JP2011089059A - Epoxy resin composition, method for producing electrically insulated wire ring and rotary electric machine by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition equipped with a long term usable life, an excellent heat resistance and an electrical insulating properties, or to provide a method for producing a rotary electric machine and an electrically insulated wire ring by using the same. <P>SOLUTION: The epoxy resin composition includes an epoxy resin and onium salt [I] expressed by chemical formula (1) [wherein, A is a cationic site of an acid generator from which a cationic moiety is generated by light or heat; X is a compound having a negative electric charge such as -SO<SB>3</SB><SP>-</SP>, -PO<SB>3</SB><SP>-</SP>, -CO<SB>2</SB><SP>-</SP>, -SO<SB>2</SB><SP>-</SP>, -NO<SB>2</SB><SP>-</SP>, -CN<SP>-</SP>or -SH<SP>-</SP>; and B is a compound obtained by continuously bonding ≥8 atoms selected from the group consisting of carbon, oxygen and nitrogen to form an organic chemical bond with the X]. A method for producing the electrically insulated wire ring and the rotary electric machine by using the epoxy resin composition is also provided. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an epoxy resin composition, an electrically insulated wire ring using the same, and a method for manufacturing a rotating electrical machine. In particular, the present invention relates to an epoxy resin composition having a long service life, heat resistance, and electrical insulation, and an electrical insulated wire ring and a rotating electrical machine manufacturing method using the same.

  A conductor part to which a high voltage is applied, such as a rotating electrical machine or an electric insulated wire ring, is usually impregnated with a thermosetting resin, and a thermosetting resin is adhered to the periphery thereof to obtain necessary electric insulation ( For example, Patent Document 1 and Patent Document 2).

As a required characteristic of resin used for rotating electrical machines and electrical insulated wire rings,
(1) In order to withstand a high temperature environment during operation of a rotating electrical machine or the like, the glass transition temperature indicating the heat resistance of the epoxy resin composition is high,
(2) In order to electrically insulate a conductor part to which a high voltage is applied, such as a rotating electrical machine, the volume resistivity indicating the electrical insulation characteristics of the epoxy resin composition is high,
At present, an epoxy resin composition composed of an epoxy resin and an acid anhydride is mainly used (for example, Patent Document 1).

  However, an epoxy resin composition composed of an epoxy resin and an acid anhydride, when stored for a long period of time or used multiple times, a curing reaction between a free acid and an epoxy resin produced by a hydrolysis reaction of an acid anhydride, or an epoxy resin Since the curing reaction of the hydroxyl groups present therein and the acid anhydride groups contained in the curing agent proceeds, there is a problem that the viscosity of the resin increases and the gaps and details of the conductor member cannot be sufficiently impregnated with the resin ( For example, Patent Document 2).

  In addition, there are problems such as a drop in workability such as disposal of resin that has become unusable and reduction of waste resin, such as mixing and mixing only a minimum amount of use each time.

  For this reason, resins that are used in rotating electrical machines, electrical insulated wire rings, and the like are expected to have a significantly longer usable life. Epoxy that does not use acid anhydride, which is considered a material that can shorten the usable life. Resin compositions are being studied.

  For example, in Patent Document 3, there is a method of achieving both a long usable life and heat resistance of a cured resin by using an epoxy resin composition composed of an epoxy resin and a sulfonium salt which is a kind of onium salt.

JP 2000-239356 A JP 2000-297204 A JP 2005-245143 A JP 2006-199778 A

However, the method described in Patent Document 3 considers the usable life and heat resistance of the epoxy resin composition, but does not consider the volume resistivity that is an index of electrical insulation of the resin alone. It is generally known that anion sites (for example, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ^−, etc.) frequently used in onium salts such as sulfonium salts remain as ionic impurities in the cured product. (For example, Patent Document 4), there is a concern about a decrease in electrical insulation due to the remaining of such impurities.

  From the background as described above, it is necessary to develop an epoxy resin composition that solves the above-mentioned problems, and the problem of the present invention is that the epoxy resin composition has a long usable life and an excellent cured product. It is to achieve both heat resistance and electrical insulation.

  The epoxy resin composition of the present invention is an epoxy resin composition containing an epoxy resin and an onium salt [I] represented by the following chemical formula (1), and the compound has the following characteristics.

In the above chemical formula (1),
A is a cation site of an acid generator that generates a cationic species by light or heat,
X is a compound having a negative _{^{charge, -SO 3 -, -PO 3 -}} , -CO 2 -, -SO 2 -, -NO 2 -, -CN - or -SH, ^-,
B is a compound in which 8 or more atoms selected from the group consisting of carbon, oxygen, and nitrogen are continuously bonded, and is formed through organic chemical bonding with X.

  According to this invention, an epoxy resin composition having a long usable life, excellent heat resistance and electrical insulation can be obtained. Furthermore, by using it, an electrically insulated wire ring and a rotating electrical machine having excellent heat resistance and electrical insulation can be provided.

(A) And (b) is typical explanatory drawing for demonstrating an example of a rotary electric machine.

