 19. % to 6 wt%, and greater than 6 wt% in Examples 20 and 21.
  • the cured product (Y) in any case also exhibits excellent tactile properties compared to those of Comparative Examples 1 and 2. On the other hand, in Example 15, tackiness was felt even though there was no adhesion to the finger after being touched with the finger.
  • the amount of liquid paraffin (D) is 5.3 wt% or less, preferably 2.9 wt% or less, more preferably 0.008 wt% to 1.2 wt% of the total amount of varnish component (Z). % was found to be desirable.
  • the curing heating time was 25 minutes in Example 22, 30 minutes in Example 23, 120 minutes in Example 24, 180 minutes in Example 25, and 240 minutes in Example 26.
  • the results corresponding to those of Example 7, in which the same formulation was used and the heating time for curing was 60 minutes, are shown side by side in Examples 22 to 26 in Table 1.
  • a mechanical strength of 100 N or more is obtained in any of the examples.
  • the mechanical strength reaches about 200 N from the curing heating time of 60 minutes, and the increase in the mechanical strength is saturated with the curing heating time longer than that.
  • the curing heating time is preferably 1 hour to 4 hours, more preferably 1 hour to 2 hours.
  • a rotating machine according to the present disclosure can be applied to a hoisting machine for a rope elevator.
  • a coil according to the present disclosure can be applied to the rotating machine.
  • the insulating resin processed product and the cured product thereof according to the present disclosure can be applied to maintaining the insulating properties and mechanical strength of the coil.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
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  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Organic Insulating Materials (AREA)
  • Cage And Drive Apparatuses For Elevators (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
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WO2013146706A1 (ja) * 2012-03-30 2013-10-03 太陽ホールディングス株式会社 光硬化性熱硬化性組成物、その硬化物の製造方法、硬化物およびこれを有するプリント配線板
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JPS53119949A (en) * 1977-03-29 1978-10-19 Hitachi Chem Co Ltd Thermoplastic resin composition
JPS568418A (en) * 1979-06-27 1981-01-28 Shinteesu Ab Unsaturated hardening polyester composition
JPH09239756A (ja) * 1996-03-11 1997-09-16 Inax Corp アクリル系人造大理石製品の成形法
JP2006330301A (ja) * 2005-05-25 2006-12-07 Shin Etsu Chem Co Ltd 液晶表示素子用シール剤組成物
JP2008179796A (ja) * 2006-12-26 2008-08-07 Mitsui Chemicals Inc （メタ）アクリロイル基およびグリシジル基を有する化合物、および当該化合物を含む重合性組成物
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