WO2019130586A1

WO2019130586A1 - Prepreg mica tape, coil for rotating electrical machine, and method for manufacturing same

Info

Publication number: WO2019130586A1
Application number: PCT/JP2017/047386
Authority: WO
Inventors: 駿介長井; 貴耶山本; 西山　雅也; 斉藤　晃一; 敬二福島
Original assignee: 日立化成株式会社
Priority date: 2017-12-28
Filing date: 2017-12-28
Publication date: 2019-07-04

Abstract

This prepreg mica tape has: a backing material; and a mica-containing layer which is provided to one surface side of the backing material and which comprises mica, a thermosetting resin, and a curing agent that contains, as an anion species, one of SbF6 -, PF6 -, BF4 -, or (Rf)bPF6-b - (wherein, Rf represents an alkyl group in which at least 80% of hydrogen atoms are substituted by fluorine atoms, and b represents an integer between 1 and 5).

Description

Prepreg mica tape, coil for rotating electrical machine and method of manufacturing the same

The present invention relates to a prepreg mica tape, a coil for a rotating electrical machine, and a method of manufacturing the same.

In the field of a generator employing a method of indirect cooling in which hydrogen gas or air is cooled to the outside of a coil provided with an insulating layer, high thermal conductivity in the thickness direction of the insulating layer of the coil is desired.
As an insulating layer of a coil, a prepreg (resin rich) mica tape composed of a resin, mica and a backing material is often used. In order to increase the thermal conductivity of a prepreg mica tape, a method is often used in which an inorganic filler having a thermal conductivity higher than that of a resin and mica is added to the tape.
On the other hand, in order to improve the reliability of the coil, it is desired that the cured product of the prepreg mica tape has a high glass transition temperature. Therefore, for example, in WO 2015/053374, BF ₃ monoethylamine complex is used as a curing agent for epoxy resin.

When BF ₃ monoethylamine complex is used as a curing agent for epoxy resin, it is possible to realize a high glass transition temperature of a cured product of a prepreg mica tape, but there are problems in coil production.
For example, a hydrostatic pressing method has become mainstream as a method of manufacturing a coil. However, in this method, since it takes time to press in the coil molding process, it is necessary to prolong the gel time of the resin. However, when BF ₃ monoethylamine complex is used, the gel time of the resin tends to be short.
One embodiment of the present invention has been made in view of the above-described conventional circumstances, and is capable of forming a cured product having a high glass transition temperature, and capable of securing a long gel time, and a rotating electrical machine using the same. It aims at providing a coil and its manufacturing method.

The specific means for achieving the said subject are as follows.
<1> backing material,
Provided on one surface side of the backing, and mica, and a thermosetting _{^{_{^{resin, SbF 6 -, PF 6 -}}}} , BF 4 - and _{_{^{(Rf) b PF 6-b}}} - (Rf 80% or more of the hydrogen And M represents a fluorine atom-substituted alkyl group, and b represents an integer of 1 to 5. A curing agent containing any of the following as an anionic species:
Prepreg mica tape.
<2> The prepreg mica tape according to <1>, wherein the cationic species contained in the curing agent contains an aromatic sulfonium cation.
The prepreg mica tape as described in <2> whose <3> above-mentioned aromatic sulfonium cation is a cation seed | species represented with the following general formula (I).

(In the general formula (I), R ¹ and R ² each independently represent an alkyl group, a phenyl group, a benzyl group, a naphthyl group or a naphthylmethyl group. R ³ independently represents an alkyl group, a hydroxy group, Carboxy group, alkoxy group, aryloxy group, alkylcarbonyl group, arylcarbonyl group, aralkylcarbonyl group, aralkylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, aralkylcarbonyloxy group , Alkoxycarbonyloxy group, aryloxycarbonyloxy group, aralkyloxycarbonyloxy group, arylthiocarbonyl group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, alkylsulfinyl group And arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfonyloxy group, arylsulfonyloxy group, hydroxy (poly) alkyleneoxy group, amino group, cyano group, nitro group or halogen atom, n is 0 to 5 Indicates an integer.)
<4> The prepreg mica tape according to <3>, wherein the cationic species represented by the general formula (I) is a cationic species represented by the following general formula (II).

(In the general formula (II), ^{R 1} represents an alkyl group, a benzyl group, a naphthyl group or naphthylmethyl group of 1 to 4 carbon atoms, ^{R 2} is .R ⁴ represents an alkyl group having 1 to 4 carbon atoms Represents a hydrogen atom, an R-CO- group or an R-SO ₂ -group (R represents an alkyl group having 1 to 4 carbon atoms which may be substituted with one or more halogen atoms). Each R ⁵ independently represents an alkyl group having 1 to 4 carbon atoms or a halogen atom, and m represents an integer of 0 to 4.)
<5> R ⁴ in the general formula (II) is an R—CO— group (R represents an alkyl group having 1 to 4 carbon atoms which may be substituted with one or more halogen atoms) Prepreg mica tape described in <4>.
<6> The prepreg mica tape according to <4> or <5>, wherein R ¹ in the general formula (II) is an alkyl group having 1 to 4 carbon atoms.
<7> the anion species, SbF ₆ ^- and is <1> prepreg mica tape according to any one of - <6>.
<8> The prepreg mica tape according to any one of <1> to <7>, wherein the thermosetting resin contains an epoxy resin.
<9> coil conductor,
An insulating layer including the cured product of the laminate of prepreg mica tapes according to any one of <1> to <8> and disposed to cover at least a part of the outer periphery of the coil conductor.
A coil for a rotating electrical machine having a.
<10> A step of forming a laminate of a prepreg mica tape according to any one of <1> to <8>, covering at least a part of the outer periphery of the coil conductor.
Curing the laminate of the prepreg mica tape to form an insulating layer;
The manufacturing method of the coil for rotary electric machines which has.

According to one aspect of the present invention, a prepreg mica tape capable of forming a cured product having a high glass transition temperature and capable of securing a long gel time, a coil for a rotating electrical machine using the same, and a method of manufacturing the same are provided. it can.

