JPS5917218A - Electrically insulated coil - Google Patents

Abstract

PURPOSE:To cure both resin compositions through heating at a low temperature, and to obtain excellent mechanical characteristics at a high temperature by impregnating a mica tape containing the resin composition, essential components thereof are an epoxy resin and a sepcific element compound, with the resin composition consisting of an epoxy resin and an acid anhydride hardener and curing both resin compositions. CONSTITUTION:The mica tape containing 5wt% or 30wt% resin composition, essential components thereof are the epoxy resin, the polysiloxane compound, the aluminum compound in quantity required for a catalyst as the latent curing catalyst, and an organic silicon compound with a hydrolytic group in quantity required for a catalyst, as adhesives is wound, the tape is impregnated with the resin composition consisting of the epoxy resin and the acid anhydride hardener, and both resin compositions are cured, thus manufacturing the electrically insulated coil. The polysiloxane compound mainly gives heat resistance, and an acid anhydride displays effects which lower viscosity in order to easily impregnate the resin composition and lengthen the life of storage. The mixture of the epoxy resin gives electrically, mechanically and thermally balanced performance as a heat-resisting insulating system and displays an effect reducing cost. The aluminum compound and the organic silicon compound with the hydrolytic groups are the catalysts which cure the resin at a not very high temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to an electrically insulated wire ring used in rotating electric machines, dry type transformers, and the like.

[Technical background of the invention and its problems] As an electrically insulated coil with high heat resistance of heat resistance class H class,
Conventionally, it is known that an insulating tape impregnated with a thermosetting resin such as silicone or polyimide is wound around a wire conductor and then heated and cured. However, silicone and polyimide generally require heating at a high temperature of 180° C. or higher for a long time of 15 hours or more for curing. However, silicone still has the drawback of poor mechanical properties, especially at high temperatures, and its range of use has been limited.

OBJECT OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks.The present invention has been made in view of the above drawbacks. The purpose is to provide insulated coils.

[Summary of the invention]

In order to achieve the above object, the present invention provides a resin composition containing as essential components an epoxy resin, a polysiloxane compound, a catalytic amount of an aluminum compound as a latent curing catalyst, and a catalytic amount of an organosilicon compound having a hydrolyzable group. After winding a mica tape containing 5% to 30% by weight of 5% to 30% by weight as an adhesive, the tape is impregnated with a resin composition consisting of an epoxy resin and an acid anhydride curing agent and cured to produce an electrically insulating coil.

Examples of the epoxy resin compound of the mica tape adhesive used in the present invention include bisphenol A epoxy resin, bisphenol P epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, alicyclic epoxy resin; triglycidyl isocyanate. , heterocyclic epoxy resins such as hydantoin epoxy resins, water-soluble bisphenol A type epoxy resins, aliphatic epoxy resins such as brohylene glycol-diglycidyl ether, pentaerythritol-polyglycidyl ether, aromatic, aliphatic or alicyclic resins. Epoxy resins obtained by the reaction of the carboxylic acid of the formula with epichlorohydrin, spiro ring-containing epoxy resins, reaction products of 0-allylphenol novolac compounds and epichlorohydrin, reaction products of diallylbisphenol compounds and epichlorohydrin, etc. Examples include polyfunctional epoxy compounds such as ether type epoxy resin.

The polysiloxane compound used as the adhesive for the mica tape in the present invention is a presiloxane compound having at least 11 of the following chemical structures in its molecular chain.

1, φ represents a phenyl group, and Me represents a methyl group. Here, it is preferable that φ/Me≧1, and it is preferable that the active terminal contains 5i-Off in an amount of 1% or less per weight.

In addition, as an organic group, the aluminum compound which is a component of the catalyst of the Mylar 1 tape adhesive used in the present invention includes an alkyl group having 1 to 5 carbon atoms: 1 to 5 carbon atoms... Loalkyl group: Alkoxyl group having 1 to 5 carbon atoms such as methoxy group, ethoxy group, isopropoxy group: Acyloxy group such as acetoxy group, propionyloxy group, isopropionyloxy group, butyryloxy group, stearoyloxy group, benzoyloxy group, etc. Groups: Those having aryloxy groups such as phenoxy, tolyloxy, and para-methoxyphenoxy groups, and those having acetylacetone, trifluoroacetylacetone, pentafluoroacetylacetone, ethylacetoacetate, salicylaldehyde, diethylmalonate, etc. as ligands. Examples include aluminum complexes.

