WO2023170891A1

WO2023170891A1 - Insulating resin composition, cured object, wire coil, and rotating machine

Info

Publication number: WO2023170891A1
Application number: PCT/JP2022/010721
Authority: WO
Inventors: あずさ大澤
Original assignee: 三菱電機株式会社
Priority date: 2022-03-10
Filing date: 2022-03-10
Publication date: 2023-09-14
Also published as: JPWO2023170891A1

Abstract

Provided are: an insulating resin composition which contains a biomass material as a starting material and nevertheless can give cured objects having a better surface touch; a cured object obtained from the insulating resin composition; a wire coil having a satisfactory surface touch; and a rotating machine including the wire coil. The insulating resin composition comprises a heat-curable resin having both an epoxy group and a (meth)acryloyl group, a free-radical polymerization initiator, a hardener for epoxy groups, a polyfunctional vinyl monomer produced from a biomass material as a starting material, and monofunctional vinyl monomers produced from a biomass material as a starting material. The monofunctional vinyl monomers comprise both a vinyl monomer having an isobornyl skeleton and a vinyl monomer having the skeleton of a cyclic ether of a saturated hydrocarbon. The insulating resin composition has a biomass ratio of 60-84%.

Description

Insulating resin compositions, cured products, wire-wound coils, and rotating machines

The present disclosure relates to an insulating resin composition, a cured product, a wire-wound coil, and a rotating machine.

Patent Document 1 discloses an example of a solvent-free varnish composition used as an insulating varnish. In a solvent-free varnish composition, a monofunctional vinyl monomer such as 2-hydroxyethyl methacrylate (2-HEMA) is added as a reactive diluent to adjust the viscosity. After impregnating the coil with the solvent-free varnish composition, it is heated and cured.

International Publication No. 2017/061006

However, in an insulating resin composition such as the solvent-free varnish composition of Patent Document 1, a part of the monofunctional vinyl monomer may volatilize into the curing furnace during curing heating. Here, 2-hydroxyethyl methacrylate used as a monofunctional vinyl monomer has high hydrophilicity due to its molecular structure, that is, it has a hydroxyl group with a high degree of freedom in a relatively short hydrocarbon main chain. Therefore, 2-hydroxyethyl methacrylate easily reacts with moisture in the air and can redeposit on the surface of the cured product. This may leave stickiness on the surface of the cured product. Furthermore, there is an increasing need for insulating resins that use fewer raw materials derived from petroleum, for example, in order to comply with environmental regulations that have tended to be tightened due to recent international concerns about environmental issues.

The present disclosure relates to solving such problems. The present disclosure provides an insulating resin composition that uses biomass material as a raw material and can further improve surface tactility of the cured product, a cured product thereof, a wound coil with good surface tactility, and a rotating machine using the same. do.

The insulating resin composition according to the present disclosure includes a thermosetting resin having both an epoxy group and a meth (acryloyl) group, a radical polymerization reaction initiator and a curing agent for the epoxy group, and a polyfunctional resin composition made from a biomass material. and a monofunctional vinyl monomer made from a biomass material, the monofunctional vinyl monomer having an isobornyl skeleton and a cyclic ether skeleton of a saturated hydrocarbon. It contains both vinyl monomers and has a biomass degree of 60% or more and 84% or less.

The cured product according to the present disclosure is obtained by curing the above-mentioned insulating resin composition.

A wire-wound coil according to the present disclosure is impregnated with the above-mentioned insulating resin composition.

A rotating machine according to the present disclosure is a rotating machine used for a hoisting machine that drives a car of a rope elevator, and includes a stator using the above-described wire-wound coil.

With the insulating resin composition according to the present disclosure, the surface touchability of the cured product can be further improved while using biomass material as a raw material. Furthermore, the surface touchability of the wire-wound coil using the biomass material as a raw material is further improved.

FIG. 2 is a conceptual diagram showing an example of a situation where an insulating resin is hardened. 1 is a sectional view of a hoisting machine according to Embodiment 1. FIG.

Embodiment 1.
Hereinafter, embodiments for implementing the subject matter of the present disclosure will be described. Note 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 may be made without departing from the spirit of the present disclosure. Can be omitted. Further, the embodiments and examples in this disclosure are illustrative in all respects and should not be interpreted in a restrictive manner.

In Embodiment 1, a liquid insulating resin composition (X) and its cured product (Y) will be described. Further, a winding coil for a rotating machine using the insulating resin composition (X) and a rotating machine using the same for a stator will also be described.

1. Insulating resin composition (X) and its cured product (Y)
The insulating resin composition (X) of Embodiment 1 is used, for example, to maintain insulation and mechanical strength in a coil of a rotating machine. A coil is formed, for example, by winding a winding such as enameled wire around an iron core. The device to which the coil is applied is not limited to a specific device. 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 coil is impregnated with the insulating resin composition (X), for example, by a dipping method in which the coil is immersed in an impregnating tank filled with the insulating resin composition (X). The insulating resin composition (X) becomes a cured product (Y) by being heated and cured in a curing furnace.

The insulating resin that is impregnated to ensure the insulation and mechanical strength of the coil of a rotating machine is generally of high viscosity, and in that case, the insulating resin penetrates between the windings to the inside of the coil. It's difficult to make it happen. In particular, in large rotating machines, the length of the coil is long and the thickness thereof is large, making it more difficult for high-viscosity insulating resin to penetrate.

In particular, when applying insulating resin to large rotating machines, a material design suitable for the coils of large rotating machines is required. Methods for filling insulating resin between the windings of a coil of a rotating machine include a dipping method and a dripping method. For example, in a coil that is relatively small in size and has a low winding density, such as is applied to a compressor, either the dipping method or the dripping method can be adopted. On the other hand, in large rotating machines such as generators or hoisting machines, it is difficult to apply the insulating resin uniformly between the windings to the inside of the coil using the dripping method. For this reason, in large rotating machines, an immersion method in the atmosphere or in a vacuum is generally adopted.