Hereinafter, a form for carrying out a prepreg mica tape, a coil for a rotating electrical machine, and a method for manufacturing the same of the present invention will be described in detail. However, the present invention is not limited to the following disclosure. In the following disclosure, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and ranges thereof, and does not limit the present invention.
In the present disclosure, the term “step” includes, in addition to steps independent of other steps, such steps as long as the purpose of the step is achieved even if it can not be clearly distinguished from other steps. .
In the present disclosure, numerical values described before and after “to” are included in the numerical range indicated using “to” as the minimum value and the maximum value, respectively.
The upper limit value or the lower limit value described in one numerical value range may be replaced with the upper limit value or the lower limit value of the other stepwise description numerical value range in the numerical value range described stepwise in the present disclosure. . In addition, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the example.
In the present disclosure, each component may contain a plurality of corresponding substances. When a plurality of substances corresponding to each component are present in the composition, the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified. Means quantity.
In the present disclosure, particles corresponding to each component may contain a plurality of types. When there are a plurality of particles corresponding to each component in the composition, the particle diameter of each component means the value for the mixture of the plurality of particles present in the composition unless otherwise specified.
In the present disclosure, the term “layer” may mean that when the region in which the layer is present is observed, it is formed in only a part of the region, in addition to the case where the region is entirely formed. included.
The term "laminate" in the present disclosure refers to stacking layers, two or more layers may be combined, and two or more layers may be removable.

<< Prepreg mica tape >>
The prepreg mica tape of the present disclosure is provided on a backing material, on one side of the backing material, and mica, thermosetting resin, SbF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ and (Rf) _b PF _{6-b -} ^(. Rf represents an alkyl group in which at least 80% of the hydrogen is substituted with a fluorine atom, b is of an integer of 1 to 5) a curing agent comprising any of the anionic species (hereinafter, specific cure And (d) may be referred to as an agent)).
Since the mica-containing layer of the prepreg mica tape of the present disclosure contains a specific curing agent as a curing agent for a thermosetting resin, the prepreg mica tape of the present disclosure can form a cured product having a high glass transition temperature and is long It is presumed that gel time can be secured.

Prepreg mica tape is also referred to as resin rich mica tape. That is, the composition containing the thermosetting resin is contained in a large amount in advance in the entire prepreg mica tape, and the impregnation varnish is not required to be injected. The content of the composition containing the thermosetting resin is generally in the range of about 15% by mass to 50% by mass relative to the total mass of the prepreg mica tape as described in JP-A-2010-197363. Is set according to the usage.
When the prepreg mica tape is taped on a coil conductor or the like, the prepreg mica tape can be wound on the coil conductor or the like while applying tension, so a compressive force resulting from this tension is applied to the mica-containing layer in the prepreg state. As a result, when the coil conductor or the like wound with the prepreg mica tape is subjected to heat treatment or the like, the transfer of the resin component present in the mica containing layer is more effectively performed, and the mica density of the mica containing layer is increased. The electrical insulation as the insulating material of the disclosed prepreg mica tape can be more effectively exhibited.

The thickness of the prepreg mica tape is preferably 200 μm to 400 μm, and more preferably 250 μm to 350 μm.
The average thickness of the prepreg mica tape is obtained by measuring the thickness at 10 points using a micrometer (MDC-SB, Mitutoyo Co., Ltd.) and calculating the arithmetic average value thereof.

<Layer Configuration of Prepreg Mica Tape>
The configuration of the prepreg mica tape of the present disclosure may be any one having a backing material and a mica-containing layer provided on one surface side of the backing material, and may have other layers as necessary. Good. As other layers, a boron nitride-containing layer including a boron nitride provided on one side of the backing material, a thermosetting resin, and a curing agent for curing the thermosetting resin, and a mica-containing layer of the backing material are provided. The protective layer (protective film) provided in the outermost surface of the other side, an adhesive layer, etc. are mentioned.
When the prepreg mica tape of the present disclosure has a boron nitride-containing layer as another layer, the order of the boron nitride-containing layer and the mica-containing layer provided on one side of the backing material is not particularly limited, and the backing material The boron nitride-containing layer and the mica-containing layer may be sequentially formed, or the backing material, the mica-containing layer and the boron nitride-containing layer may be sequentially formed.
When the prepreg mica tape of the present disclosure has a boron nitride-containing layer as another layer, a boron nitride-containing layer and a mica-containing layer are provided in this order on one surface side of the backing material from the viewpoint of easiness of production. Is preferred.

When the prepreg mica tape of the present disclosure has a boron nitride-containing layer as another layer, the prepreg mica tape can have high thermal conductivity and combine good flexibility and high withstand voltage. The reason why a prepreg mica tape having a boron nitride-containing layer has high thermal conductivity and has both good flexibility and high insulation withstand voltage is not clear, but is presumed as follows.
Since boron nitride contained in the boron nitride-containing layer is a filler exhibiting high thermal conductivity, it is presumed that a prepreg mica tape having a boron nitride-containing layer containing boron nitride has high thermal conductivity.
In addition, since the hardness of boron nitride is about half or less compared to that of alumina, it is presumed that it exhibits better flexibility as compared with a prepreg mica tape using alumina as a high thermal conductivity filler.
Furthermore, by separately providing the boron nitride-containing layer and the mica-containing layer, it is possible to prevent the boron nitride particles from being mixed between the mica pieces. When the boron nitride particles are mixed between the mica pieces, the current path may be shortened and the insulation withstand voltage of the prepreg mica tape may be lowered. However, in the prepreg mica tape having the boron nitride-containing layer, the boron nitride particles are prevented from mixing between mica pieces, so that the current path is unlikely to be short. Therefore, it is surmised that a prepreg mica tape having a boron nitride-containing layer comes to have a high insulation withstand voltage.
Furthermore, by providing both the boron nitride-containing layer and the mica-containing layer on one side of the backing material, the workability at the time of taping the prepreg mica tape to a coil conductor or the like is improved.

-Mica containing layer-
The mica-containing layer according to the present disclosure contains mica, a thermosetting resin and a specific curing agent. The mica-containing layer according to the present disclosure may contain other components other than the mica, the thermosetting resin, and the specific curing agent, as necessary. As other components, various additives can be mentioned, for example.
The thickness of the mica-containing layer is not particularly limited, and is preferably in the range of 100 μm to 250 μm, and more preferably in the range of 110 μm to 230 μm.
For the thickness of the mica-containing layer, observe a secondary electron image at an accelerating voltage of 10 kV under high vacuum after depositing platinum on a cross section of a prepreg mica tape using a scanning electron microscope (SEM) (for example, Philips, XL30) You can ask for it by doing.

The mica-containing layer preferably does not contain any other inorganic filler (such as boron nitride) other than mica, which is used as required. 3 mass% or less is preferable, as for the content rate of other inorganic fillers other than mica which occupy the whole quantity of the inorganic filler contained in a mica containing layer, 2 mass% or less is more preferable, 1 mass% or less is more preferable, and 0 Particularly preferred is mass%.

