KR101779088B1 - Method for manufacturing insulating material using resin composition having hydrophobicity - Google Patents

Abstract

Disclosed are a resin composition with hydrophobicity and a manufacturing method for an insulating material using the same. The resin composition with hydrophobicity according to the present invention contains 50-80 wt% of an epoxy resin, 19-40 wt% of a curing agent containing acid anhydride, and 1-10 wt% of an additive containing an epoxy based compound, wherein the epoxy based compound includes fluoro to have hydrophobicity.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of manufacturing an insulating material using a resin composition having a hydrophobic property,

More particularly, the present invention relates to a resin composition having a hydrophobic property including an epoxy resin, a curing agent, and an additive including fluoro, and a method of manufacturing an insulation using the same. ≪ / RTI >

In general, insulating materials used in heavy electric equipment including transformers, generators, transformers, electric wires and the like are produced by curing an epoxy resin composition. The cured product of the epoxy resin composition is excellent in adhesive strength, chemical resistance and mechanical properties, and is widely used as an electrical insulating material.

However, when a cured product formed from an epoxy resin composition is used as an outdoor insulating material, the weather resistance and water repellency are lowered due to factors such as ultraviolet rays, temperature change, rain and persistence of pollution.

Therefore, there is a demand for a method for producing an insulator having excellent water repellency and mechanical strength while maintaining the basic electrical resistance characteristic even under severe external environmental conditions.

A background art related to the present invention is Korean Patent Registration No. 10-0485962 (registered on Apr. 20, 2005), which discloses a high weather-resistant epoxy resin composition for outdoor electrical insulations.

An object of the present invention is to provide a resin composition having hydrophobicity, including an epoxy resin, a curing agent, and an additive containing fluoro.

Another object of the present invention is to provide a method for producing an insulator having water repellency on the surface of a heavy electric apparatus using a resin composition having hydrophobicity.

According to an aspect of the present invention, there is provided a hydrophobic resin composition comprising 50 to 80% by weight of an epoxy resin; 19 to 40% by weight of a curing agent comprising an acid anhydride; And 1 to 10% by weight of an additive comprising an epoxy compound, wherein the epoxy compound contains fluoro and is hydrophobic.

The resin composition may contain 2 to 5% by weight of an additive comprising the epoxy compound.

The epoxy compound may be prepared by reacting a fluorinated alcohol and epichlorohydrin (ECH).

The epoxy compound may be prepared under an alkaline hydroxide catalyst.

The acid anhydride may include at least one of HHPA (Hexahydrophthalic anhydride), MeHHPA (Methyl hexahydrophthalic anhydride), THPA (Tetra hydro phthalic anhydride) and MeTHPA (Methyl tetrahydrophthalic anhydride).

According to another aspect of the present invention, there is provided a method of manufacturing an insulator, comprising: (a) preparing an epoxy compound by reacting a fluorinated alcohol and epichlorohydrin (ECH); (b) mixing 50 to 80% by weight of an epoxy resin and 19 to 40% by weight of a curing agent containing an acid anhydride, adding 1 to 10% by weight of an additive comprising the epoxy compound, and stirring the mixture; And c) curing the result of step (b) in a mold at 120 to 140 ° C for 30 minutes to 3 hours, and then separating the resultant from the mold to prepare an insulating material, wherein the epoxy compound Is characterized by having hydrophobicity including fluoro.

The epoxy compound of step (a) may be prepared in the presence of an alkaline hydroxide catalyst.

The reaction of step (a) may be performed at 80 to 110 ° C.

The resin composition according to the present invention contains an epoxy resin, a curing agent containing an acid anhydride, and an epoxy compound containing fluoro, and has a hydrophobic effect.

In addition, it is possible to produce an insulator having water repellency on the surface of a heavy electric apparatus by using a resin composition having a hydrophobic property, and can be applied to an outdoor insulator excellent in weather resistance and durability.

1 is a flowchart showing a method of manufacturing an insulator according to the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving them will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.

Hereinafter, a resin composition having hydrophobicity according to a preferred embodiment of the present invention and a method for producing an insulator using the same will be described in detail with reference to the accompanying drawings.

1 is a flowchart showing a method of manufacturing an insulator according to the present invention.

Referring to FIG. 1, the method for manufacturing an insulating material of the present invention includes an epoxy compound preparation step (S110), an epoxy resin, a curing agent, an additive mixing step (S120), and a post-curing insulation preparation step (S130).

The epoxy compound preparation step (S110)

First, an epoxy compound is prepared by reacting a fluorinated alcohol and epichlorohydrin (ECH) under an alkaline hydroxide catalyst.

Examples of fluorinated alcohols include 1H-trifluoroethanol, 1H-pentafluoropropanol, 6- (perfluoroethyl) hexanol 1H, 1H-heptafluorobutanol, 2- (perfluorobutyl) ethanol, 3- (perfluorobutyl) propanol, 6- ethanol, 3- (perfluorohexyl) propanol, 6- (perfluorohexyl) hexanol, perfluorooctylethanol and the like, and any alcohol containing fluoro may be included.

As the alkaline hydroxide catalyst, NaOH or the like can be used, and NaOH serves as a catalyst to cause the epoxidation reaction to proceed by the combination of the fluorinated alcohol and ECH. The epoxidation reaction is carried out at about 80 to 110 ° C. If the reaction temperature is lower than 80 ° C, the effect on the reaction rate is not expected because the temperature is low. If it exceeds 110 ° C, And the physical properties of the epoxy compound may be lowered.