  Hereinafter, the present invention will be described in more detail. In the following description of the embodiments, the description is made with reference to the drawings. In the drawings of the present application, the same reference numerals denote the same or corresponding parts.

  The epoxy resin used in the present invention contains an epoxy compound having one or more epoxy groups per molecule. As such an epoxy compound, any compound that has one or more three-membered rings composed of two carbon atoms and one oxygen atom in one molecule and can be cured can be used as appropriate. Is not particularly limited.

  Specific examples of the epoxy resin containing such an epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, Bisphenol A type novolak type epoxy resin, bisphenol F type novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy Resin, salicylaldehyde novolak type epoxy resin, diglycidyl etherified product of other bifunctional phenols, diglycidyl etherified product of bifunctional alcohols, and the like Halides, include such hydrogenated products, which are either used alone, or in combination of two or more. When using 2 or more types together, these mixing ratios are not specifically limited, What is necessary is just what can harden | cure as mentioned above.

  Next, the onium salt [I] used in the present invention has the following characteristics represented by the following chemical formula (1).

(In the above chemical formula (1),
A is a cation moiety of an acid generator that generates a cationic species by light or heat,
X is a compound having a negative _{^{charge, -SO 3 -, -PO 3 -}} , -CO 2 -, -SO 2 -, -NO 2 -, -CN - or -SH, ^-,
B is a compound in which 8 or more atoms selected from the group consisting of carbon, oxygen and nitrogen are continuously bonded, and forms an organic chemical bond with X. )
Although it is onium salt [I] used by this invention, A shown by Chemical formula (1) is an acid generator (cationic polymerization which generate | occur | produces a cation seed | species by the external energy, such as light or a heat, as mentioned above. It is a cationic site of the initiator. In the present invention, only the cation portion of the acid generator is used in the manner described later.

Examples of the acid generator include
4-hydroxyphenyl benzyl methyl sulfonium hexafluoroantimonate,
4-hydroxyphenyl benzyl methyl sulfonium hexafluorophosphate,
4-hydroxyphenyl benzyl methyl sulfonium hexafluoroarsenate,
4-hydroxyphenyl benzyl methyl sulfonium tetrafluoroborate,
4-acetoxyphenyl benzyl methyl sulfonium hexafluoroantimonate,
4-hydroxyphenyl (o-methylbenzyl) methyl sulfonium hexafluoroantimonate,
4-hydroxyphenyl (o-methylbenzyl) methyl sulfonium hexafluorophosphate,
4-hydroxyphenyl (p-nitrobenzyl) methyl sulfonium hexafluoroantimonate,
4-hydroxyphenyl methyl (α-naphthylmethyl) sulfonium hexafluoroantimonate,
4-hydroxyphenyl methyl (α-naphthylmethyl) sulfonium hexafluorophosphate,
4-hydroxyphenyl methyl (α-naphthylmethyl) sulfonium tetrafluoroborate,
4-acetoxyphenyl methyl (α-naphthylmethyl) sulfonium hexafluoroantimonate,
Benzyl tetramethylene sulfonium hexafluoroantimonate,
Benzyl tetramethylene sulfonium hexafluorophosphate,
(O-methylbenzyl) tetramethylene sulfonium hexafluoroantimonate,
(Α-naphthylmethyl) tetramethylene sulfonium hexafluoroantimonate,
Triphenylsulfonium hexafluoroantimonate,
Triphenylsulfonium hexafluorophosphate,
p-methoxybenzyl-o-cyanopyridinium hexafluoroantimonate,
Examples include, but are not limited to, p-methoxybenzyl dimethyl anilinium hexafluoroantimonate and the like, and those having a cationic polymerization initiating ability to generate a cationic species by external energy such as light or heat. Sites can be used.

X is a compound having a negative charge, and specific examples thereof include —SO ₃ ⁻ , —PO ₃ ⁻ , —CO ₂ ⁻ , —SO ₂ ⁻ , —NO ₂ ⁻ , —CN ⁻ and —SH ^−. . In order to increase the reactivity of the onium salt, a non-nucleophilic or basic compound having a low negative charge is desirable. From such a viewpoint, X is not limited to the above examples, and it is also possible to use a non-nucleophilic or basic compound having an uncharged equivalent to the above examples.

  B is an organic chemical bond with X, and is a compound in which 8 or more atoms selected from the group consisting of carbon, oxygen and nitrogen are continuously bonded. In the compound, the state in which 8 or more atoms are continuously bonded may be linear, branched, or cyclic (including condensed ring). When it includes a branch or the like, the number of atoms that are continuously bonded refers to the number of chains that have the longest bond chain. B is a compound having a skeleton in which 8 or more atoms selected from the group consisting of carbon, oxygen, and nitrogen are continuously bonded, and may contain other atoms such as hydrogen.

  The organic chemical bond between B and X refers to a bond such as a covalent bond. In addition to the covalent bond, for example, B and X do not directly form a covalent bond, And the case where atoms other than carbon, oxygen and nitrogen are present in a bond or coordination.