-Boron nitride containing layer-
The boron nitride-containing layer used as needed contains boron nitride, a thermosetting resin, and a curing agent for curing the thermosetting resin. The boron nitride-containing layer may optionally contain other components other than boron nitride, a thermosetting resin and a curing agent. As other components, various additives can be mentioned, for example.
The thickness of the boron nitride-containing layer is not particularly limited, and is preferably in the range of 80 μm to 200 μm.
For the thickness of the boron nitride-containing layer, after depositing platinum on a cross section of a prepreg mica tape using a scanning electron microscope (SEM) (for example, Philips, XL30), secondary electron images are obtained at an acceleration voltage of 10 kV under high vacuum It can be determined by observing.

The boron nitride-containing layer may contain other inorganic fillers other than boron nitride. The content of boron nitride in the total amount of the inorganic filler contained in the boron nitride-containing layer is preferably 90% by mass to 100% by mass, more preferably 95% by mass to 100% by mass, and 98% by mass. More preferably, it is% to 100% by mass. When the boron nitride-containing layer contains other inorganic fillers other than boron nitride, examples of the other inorganic fillers include alumina, magnesium oxide, aluminum nitride, silicon nitride, silicon oxide and the like.

<Material of prepreg mica tape>
Hereinafter, the backing material, the mica, the thermosetting resin, the specific curing agent, and other materials used as needed, which constitute the prepreg mica tape of the present disclosure, will be described.

-Backing material-
As the backing material used in the present disclosure, for example, a cloth obtained by using all or part of fibers made of an organic material may be used. Examples of the organic material used to obtain the cloth include aramid, polyamide, polyimide, polyester and the like. When a part of fibers composed of an organic material is used, the fibers composed of an organic material may be used as warp, weft or both. Inorganic fibers such as glass fibers may be used as fibers other than fibers composed of organic materials. A glass cloth using glass fiber and an organic polymer film may be used in combination. As the backing material, a glass cloth formed of glass fibers can also be used.

-Mica-
As the mica contained in the mica-containing layer, unfired hard mica, fired hard mica, unfired soft mica, fired soft mica, synthetic mica, flake mica, etc. can be used. Among these, it is preferable to use unfired hard mica as mica from the viewpoint of price and availability.
Further, from the viewpoint of improving the insulating property, it is preferable that the proportion of mica pieces having a particle diameter of 2.8 mm or more when sifted using a JIS standard sieve is 50% by mass or more, and 55% by mass The content is more preferably 60% by mass or more. If the proportion of mica pieces having a particle diameter of 2.8 mm or more is 50% by mass or more, mica paper can stand on its own even without fibrils. It is advantageous to the heat conductivity that it does not put fibrilt.

Specifically, the measurement of the particle size of the mica pieces is carried out according to the following method.
1% by mass of mica to be measured is added to 20 g of pure water, and the mica is dispersed by an ultrasonic dispersion machine to prepare a dispersion. After the dispersion is applied on the film, the film is placed on a hot plate and dried at 110 ° C. for 30 minutes. After drying, the particle size of mica is measured by visually observing the size of mica pieces on the film.
Moreover, the ratio (mass reference | standard) of the mica piece whose particle diameter is 2.8 mm or more is measured by the following method.
Using a JIS standard sieve with an aperture of 2.8 mm, equipped with a low-tapping sieve vibrator, pass 1.2 g of mica through the sieve while vibrating (the number of hammer strokes: 60 times / minute) over 15 minutes. The ratio (mass standard) of mica pieces of 2.8 mm or more is determined from the ratio of coarse particles remaining on the sieve of 2.8 mm with respect to the sample weight before classification.

In the present disclosure, one type of mica may be used alone, or two or more types may be used in combination. When two or more types of mica are used in combination, for example, when two or more types of mica having the same component but different average particle sizes are used, the case where two or more types of mica having the same average particle size but different components are used, and the average particle size and There are cases where two or more kinds of different types of mica are used.

-Thermosetting resin-
As the thermosetting resin used in the present disclosure, epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, cyanate ester resin, polyimide resin, bismaleimide triazine resin, phenol aralkyl resin, etc. It can be used alone or in combination of two or more.
Among the thermosetting resins, epoxy resins are preferred. As the epoxy resin, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin and alicyclic epoxy resin can be used alone or in combination of two or more kinds. .
When the prepreg mica tape of the present disclosure has a boron nitride-containing layer as another layer, the thermosetting resin contained in the boron nitride-containing layer is the same as or different from the thermosetting resin contained in the mica-containing layer. It is also preferable that it is the same.

-Hardener-
As the curing agent used in the present disclosure, SbF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ and (Rf) _b PF _6-b ⁻ (Rf represents an alkyl group in which 80% or more of hydrogen is substituted with a fluorine atom) B is not particularly limited as long as it contains any of 1 to 5) as an anionic species.
_{_{(Rf) b PF 6-b}} - in Rf may each be the same or different.
As Rf, CF ₃ , C ₂ F ₅ , (CF ₃ ) ₂ CF, C ₃ F ₇ , C ₄ F ₉ , (CF ₃ ) ₂ CFCF ₂ , CF ₃ CF ₂ (CF ₃ ) CF, (CF ₃ ) A linear or branched alkyl group having 1 to 4 carbon atoms (perfluoroalkyl group) in which 100% of hydrogen atoms are substituted by fluorine atoms, such as ₃ C, may be used. _{_{(Rf) b PF 6-b}} - The (fluorinated alkyl fluorophosphate _{_{_{_{ion), [(C 2 F 5}}}} ) 3 PF 3] -, [(C 3 F 7) 3 PF 3] -, [(( CF ₃ ) ₂ CF) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ^- , [(CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ ) CFCF _{₂₎ 2} PF _4] ^-, and the like.
Examples of the anionic species, SbF ₆ from the viewpoint of stability of the curing agent ^- preferably a.
When the prepreg mica tape of the present disclosure has a boron nitride-containing layer as another layer, the curing agent contained in the boron nitride-containing layer may be the same as or different from the curing agent contained in the mica-containing layer, and is the same Is preferred.
As a curing agent, other curing agents other than the specific curing agent may be used in combination. Other curing agents include polyfunctional novolac resins, cresol novolac resins, polyfunctional phenol compounds such as aminotriazine novolac resins, amine compounds such as dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, phthalic anhydride, pyromellitic anhydride, and maleic anhydride Examples thereof include acid and acid anhydrides such as maleic anhydride copolymer.
The ratio of the specific curing agent to the curing agent is preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and further preferably 95% by mass to 100% by mass. preferable.