The immersion method is a method in which the coil is immersed in a tank or impregnating tank filled with insulating resin in the atmosphere or under vacuum, thereby infiltrating the insulating resin between the wound wires. Here, when the coil is pulled up from the dipping tank after being impregnated by the dipping method, a large amount of excess insulating resin adheres to the windings, core, and other components of the coil. The coils are pulled out of the immersion tank and placed in a curing furnace for curing heating, often with excess insulating resin still attached. Therefore, the excess insulating resin adhering to the coil may harden as it is, forming a lumpy cured material on, for example, the lower part of the coil, the recess of the iron core, or other constituent members. Further, the insulating resin whose viscosity decreases due to curing heating and drips down the coil may form a large resin pool in the curing furnace.

Hardened lumps formed on the bottom of the coil, in the recesses of the core, or on other structural members may damage the windings and components due to thermal stress such as curing shrinkage, which may cause a decrease in insulation properties. sell. Furthermore, since the lump-like cured material obstructs the work of assembling the coil into the fixing member, it is necessary to remove the lump-like cured material. Furthermore, resin puddles formed in the curing furnace may generate smoke due to curing heat. Since the resin pool becomes a huge cured product formed on the hearth of the curing furnace, regular cleaning of the curing furnace is essential. Such problems are particularly noticeable in large rotating machines, and there is an increasing need for low-viscosity insulating resins that can suppress the formation of lumpy cured products and resin pools.

In order to lower the viscosity of such an insulating resin and improve its permeability, it is effective to add an organic solvent such as styrene or vinyltoluene to the insulating resin. However, as interest in environmental issues has increased in recent years, there has been a growing demand for reducing the environmental impact of insulating resins, so it is preferable to suppress the use of these organic solvents. Therefore, instead of adding these organic solvents, low-molecular materials that have active groups that can contribute to the curing reaction and can reduce volatile substances caused by curing heating, that is, reactive diluents, are added to the insulating resin to adjust the viscosity. Means to do this may be adopted. Monofunctional monomers, particularly 2-hydroxyethyl methacrylate, are effective as such reactive diluents.

FIG. 1 is a conceptual diagram showing an example of a situation where the insulating resin is hardened. In FIG. 1, an example of an insulating resin 2 hardening on the surface of a winding of a coil 1 is shown. During the curing reaction, most of the reactive diluent added to the insulating resin 2 is incorporated into the cured product, but a portion 3 of the reactive diluent evaporates and fills the inside of the curing furnace. Here, moisture 4 is contained in the air inside the furnace. Note that a thin film 5 made of paraffin may be formed on the surface of the hardened insulating resin 2.

2-Hydroxyethyl methacrylate has high hydrophilicity due to its molecular structural characteristics, namely, having a hydroxyl group with a high degree of freedom in a relatively short hydrocarbon main chain. Therefore, when 2-hydroxyethyl methacrylate is used as a reactive diluent, a part of the volatilized part easily reacts with moisture in the air and can re-deposit on the surface of the cured product. This may leave stickiness on the surface of the cured product. Since stickiness on the surface of the cured product hinders assembly work, which is a post-impregnation process, insulating resins are required to eliminate stickiness on the surface of the cured product and improve touchability.

The insulating resin composition (X) of Embodiment 1 includes a thermosetting resin (A) having both an epoxy group and a meth (acryloyl) group, a radical polymerization reaction initiator, and a curing agent for the epoxy group (B). , a polyfunctional vinyl monomer (C) made from a biomass material, and a monofunctional vinyl monomer (D) made from a biomass material. The monofunctional vinyl monomer (D) has a cyclic structure in its molecule. The monofunctional vinyl monomer (D) includes both a vinyl monomer (D-1) having an isobornyl skeleton and a vinyl monomer (D-2) having a saturated hydrocarbon cyclic ether skeleton. Here, the meth (acryloyl) group represents an acryloyl group or a methacryloyl group. Further, in the present disclosure, a numerical range expressed using "x to y" represents a numerical range including a lower limit value x and an upper limit value y.

The insulating resin composition (X) preferably has a low viscosity and good drainage so as to suppress excessive adhesion to the coil pulled up from the dipping tank after impregnation by the dipping method. The overall viscosity of the insulating resin composition (X) is desirably 10 mPa·s to 200 mPa·s, preferably 10 mPa·s to 100 mPa·s, more preferably 15 mPa·s to 50 mPa·s.

1.1. Thermosetting resin (A)
The thermosetting resin (A) includes a resin having both an epoxy group and a meth (acryloyl) group in one molecule. The thermosetting resin (A) may be a resin used alone, or a second resin containing one or both of an epoxy group and a meth (acryloyl) group in one molecule in addition to the resin. A mixture of resins and the like may be used. The second resin may be a mixture of a plurality of resins.

The thermosetting resin (A) undergoes an addition reaction via free radicals generated from an organic peroxide with a meth (acryloyl) group as a reactive group, and a ring-opening polymerization reaction with an epoxy group as a reactive group. The three-dimensional crosslinking reaction by both is promoted. This accelerates the curing reaction and increases the heat resistance and mechanical strength of the cured product.

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.

The epoxy equivalent of the thermosetting resin (A) blended into the insulating resin composition (X) is preferably 500 to 5,000, more preferably 1,000 to 4,000. 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 crosslinking density of the cured product (Y). You will be able to do this.

1.2. Radical polymerization reaction initiator and curing agent for epoxy groups (B)
In order to cure thermosetting resins (A) and monofunctional vinyl monomers (D), organic peroxides are used as radical polymerization reaction initiators that mainly act on meth (acryloyl) groups and epoxy groups. A curing catalyst is used in combination.

1.2.1. Organic peroxide Organic peroxides are mainly used as reaction initiators for meth (acryloyl) groups, and those known in the art can be used. The organic peroxide is not particularly limited as long as it has a 10-hour half-life temperature of 40°C or higher, but from the viewpoint of shortening the curing time and adjusting the curing temperature, the 10-hour half-life temperature should be 100°C to 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, peroxydicarbonate-based peroxides, etc. can be used. These organic peroxides may be used alone or in combination of two or more types.

Examples of organic peroxides with such 10 hour half-life temperatures include 1,1-di(t-butylperoxy)cyclohexane; -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-butylperoxyisopropyl monocarbonate, t-butylperoxybenzoate, t- Butylperoxyacetate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxy 2-ethylhexyl monocarbonate, di(2-t-butylperoxy) isopropyl)benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide oxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, p-menthane hydroperoxide, t-butylperoxyallyl monocarbonate, methyl ethyl ketone peroxide, 1,1,3, Examples include 3-tetramethylbutyl hydroperoxide, t-butyl hydroperoxide, cumin hydroperoxide, and diisopropylbenzene hydroperoxide. These may be used alone or in combination of two or more.