  With the above-described configuration of the epoxy resin composition, it is possible to obtain an epoxy resin composition having a long service life, excellent electrical insulation and heat resistance provided by the present invention. Furthermore, a rotary electric machine and an electrically insulated wire ring using the same can be obtained.

  This is considered based on the following principle. First, it has a long usable life, but in a system consisting of a conventional epoxy resin and acid anhydride, a curing reaction occurs due to hydrolysis of the contained composition, so an increase in viscosity during storage is inevitable. Poor life characteristics. On the other hand, in the epoxy resin composition containing the epoxy resin of the present invention and the onium salt [I], the curing reaction proceeds by acid generation from the cation site of the onium salt [I]. Acid generation from the cation site occurs by obtaining a certain amount of heat or light energy from the outside, and a long usable life is obtained by selecting a cation site having a large amount of heat or light energy required for acid generation. be able to.

  Next, regarding electrical insulation, it is known that the electrical conduction mechanism of an epoxy resin is based on ionic conduction, and ionic conduction is expressed by the product of the number of ions, their charge, and mobility.

For example, in the case of epoxy resin composition comprising an onium salt represented by the following chemical formula (2), in the cured resin, onium Shiozan渣after the reaction, BF ₆ is the anion portion of an onium salt ^- or PF ₆ ^- is included It is. This anion is considered to be able to move within the resin relatively easily because its size is equal to or smaller than the epoxy resin network size. Therefore, since mobility is large and electrical conduction by ionic conduction is large, the volume resistivity is significantly higher than that of a resin composition comprising an epoxy resin and an acid anhydride not containing an onium salt as described in Patent Document 1. Will be reduced.

On the other hand, the anion moiety [BX] ^{− according to} the present invention has a skeleton in which B is bonded to 8 or more atoms selected from the group consisting of carbon, oxygen and nitrogen, so that the molecular size of the compound is not less than the epoxy resin network size. For this reason, the mobility is extremely limited by the entanglement between the epoxy resin and the anionic molecular chain, and the volume resistivity is increased.

  Next, regarding heat resistance, when an active cation species is generated from the onium salt and the ring-opening reaction of the epoxy proceeds, the anion site shown in the system described in Patent Document 3 is in the vicinity of the cation by diffusion in the resin. Since the anion site and the active cationic species form an ion pair, the ring-opening reaction of the epoxy resin is suppressed, and an epoxy resin having a sufficient crosslinking density cannot be obtained, and the heat resistance is improved. May decrease.

  However, when an onium salt having an anion moiety described in the present invention is used, when the epoxy ring-opening reaction proceeds, the anion moiety is entangled with the epoxy resin by the long-chain compound skeleton, and diffusion thereof is difficult to occur. As described above, the ring-opening reaction is not inhibited, and a cured resin having high heat resistance can be obtained.

  In order to have more excellent electrical insulation and heat resistance, it is desirable that 10 or more atoms selected from the group consisting of carbon, oxygen and nitrogen are continuously bonded.

  Furthermore, when the number of atoms bonded continuously is 15 or more, the solubility in the resin decreases, and when the number of B atoms is large, the molecular weight of the onium salt increases, and the acid per mass of the onium salt increases. Since the generation amount may decrease, it is desirable that atoms selected from the group consisting of carbon, oxygen, and nitrogen are continuously 10 or more and 15 or less.

  Examples of the compound in which 8 or more atoms selected from the group consisting of carbon, oxygen and nitrogen are continuously bonded include, for example, in the structural isomer of n-octane, one or more carbon atoms of the skeleton are oxygen atoms or nitrogen. Includes atoms substituted. The structural isomers of n-octane are n-octane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2,2-dimethylhexane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2 , 5-dimethylhexane, 3,3-dimethylhexane, 3,4-dimethylhexane, 3-ethylhexane (or 2-ethylheptane), 2,2,3-trimethylpentane, 2,2,4-trimethylpentane, 18 kinds of 2,3,3-trimethylpentane, 2,3,4-trimethylpentane, 2-methyl-3-ethylpentane, 3-methyl-3-ethylpentane, 2,2,3,3-tetramethylbutane It is. These names have nothing to do with how to count the number of atoms bonded in series.

Examples of the anion site [BX] ⁻ include sodium laurate, monododecyl sodium phosphate, sodium 1-dodecanesulfonate, 12-aminolauric acid, sodium n-dodecyl sulfate, sodium myristate, and sodium N-lauroyl sarcosine. Hydrates, sodium tetradodecyl sulfate, sodium 1-pentadecane sulfonate, sodium palmitate, sodium tetradecyl sulfate, sodium 1-hexadecane sulfonate, sodium stearate, sodium oleate, sodium 1-octadecane sulfonate, benzamide cyclohexanecarboxylic acid , Sodium anthraquinone-1-sulfonate, disodium anthraquinone-2,6-disulfonate, dimethyl sodium 5-sulfoisophthalate, Sodium le acid, anionic sites of disodium (2-ethylhexyl) sulfosuccinate, and the like.