The "hydrolyzable group" of the organosilicon compound used in the mica tape adhesive (1) in the present invention is a residue directly bonded to a silicon atom, and is hydrolyzed at a certain temperature or higher in the presence of water to form a silanol hydroxyl group. =S i -OH), for example, an alkoxy group having 1 to 5 carbon atoms: an aryloxy group such as a phenoxy group, tolyloxy group, paramethoxyphenoxy group, paranitrophenoxy group, benzyloxy group, etc. : Acyloxy groups such as acetoxy group, globionyloxy group, butanoyloxy group, benzoyloxy group, phenylacetoxy group, formyloxy group; Vinylmexy group such as isobutenyloxy, edenyloxy, isopropenyloxy, the following formula; ( In the formula, R' and R'' may be the same or different and are an alkyl group having 1 to 5 carbon atoms.

Furthermore, the organic group possessed by the organosilicon compound of the present invention refers to an organic group having 1 to 5 carbon atoms, such as an alkyl group, a vinyl group, a propenyl group, a 1- or 2-butenyl group, or a 1- or 2-pentenyl group. Alkenyl group; alkynyl group having 1 to 5 carbon atoms such as ethynyl group, flovinyl group, 1- or 2-butenyl group, 1- or 2-pentenyl, S; phenyl group, ) lyl group, varanitrophenyl Base.

Aryl group such as para-methoxyphenyl group; acetyl group,
These include trifluoroacetyl group and benzoyl group.

More specifically, the organosilicon compounds used in the present invention include the following organosilanes and organopolysiloxanes.

Organosilane has the general formula (1) (llydr)q-8i-(X)<-(p-+q)
--・if) In the above formula, R represents an organic group, 1jydr represents a hydrolyzable group, and X represents a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms (however, the substituent is a polymerization reaction It represents an inert group that does not participate in the polymerization reaction) and an aralkyl group (which may have a substituent that is unrelated to the polymerization reaction). p
and q are integers of 1 to 3, and p+q is 4 or less. ].

Among the above organosilanes, those more preferable for the present invention are, for example, triphenylmethoxysilane, diphenylvinylmethoxysilane, triphenylethoxysilane, phenyldivinylmethoxysilane, diphenyljethoxysilane, ) IJ (paranitrophenyl) Methoxysilane, triacetylmethoxysilane, 2-butenyldiphenylmethoxysilane, di(2-
benzonyl)phenylethoxysilane, trifluoroacetylphenyldiethoxysilane, diphenylbenzylmethoxysilane, tri(halethylphenyl)propoxysilane, diphenyldiacetoxysilane, diphenyldibropionyloxysilane, diphenylbis(triphenylacetoxy)silane .

φ φ dimethyl-bis(1-phenyl-1-ethynyloxy)
Examples include silane, diphenyl-bis(1-butenyloxy)silane, phenylmethylbis(1-isobutenyloxy)silane, methyldiphenylvinyloxysilane, dimethylphenylisopropenyloxysilane, and triphenylvinyloxysilane.

The organosiloxane is composed of a bifunctional unit represented by the following formula (6) and/or a trifunctional unit represented by the formula (I), and the terminal of the organosiloxane is a monofunctional unit represented by the formula (IV). It is sealed by a functional unit, (hereinafter blank) [In the above formula, yl, Y2. Y3. Y4. Y% and Y
6 may be the same or different, a hydrolyzable group; a multiple bond group, or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms (however, the substituent is an inert group that does not participate in the polymerization reaction) )] Particularly, it contains at least one of a difunctional unit represented by the following formula and a monofunctional unit represented by the following formula.

In the above formula, ■ and Hyd r represent the same meanings as above, and y? represents the same meaning as yl-Y6 above. ” Among the above organosiloxanes, the degree of polymerization is 50 or less, and the formula (v)
Or the siloxane unit represented by 2■! Those having (average molecular weight+average number of sylogisan units of formula (V) and formula (6) contained in one molecule) 700 or less are suitable for the present invention.

Among the organosiloxanes mentioned above, those more preferable for the present invention include, for example, 1°3-dimethoxy-t,3-dimethyl-L3-diphenyldisiloxane + 1+5-jetoxy-1,315-, trimethyl-1,3 , 5-) Riphenyltrisiloxane, 1.7-
cymethoxy1.3.5.7-tetramethyl-113,
51 footy traphenyltetrasiloxane, l,3-dimethoxytetraphenyldisiloxane, 1,5-dimethoxy-3,3-dimethyl-1,1°5.5-tetraphenyltrisiloxane + 1+3+5-trimethoxypentaphenyltrisiloxane .

1.5-Dimethoxyhex(p-)lyl)trisiloxane.

1.3-di(1-propenyloxy)tetraphenyldisiloxane1. s-di(t-)benyloxy)hexaphenyltrisiloxane force? can give.

The catalyst of the present invention obtained as described above is stable in the air at room temperature, and does not require special care or containers for handling or storage, so it has excellent workability≦1.