The blending amount of the organic peroxide in the insulating resin composition (X) is not particularly limited, but the amount of the thermosetting resin (A), the polyfunctional vinyl monomer (C), and the monofunctional vinyl monomer (D) is The amount is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.5 parts by mass to 5 parts by mass, based on a total of 100 parts by mass. If the amount of organic peroxide is less than 0.1 part by mass, the crosslinking density will be low and the required mechanical strength will not be obtained. On the other hand, if the amount of organic peroxide blended is more than 10 parts by mass, the pot life of the insulating resin composition tends to be significantly shortened.

1.2.2. Curing Agent for Epoxy Group As the curing agent for epoxy group, those known in the technical field can be used. Examples of curing agents for epoxy groups include amine compounds, boric acid ester compounds, organometallic compounds, organophosphorus compounds, quaternary ammonium salts, quaternary phosphonium salts, amine complexes, imidazole compounds, titanium and cobalt. Examples include compounds containing transition metals such as, acid anhydrides, imidazole compounds, polymercaptan compounds, phenols, Lewis acid compounds, isocyanate compounds, and the like. These may be used alone or in combination of two or more.

Specific examples of amine curing agents include tertiary amines and tertiary amine salts. For example, lauryldimethylamine, N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine, N,N-dimethylaniline, (N,N-dimethylaminomethyl)phenol, 2,4,6-tris(N, N-dimethylaminomethyl)phenol, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), ethylenediamine, 1, 3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, dipropylenediamine, polyetherdiamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis(hexamethyl)triamine , triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, aminoethylethanolamine, tri(methylamino)hexane, dimethylaminopropylamine, diethylaminopropylamine, methyliminobispropylamine, menthendiamine, isophoronediamine, bis (4-Amino-3-methyldicyclohexyl)methane, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, N-aminoethylpiperazine, 3,9-bis(3-aminopropyl)-2,4,8,10 -tetraoxaspiro[5,5]undecane, m-xylene diamine, metaphenylene diamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane, dicyandiamide, organic acid dihydrazide, and the like. Examples of tertiary amine salts include the above-mentioned tertiary amine carboxylates, sulfonates, and inorganic acid salts. Examples of carboxylates include salts of carboxylic acids having 1 to 30 carbon atoms (especially 1 to 10 carbon atoms) such as octylates (especially salts of fatty acids). Examples of sulfonates include p-toluenesulfonate, benzenesulfonate, methanesulfonate, ethanesulfonate, and the like. Typical specific examples of tertiary amine salts include salts of 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) (e.g., p-toluenesulfonate, octylate), etc. Can be mentioned. However, these are just examples. Use of amine curing agents other than these does not depart from the scope of the present disclosure.

Examples of borate esters include trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, and cyclic borate compounds. However, these are just examples. The use of boric acid esters other than these does not depart from the scope of the present disclosure.

Examples of organometallic compounds include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, aluminum acetylacetone complex, and the like. However, these are just examples. Use of organometallic compounds other than these does not depart from the scope of this disclosure.

Examples of organic phosphorus compounds include tetraphenylphosphonium tetraphenylborate, triphenylphosphine, and the like. However, these are just examples. The use of organic phosphorous compounds other than these does not depart from the scope of the present disclosure.

Examples of quaternary ammonium salts include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrabutylammonium chloride, and tetrabutyl bromide. Examples include ammonium, tetrabutylammonium iodide, triethylbenzylammonium chloride, triethylbenzylammonium bromide, triethylbenzylammonium iodide, triethylphenethylammonium chloride, triethylphenethylammonium bromide, and the like. However, these are just examples. The use of quaternary ammonium salts other than these does not depart from the scope of the present disclosure.

Examples of quaternary phosphonium salts include tetrabutylphosphonium chloride, tetrabutylphosphonium iodide, tetrabutylphosphonium acetate, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, ethyltriphenylphosphonium chloride, Ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, ethyltriphenylphosphonium phosphate, propyltriphenylphosphonium chloride, propyltriphenylphosphonium bromide, propyltriphenylphosphonium iodide, butyltriphenyl chloride Examples include phosphonium, butyltriphenylphosphonium bromide, butyltriphenylphosphonium iodide, and the like. However, these are just examples. The use of quaternary phosphonium salts other than these does not depart from the scope of this disclosure.

Examples of 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. Here, examples of amine compounds include aliphatic tertiary amines such as trimethylamine, tri-n-propylamine, N,N-dimethyloctylamine, N,N-dimethylbenzylamine, N,N-dimethylaniline, etc. aromatic tertiary amines, heterocyclic tertiary amines such as substituted or unsubstituted imidazole or pyridine with alkylation at position 1, aliphatic primary amines such as monoethylamine and n-hexylamine, benzylamine, etc. Examples include aliphatic primary amines containing an aromatic ring, aromatic primary amines such as aniline, and secondary amines such as piperidine. Typical specific examples of boron trifluoride amine complexes include boron trifluoride monoethylamine complex, boron trifluoride diethylamine complex, boron trifluoride isopropylamine complex, boron trifluoride chlorophenylamine complex, and 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, Examples include N-dimethyloctylamine complex, boron trichloride N,N-dimethyldodecylamine complex, and boron trichloride N,N-diethyldioctylamine complex. However, these are just examples. The use of amine complexes other than these does not depart from the scope of this disclosure.

Examples of imidazole compounds include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1- Benzyl-2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-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, 2,4-diamino-6 (2'-ethyl, 4-methylimidazole (1')) ethyl-s-triazine, 2,4-diamino -6(2'-Methylimidazole(1'))ethyl-s-triazine isocyanuric acid adduct, 2:3 adduct of 2-methylimidazole isocyanuric acid, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl- Examples include 3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, and 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole. However, these are just examples. The use of imidazole curing agents other than these does not depart from the scope of the present disclosure.

Specific examples of acid anhydride curing agents include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and the like. However, these are just examples. The use of acid anhydride curing agents other than these does not depart from the scope of the present disclosure.