In the present invention, as described above, the presence of B having a larger number of atoms than the conventional onium salt ([A] ⁺ [X] ⁻ ) increases the molecular weight of the onium salt as a whole. Therefore, the mobility is extremely limited by the entanglement of the anionic molecular chain of the epoxy resin and the onium salt, and the volume resistivity can be increased. In the structural isomer, the same effect can be obtained even if one or more carbon atoms of the skeleton are substituted with an oxygen atom or a nitrogen atom.

  These onium salts [I] may be used alone or in combination of two or more. When two or more kinds of onium salts [I] are used in combination, it is desirable to use those having similar conditions for generating active cationic species for curing the epoxy resin.

The onium salt [I] in the present invention can be produced by anion exchange of an acid generator that provides the cation moiety [A] ⁺ . Specifically, the solution containing the acid generator is passed through a column packed with an ion exchange resin to cause the ion exchange resin to hold the acid generator, and then a compound that provides an anion site [BX] ⁻ is provided. The solution containing the solution is passed through the column for ion exchange. Thereafter, in order to extract the solution containing the onium salt, a solvent such as methanol is passed through the column. The solution thus extracted is distilled off under reduced pressure to obtain a solid, and the solid is recrystallized with a solvent such as methanol as necessary. Onium salt [I] is manufactured by the above method.

  In the production of the onium salt [I], the ion exchange resin is selected to be strong ion or weak ion exchange so that it can be more easily exchanged depending on the anionic degree of the anion site. Such an ion exchange resin may have high selectivity according to a known method. Examples of the resin or the like packed in such a column include Diaion (registered trademark) SK104 (trade name, manufactured by Mitsubishi Chemical Corporation) and Sepa Beads (registered trademark) SP70 (trade name, Mitsubishi Chemical Corporation). In addition, a commercially available column filler can be used. A solution containing an acid generator or a compound providing an anion moiety to be passed through the column may be prepared by dissolving or dispersing an acid generator or an anion moiety in water. Moreover, the manufacturing method of onium salt [I] is not limited to the said method, It can manufacture also by methods, such as an anion exchange method, the acid ester method, and the neutralization method.

  The onium salt [I] is preferably added in an amount of about 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, with respect to 100 parts by weight of the epoxy resin. When using multiple types of onium salt [I], it is preferable to add so that these sum may satisfy | fill the weight range with respect to the said epoxy resin. When an onium salt is included in the above-mentioned addition amount, the cured epoxy resin obtained by curing the epoxy resin composition has no uncured epoxy resin (monomer: monomer) and is completely solidified without tackiness. Since a thing can be obtained, it is preferable. When the amount of the onium salt [I] added to the epoxy resin is 0.5 to 10 parts by weight, the solubility or dispersibility in the epoxy resin is particularly good, and excessive heat generation during the reaction is suppressed. Therefore, electrical insulation can be improved.

  In addition, in the epoxy resin composition of the present invention, as long as the epoxy resin and the onium salt [I] described above are included, a reactive diluent such as styrene used in this field in the epoxy resin composition, Generally, it may contain a curing catalyst, a curing accelerator and the like which are added to the epoxy resin composition.

  The epoxy resin composition according to the present invention can be obtained by uniformly mixing the epoxy resin and the onium salt [I] at a desired ratio. When the reaction diluent is contained as described above, it is added simultaneously with the onium salt [I], or after the onium salt [I] is mixed, it is added and mixed uniformly again. Further, when a curing catalyst, a curing accelerator or the like as described above is included, it may be added to the system and mixed uniformly as in the case of the reaction diluent.

  Next, the manufacturing method of the electrical insulated wire ring and rotary electric machine using the said epoxy resin composition is demonstrated. FIG. 1A and FIG. 1B are schematic views of a part of a rotating electric machine including an electrically insulated wire ring. As shown in FIGS. 1A and 1B, the electrically insulated wire ring 2 includes a conductor 3 and an insulating layer 4. A protective insulating layer 8 may be provided on the outer periphery of the electrically insulated wire ring 2, that is, on the outer surface of the insulating layer 4 in order to enhance or maintain the insulating property.

  As the conductor 3, a so-called coil conductor can be used in which a predetermined shape is formed by combining wires with appropriate insulation coating.

  The insulating layer 4 and the protective insulating layer 8 are each made of, for example, an insulating tape and can be formed by winding an insulating tape on the conductor 3. The insulating layer 4 may be formed by laminating and winding the insulating tape several times, but usually, the insulating layer 4 is formed by overlapping and winding a part of the insulating tape like a grip. Further, the insulating layer 4 and the protective insulating layer 8 may be made of the same material insulating tape.

  The conductor 3 provided with the insulating layer 4 is vacuum-dried in a tank to remove volatile components and air from the insulating layer 4. Thereafter, the conductor 3 provided with the insulating layer 4 is impregnated with the epoxy resin composition of the present invention. Such a process can be performed by, for example, immersing the epoxy resin composition of the present invention in the insulating layer 4 and allowing the epoxy resin composition to permeate the insulating layer 4 formed by optionally pressing and winding the insulating sheet. it can.