The cationic species to be paired with the anionic species contained in the curing agent is not particularly limited, and aromatic sulfonium cations, aromatic iodonium cations and the like can be used. Among these, the cationic species preferably contains an aromatic sulfonium cation from the viewpoint of the curing agent's potential.

The aromatic sulfonium cation contained as a cationic species in the curing agent is preferably a cationic species represented by the following general formula (I).

In General Formula (I), R ¹ and R ² each independently represent an alkyl group, a phenyl group, a benzyl group, a naphthyl group or a naphthylmethyl group. Each R ³ independently represents an alkyl group, a hydroxy group, a carboxy group, an alkoxy group, an aryloxy group, an alkylcarbonyl group, an arylcarbonyl group, an aralkylcarbonyl group, an alkoxycarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, Alkyl carbonyloxy group, aryl carbonyloxy group, aralkyl carbonyloxy group, alkoxy carbonyloxy group, aryloxy carbonyloxy group, aralkyl oxy carbonyloxy group, arylthio carbonyl group, arylthio group, alkylthio group, aryl group, heterocyclic carbonization Hydrogen group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfonyloxy group, arylsulfonyloxy group, Hydroxy (poly) alkylene oxy group, amino group, cyano group, nitro group or halogen atom is shown. n is an integer of 0 to 5;

In the general formula (I), examples of the alkyl group represented by R ¹ to R ³ include a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 1 to 18 carbon atoms, and a cycloalkenyl having 3 to 18 carbon atoms. An alkyl group etc. are mentioned.
Specific examples of the linear alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-octyl group, n-decyl group and n-dodecyl group. Groups, n-tetradecyl group, n-hexadecyl group, n-octadecyl group and the like.
Specific examples of the branched alkyl group having 1 to 18 carbon atoms include an isopropyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an isopentyl group, a neopentyl group, a t-pentyl group, an isohexyl group and an isooctadecyl group. Etc.
Specific examples of the cycloalkyl group having 3 to 18 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 4-decylcyclohexyl group and the like.

Examples of the alkoxy group represented by R ³ in the general formula (I) include a linear or branched alkoxy group having 1 to 18 carbon atoms.
Specifically as an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, a hexyloxy group, a decyloxy group, a dodecyloxy group, an octadecyloxy group. And the like.

Examples of the aryloxy group represented by R ³ in the general formula (I) include aryloxy groups having 6 to 10 carbon atoms.
Specific examples of the aryloxy group include phenoxy group and naphthyloxy group.

In the general formula (I), examples of the alkylcarbonyl group represented by R ³ include linear or branched alkylcarbonyl groups having 2 to 18 carbon atoms.
Specifically as an alkylcarbonyl group, an acetyl group, a propionyl group, a butanoyl group, a 2-methylpropionyl group, a heptanoyl group, a 2-methylbutanoyl group, a 3-methylbutanoyl group, an octanoyl group, a decanoyl group, a dodecanoyl group, Octadecanoyl group etc. are mentioned.

In the general formula (I), examples of the arylcarbonyl group represented by R ³ include arylcarbonyl groups having 7 to 11 carbon atoms.
Specific examples of the arylcarbonyl group include benzoyl group and naphthoyl group.

Examples of the aralkylcarbonyl group represented by R ³ in the general formula (I) include lower alkylcarbonyl groups substituted with an aryl group having 6 to 10 carbon atoms.
Specific examples of the aralkylcarbonyl group include benzylcarbonyl group, 2-methylbenzylcarbonyl group, 1-naphthylmethylcarbonyl group, 2-naphthylmethylcarbonyl group and the like.

Examples of the alkoxycarbonyl group represented by R ³ in the general formula (I) include a linear or branched alkoxycarbonyl group having 2 to 19 carbon atoms.
Specific examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, t-butoxycarbonyl, octyloxycarbonyl Groups, tetradecyloxycarbonyl group, octadecyloxycarbonyl group and the like.

Examples of the aryloxycarbonyl group represented by R ³ in the general formula (I) include an aryloxycarbonyl group having 7 to 11 carbon atoms.
Specific examples of the aryloxycarbonyl group include phenoxy carbonyl group and naphthoxycarbonyl group.

In the general formula (I), examples of the aralkyloxycarbonyl group represented by R ³ include a lower alkoxycarbonyl group substituted with an aryl group having 6 to 10 carbon atoms.
Specific examples of the aralkyloxycarbonyl group include benzyloxycarbonyl group, 2-methylbenzyloxycarbonyl group, 1-naphthylmethyloxycarbonyl group, 2-naphthylmethyloxycarbonyl group and the like.

In the general formula (I), examples of the alkylcarbonyloxy group represented by R ³ include linear or branched alkylcarbonyloxy groups having 2 to 19 carbon atoms.
Specifically as an alkyl carbonyloxy group, an acetoxy group, an ethyl carbonyloxy group, a propyl carbonyloxy group, an isopropyl carbonyloxy group, a butyl carbonyloxy group, an isobutyl carbonyloxy group, a sec-butyl carbonyloxy group, a t-butyl carbonyloxy group Groups, octyl carbonyloxy group, tetradecyl carbonyloxy group, octadecyl carbonyloxy group and the like.

Examples of the arylcarbonyloxy group represented by R ³ in the general formula (I) include arylcarbonyloxy groups having 7 to 11 carbon atoms.
Specific examples of the arylcarbonyloxy group include benzoyloxy group and naphthoyloxy group.

In the general formula (I), examples of the aralkylcarbonyloxy group represented by R ³ include lower alkylcarbonyloxy groups substituted with aryl groups having 6 to 10 carbon atoms.
Specific examples of the aralkylcarbonyloxy group include benzylcarbonyloxy group, 2-methylbenzylcarbonyloxy group, 1-naphthylmethylcarbonyloxy group, 2-naphthylmethylcarbonyloxy group and the like.

Examples of the alkoxycarbonyloxy group represented by R ³ in the general formula (I) include a linear or branched alkoxycarbonyloxy group having 2 to 19 carbon atoms.
Specific examples of the alkoxycarbonyloxy group include methoxycarbonyloxy group, ethoxycarbonyloxy group, propoxycarbonyloxy group, isopropoxycarbonyloxy group, butoxycarbonyloxy group, isobutoxycarbonyloxy group, sec-butoxycarbonyloxy group, t And -butoxycarbonyloxy group, octyloxycarbonyloxy group, tetradecyloxycarbonyloxy group, octadecyloxycarbonyloxy group and the like.