The amount of the above-mentioned curing agent for epoxy group can be adjusted as appropriate depending on the type of thermosetting resin (A), the type of curing agent, etc. The blending amount of the curing agent is preferably about 0.5 equivalent or more and 2 equivalents 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 equivalent, curing of the thermosetting resin (A) may not proceed sufficiently. If the amount of the curing agent exceeds 2 equivalents, the heat resistance, mechanical properties, etc. of the cured product may deteriorate.

1.2.3. Curing Accelerator for Epoxy Groups In addition to the above-mentioned curing agents for epoxy groups, a curing accelerator may be used in combination to accelerate or control the curing reaction. Examples of the curing accelerator include tertiary amines and salts thereof, quaternary ammonium compounds, imidazole, and alkali metal alkoxides. However, these are just examples. The use of curing accelerators other than these does not depart from the scope of this disclosure.

The blending 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) based on the mass of the thermosetting resin (A). It is. If the amount is less than 0.01% by mass, the promoting 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 may deteriorate.

1.3. Polyfunctional vinyl monomer (C)
The polyfunctional vinyl monomer (C) uses biomass material as a part of its raw material. The polyfunctional vinyl monomer (C) is optionally blended as one of the reactive diluents in the insulating resin composition (X). The polyfunctional vinyl monomer (C) is not limited to a specific one as long as it contributes to the radical polymerization reaction, but it has two meth (acryloyl) groups or allyl groups in one molecule, which are reactive groups. It is desirable to include those who have. Since such a polyfunctional vinyl monomer (C) has two active groups that contribute to the reaction in one molecule, it is polymerized and completely incorporated during the curing process of the insulating resin composition (X). Volatization during the curing process is also extremely low. Therefore, by adding it as a reactive diluent, it is possible to lower the viscosity of the insulating resin composition (X), and re-adsorption due to volatilization during curing and heating is also suppressed. Furthermore, since the polyfunctional vinyl monomer (C) has a plurality of reactive groups, it actively participates in the polymerization reaction of the insulating resin composition (X) and three-dimensional crosslinking of the insulating resin composition (X). It is possible to promote the Therefore, the heat resistance and mechanical strength of the cured product (Y) can also be increased.

The blending amount of the polyfunctional vinyl monomer (C) may be within a range that can ensure the blending amount of the monofunctional vinyl monomer (D), and from the viewpoint of mechanical strength and heat resistance, the thermosetting resin It is desirable that the amount is within the range of 3 wt% to 20 wt% of the total of (A), the polyfunctional vinyl monomer (C), and the monofunctional vinyl monomer (D).

1.4. Monofunctional vinyl monomer (D)
The monofunctional vinyl monomer (D) uses biomass material as a part of its raw material. The monofunctional vinyl monomer (D) is used mainly for adjusting the viscosity of the insulating resin composition (X) in addition to adjusting the crosslinked structure. In order to maintain the usable life of the insulating resin composition (X), the monofunctional vinyl monomer (D) is desirably a monofunctional one in which the number of functional groups contributing to the reaction is one per molecule.

As the monofunctional vinyl monomer (D), a low-viscosity monomer having an ether bond or an ester bond and a cyclic structure is used. Here, a vinyl monomer (D-1) having an isobornyl skeleton and a vinyl monomer (D-2) having a cyclic ether skeleton of a saturated hydrocarbon are used together. Examples of the vinyl monomer (D-1) having an isobornyl skeleton include isobornyl methacrylate and isobornyl acrylate. Examples of the vinyl monomer (D-2) having a saturated hydrocarbon cyclic ether skeleton include tetrahydrofurfuryl methacrylate and tetrahydrofurfuryl acrylate.

The blending amount of the monofunctional vinyl monomer (D) is determined from the viewpoint of increasing the biomass content of the insulating resin composition (X) and increasing the environmental load reduction effect, and from the viewpoint of increasing the biomass content of the insulating resin composition (X) and increasing the environmental load reduction effect when the coil is pulled up from the immersion tank. ) is preferably as large as possible from the viewpoint of improving liquid drainage and suppressing the formation of lumpy cured products on the coil and other structural members. On the other hand, although the monofunctional vinyl monomer (D) contributes to increasing the number of crosslinking points, it is a low molecular weight and part of it evaporates during curing heating, so the entire amount does not contribute to the curing reaction, so the blending amount If the amount is too large, the mechanical strength of the cured product (Y) will be reduced. That is, the blending amount of the monofunctional vinyl monomer (D) should be set within a range that can achieve both of the contradictory required functions, namely, improving the degree of biomass and suppressing the formation of a lumpy cured product, and increasing the mechanical strength of the cured product (Y). It must be prepared within From the viewpoint of improving the degree of biomass and suppressing the formation of clumped cured products, the blending amount of the monofunctional vinyl monomer (D) may be 60 wt% or more, preferably 65 wt% or more of the total amount of the insulating resin composition (X). desirable. On the other hand, from the viewpoint of mechanical strength of the cured product (Y), the blending amount of the monofunctional vinyl monomer (D) is 85 wt% or less, preferably 75% or less, more preferably 75% or less of the total amount of the insulating resin composition (X). is desirably 70 wt% or less. Therefore, in order to achieve both of the two required functions, the blending amount of the monofunctional vinyl monomer (D) is preferably 60 to 85 wt% of the total amount of the insulating resin composition (X). It is 60 to 85 wt%, more preferably 65 to 85 wt%.

In the monofunctional vinyl monomer (D), in addition to the above vinyl monomers (D-1) and (D-2), a monofunctional vinyl monomer having one meta (acryloyl) group or allyl group in one molecule A vinyl monomer may also be blended. Examples of these monofunctional vinyl monomers include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, lauryl methacrylate, ethoxydiethylene glycol methacrylate, 4-hydroxybutyl methacrylate, n-octyl acrylate, and the like. These monofunctional vinyl monomers may be used singly or in combination.

2. Method for producing insulating resin composition (X) and cured product thereof (Y) 2.1. Insulating resin composition (X)
The insulating resin composition (X) can be manufactured by the following manufacturing method. The blending amounts of (A) to (D) are as described in Examples and Comparative Examples. Furthermore, the mixing method is not particularly limited as long as it can be mixed uniformly, and any method known in the technical field can be used.