Then, the electrically insulated wire ring 2 can be formed by the process which takes out the conductor which impregnated the insulating layer 4 with the epoxy resin composition, and hardens the epoxy resin composition. In the step of curing the epoxy resin composition, heat or light is applied so that the onium salt in the present invention functions as an acid generator. Specifically, the epoxy resin composition is cured by heating under a pressure of about atmospheric pressure at 90 ° C. for 2 hours and then at 180 ° C. for 3 hours. By performing such curing, the electrically insulated wire ring 2 or the rotating electrical machine including the cured product of the epoxy resin composition of the present invention (hereinafter also referred to as an epoxy resin cured product) can be manufactured. The electrically insulated wire ring has, for example, a volume resistivity (insulating property) that is higher than that of conventional ones, such as 1 × 10 ¹⁰ Ωm or more at room temperature and 1.8 × 10 ¹⁸ Ωm or more at 100 ° C. Moreover, when using the epoxy resin composition of this invention, the glass transition temperature ( _Tg ) of the hardened | cured material of this epoxy resin composition can be 150 degreeC or more, and heat resistance can be improved. The cured product has a bending strength of 30 MPa or more measured according to JIS standard B7721.

  The insulating tape constituting the insulating layer 4 is obtained by bonding a reinforcing material to an insulating material with a binder resin. The insulating tape is prepared by dissolving a binder resin in a solvent, coating this on an insulating material and a reinforcing material, and volatilizing the solvent. The insulation material for the insulating tape is made of thin mica foil obtained by thinly peeling the mica raw ore, and the mica raw or remaining mica foil is processed by the firing method, water jet method, etc. to make fine scales. A laminated mica foil formed by making a paper into a sheet is used. The material for forming the reinforcing material for reinforcing the insulating material is not particularly limited as long as it can reinforce the mica foil. For example, insulation such as glass cloth, polyester film, polyimide film, polyester nonwoven fabric, etc. A material having properties can be used.

  A method for manufacturing the rotating electrical machine of the present invention will be described. As shown in FIGS. 1 (a) and 1 (b), the slot outlet portion of the rotating electrical machine has a conductor 3 and an insulating layer in a stator core slot 7 surrounded by a stator core 1 in which silicon steel plates are laminated. The electric insulation wire 2 provided with the protective insulation layer 8 by further winding a glass tape around the electric insulation wire 2 having 4 is inserted (here, the electric insulation wire is impregnated with an epoxy resin composition). It is in a state not letting. The inserted electrically insulated wire ring 2 drives and fixes the wedge 5. Then, after immersing the whole rotating electrical machine in the impregnation tank filled with the above epoxy resin composition of the present invention, the epoxy resin composition is left to stand for about 3 to 4 hours at a heating temperature at which a cation site is generated. Is cured to produce a rotating electrical machine. What is necessary is just to change a heating condition suitably according to the conditions which the cation part of the onium salt in the epoxy resin composition to be used generate | occur | produces.

  The example which produces a rotary electric machine using the epoxy resin composition by this invention is demonstrated. The electrically insulating wire ring 2 provided with the conductor 3 and the insulating layer 4 (or the insulating layer 4 and the protective insulating layer 8) is immersed in an impregnation tank filled with the epoxy resin composition. Then, the said electric insulated wire ring 2 is taken out from the tank for impregnation, and is left still for about 3 to 4 hours in a heating furnace, and an epoxy resin composition is hardened. The heating temperature is set such that, for example, cation sites are generated in the same manner as the above heating conditions. Thereafter, the electrically insulated wire ring 2 is inserted into the stator core slot 7, and the wedge 5 is driven and fixed from above. Thereafter, the electric insulated wire ring 2 is assembled and connected to produce a rotating electrical machine.

  As described above, since the epoxy resin composition of the present invention contains the specific onium salt [I], the insulating properties of the electric insulated wire ring and the rotating electric machine using the epoxy resin composition are improved as compared with the conventional one. be able to.

  Specific examples will be described below. EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these. Diaion (registered trademark) SK104 (trade name, manufactured by Mitsubishi Chemical Corporation) was used as the column packing material.

Example 1.
(1) Preparation of onium salt a “San-Aid SI180” (trade name) manufactured by Sanshin Chemical Industry Co., Ltd. dissolved in 200 ml of water was replaced with “Diaion SK104” (trade name) manufactured by Mitsubishi Chemical Corporation. Flowed through packed column. Subsequently, 20 g of sodium dodecyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 200 ml of water was passed through the column. Next, methanol was passed through the column, and the extracted solution was distilled off under reduced pressure to obtain a white solid. This solid was recrystallized from methanol to obtain an onium salt a represented by the following chemical formula (3). The compound that provides the anion site ([BX] ⁻ ) of the obtained onium salt a, X, and the number of continuous bonds of atoms selected from the group consisting of carbon, oxygen, and nitrogen (“α + β + γ” in Table 1) It is shown in 1.