Examples of the aryloxycarbonyloxy group represented by R ³ in the general formula (I) include an aryloxycarbonyloxy group having 7 to 11 carbon atoms.
Specific examples of the aryloxycarbonyloxy group include phenoxycarbonyloxy group and naphthoxycarbonyloxy group.

In the general formula (I), examples of the aralkyloxycarbonyloxy group represented by R ³ include lower alkoxycarbonyloxy groups substituted with an aryl group having 6 to 10 carbon atoms.
Specific examples of the aralkyloxycarbonyloxy group include benzyloxycarbonyloxy group, 2-methylbenzyloxycarbonyloxy group, 1-naphthylmethyloxycarbonyloxy group, 2-naphthylmethyloxycarbonyloxy group and the like.

Examples of the arylthiocarbonyl group represented by R ³ in the general formula (I) include arylthiocarbonyl groups having 7 to 11 carbon atoms.
Specific examples of the arylthiocarbonyl group include phenylthiocarbonyl group and naphthylthiocarbonyl group.

Examples of the arylthio group represented by R ³ in the general formula (I) include arylthio groups having 6 to 20 carbon atoms.
Specific examples of the arylthio group include phenylthio group, 2-methylphenylthio group, 3-methylphenylthio group, 4-methylphenylthio group, 2-chlorophenylthio group, 3-chlorophenylthio group, 4-chlorophenylthio group, 2-bromophenylthio group, 3-bromophenylthio group, 4-bromophenylthio group, 2-fluorophenylthio group, 3-fluorophenylthio group, 4-fluorophenylthio group, 2-hydroxyphenylthio group, 4 -Hydroxyphenylthio group, 2-methoxyphenylthio group, 4-methoxyphenylthio group, 1-naphthylthio group, 2-naphthylthio group, 4- [4- (phenylthio) benzoyl] phenylthio group, 4- [4- (phenylthio) group ) Phenoxy] phenylthio group, 4- [4- (phenylthio) phenyl] 4- (phenylthio) phenylthio group, 4-benzoylphenylthio group, 4-benzoyl-2-chlorophenylthio group, 4-benzoyl-3-chlorophenylthio group, 4-benzoyl-3-methylthiophenylthio group, 4 -Benzoyl-2-methylthiophenylthio group, 4- (4-methylthiobenzoyl) phenylthio group, 4- (2-methylthiobenzoyl) phenylthio group, 4- (p-methylbenzoyl) phenylthio group, 4- (p-ethylbenzoyl) And the like), phenylthio group, 4- (p-isopropylbenzoyl) phenylthio group, 4- (pt-butylbenzoyl) phenylthio group and the like.

In the general formula (I), examples of the alkylthio group represented by R ³ include linear or branched alkylthio groups having 1 to 18 carbon atoms.
Specific examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group, t-butylthio group, pentylthio group, isopentylthio group, neopentylthio group. And t-pentylthio group, octylthio group, decylthio group, dodecylthio group, isooctadecylthio group and the like.

Examples of the aryl group represented by R ³ in the general formula (I) include aryl groups having 6 to 10 carbon atoms.
Specific examples of the aryl group include phenyl group, tolyl group, dimethylphenyl group and naphthyl group.

Examples of the heterocyclic hydrocarbon group represented by R ³ in the general formula (I) include heterocyclic hydrocarbon groups having 4 to 20 carbon atoms.
Specific examples of the heterocyclic hydrocarbon group include thienyl group, furanyl group, pyranyl group, pyrrolyl group, oxazolyl group, thiazolyl group, pyridyl group, pyrimidyl group, pyrazinyl group, indolyl group, benzofuranyl group, benzothienyl group, quinolyl. Group, isoquinolyl group, quinoxalinyl group, quinazolinyl group, carbazolyl group, acridinyl group, phenothiazinyl group, phenazinyl group, xanthenyl group, tianthrenyl group, phenoxazinyl group, phenoxatinyl group, chromanyl group, isochromanyl group, dibenzothienyl group, xanthonyl group Groups, thioxanthonyl groups, dibenzofuranyl groups and the like.

In the general formula (I), examples of the alkylsulfinyl group represented by R ³ include linear or branched alkylsulfinyl groups having 1 to 18 carbon atoms.
Specific examples of the alkylsulfinyl group include methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, isobutylsulfinyl group, sec-butylsulfinyl group, t-butylsulfinyl group, pentylsulfinyl group, iso Examples thereof include pentylsulfinyl group, neopentylsulfinyl group, t-pentylsulfinyl group, octylsulfinyl group, isooctadecylsulfinyl group and the like.

In the general formula (I), examples of the arylsulfinyl group represented by R ³ include arylsulfinyl groups having 6 to 10 carbon atoms.
Specific examples of the arylsulfinyl group include phenylsulfinyl group, tolylsulfinyl group, and naphthylsulfinyl group.

In the general formula (I), examples of the alkylsulfonyl group represented by R ³ include a linear or branched alkylsulfonyl group having 1 to 18 carbon atoms.
Specific examples of the alkylsulfonyl group include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, isobutylsulfonyl group, sec-butylsulfonyl group, t-butylsulfonyl group, pentylsulfonyl group, iso Examples thereof include pentyl sulfonyl group, neopentyl sulfonyl group, t-pentyl sulfonyl group, octyl sulfonyl group, octadecyl sulfonyl group and the like.

Examples of the arylsulfonyl group represented by R ³ in the general formula (I) include an arylsulfonyl group having 6 to 10 carbon atoms.
Specific examples of the arylsulfonyl group include phenylsulfonyl group, tolylsulfonyl group (tosyl group), and naphthylsulfonyl group.

In the general formula (I), examples of the alkylsulfonyloxy group represented by R ³ include linear or branched alkylsulfonyloxy groups having 1 to 18 carbon atoms.
Specifically, as the alkylsulfonyloxy group, methylsulfonyloxy group, ethylsulfonyloxy group, propylsulfonyloxy group, isopropylsulfonyloxy group, butylsulfonyloxy group, isobutylsulfonyloxy group, sec-butylsulfonyloxy group, t-butyl A sulfonyloxy group, a pentyl sulfonyloxy group, an isopentyl sulfonyloxy group, a neopentyl sulfonyloxy group, a t-pentyl sulfonyloxy group, an octyl sulfonyloxy group, an octadecyl sulfonyloxy group and the like can be mentioned.

Examples of the arylsulfonyloxy group represented by R ³ in the general formula (I) include an arylsulfonyloxy group having 6 to 10 carbon atoms.
Specific examples of the arylsulfonyloxy group include phenylsulfonyloxy group, tolylsulfonyloxy group, and naphthylsulfonyloxy group.