(a) Mixing of thermosetting resin, polyfunctional vinyl monomer, and monofunctional vinyl monomer The thermosetting resin (A) and the polyfunctional vinyl monomer (C) are mixed to have fluidity from a semi-solid state. Heat to approximately 50°C and weigh to obtain a viscosity that will give . A monofunctional vinyl monomer (D) is added thereto, and the mixture is stirred using a rotation-revolution stirrer until a homogeneous solution is obtained.

(b) Preparation of insulating resin composition (X) Add a radical polymerization reaction initiator and a curing agent for epoxy groups (B) to the mixed solution of (A), (C), and (D) prepared in (a) above. Mix evenly.

2.2. Cured product (Y)
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 purpose. The cured product (Y) can be molded into a desired shape by various molding methods such as impregnation, coating, casting, and 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, for insulating members of heavy electrical equipment such as rotating machines and power transmission and transformation equipment. Examples of the insulating member include varnish, insulating paint, cable covering material, insulating sheet, and sealing material.

When the cured product (Y) is obtained by impregnating a coil of a rotating machine or the like with the insulating resin composition (X) and curing it, the step of impregnating the coil is not particularly limited. Here, an example of a manufacturing method consisting of a total of five steps including a preheating step and an air cooling step before impregnation, followed by an impregnation step, a drip removal step, and a heat curing step will be described.

The preheating step is a step in which annealing treatment is performed for the purpose of improving the crazing resistance of the coil winding such as enameled wire. In the preheating step, 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 of the coil 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), but for example, 30° C. to 50° C. is suitable.

In the impregnation process, treatment methods known in the technical field such as dipping, dripping, pressure impregnation, and vacuum impregnation can be used; however, in the case of coils for large rotating machines, impregnation treatment by dipping or pressure/vacuum impregnation is generally used. It will be done. When the immersion treatment is performed by immersion impregnation, the coil is gently immersed in an impregnation bath filled with the insulating resin composition (X). The soaking time is not particularly limited, but especially in coils that are tightly wound in an aligned manner, the air that adheres between the enamelled wires and on the component parts becomes bubbles and floats to the surface, so the generation of these bubbles can be avoided. It is desirable to soak it until it runs out. The time it takes for bubble generation to settle down varies depending on the size of the coil, but for large rotating machines it takes about 10 to 60 minutes, and from the perspective of improving the efficiency (shortening of time) of the manufacturing process, it takes about 15 to 30 minutes. is desirable. If the immersion time is less than 10 minutes, the insulating resin composition (X) will not penetrate into the entire coil, and even if it is immersed for more than 60 minutes, at which time bubble generation will stop, the amount of insulating resin composition (X) that will penetrate into the coil will be This is because it does not increase. 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 begin to thicken due to curing. For many insulating resins, the room temperature is set at 25°C to 60°C. Since the insulating resin composition (X) has a low viscosity, it can be impregnated at room temperature of 25°C.

In the heat curing step, the insulating resin composition (X) impregnated into the coil in the impregnation step is heated and cured in a curing furnace to become a cured product (Y). The heating temperature in the heat curing step is not particularly limited as long as it is higher than the reaction start temperature (half-life temperature) of the reaction initiator added to the insulating resin composition (X), and is generally 130 ° C. to 180 ° C., preferably The temperature is 140°C to 170°C. Generally, the heating time of the heat curing step is influenced by the curing speed of the insulating resin composition (X) and the amount of adhesion to the coil, and also changes depending on the raw material composition. Further, the time required for curing depends on the heating temperature, and generally the higher the temperature, the shorter the time required for complete curing. Therefore, the heating temperature and heating time in the heat curing step are set to the temperature and time necessary for complete curing, depending on the composition of the insulating resin composition (X). Here, if the heating temperature or heating time is insufficient, the insulating resin composition (X) may not be completely cured, and uncured portions may occur. At this time, various properties such as electrical properties, mechanical properties, and heat resistance may deteriorate in the cured product (Y). On the other hand, if the heating temperature or heating time is excessive, the balance of the crosslinking reaction due to curing heating may be lost, which may cause cracks to occur in the cured product (Y). The heating temperature and heating time are set within a range that does not cause these problems. The insulating resin composition (X) of the present disclosure is completely cured in 30 minutes to 8 hours at 130 to 180°C. A curing time of less than 30 minutes will not result in complete curing. On the other hand, the mechanical strength (adhesion strength of the electric wire) of the cured product (Y) gradually develops and improves after curing, and tends to converge after a predetermined time, here 4 hours. Therefore, from the viewpoint of complete curing and strength convergence, the heating time in the heat curing step is preferably 1 to 4 hours, more preferably 1 to 2 hours.

2.3. Winding coil for rotating machine and stator using the same The insulating resin composition (X) of Embodiment 1 is applied to, for example, a large rotating machine for a hoisting machine of a rope elevator.
FIG. 2 is a sectional view of the hoist 10 according to the first embodiment.

The hoisting machine 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 connected by a rotating shaft 17. A main rope (not shown) is wound around the sheave 14. An elevator car (not shown) supported by the main rope is driven by the friction between the main rope and the sheave 14.

The brake section 12 includes a movable brake shoe (not shown). The brake part 12 generates a force for braking the rotating part 11 by the 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 includes an annular iron core 20 . A winding 21 is wound around each tooth of the iron core 20. Further, the winding 21 and the iron core 20 are insulated by an insulator 22. Further, the winding 21 is fixed by an insulator 22. The windings 21 wound around each tooth are connected to each other in a set order, and generate magnetic flux when energized.

The stator 19 is manufactured, for example, by a method including the following steps. First, a wire coated with enamel is prepared. The wire has conductivity. The material of the wire is, for example, copper, aluminum, silver, etc. The type of enamel is not particularly limited, but combinations of polyesterimide, polyamideimide, polyamide, etc. are used. These enamel insulation coating layers may contain an inorganic filler to improve dielectric strength. As these enamelled wires, commercially available wires for motor coils can be used. Such an insulated enameled wire is wound around each tooth of the iron core 20 to form a winding 21. Thereafter, the winding 21 is impregnated with the insulating resin composition (X) by the above-described impregnation process, and the insulating resin composition (X) is cured by the heat curing process.