(2) Preparation of cured epoxy resin 2 parts by weight of the onium salt a represented by the above chemical formula (3) and "Celoxide 2021P" (trade name) manufactured by Daicel Chemical Industries, which is an alicyclic epoxy resin, 100 weights Parts were mixed to obtain an epoxy resin composition. The epoxy resin composition was allowed to stand at 180 ° C. for 3 hours to obtain a cured epoxy resin.

(3) Evaluation of liquid properties and cured product properties of epoxy resin composition (3-1)
The solubility of the onium salt was evaluated. The results are shown in Table 2 as ○ when the onium salt of 2 parts by weight is dissolved with respect to 100 parts by weight of the epoxy resin, and X when it is easily dissolved by heating or ultrasonic irradiation. It was shown to.

(3-2)
In order to evaluate the usable life of the obtained epoxy resin composition, 100 g of the composition was weighed in a sample bottle, left in an oven at 40 ° C., and taken out after 2 weeks.

  Table 2 shows the results of the usable life judgment as ○ when the viscosity after standing is 2 times or less compared with that before standing, and × when the viscosity exceeds 2 times. Viscosity measurement conforms to JIS standard, K7117-1 (2000), using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE105U). And measured at 25 ° C.

(3-3)
In order to evaluate the heat resistance of the cured product of the obtained epoxy resin composition, the glass transition temperature was measured using TMA (thermomechanical analyzer, Thermo Mechanical Analysis). The measurement results are shown in Table 2.

(3-4)
In order to evaluate the electrical insulation properties of the resulting epoxy resin composition and its cured product, volume resistivity (based on JIS standard K6911) at 25 ° C. and 150 ° C. was measured. The measurement results are shown in Table 2.

Example 2
Preparation of onium salt b was performed using monododecyl sodium phosphate (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of sodium dodecyl sulfate of Example 1. Other cured products were produced and evaluated in the same manner as in Example 1. The anion sites ([BX] ⁻ ) of the obtained onium salt b are shown in Table 1, and the evaluation results are shown in Table 2.

Example 3
The onium salt c was prepared using a sodium salt of benzamide cyclohexanecarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of the sodium dodecyl sulfate of Example 1. Other cured products were produced and evaluated in the same manner as in Example 1. The anion sites ([BX] ⁻ ) of the obtained onium salt c are shown in Table 1, and the evaluation results are shown in Table 2.

Example 4
The onium salt d was prepared using sodium tetradecyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) instead of the sodium dodecyl sulfate of Example 1. Other cured products were produced and evaluated in the same manner as in Example 1. The anion sites ([BX] ⁻ ) of the obtained onium salt d are shown in Table 1, and the evaluation results are shown in Table 2.

Example 5 FIG.
The onium salt e was prepared using sodium laurate (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of the sodium dodecyl sulfate of Example 1. Other cured products were produced and evaluated in the same manner as in Example 1. The anion sites ([BX] ⁻ ) of the obtained onium salt e are shown in Table 1, and the evaluation results are shown in Table 2.

Example 6
The onium salt f was prepared using N-lauroyl sarcosine sodium hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of sodium dodecyl sulfate in Example 1. Other cured products were produced and evaluated in the same manner as in Example 1. The anion sites ([BX] ⁻ ) of the obtained onium salt f are shown in Table 1, and the evaluation results are shown in Table 2.

Example 7
The onium salt g was adjusted using sodium anthraquinone-1-sulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of sodium dodecyl sulfate in Example 1. Other cured products were produced and evaluated in the same manner as in Example 1. The anion sites ([BX] ⁻ ) of the obtained onium salt g are shown in Table 1, and the evaluation results are shown in Table 2.

Example 8 FIG.
The onium salt h was prepared by using anthraquinone-2,6-disulfonic acid disodium (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of sodium dodecyl sulfate of Example 1. Other cured products were produced and evaluated in the same manner as in Example 1. The anion sites ([BX] ⁻ ) of the obtained onium salt h are shown in Table 1, and the evaluation results are shown in Table 2.

Example 9
Onium salt i was prepared using dimethyl sodium 5-sulfoisophthalate (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of sodium dodecyl sulfate of Example 1. Other cured products were produced and evaluated in the same manner as in Example 1. The anion sites ([BX] ⁻ ) of the obtained onium salt i are shown in Table 1, and the evaluation results are shown in Table 2.

Example 10
Onium salt j was prepared using sodium 1-pentadecanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of sodium dodecyl sulfate of Example 1. Other cured products were produced and evaluated in the same manner as in Example 1. The anion sites ([BX] ⁻ ) of the obtained onium salt j are shown in Table 1, and the evaluation results are shown in Table 2.

Example 11
Onium salt k was adjusted using sodium 1-dodecanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of sodium dodecyl sulfate of Example 1. Other cured products were produced and evaluated in the same manner as in Example 1. The anion sites ([BX] ⁻ ) of the obtained onium salt k are shown in Table 1, and the evaluation results are shown in Table 2.

Example 12 FIG.
The onium salt l was prepared using sodium myristate (Tokyo Chemical Industry Co., Ltd.) instead of the sodium dodecyl sulfate of Example 1. Other cured products were produced and evaluated in the same manner as in Example 1. The anion sites ([BX] ⁻ ) of the obtained onium salt l are shown in Table 1, and the evaluation results are shown in Table 2.