In the general formula (I), as the hydroxy (poly) alkyleneoxy group represented by R ³ , [HO (-AO) _q- (AO represents at least one of an ethyleneoxy group and a propyleneoxy group, and q is 1 to The integer of 5 is shown.)], Etc. are mentioned.

In the general formula (I), examples of the amino group represented by R ³ include an amino group (—NH ₂ ), a substituted amino group having 1 to 15 carbon atoms, and the like.
Specifically as a substituted amino group, methylamino group, dimethylamino group, ethylamino group, methylethylamino group, diethylamino group, n-propylamino group, methyl-n-propylamino group, ethyl-n-propylamino group Isopropylamino, isopropylmethylamino, isopropylethylamino, diisopropylamino, phenylamino, diphenylamino, methylphenylamino, ethylphenylamino, n-propylphenylamino, isopropylphenylamino and the like It can be mentioned.

Examples of the halogen atom represented by R ³ in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the formula (1), n represents the number of R ³ and is preferably an integer of 0 to 5, more preferably 0 to 3, still more preferably 0 to 2, particularly preferably 0 or 1 It is.

Each group represented by R ¹ to R ³ may further have a substituent. Specific examples of the substituent include an alkyl group, an aryl group, an amino group, a cyano group, a nitro group, a halogen atom and the like.

The cation represented by the general formula (I) is preferably a cation represented by the general formula (II).

In the general formula (II), R ¹ represents an alkyl group having 1 to 4 carbon atoms, a benzyl group, a naphthyl group or a naphthylmethyl group, and R ² represents an alkyl group having 1 to 4 carbon atoms. R ⁴ is a hydrogen atom, R-CO- group or R-SO ₂ -group (R represents an alkyl group having 1 to 4 carbon atoms which may be substituted by one or more halogen atoms). Show. Each R ⁵ independently represents an alkyl group having 1 to 4 carbon atoms or a halogen atom. m is an integer of 0 to 4;

In the general formula (II), specific examples of the alkyl group having 1 to 4 carbon atoms in R ¹ , R ² , R ⁴ or R ⁵ include methyl, ethyl, n-propyl, isopropyl and n- Examples thereof include a butyl group, an isobutyl group, a sec-butyl group and a t-butyl group. m is an integer of 0 to 4, preferably 0 to 3, more preferably 0 to 2, and still more preferably 0 or 1.

In the general formula (II), R ⁴ is an R-CO- group or an R-SO ₂ -group (R is an alkyl group having 1 to 4 carbon atoms which may be substituted with one or more halogen atoms Is preferable, and R-CO- group is more preferable. The R-CO- group represented as R ⁴ is more preferably an acetyl group.
When R ⁴ is an R-CO- group, specific examples of the R ⁴ O- group are those having 2 to 5 carbon atoms of the specific examples when R ³ in the general formula (I) is an alkylcarbonyloxy group It is similar to Also, specific examples of the R ⁴ O- group when R ⁴ is a R-SO ₂ -group are the carbon numbers of the specific examples when R ³ in the general formula (I) is an alkylsulfonyloxy group It is similar to that of 1 to 4.

In the general formula (I) or the general formula (II), R ¹ is preferably an alkyl group, a naphthyl group or a naphthylmethyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and a methyl group It is further preferred that
In general formula (I) or general formula (II), the preferable combination of ^{R 1} and ^{R 2,} ^{R 1} and ^{R 2} are both include a combination of a methyl group.

Specific examples of the specific curing agent include dimethyl-p-acetoxyphenylsulfonium = hexafluoroantimonate, benzylmethyl p-hydroxyphenylsulfonium = hexafluoroantimonate, dimethylacetoxyphenylsulfonium = fluorinated alkyl fluorophosphate and the like.

The content of the curing agent is not particularly limited. The ratio of the curing agent to the thermosetting resin is preferably 0.001 to 0.05 in mass ratio (curing agent / thermosetting resin). From the viewpoint of increasing the glass transition temperature of the cured product, it is more preferable to set it to 0.004 to 0.05, and from the viewpoint of increasing the gel time, it is more preferable to set it to 0.004 to 0.015, and the catalyst From the viewpoint of reducing the amount used, it is particularly preferable to set it to 0.004 to 0.01.

-Boron Nitride-
Boron nitride may be used as a means for increasing the thermal conductivity of the prepreg mica tape.
Examples of boron nitride contained in the boron nitride-containing layer include hexagonal boron nitride (h-BN), cubic boron nitride (c-BN), wurtzite boron nitride and the like. Among these, hexagonal boron nitride (h-BN) is preferable. The boron nitride may be a primary particle of boron nitride formed in a scaly shape or a secondary particle formed by aggregating such primary particles.

The average particle diameter of boron nitride is preferably 1 μm to 40 μm, more preferably 5 μm to 20 μm, and still more preferably 5 μm to 10 μm.
When the average particle diameter of boron nitride is 1 μm or more, the thermal conductivity and the insulation withstand voltage tend to be further improved. It can suppress that the anisotropy of the heat conductivity by the anisotropy of particle shape becomes it large that the average particle diameter of boron nitride is 40 micrometers or less is too large.

The average particle size of boron nitride can be measured by using a laser diffraction / scattering particle size distribution measuring apparatus (for example, Microtrac MT3000II, Nikkiso Co., Ltd.). After the boron nitride powder is introduced into pure water, it is dispersed by an ultrasonic dispersion machine. The particle size distribution of boron nitride is measured by measuring the particle size distribution of this dispersion. Based on the particle size distribution, the average particle size is determined as the particle size corresponding to 50% of the volume accumulation from the small diameter side.

One type of boron nitride may be used alone, or two or more types may be used in combination. When two or more types of boron nitride are used in combination, for example, when using two or more types of boron nitride having the same component and different average particle sizes, the case of using two or more types of boron nitride having the same average particle size and different components The case where two or more types of boron nitrides different in particle diameter and type are used may be mentioned.

When the prepreg mica tape of the present disclosure has a boron nitride-containing layer, the boron nitride content is 10% by volume to 50% of the total amount of the solid content excluding the backing material and mica contained in the prepreg mica tape. It is preferably volume%, more preferably 15 volume% to 35 volume%. If the content of boron nitride is 10% by volume or more, the thermal conductivity of the prepreg mica tape tends to be further improved. If the content of boron nitride is 50% by volume or less, the filling of the boron nitride into the resin tends to be difficult.