In the insulating resin composition (X), a low molecular weight monofunctional vinyl monomer (D) is used as a reactive diluent that lowers the viscosity in order to improve impregnation into the coil. Therefore, even if the coil of a large rotating machine has a long coil length and a thick coil thickness, the insulating resin composition (X) is easily impregnated into the inside. Moreover, since the viscosity of the insulating resin composition (X) is low, the formation of excess clumped cured material is suppressed. This improves the manufacturability of large rotating machines.

3. Examples Examples will be described below. Note that the following examples do not limit the scope of the present disclosure.

3.1. Production of insulating resin composition (X) and its cured product (Y) The insulating resin composition (X) and its cured product (Y) of each Example and each comparative example were produced as follows.

3.1.1. Preparation of materials The following materials were prepared.

・Thermosetting resin (A)
A thermosetting resin that has both an epoxy group and a meth (acryloyl) group in one molecule, a number average molecular weight of about 2000, and a viscosity at 60°C of about 3900 mPa・s, a curing agent for epoxy groups, and radical polymerization. Reaction initiator (B)
Curing agent: Zinc octylate Reaction initiator: 2,5-dimethyl-2,5-di(t-butylperoxy)hexane/polyfunctional vinyl monomer (C)
Bis A type epoxy acrylate monofunctional vinyl monomer (D) with a weight average molecular weight of about 500
(D-1) Biomass-derived isobornyl methacrylate (D-2) Biomass-derived tetrahydrofurfuryl methacrylate (D-3) 2-hydroxyethyl methacrylate (2-HEMA)

3.1.1.1. Examples 1 to 9
The thermosetting resin (A) and the polyfunctional vinyl monomer (C) are heated to 40°C in advance so that they have a viscosity that is easy to stir, and the thermosetting resin (A) is mixed according to the blending amounts shown in Table 1 below. , a polyfunctional vinyl monomer (C), and a monofunctional vinyl monomer (D) were weighed. Next, the weighed thermosetting resin (A), polyfunctional vinyl monomer (C), and monofunctional vinyl monomer (D) are all mixed and stirred using a rotation-revolution type stirrer to make a uniform mixture. A mixed solution was obtained. A curing agent for epoxy groups and a radical polymerization reaction initiator (B) were added to this mixed solution in the ratios shown in Table 1 below to obtain an insulating resin composition (X).

In Table 1, the weight percentage (wt%) of the reaction initiator represents the weight ratio of the thermosetting resin (A) and the monofunctional vinyl monomer (D) to the total weight. In addition, in Table 1, 1 phr means 1 part by mass of curing for a total of 100 parts by mass of the thermosetting resin (A), the polyfunctional vinyl monomer (C), and the monofunctional vinyl monomer (D). represents the amount of the agent to be mixed. In addition, in the "Main component" column of the monofunctional vinyl monomer (D) in Table 1, "(D-1), (D-2)" means that the monofunctional vinyl monomer (D) is an isovolume. This indicates that it contains both nil methacrylate (D-1) and tetrahydrofurfuryl methacrylate (D-2). In the same column, "(D-3)" means that the monofunctional vinyl monomer (D) is 2-HEMA (D) instead of isobornyl methacrylate (D-1) and tetrahydrofurfuryl methacrylate (D-2). -3) is used. In the same column, "(D-1)" indicates that the monofunctional vinyl monomer (D) contains isobornyl methacrylate (D-1) and does not contain tetrahydrofurfuryl methacrylate (D-2). . In the same column, "(D-2)" indicates that the monofunctional vinyl monomer (D) contains tetrahydrofurfuryl methacrylate (D-2) and does not contain isobornyl methacrylate (D-1). .

3.1.1.2. Comparative example 1 to comparative example 4
Insulating resin compositions were produced in the same manner as in Examples 1 to 9 according to the blending amounts shown in Table 1. As shown in Table 1, in Comparative Example 1 and Comparative Example 2, the total amount of (D-1) and (D-2) was 85 wt% of the total amount of the insulating resin composition (X). Over. In Comparative Example 3 and Comparative Example 4, the total amount of (D-1) and (D-2) is less than 60 wt% of the total amount of the insulating resin composition (X).

3.1.1.3. Comparative example 5 to comparative example 6
According to the blending amounts shown in Table 1, 2-HEMA (D-3) was used as the monofunctional vinyl monomer (D) in place of isobornyl methacrylate (D-1) and tetrahydrofurfuryl methacrylate (D-2). An insulating resin composition (X) was prepared in the same manner as in Example 3 except that the following was used.

3.1.1.4. Comparative example 7
An insulating resin composition (X) was prepared in the same manner as in Example 3, except that only isobornyl methacrylate (D-1) was used as the monofunctional vinyl monomer (D) according to the blending amounts shown in Table 1. Prepared.

3.1.1.5. Comparative example 8
An insulating resin composition (X) was prepared in the same manner as in Example 3, except that only tetrahydrofurfuryl methacrylate (D-2) was used as the monofunctional vinyl monomer (D) according to the blending amounts shown in Table 1. Prepared.

3.2. Evaluation The insulating resin composition (X) and its cured product (Y) were evaluated as follows.

3.2.1. Biomass degree The biomass degree of the insulating resin composition (X) was calculated from the number of ¹⁴ C atoms. The measurement method used was a method based on ASTM D6866, and the prepared insulating resin composition (X) was oxidized to carbon dioxide or graphite, then dissolved in a scintillator liquid, and used as a liquid scintillation counter (LSC) measurement sample. did. Next, the number of radioactive carbon ^14C in this sample was measured using a liquid scintillation counter, and the number was determined from the proportion of 14C in the total carbon ( ^12C , ^13C , ^14C ) constituting the insulating resin composition (X). The biomass degree of the insulating resin composition (X) was determined. The obtained results are shown in the "Biomass degree" column of Table 1. Note that the method for measuring ¹⁴ C is not limited to the above method, and for example, accelerator mass spectrometry (AMS) may be used.

3.2.2. Viscosity The viscosity of the insulating resin composition (X) was measured using an E-type viscometer. The results of the measurements at room temperature are shown in the "Total viscosity" column of Table 1.