Example 13
The onium salt m was adjusted using sodium palmitate (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of sodium dodecyl sulfate in Example 1. Other cured products were produced and evaluated in the same manner as in Example 1. The anion sites ([BX] ⁻ ) of the obtained onium salt m are shown in Table 1, and the evaluation results are shown in Table 3.

Example 14
The onium salt n was prepared using 12-aminolauric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of sodium dodecyl sulfate of Example 1. Other cured products were produced and evaluated in the same manner as in Example 1. The anion sites ([BX] ⁻ ) of the obtained onium salt n are shown in Table 1, and the evaluation results are shown in Table 2.

Example 15.
Onium salt o was prepared using sodium 1-hexadecanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of sodium dodecyl sulfate of Example 1. Other cured products were produced and evaluated in the same manner as in Example 1. The anion sites ([BX] ⁻ ) of the obtained onium salt o are shown in Table 1, and the evaluation results are shown in Table 3.

Example 16
The onium salt p was adjusted using sodium 1-octadecanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of the sodium dodecyl sulfate of Example 1. Other cured products were produced and evaluated in the same manner as in Example 1. The anion sites ([BX] ⁻ ) of the obtained onium salt p are shown in Table 1, and the evaluation results are shown in Table 3.

Example 17.
The onium salt q was adjusted using sodium stearate (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of sodium dodecyl sulfate in Example 1. Other cured products were produced and evaluated in the same manner as in Example 1. The anion sites ([BX] ⁻ ) of the obtained onium salt q are shown in Table 1, and the evaluation results are shown in Table 3.

Example 18
The onium salt r was adjusted using sodium oleate (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of sodium dodecyl sulfate in Example 1. Other cured products were produced and evaluated in the same manner as in Example 1. The anion sites ([BX] ⁻ ) of the obtained onium salt r are shown in Table 1, and the evaluation results are shown in Table 3.

Example 19.
The onium salt s was prepared using sodium cholate (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of sodium dodecyl sulfate in Example 1. Other cured products were produced and evaluated in the same manner as in Example 1. The anion sites ([BX] ⁻ ) of the obtained onium salt s are shown in Table 1, and the evaluation results are shown in Table 3.

Example 20.
The onium salt t was adjusted using sodium tetradecyl sulfate (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of the sodium dodecyl sulfate of Example 1. Other cured products were produced and evaluated in the same manner as in Example 1. The anion sites ([BX] ⁻ ) of the obtained onium salt t are shown in Table 1, and the evaluation results are shown in Table 3.

Example 21.
The onium salt u was prepared using sodium di (2-ethylhexyl) sulfosuccinate (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of sodium dodecyl sulfate in Example 1. Other cured products were produced and evaluated in the same manner as in Example 1. The anion sites ([BX] ⁻ ) of the obtained onium salt u are shown in Table 1, and the evaluation results are shown in Table 3.

Comparative Example 1
Similar evaluation of “Celoxide 2021P” and acid anhydride 3 / 4-methyl-1,2,3,6-tetrahydrophthalic anhydride (“HN-2000” (trade name) manufactured by Hitachi Chemical Co., Ltd.) Was done. The results are shown in Table 3. Comparative Example 1 is a system composed of an epoxy resin and an acid anhydride conventionally used in rotating electrical machines and the like.

Comparative Example 2
The same evaluation was performed for “Celoxide 2021P” and “Sun-Aid SI180”. The results are shown in Table 3. Comparative Example 2 is the anion site is PF ₆ ^- is an epoxy resin composition comprising a is onium salt.

Comparative Example 3
The onium salt v was adjusted using sodium 1-heptanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of sodium dodecyl sulfate in Example 1. Other cured products were produced and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

  In Tables 2 and 3, "-" in the formulation indicates that no addition was made. Moreover, "-" in the column of characteristics in Table 3 indicates that a cured product was not formed and evaluation could not be performed.

From Table 2 and Table 3, it can be seen that the epoxy resin compositions (Examples 1 to 21) having the onium salt structure of the present invention have a longer usable life than Comparative Example 1. In addition, the glass transition temperature of the cured product is 150 ° C. or more, and it can be said that the epoxy resin has high heat resistance. Furthermore, their volume resistivity at 100 ° C. is 2 digits or more higher than that of Comparative Example 2 in which the anion portion of the onium salt is PF ₆ ⁻ , and therefore has excellent electrical insulation. I know that there is. Further, those in which atoms selected from the group consisting of carbon, oxygen and nitrogen are continuously bonded through X and organic chemical bond in onium salt b, particularly from the viewpoint of solubility and electrical insulation. It can be seen that the other onium salts are superior.

Example 22.
Next, an example in which an electrically insulated wire ring is produced using the epoxy resin composition of the present invention will be described. For the electric insulated wire ring, an insulating layer is formed by winding an insulating tape 10 times around the outer periphery of the insulation coated conductor, impregnated in a tank filled with the epoxy resin of Example 1, and then allowed to stand at 180 ° C. for 4 hours. It was produced by doing.