-Additive-
The additives used in the present disclosure may include various additives generally used in resin compositions, such as coupling agents, elastomers, antioxidants, anti-aging agents, stabilizers, flame retardants, thickeners and the like. it can. The content of these additives is not particularly limited as long as the effects of the present disclosure are not impaired.
In addition, a curing retarder can be used for the purpose of suppressing the curing rate of the curing agent. The content of the curing retarder can be appropriately set according to the curing rate, and is not particularly limited as long as the effects of the present disclosure are not impaired.

<Production method of prepreg mica tape>
The prepreg mica tape may be produced through any process, and a conventionally known production method can be applied.
As an example of a method for producing a prepreg mica tape, a resin varnish preparing step of preparing a resin varnish in which a thermosetting resin, a curing agent and boron nitride and other materials used as needed are mixed in a solvent, and a resin varnish And the pasting process of pasting mica paper on the side of the backing material on which the resin varnish is applied.
As another example of a method for producing a prepreg mica tape, a resin varnish preparing step of preparing a resin varnish in which a thermosetting resin, a curing agent and boron nitride and other materials used as needed are mixed in a solvent, The method includes a laminating step of laminating a backing material and mica paper to obtain a laminate, and an applying step of applying a resin varnish from the backing material side of the laminate.

When the resin varnish contains boron nitride, the resin may be diluted with a solvent in order to fill the thermosetting resin with boron nitride. As a solvent to be used, it is suitably selected from the organic solvent used normally. Specifically, solvents such as methyl ethyl ketone, methanol and cyclohexanone can be mentioned.

When the resin varnish contains boron nitride, in the coating step, the resin varnish is applied to one surface side of the backing material, and the resin varnish is dried to form a boron nitride-containing layer. By impregnating the mica paper laminated on the coated side of the resin varnish in the backing material with the thermosetting resin and the curing agent contained in the resin varnish, the portion which was the mica paper is a mica-containing layer Be done.

When the prepreg mica tape of the present disclosure has a boron nitride-containing layer together with a mica-containing layer, the thermosetting resin and the curing agent in the mica-containing layer and the heat in the boron nitride-containing layer of the prepreg mica tape produced through the above steps Both the curable resin and the curing agent are of the same type originating from the thermosetting resin and the curing agent contained in the resin varnish.
In addition, when the resin varnish contains boron nitride, when the resin varnish is applied to one surface side of the backing material in the coating step, when a cloth such as glass cloth is used as the backing material, part of the resin varnish is the backing material It may exude to the other side of the By drying this, a boron nitride-containing layer may be formed on the other surface side of the backing material. A prepreg mica tape having a boron nitride-containing layer formed on the other side of the backing material is also included in the scope of the prepreg mica tape of the present disclosure.

The prepreg mica tape of the present disclosure can be used to form an insulating layer of a coil conductor. The prepreg mica tape of the present disclosure can also be used as a heat-resistant, electrically-insulating, heat-radiating spacer, for example, as a material for improving the heat radiation of a power transistor heat-dissipating insulating plate.

<< Coil for electric rotating machine >>
The coil for a rotating electrical machine of the present disclosure has a coil conductor, and an insulating layer including a cured product of the laminate of the prepreg mica tape of the present disclosure and covering at least a part of the outer periphery of the coil conductor.
The insulating layer contained in the coil for a rotating electrical machine of the present disclosure includes the cured product of the laminate of the prepreg mica tape of the present disclosure, so the glass transition temperature of the insulating layer can be increased. Therefore, the coil for a rotating electrical machine of the present disclosure is excellent in heat resistance.
The material, shape, size and the like of the coil conductor used for the coil for a rotating electrical machine of the present disclosure are not particularly limited, and can be selected according to the application and the like of the coil for a rotating electrical machine.

<< Method of manufacturing coil for rotary electric machine >>
The method of manufacturing a coil for a rotating electrical machine according to the present disclosure comprises the steps of forming a laminate of the prepreg mica tape of the present disclosure covering at least a part of the outer periphery of the coil conductor, curing the laminate of the prepreg mica tape and insulating Forming a layer.
The process in particular of forming the laminated body of a prepreg mica tape is not restrict | limited, The method normally performed can be employ | adopted. For example, there is a method of winding mica tape around the outer periphery of the coil conductor. In this case, the prepreg mica tape may be wound multiple times so that parts (for example, a half of the width of the prepreg mica tape) overlap each other.
The step of forming the insulating layer is not particularly limited, and a method which is usually performed can be employed. For example, a thermosetting resin is cured by heating and pressing a coil conductor covered at least a part of the outer periphery with a laminate of a prepreg mica tape or after vacuum treatment, thereby curing a thermosetting resin and a prepreg mica tape Are integrated to form an insulating layer.
The prepreg mica tape of the present disclosure can ensure a long gel time, so the method of manufacturing a coil for a rotating electrical machine of the present disclosure can extend the pressing time.

Hereinafter, the present disclosure will be specifically described by way of examples, but the present disclosure is not limited to these examples.

Example 1
(1) Preparation of mica paper mica (a content of mica pieces having a particle diameter of 2.8 mm or more is 63% by mass) is dispersed in water to form mica particles, which are made into paper by a paper machine and mica having an average thickness of 0.13 mm Paper was made. The average thickness of mica paper was obtained by measuring the thickness of 10 points using a micrometer (Mitutoyo, MDC-SB) and calculating the arithmetic average value thereof.

(2) Preparation of resin varnish 143 parts by mass of epoxy resin (Dow Chemical Japan Ltd., trade name "DEN 438") and 1.0 parts by mass of dimethyl-p-acetoxyphenylsulfonium = hexafluoroantimonate as a curing agent, As a solvent, 173 parts by mass of methyl ethyl ketone (Wako Pure Chemical Industries, Ltd.) was mixed. Thereafter, 144 parts by mass of boron nitride (average particle diameter: 5 μm, Denka Co., Ltd., trade name “SP-3”) was added and further mixed to obtain a resin varnish.
In addition, the content rate of boron nitride in the total solid volume of a resin varnish was 35 volume%.

(3) Preparation of Prepreg Mica Tape The obtained resin varnish was applied to a glass cloth (SOHYO Co., Ltd., WEA 03G 103) with a roll coater, and was further bonded to mica paper. After drying, it was cut into a width of 30 mm to form a prepreg mica tape. The average thickness of the obtained prepreg mica tape was 280 μm. The average thickness of the prepreg mica tape was determined by measuring the thickness of 10 points using a micrometer (Mitutoyo, MDC-SB) and calculating the arithmetic average value thereof. Hereinafter, the average thickness of the prepreg mica tape was measured by the same method.

