JPS6070712A - Resin composite material for insulation of transformer - Google Patents

Abstract

PURPOSE:To obtain a low beat noise transformer by insulating with a resin composite material wherein unsaturated polyester resin denatured with vegetable fats and oils or their fatty acids dissolved in a reactive diluent consisting of one, two or more materials selected from acrylic ester and its substituted derivatives and styrene monomers. CONSTITUTION:As an unsaturated polyester resin denatured with vegetable fats and oils or their fatty acids, raw materials of alpha,beta-unsaturated polybasic acids, saturated polybasic acids, polyhydric alcohols, etc. are used and these are denatured with soybean oil, olive oil, coconut oil, tall oil, etc. or their fatty acids. As a reactive diluent, acrylic ester or its substituted derivative, e.g., 2-hydroxyethylmethacrylate, 2-hydroxypropylmethacrylate, laurylmethacrylate, fumaric acid butyl, fumaric acid dioctyl, itaconic acid dibutyl, etc. are mentioned. As a styrene monomer, styrene, vinyltoluene, divinylbenzene, etc. are mentioned. The obtained resin composite material can be hardened by a well-known method such as redox hardening combining a peroxide and a hardening accelerator, ultraviolet ray hardening combining a well-known optical sensitizer, far infrared ray hardening, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a resin composition for transformer treatment suitable for producing a 1-lance with low whirring noise.

[Technical background of the invention and its problems]

Conventionally, transformers have generally been treated with insulating materials for the purpose of electrical insulation, heat dissipation during operation, absorption of humming noise generated by electrical vibration, and the like.
As such insulating materials, unsaturated polyester resin A'D polybutadiene resin and the like have been used conventionally. The former has a large shrinkage during curing, is prone to cracking, and does not have sufficient adhesion, so it has little effect in reducing whining noise, while the latter has poor electrical properties and chemical resistance (0), compared to unsaturated polyester resin. The former has good adhesion, but is expensive and lacks versatility.Also, both the former and the repeater use styrene monomer, so the noise reduction effect was insufficient.

[Purpose of the invention]

An object of the present invention is to solve the problem of the fin points of the prior art, and to provide a resin composition for transformer treatment that has a remarkable effect of reducing whining noise and has excellent crack resistance. be.

[Summary of the invention]

The present invention was made as a result of extensive research to achieve the above object, and it was discovered that the resin composition described below achieves the above object.

That is, the present invention combines (A) vegetable oil or unsaturated polyester resin modified with this fatty acid with (B) one or two selected from acrylic esters, substituted derivatives thereof, and styrene monomers.
This is a resin composition for transformer processing, characterized in that it is dissolved in a reactive diluent consisting of at least one species.

As <A) vegetable oil or unsaturated polyester resin modified with this fatty acid used in the present invention, raw materials such as α, β-unsaturated polybasic acid, saturated polyhydric M acid, polyhydric alcohol, etc. are used, and soybean oil , linseed oil, olive oil, coconut oil, tall oil, etc., or those modified with these fatty acids.

Modification with vegetable fats and oils or these fatty acids has the effect of increasing the solubility of the resin, lowering the viscosity of the resin, and further improving properties such as surface drying properties and flexibility of the cured resin. Representative examples of α,β-unsaturated polybasic acids include maleic acid, fumaric acid, and itaconic acid; representative examples of saturated polybasic acids include phthalic acid, isophthalic acid, adipic acid, malonic acid, het acid, and their anhydrides, etc. Main examples of polyhydric alcohols include edi non-glycol, diethylene glycol, propylene glycol, glycerin, trimethylolethane, i
- Limethylolpropane, pentaerythritol, tris-2-hydroxyethyl isocyanurate, etc. To prepare a modified unsaturated polyester resin, vegetable oil or one or more of these fatty acids and a predetermined unsaturated polyester raw material are heated in a reaction vessel at usually about 150 to 220°C while blowing an inert gas. The condensation reaction may be carried out at a temperature of . The reaction must be continued until the reaction system becomes at least transparent, and it is desirable that the acid value of the resulting resin be 30 or less, preferably 25 or less.

Examples of the (B) reactive diluent selected from acrylic esters, substituted derivatives thereof, and styrene monomers used in the present invention include the following.

First, as the acrylic ester or its substituted ii, for example, 2-hydroxyethyl methacrylate, 2
-Hydroxypropyl methacrylate, lauryl methacrylate, stearyl methacrylate, ethylene dimethacrylate-1-, dibutyl maleate, dioctyl maleate, dibutyl fumarate, dioctyl fumarate, dibutyl itaconate, and the like. Examples of the styrene monomer include styrene, vinyl 1-toluene, divinylbenzene, and the like.