The mica tape used in the present invention does not change in quality even during long-term storage, has excellent storage stability, does not require a very high curing temperature, and can be cured quickly to shorten the time required for heat curing. It is characterized by being able to be cured, and furthermore, after being cured, it has excellent electrical insulation properties, especially thermal stability.

In the present invention, examples of the epoxy resin that is one component of the resin composition impregnated into the coil around which the mica tape is wound include the following.

Namely, bisphenol doll epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin such as triglycidyl isocyanate and hydantoin epoxy, hydrogenated bisphenol doll epoxy. resins, aliphatic epoxy resins such as propylene glycol diglycidyl ether and pentaerythritol polyglycidyl ether, epoxy resins obtained by the reaction of aromatic, aliphatic or alicyclic carboxylic acids with epichlorohydrin, spiro ring-containing epoxy resins, Glycidyl ether type epoxy resin is a reactive product of an orthoallylphenol novolac compound and epichlorohydrin, and a glycidyl ether type epoxy resin is a reaction product of a diallyl bisphenol compound having a nearlyl group ortho to each hydroxyl group of bisphenol A and epichlorohydrin. Such as resin.

In addition, monoepoxy resins such as octylene oxide, butyl glycidyl ether, styrene oxide, phenyl glycidyl ether, P-butylphenol glycidyl ether, cresyl glycidyl ether, glycidyl methacrylate, allyl glycidyl ether, and cyclohexene can be used as diluents if necessary. Vinyl monooxide, other aniline conductor epoxy, etc. may be added. However, in general, although the diluent has the effect of lowering the viscosity, it also lowers the properties, so it should be limited to 30% by weight or less based on the polyepoxide.

Furthermore, the acid anhydride which is another component of the impregnated resin composition includes hexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3 (or 4)-methyl-tetrahydro-phthalic anhydride, nadic acid anhydride, methyl-nadic anhydride, Acid anhydrides, dodecyl-succinic anhydride, succinic anhydride, octadecyl-succinic anhydride, etc. can be used alone or in mixtures.

Here, the polysiloxane compound is added to impart main C2 heat resistance, and the acid anhydride is effective in lowering the viscosity to facilitate impregnation and extending the shelf life. Furthermore, by incorporating epoxy resin, the heat-resistant insulation system has the effect of having well-balanced electrical, mechanical, and thermal performance and being inexpensive. The movable aluminum compound and the organosilicon compound having hydrolyzable groups are catalysts that allow the resin to be cured at moderate temperatures.

The ratio of the epoxy resin to the polysiloxane compound in the mica tape is preferably about 0.3 (epoxy resin/polysiloxane compound≦1) by weight. If it is higher than this, the mechanical properties will deteriorate, it will be expensive, and the life of the mica tape will be unstable, and if it is lower than this, there will be disadvantages such as poor electrical properties and heat resistance at high temperatures. .

Still latent curing catalyst per mole of aluminum compound,
It is desirable to blend the organosilicon compound so that the hydrolyzable group in the silicon compound is 1 equivalent or more, and more preferably 1 to 5 equivalents (2 equivalents).The catalyst amount is per 100 parts by weight of the epoxy resin and polysiloxane. It is common to add 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight.If the amount of catalyst is more than this, the mica tape shelf life will be shortened or the reaction will occur rapidly. The high-temperature properties will be poor.If the amount of catalyst is less than this, there is a drawback that the resin will be cleaved for a long time at high temperature due to curing.

Here, the mutual curing reaction between the epoxy resin, polysiloxane compound, and acid anhydride can only be cured at a moderate temperature of about 150'CJ by the coexistence of the aluminum compound and the organosilicon compound having a hydrolyzable group. An electrically insulating wire ring having excellent thermal, electrical and mechanical properties can be obtained, and when an aluminum compound or an organosilicon compound having a hydrolyzable group is mixed alone, both of them are included in the present invention. The remarkable effect of the cocatalyst system cannot be obtained.

The amount of the resin composition as an adhesive in the mica tape is preferably 5% to 30% by weight. If the weight is less than 5, mica pieces will scatter when the mica tape is wound around the coil 62. On the other hand, if it is 30% by weight or more, impregnation with the epoxy resin in the subsequent process will be inhibited. When the content is 5% to 30% by weight, scattering of mica pieces and inhibition of impregnation of the epoxy resin will not be reduced, and the latent curing catalyst in the adhesive will make a necessary and sufficient contribution to the curing of the epoxy resin. .

Examples of the invention] Next, examples of the present invention will be described.