3.2.3. Mechanical strength (helical coil fixing force)
A helical coil as a test piece was prepared using a linear 1 mm magnet wire (KMK-20E manufactured by Hitachi Metals) in accordance with JISC3216-1 and 6. Next, this helical coil was preheated by heating at 150° C. for 120 minutes, and then cooled to room temperature. These helical coils were gently immersed in the insulating resin composition (X), left to stand for 1 minute, then pulled up, and suspended in a heating furnace with an appropriate interval maintained. These coils were heated for a predetermined period of time to cure the insulating resin composition (X). The heating conditions were 170°C for 2 hours. The helical coil obtained by heating and curing was subjected to a three-point bending test using an autograph (strength testing machine). The evaluation results are shown in the "Strength" column of Table 1. In this evaluation, it is desirable that the adhesion force is 100N or more, and if the adhesion force is 100N or more, it is +, if the adhesion force does not reach 100N, it is -, and if the adhesion force exceeds 120N, it is considered as -. ++.

3.2.4. A sample simulating the stator 19 shown in FIG. 2 was prepared and impregnated with the insulating resin composition (X) listed in Table 1 and cured. The thickness of the cured mass formed on the coil end) and the insulator was measured. The evaluation results are shown in the "Icicle" column of Table 1. In this evaluation, the necessity of removal processing is used as the standard for thicknesses of 10 mm or more that require cutting and shaving, thicknesses of 5 mm or more but less than 10 mm that do not require cutting but require shaving, and 2 mm that require shaving depending on the location. A thickness of less than 5 mm was defined as +, and a thickness of less than 2 mm that required no cutting was defined as ++.

3.2.5. Touchability with fingers The cured product of the insulating resin composition (X) formed on the surface of the sample coil or component simulating the helical coil and stator 19 described above is touched, and the touchability is determined by the presence or absence of finger attachment. was evaluated. The results of the evaluation are shown in the "Touchability" column of Table 1. In this evaluation, the insulating resin composition (X) adheres to the fingers in liquid or gel form, the tackiness is felt but it does not stick to the fingers, and the insulating resin composition (X) is non-tacky and sticks to the fingers. Those with no adhesion were rated +.

3.2.6. Comprehensive Evaluation The insulating resin composition (X) is required to have both mechanical strength and suppression of clumped cured product formation, as well as good touchability and a biomass degree of 60% or more. The results of such comprehensive evaluation are shown in the "Judgment" column of Table 1. In Table 1, the final judgment results are shown as + for those that can satisfy all of these requirements, and - for those that do not satisfy any one or more of the requirements.

3.3. Results and Discussion As can be seen from Table 1, Examples 1 to 9 have improved tactility compared to Comparative Examples 5 and 6. This is because the monofunctional vinyl monomers (D-1) and (D-2), which do not have a highly flexible hydroxyl group in their molecules and have a cyclic skeleton, can suppress moisture adsorption in the air. It is thought that this was due to an accident.

Next, based on the results of Examples 1 to 9 and Comparative Examples 1 to 4, we will discuss the amount of monofunctional vinyl monomers (D-1) and (D-2) derived from biomass materials. .

The total amount of monofunctional vinyl monomers (D-1) and (D-2) was 82 wt% to 84 wt% for Examples 1 and 2, 65 wt% to 78 wt% for Examples 3 to 6, and 65 wt% to 78 wt% for Examples 3 to 6. Examples 7 to 9 are 60 wt% to 64 wt%. In Examples 1 to 6, the thickness of the cured lumps was 2 mm or less, which made removal unnecessary, and the mechanical strength was also a good value exceeding 100 N, which is a standard. In particular, in Examples 3 to 6, the mechanical strength exceeded 120N. In Examples 7 to 9, the mechanical strength exceeded 100N, and the thickness of the cured lumps was 2 mm to 5 mm. In Examples 7 to 9, although the step of removing the clumped cured material cannot be completely eliminated, it is possible to significantly reduce the process time and the number of locations required for processing, resulting in the effect of improving productivity. In Examples 1 to 9, the overall viscosity of the insulating resin composition (X) was 10 mPa·s to 80 mPa·s. Further, in Examples 1 to 9, good results were obtained in terms of touchability after curing.

On the other hand, in Comparative Example 1 and Comparative Example 2, the total amount of monofunctional vinyl monomers (D-1) and (D-2) exceeds 85 wt%. Although the thickness of the cured mass is 2 mm or less, which makes removal completely unnecessary, the required mechanical strength of 100 N cannot be achieved. Furthermore, stickiness was confirmed in some areas when touchable to the fingers. We speculate that this is because the amount of monofunctional vinyl monomer blended is extremely large, and some of it evaporates in the curing furnace without contributing to the curing reaction, filling the furnace and re-adhering to the surface of the coil. . In addition, in Comparative Examples 3 and 4, in which the total amount of monofunctional vinyl monomers (D-1) and (D-2) is 57 wt% or less, mechanical strength was evaluated as +, but bulk hardening The thickness of the object exceeded 5 mm or 10 mm, resulting in a - or -- rating.

This is because the monofunctional vinyl monomer (D) reduces the viscosity of the insulating resin composition (X), thereby contributing to improving drainage properties and suppressing the formation of lumpy cured products. This is because it has a low molecular weight and a property of volatilizing during curing, which affects the reduction in mechanical strength and touchability of the cured product (Y). That is, this is due to the fact that suppression of clumpy cured products, mechanical strength and finger touchability are in a trade-off relationship depending on the blending amount of the monofunctional vinyl monomer (D). As a result of intensive studies in the present disclosure, in order to achieve both of these characteristics, the blending amount of the monofunctional vinyl monomer (D), especially the blending amount of the monofunctional vinyl monomers (D-1) and (D-2). It has become clear that it is sufficient that the amount is from 60 wt% to 84 wt%, and more preferably from 65 wt% to 78 wt%.

Next, from a comparison between Example 3 and Comparative Example 5, the effects of the monofunctional vinyl monomer having a cyclic structure will be discussed. Example 3 contains isobornyl methacrylate (D-1) having a cyclic skeleton and tetrahydrofurfuryl methacrylate (D-2). Comparative Example 5 is an example in which 2-HEMA (D-3) was used instead of these, and the blending amount of the monofunctional vinyl monomer (D) was the same. Although good results are obtained in both cases in terms of the thickness of the clumped cured product of 2 mm or less, there are differences in mechanical strength and touchability. In Example 3 using a monofunctional vinyl monomer having a cyclic structure, the mechanical strength exceeds 120N and the touchability to the fingers is also good. On the other hand, in Comparative Example 5 using 2-HEMA, not only the mechanical strength was less than 100N, but also no improvement in tactility was observed. This is because the molecular skeleton of a monofunctional vinyl monomer with a cyclic skeleton is stronger than 2-HEMA, which has a chain structure, and the monofunctional vinyl monomer with a cyclic skeleton has a high degree of freedom in hydroxyl groups. This is thought to be due to the fact that it has high hydrophobicity (hydrophilicity is suppressed) because it does not have.