Comparative Examples 4 and 5.
On the other hand, in the same method as above, Comparative Example 4 using the epoxy resin composition of Comparative Example 1 instead of the epoxy resin composition of Example 1, Comparative Example 5 using the epoxy resin composition of Comparative Example 2 An electrically insulated wire ring was produced.

(Evaluation of electrical insulated wire ring)
The electrically insulated wire rings of Example 22 and Comparative Examples 4 and 5 were heat-degraded at 180 ° C./3 days, and the volume resistivity of the composite part of the epoxy resin composition and insulating tape at 100 ° C. was measured. As a result, the volume resistance of Example 22 was 3.5 × 10 ¹⁴ Ωm, and the volume resistance of Comparative Example 4 was 6.0 × 10 ¹⁰ Ωm. Moreover, since the electrical insulation wire ring of the comparative example 5 had the short usable life of the epoxy resin composition of the comparative example 2 used, and the viscosity increased at the time of use, the non-impregnation defect generate | occur | produced between insulating tape layers.

  From the above, it can be seen that the electrically insulated wire ring of Example 22 has a longer usable life than Comparative Example 5 and thus has good impregnation properties, and further has higher electrical insulation properties than Comparative Example 4.

Example 23.
Next, an example in which a rotating electrical machine is manufactured using the epoxy resin composition shown in the present invention will be described. Fig.1 (a) and FIG.1 (b) are typical explanatory drawings for demonstrating an example of a rotary electric machine, and show the slot exit part of a rotary electric machine. As shown in FIGS. 1 (a) and 1 (b), the slot outlet portion of the rotating electrical machine has a conductor 3 and an insulating layer in a stator core slot 7 surrounded by a stator core 1 in which silicon steel plates are laminated. The electrical insulating wire ring 2 provided with the protective insulating layer 8 by further winding a glass tape around the electrically insulating wire ring 2 provided with 4 is inserted. The inserted electrically insulated wire ring 2 was driven and fixed with a wedge 5. Thereafter, after dipping in an impregnation tank filled with the epoxy resin composition of Example 1, the rotary electric machine was produced by leaving still at 180 ° C. for 4 hours. In this embodiment, the electrically insulated wire ring 2 is formed by winding an insulating tape around a conductor 3 a predetermined number of times (20 times in this embodiment 23) to form a coil insulating layer 4.

Comparative Examples 6 and 7
On the other hand, a rotating electrical machine of Comparative Example 6 or 7 using the epoxy resin composition of Comparative Example 1 or 2 instead of the epoxy resin composition of Example 1 was produced in the same manner as in Example 23.

(Evaluation of rotating electrical machines)
The rotating electrical machine of Example 23 and Comparative Examples 6 and 7 was heat-degraded at 180 ° C./3 days, and the volume of the composite part of epoxy resin composition and insulating tape at 100 ° C. (part of insulating layer 1 in FIG. 1). The resistivity was measured. As a result, the volume resistance of Example 23 was 3.5 × 10 ¹⁴ Ωm. On the other hand, the volume resistance of Comparative Example 6 was 5.5 × 10 ¹⁰ Ωm. In the rotating electric machine of Comparative Example 7, the pot life of the epoxy resin composition of Comparative Example 2 used was short, so that the viscosity increased and increased during use.

  As mentioned above, it turned out that the electrical insulation improves the rotary electric machine of this Example 23 by using the epoxy resin composition of Example 1. FIG.

  Although the embodiments and examples of the present invention have been described as described above, it is also planned from the beginning to appropriately combine the configurations of the above-described embodiments and examples.

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

  DESCRIPTION OF SYMBOLS 1 Stator core, 2 Electrically insulated wire ring, 3 Conductors, 4 Insulating layer, 5 Wedge, 6 Intermediate filler, 7 Stator core slot, 8 Protective insulating layer.

Claims (4)

An epoxy resin composition comprising an epoxy resin and an onium salt [I] represented by the following chemical formula (1).

(In the above chemical formula (1),
A is a cation moiety of an acid generator that generates a cationic species by light or heat,
X is a compound having a negative _{^{charge, -SO 3 -, -PO 3 -}} , -CO 2 -, -SO 2 -, -NO 2 -, -CN - or -SH, ^-,
B is a compound in which eight or more atoms selected from the group consisting of carbon, oxygen and nitrogen are continuously bonded, and forms an organic chemical bond with X. )   2. The epoxy resin according to claim 1, wherein B is a compound in which atoms selected from the group consisting of carbon, oxygen, and nitrogen are continuously bonded by 10 to 15 and forms an organic chemical bond with X. 3. Composition. Impregnating a conductor having an insulating layer with the epoxy resin composition according to claim 1 or 2,
And heating the conductor provided with the insulating layer to cure the epoxy resin composition. Impregnating a conductor having an insulating layer with the epoxy resin composition according to claim 1 or 2,
Heating the conductor provided with the insulating layer to cure the epoxy resin composition.

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