In the present invention, the modified unsaturated polyester resin is mixed and dissolved in a reactive diluent and used, but the blending ratio is preferably limited as follows. That is, the reactive diluent used is one containing 100 to 40% by weight of acrylic ester or its substituted derivative and 60% or less of styrene monomer.

The blending ratio of acrylic ester or its substituted derivative is less than 40% by weight, and the blending ratio of styrenic monomer is 6%.
If it exceeds 0mff1%, the adhesion of the cured product will be poor and the whine reduction effect will not be sufficient, and the crack resistance of the crosslinked polyvinyl chloride resin coated lead wire used in the transformer at low temperatures will deteriorate. be.

Furthermore, among acrylic esters or substituted derivatives thereof, hydroxyalkyl methacrylate-1 to 30 to 10
It is preferable to use 0% by weight, 1. This is because, outside this range, a resin composition for transformer treatment with good adhesion and excellent whirring reduction effect cannot be obtained.

The resin composition thus obtained can be cured by a known curing method such as redox curing using a combination of peroxide and a curing accelerator, ultraviolet curing using a known photosensitizer, or far infrared curing. I can do it. Examples of the peroxides include benzoyl peroxide, methyl ethyl ketone peroxide, ditertiary butyl peroxide,
lauryl peroxide, cumene hydroperoxide.

Examples include tertiary butyl peroxide. Examples of hardening accelerators include metal soaps such as cobalt, copper, manganese, and lead, and tertiary amines.

Using the resin composition of the present invention obtained in this way,
．． To insulate lances weighing 5 to 3 kg,
For example, after drying the transformer in a furnace at 100 to 120°C, and cooling it to a temperature of room temperature to 60°C,
After immersing in a resin composition containing a curing agent (organic peroxide) for 2 to 10 minutes at normal pressure or vacuum,
A method of curing and drying at a temperature of 20° C. for several hours is adopted.

[Embodiments of the invention]

Next, the present invention will be specifically explained using examples.

Hereinafter, "parts" means "parts by weight."

Example 1 90 parts of soybean oil fatty acid, 69 parts of maleic anhydride, 44 parts of phthalic anhydride, 70 parts of propylene glycol, and 30 parts of glycerin were charged into a reaction vessel, and heated at 160°C in a nitrogen gas stream.
The mixture was heated for 1 hour, and the temperature was gradually raised to 200°C to carry out a dehydration condensation reaction. When the acid value reached 20, dehydration was performed under reduced pressure, and 0.05 part of hydroquinone was added.
15'0 parts of 2-hydroxyethyl methacrylate at °C;
150 parts of dibutyl itaconate and 15 parts of styrene monomer
0 parts were mixed and diluted, and 3.5 parts of a 6% cobalt naphdate solution was further added to obtain a resin composition (1).

Example 2 95 parts of linseed oil fatty acid, 136 parts of maleic anhydride, 66 parts of adivic acid, and 103 parts of ethylene glycol were charged, heated at 160°C for 1 hour under a nitrogen gas stream, and then gradually raised to 200°C. Perform a dehydration condensation reaction.

When the acid value reached 20, vacuum dehydration was performed, the mixture was cooled and 0.05 part of hydroquinone was added, and the mixture was heated at 100°C for 2 hours.
-200 parts of hydroxyethyl methacrylate, 100 parts of stearyl methacrylate, and 100 parts of vinyltoluene
Mix and dilute 1 part, and then add 2 parts of 6% mankanate naphthenate solution.
．． 5 parts were added to obtain a resin composition (1 piece).

Example 3 112 parts of soybean oil, 18 parts of glycerin and 0.0 parts of lead oxide
4 parts were charged, and the transesterification reaction was carried out at 240° C. for about 1 hour under a nitrogen gas stream. After cooling to 130°C, 86 parts of maleic anhydride, 91 parts of inphthalic acid and 91 parts of ethylene glycol were added, and the temperature was gradually raised to 20 parts.
The dehydration condensation reaction is carried out at 0°C.

Dehydration is performed under reduced pressure at an acid value of 20, and hydroquinone is removed by cooling.
05 parts of 2-hydroxyprobyl methacrylate, 100 parts of dibutyl itaconate and 150 parts of stearyl methacrylate were mixed and diluted at 100°C, and 2 parts of 6% cobalt naphdate solution was added to a colander. A resin composition (III) was obtained.