(4) Preparation of prepreg mica tape cured product The prepreg mica tape obtained by the above-described method was heated at 110 ° C. for 10 minutes under a pressure of 10 MPa. Then, the pressure was 10 MPa and heating was performed at 170 ° C. for 60 minutes to obtain a prepreg mica tape cured product. The average thickness of the obtained prepreg mica tape cured product was 180 μm. The average thickness of the cured prepreg mica tape was determined by measuring the thickness of 10 points using a micrometer (Mitutoyo, MDC-SB) and calculating the arithmetic average value thereof.

<Evaluation>
The following evaluation was performed about the resin varnish obtained above, a prepreg mica tape, and a prepreg mica tape hardened | cured material. The results are shown in Table 1.

(Geltime of resin varnish)
The gel time of the obtained resin varnish was measured using a rheometer (Anton Pearl, MCR 301, frequency 1 Hz, swing angle 1%, temperature 120 ° C.). The point at which the storage elastic modulus value exceeded the loss elastic modulus value was defined as the gelation point for 0 minutes when the retention at 120 ° C. was started, and the gel time was determined as the gel time. As the gel time of the resin varnish becomes longer, the gel time of the prepreg mica tape also becomes longer.

(Glass transition temperature of cured resin varnish)
A cured product of the obtained resin varnish was prepared by placing an appropriate amount of resin varnish on an aluminum cup and heating at 170 ° C. for 10 hours. The visco-elastic property of the cured product of the resin varnish is measured using a visco-elastic device (TA Instrumental, RSAG2, frequency 10 Hz, load 50 g, heating rate 5 ° C./min), and the peak top temperature of tan δ is glass transition temperature And

(Glass transition temperature of prepreg mica tape cured product)
The visco-elastic characteristics of the obtained prepreg mica tape cured product are measured using a visco-elastic device (TA Instrumental, RSAG2, frequency 10 Hz, load 50 g, heating rate 5 ° C./min), and the peak top temperature of tan δ As the glass transition temperature.

(Thermal conductivity)
The heat resistance value of the mica tape cured product was measured for the obtained prepreg mica tape cured product, using a heat resistance device (Yayodo Tester Co., Ltd., YST-901S). The thermal conductivity (W / (m · K)) was calculated by back-calculating the obtained thermal resistance value.

Example 2
It produced and evaluated like Example 1 except having used dimethyl acetoxy phenyl sulfonium = fluorinated alkyl fluorophosphate as a hardening agent.

Example 3
The same preparation and evaluation as in Example 1 were carried out except that benzyl methyl p-hydroxyphenyl sulfonium = hexafluoroantimonate was used as a curing agent.

Comparative Example 1
Except for using the BF ₃ monoethylamine complex as the curing agent, it was prepared and evaluated in the same manner as in Example 1.

Comparative Example 2
The same preparation and evaluation as in Comparative Example 1 were carried out except that the amount of the curing agent used was 4.3 parts by mass.

In Table 1, "-" means that the corresponding component is not contained.

As apparent from the evaluation results in Table 1, according to the present disclosure, a prepreg mica tape having a high glass transition temperature, a long gel time, and a good coil moldability can be provided. In the comparative example, either high glass transition temperature or long gel time can not be satisfied.

All documents, patent applications, and technical standards described herein are as specific and distinct as when individual documents, patent applications, and technical standards are incorporated by reference. Incorporated herein by reference.

Claims

Backing material,
Provided on one surface side of the backing, and mica, and a thermosetting resin, SbF 6 -, PF 6 - , BF 4 - and (Rf) b PF 6-b - (Rf 80% or more of the hydrogen And M represents a fluorine atom-substituted alkyl group, and b represents an integer of 1 to 5. A curing agent containing any of the following as an anionic species:
Prepreg mica tape.
The prepreg mica tape according to claim 1, wherein the cationic species contained in the curing agent contains an aromatic sulfonium cation.
The prepreg mica tape according to claim 2, wherein the aromatic sulfonium cation is a cationic species represented by the following general formula (I).

(In the general formula (I), R 1 and R 2 each independently represent an alkyl group, a phenyl group, a benzyl group, a naphthyl group or a naphthylmethyl group. R 3 independently represents an alkyl group, a hydroxy group, Carboxy group, alkoxy group, aryloxy group, alkylcarbonyl group, arylcarbonyl group, aralkylcarbonyl group, aralkylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, aralkylcarbonyloxy group , Alkoxycarbonyloxy group, aryloxycarbonyloxy group, aralkyloxycarbonyloxy group, arylthiocarbonyl group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, alkylsulfinyl group And arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfonyloxy group, arylsulfonyloxy group, hydroxy (poly) alkyleneoxy group, amino group, cyano group, nitro group or halogen atom, n is 0 to 5 Indicates an integer.)
The prepreg mica tape according to claim 3, wherein the cationic species represented by the general formula (I) is a cationic species represented by the following general formula (II).

(In the general formula (II), R 1 represents an alkyl group, a benzyl group, a naphthyl group or naphthylmethyl group of 1 to 4 carbon atoms, R 2 is .R 4 represents an alkyl group having 1 to 4 carbon atoms Represents a hydrogen atom, an R-CO- group or an R-SO 2 -group (R represents an alkyl group having 1 to 4 carbon atoms which may be substituted with one or more halogen atoms). Each R 5 independently represents an alkyl group having 1 to 4 carbon atoms or a halogen atom, and m represents an integer of 0 to 4.)
The R 4 in the general formula (II) is an R-CO- group (R represents an alkyl group having 1 to 4 carbon atoms which may be substituted by one or more halogen atoms). The prepreg mica tape according to 4.
The prepreg mica tape according to claim 4 or 5, wherein R 1 in the general formula (II) is an alkyl group having 1 to 4 carbon atoms.
The anionic species, SbF 6 - prepreg mica tape according to any one of claims 1 to 6.
The prepreg mica tape according to any one of claims 1 to 7, wherein the thermosetting resin contains an epoxy resin.
Coil conductor,
An insulating layer that includes a cured product of the laminate of prepreg mica tapes according to any one of claims 1 to 8, and is disposed to cover at least a part of the outer periphery of the coil conductor.
A coil for a rotating electrical machine having a.
A process of forming a laminate of a prepreg mica tape according to any one of claims 1 to 8, which covers at least a part of the outer periphery of the coil conductor.
Curing the laminate of the prepreg mica tape to form an insulating layer;
The manufacturing method of the coil for rotary electric machines which has.