Next, from a comparison between Example 3 and Comparative Examples 7 and 8, the effect of using the monofunctional vinyl monomers having two types of cyclic structures together will be discussed. Example 3 contains both isobornyl methacrylate (D-1) having a cyclic skeleton and tetrahydrofurfuryl methacrylate (D-2). Comparative Example 7 and Comparative Example 8 contain only either isobornyl methacrylate (D-1) or tetrahydrofurfuryl methacrylate (D-2). In Example 3, the mechanical strength exceeded 100N, which was a good result, whereas in Comparative Examples 7 and 8, it was revealed that the mechanical strength was less than 100N, although it was slightly. This is considered to be because, in the case of only isobornyl methacrylate (D-1), the bulky isobornyl skeleton inhibits the crosslinked structure and the necessary mechanical strength cannot be obtained. On the other hand, in the case of only tetrahydrofurfuryl methacrylate (D-2), it is considered that the required mechanical strength cannot be obtained because the strength is lower than that of the isobornyl skeleton.

As explained above, in the insulating resin composition (X), (C) the polyfunctional vinyl monomer and (D) the polyfunctional vinyl monomer use plant-derived biomass materials as their raw materials. , which has a higher environmental impact reduction effect than insulating resins made from petroleum-based raw materials. In addition, the insulating resin composition (X) in the present disclosure can obtain biomass mark certification (contains 10% or more of biomass materials) from the government or a third-party organization based on its blending ratio, and contributes to the creation of a recycling-oriented society. I can do it.

Furthermore, the monofunctional vinyl monomer (D) lowers the viscosity of the insulating resin composition (X) and improves the drainability of the insulating resin composition (X) when the coil is pulled up from the immersion tank. This prevents excess insulating resin composition (X) from adhering to the inside of the coil and to the constituent members, and provides the effect of suppressing the formation of a lumpy cured product.

In addition, among the monofunctional vinyl monomers (D) contained in the insulating resin composition (X), a vinyl monomer having an isobornyl skeleton (D-1) and a vinyl monomer having a cyclic ether skeleton (D-1) contains a cyclic skeleton in its molecule, so it has superior heat resistance and strength compared to vinyl monomers with a chain skeleton. As mentioned above, the addition of reactive diluents is effective in reducing the viscosity of insulating resins, but monofunctional monomers with chain structures and small molecular weights are difficult to add in large amounts to achieve the required viscosity. Reduces heat resistance and mechanical strength of cured products. On the other hand, the vinyl monomer (D-1) having an isobornyl skeleton and the vinyl monomer (D-1) having a cyclic ether skeleton used in the present disclosure are monomers with a chain structure due to the effect of the cyclic structure in the molecule. It has superior thermal and mechanical properties compared to Therefore, even if a large amount of these monomers is blended, the heat resistance and strength characteristics of the cured product (Y) are not reduced, and the effect of improving the heat resistance and strength characteristics can be obtained.

Furthermore, the vinyl monomer (D-1) having an isobornyl skeleton and the vinyl monomer (D-1) having a cyclic ether skeleton do not have a highly flexible hydroxyl group in their molecules, so they can be used as reactive diluents. It has lower hydrophilicity than the 2-HEMA used. That is, since the insulating resin composition (X) has a low affinity with moisture in the air, re-adhesion to the surface of the cured product (Y) of the insulating resin composition (X) is prevented, and the effect of improving the surface tactility can be obtained.

Note that the vinyl monomer (D-1) having an isobornyl skeleton and the vinyl monomer (D-1) having a cyclic ether skeleton in the present disclosure are biomass materials, and these are mainly composed of the monofunctional vinyl monomer (D). It is contained as a component in an amount of about 60 wt% to 84 wt%. Therefore, the biomass degree of the insulating resin composition (X) is 60% due to the blending amount of the vinyl monomer (D-1) having an isobornyl skeleton and the vinyl monomer (D-1) having a cyclic ether skeleton. 84% or less.

Therefore, due to the effects described above, an insulating resin composition (X) is provided that can further improve the surface touchability of a cured product while using a biomass material as a raw material.

Note that the scope of the present disclosure is not limited to the examples described above, but should be defined by the claims. The scope of the present disclosure includes all changes that are equivalent to the claims. Furthermore, the scope of the present disclosure includes all changes within the scope of equivalents to the claims.

The rotating machine according to the present disclosure can be applied to a hoisting machine for a rope elevator. The winding coil according to the present disclosure can be applied to the rotating machine. The insulating resin composition and its cured product according to the present disclosure can be applied to maintaining the insulation properties and mechanical strength of the coil.

1 Coil, 2 Insulating resin, 3 Volatile reactive diluent, 4 Moisture, 5 Thin film, 10 Hoisting machine, 11 Rotating part, 12 Brake part, 13 Motor part, 14 Sheave, 15 Rotor, 16 Brake disc, 17 Rotating shaft, 18 Frame, 19 Stator, 20 Iron core, 21 Winding, 22 Insulator

Claims

A thermosetting resin having both an epoxy group and a meth (acryloyl) group,
a radical polymerization reaction initiator and a curing agent for epoxy groups;
A polyfunctional vinyl monomer made from biomass material,
A monofunctional vinyl monomer made from biomass material,
including;
The monofunctional vinyl monomer is
Contains both a vinyl monomer having an isobornyl skeleton and a vinyl monomer having a saturated hydrocarbon cyclic ether skeleton,
The biomass degree is 60% or more and 84% or less,
Insulating resin composition.
The viscosity is 10 mPa・s or more and 80 mPa・s or less,
The insulating resin composition according to claim 1.
A cured product obtained by curing the insulating resin composition according to claim 1 or 2.
A wire-wound coil impregnated with the insulating resin composition according to claim 1 or 2.
A rotating machine used in the hoisting machine that drives the car of a rope elevator.
A rotating machine comprising a stator using the wire-wound coil according to claim 4.