Resin compositions (I) for trans treatment thus obtained (
nl) To 100 parts of 1,1-di as a curing agent, add 1 part of monobutylperoxy-3.3.5-trimethylcyclohexane and mix with stirring. Using each resin composition of the resulting IC, the following conditions were applied: Insulated a power transformer weighing 12 kg. That is, after drying the transformer with residual heat in a furnace at 110°C, the transformer was immersed in a resin composition kept at room temperature at about 50°C for 5 minutes at normal pressure.
It was cured by heating at ℃ for 2 hours. In addition, in order to examine the cracking properties of PVC lead wires, test pieces shown in FIGS. 1 and 2 were prepared. That is, as shown in Figures 1 and 2, 10 UL-1 wires are placed on a 1 mm thick iron plate 1.
015)) Bend the V C lead wire 2 so that it sandwiches the iron plate 1, adhere both ends of the lead wire 2 to both sides of the iron plate 1 with adhesive tape 3, and roughly connect the lower side of the lead wire 2. An 11-thick iron plate 1 was applied to the plate and fixed using a clip. Next, the whole body was immersed in the resin composition for 5 minutes. A test piece was obtained by curing at 110°C for 2 hours.

Comparative Example 1 130 parts of maleic anhydride, 294 parts of phthalic anhydride, 304 parts of propylene glycol, and 0.03 parts of hydroquinone
The mixture was heated at 160°C for 1 hour while introducing nitrogen gas, and the temperature was gradually raised to proceed with the condensation reaction at 200°C. When the acid value reached 25, dehydration was performed under reduced pressure, and after cooling, 20.03 parts of Hydrogin was added, and 700 parts of styrene was mixed at 100°C, diluted with -C, and a 6% cocopal naphthenate solution was added. 5 to form a resin composition (IV
) was obtained.

Comparative Example 2 In Example 1, 30 parts of 2-hydroxyethyl methacrylate, 100 parts of dibutyl itaconate, and 3 parts of styrene
A similar resin composition (V) was obtained except that it was diluted with 20 parts.

Comparative Example 3 A resin composition (Vl>) was obtained which was the same as in Example 2 except that it was diluted with 100 parts of stearyl methacrylate and 300 parts of vinyl methacrylate.

Comparative Example 4 The same resin composition (Vl
[) was obtained.

The same amount of the curing agent as in the example was added to the resin compositions (Vl) to (Vll) thus obtained, insulation treatment was performed in the same manner, and crankability test pieces of PVC lead wires were prepared. did.

Next, apply your ear or a stethoscope to the lance to hear the humming sound when a voltage 1.1 times the rated voltage (100V) is loaded on the primary side of the transformer that has been insulated in the Examples and Comparative Examples. I listened to it. As a result, the whirring noise of the transformer obtained in the example was much smaller than that in the comparative example.

In addition, the level of humming noise during the same voltage load application as above was measured using a vibration tester. The results are shown in Table 1. Furthermore, I) V created in Examples and Comparative Examples
C lead wire cracking test pieces were left in a low temperature chamber at -15° C. for 1 hour, then taken out, immediately bent to an angle of 180', and the number of lead wires with cracks in the coating was counted. The result is [number of cracks]/10
It is expressed in Table 1.

Table I Since the bendability of the lead wire at low temperatures rarely exceeds 10, there is an advantage that the occurrence of cracks in the exposed portion of the lead wire in cold weather is greatly reduced.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view of a crankability test piece prepared in an example of the present invention and a comparative example, and FIG. 2 is a top view thereof. 1... Iron plate, 2... PVC covered lead wire, 3.
··Adhesive tape. Patent applicant: Toshiba Chemical Corporation Figure 1 Figure 2

Claims (1)

[Scope of Claims] 1. (A) vegetable oil or unsaturated polyester resin modified with this fatty acid, (B) one or more selected from acrylic esters, substituted derivatives thereof, and styrene spinning wheels. A resin composition for transformer processing, characterized in that it is dissolved in a reactive diluent. 2. The resin composition for trans treatment according to claim 1, wherein the reactive diluent is 40 to 100% by weight of an acrylic ester or a substituted derivative thereof and 60% by weight or less of a styrene monomer. . 3 The reactive diluent acrylic ester or its substituted derivative is a hydroxyalkyl methacrylate 30-1
Claim 1 characterized in that it is 00% by weight.
3. The resin composition for transformer treatment according to item 1 or 2.