Epikote 828 (product name of Shell Chemical Co., Ltd.) 1.2~ as an epoxy resin, and -(Tsg) as a polysiloxane compound.
10s (trade name of Toshiba Silicone Co., Ltd., 55% solution in a mixed solvent of xylene and butanol) 5.2~, aluminum triacetylacetonate as an aluminum compound) 40y, γ-brisitoxypropylene as an organosilicon compound having a hydrolyzable group Oxycilla 7 (A1
87: UCCCC product name o7 was mixed and stirred with 2.2 K5+ of methyl ethyl ketone to obtain a solution. By applying this solution to a sheet made by bonding a reinforcing material (backing material) made of glass cloth with a thickness of 35 μm and a 160 F/rn" calcined type laminated mica to a thickness of about 1207 layers, and drying it, A semi-dry mica tape containing relatively little adhesive was obtained. The test results of this mica tape are shown in Table 1.

Table 1 Characteristics of Mica Tape This mica tape has a shelf life of approximately 1 at a temperature of 15°C.
It has been a stable material for many years.

This mica tape is wound 3 times in a % pattern around a wire ring, and a 25 μm thick aramid paper tape (for example, A
After wrapping tissue insulating paper (product name of Nippon Aroma Co., Ltd.) once in a % pattern, the iron core; The ring and the simulated iron core were placed in a vacuum tank.

The pressure inside the vacuum tank was reduced to 1 mHg or less for 4 hours.

Next 1 Nibisphenol type epoxy resin Epicote 8O7 (Shell Chemical Co., Ltd. trade name) 477 parts by weight, butyl glycidyl ether 8 parts by weight acid anhydride HN2
200 (trade name of Hitachi Chemical Co., Ltd.) 45 parts by weight of an epoxy resin composition was fed until the entire wire ring was completely covered.
After pressurizing at a pressure of l/JG for 5 hours, the wire ring together with the simulated iron core was taken out from the vacuum tank and heated and hardened at 150° C. for 15 hours to obtain a motorlet (simulated stator winding).

The initial temperature of the motorlet thus insulated - tan
The δ characteristic is shown in Figure 1a. It can be seen that the insulation a according to the present invention has a lower dielectric loss at 180'Gl2 than the conventional insulation material having a track record of type F.

In addition, in accordance with IEEE Std, 275, this motorlet is repeatedly subjected to heating, vibration, moisture absorption, and pressure resistance, and the heat resistance life curve is drawn based on the time until it can no longer withstand pressure, as shown in Figure 2 a. 15 insulators with a track record of class F
It can be seen that the life at 180''G is longer than the life at 5'G, and it has sufficient performance of class H.

In addition, an aluminum plate of 1k x 50mm x 8QQa was wrapped with the mica tape three times in the same manner as the motorlet above, and then a 25 μm thick A-dish insulating paper was wrapped tightly, and the same impregnating resin as above was impregnated with vacuum pressure. , and was heated and cured to form an insulation approximately 1.85 m thick. Heat this insulation board to 180℃
A repeated bending fatigue test was conducted at a position 300M from the fulcrum with a double swing width of 10m in a cantilever type atmosphere. 5×10
The dielectric breakdown voltage after the test was 95 cm, which was the initial value, and had not decreased at all.

In the conventional F type insulation, after 5 x 10' repeated bending fatigue tests under the same conditions, the resistance was extremely reduced to about 15% of the initial value.

In this example, glass cloth is used as the reinforcing material for the mica tape, but other heat-resistant base materials such as polyimide film aramid paper may also be used. Total impregnation method with integral C2 impregnation:
Although the second method has been explained, it goes without saying that the second method is also applicable to the single coil impregnation method in which only the coil is impregnated.

[Effects of the Invention] As described above, the electric insulating wire according to the present invention has a long shelf life of the mica tape used, and is inexpensive because the amount of expensive phosphoricone resin used is relatively small. While conventional silicone and polyimide resin insulation used for H-layer insulation requires curing at a high temperature of 180°C, this material can be obtained by curing at a moderate temperature of 150°C. Moreover, it has excellent heat resistance and fatigue properties at high temperatures.

[Brief explanation of the drawing]

FIG. 1 is a characteristic diagram showing the relationship between the temperature and tan δ of an electrically insulated wire, and FIG. 2 is a characteristic diagram showing the heat-resistant life of the electrically insulated wire.゛a: Electrical insulating wire according to the present invention b: Electrical insulating wire with a proven track record of single F type (7317)
Agent Patent Attorney Kensuke Chika (and 1 other person) 1st
Figure 4 Return (C) Figure 2 Temperature/"1("()

Claims (1)

[Claims] 5% by weight of a resin composition containing as essential components an epoxy resin, a polysiloxane compound, a catalytic amount of an aluminum compound, and a catalytic amount of an organosilicon compound having a hydrolyzable group.
1. An electrical insulating wire, characterized in that it is wound with a mica tape containing 30 to 30% by weight, impregnated with a resin composition consisting of an epoxy resin and an acid anhydride curing agent, and then cured.