As the epoxy compound, 3 to 5 moles of epichlorohydrin may be added to 1 mole of the fluorinated alcohol, but the present invention is not limited thereto.

The amount of the alkaline hydroxide catalyst is preferably 1 to 4 moles, more preferably 2 to 3 moles, per 1 mole of the fluorinated alcohol. If it is less than 1 mole, it is difficult to expect the phenomenon that the reaction rate increases. On the other hand, when the molar ratio exceeds 4 mol, there is a problem that the addition amount of the catalyst increases only without increasing the reaction rate.

The epoxy-based compound prepared above has a characteristic of containing hydrophobicity by including fluoro. Thereby, the resin composition containing the hydrophobic epoxy compound can be cured to produce an insulator having water repellency on the surface of the heavy electric equipment.

Epoxy resin, curing agent and additives (S120)

Next, 50 to 80% by weight of an epoxy resin and 19 to 40% by weight of a curing agent containing an acid anhydride are mixed, and 1 to 10% by weight of an additive containing the epoxy compound is added and stirred. The stirring can be carried out at room temperature for about 10 to 60 minutes, and after the stirring, a resin composition having hydrophobicity including fluoro can be prepared.

The epoxy resin reacts with a curing agent and is excellent in adhesiveness, mechanical strength, moldability, electrical insulation and the like, and is suitable as a material for an insulating material. The epoxy resin contained in the resin composition of the present invention can be used without limitation such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and aliphatic epoxy resin.

The epoxy resin is preferably contained in an amount of 50 to 80% by weight based on 100% by weight of the resin composition. When the content of the epoxy resin is less than 50% by weight, workability and adhesiveness may be deteriorated, and when it exceeds 80% by weight, electrical characteristics and mechanical properties are deteriorated.

The resin composition preferably contains 19 to 40% by weight of a curing agent containing an acid anhydride. When the resin composition is out of this range, there is a problem that the withstand voltage resistance is lowered at high temperature accelerated load test.

 The acid anhydride is an alicyclic anhydride (Cyclo Aliphatic) and has a molecular weight of 700 to 1,700, which can improve the heat resistance of the cured product. The alicyclic acid anhydrides include HHPA (Hexahydrophthalic anhydride), MeHHPA (Methyl hexahydrophthalic anhydride), THPA (Tetra hydrophthalic anhydride) and MeTHPA (Methyl tetrahydrophthalic anhydride), and may include at least one of them. HHPA is solid at room temperature, has colorless transparency, and has excellent weather resistance. MeHHPA is liquid at room temperature and has weatherability and low viscosity. THPA is solid at room temperature and has excellent workability. MeTHPA is liquid at room temperature and is used for impregnation.

The resin composition contains a minimum amount of an additive including an epoxy compound to show a hydrophobic floating effect. More desirably, 1 to 10% by weight of an additive containing an epoxy compound is preferably contained, more preferably 2 to 5% by weight. For example, the resin composition may contain 79 wt% of an epoxy resin, 19 wt% of a curing agent, and 2 wt% of an additive. When the additive is out of the range of 1 to 10% by weight, there is a problem that the withstand voltage resistance is lowered at the high temperature accelerated load test.

After the hardening step (S130)

Next, the resultant of step S120 is put into a mold to be molded and cured.

The curing is performed at 120 to 140 ° C for 30 minutes to 3 hours. After curing, the cured product is separated from the mold to prepare an insulating material. If necessary, the cured product may be separated and post-cured at 120 to 140 ° C for 5 to 10 hours, but is not limited thereto.

As described above, an insulating material having water repellency on the surface of a heavy electric apparatus can be produced by curing a resin composition containing an epoxy compound having a hydrophobic property. In addition, there is an effect that the hydrophobic fluoro floats on the surface of the insulating material and the water repellency and the weather resistance of the insulating material are excellent.

A specific example of the resin composition having hydrophobicity and the method for producing the insulation using the resin composition will be described as follows.

1. Manufacture of insulation

Example

In a 90 DEG C reaction container, 4 mol of ECH (Sigma Aldrich) was added to 1 mol of 6- (perfluorobutyl) hexanol and mixed. 2.5 mol of 50% NaOH was added to 1 mol of 6- (perfluorobutyl) hexanol, and the reaction was carried out at 300 RPM for 3 hours. After washing, separating, neutralizing and recovering, an epoxy compound was prepared.

Next, in a container prepared by mixing 50 wt% of an alicyclic epoxy resin (CY-184, Huntsman) and 40 wt% of a curing agent (Liqacid MH-700G from Shin-Nihon Rika KK) mixed with an MEHHPA curing agent and an HHPA curing agent, 10% by weight of the epoxy compound as an additive was added and stirred.

Next, the agitated product was cured in a mold at 130 ° C for 3 hours, and the cured product was separated from the mold and post-cured at 120 ° C for 10 hours to prepare an insulator.

Comparative Example 1

An insulating material was prepared under the same conditions as those of the examples except that the epoxy resin was not included as an additive in the resin composition.

Comparative Example 2

Except that 5% by weight of a silicone compound containing no fluorine was added to a vessel in which 85% by weight of an alicyclic epoxy resin and 10% by weight of a curing agent mixed with an MEHHPA curing agent and an HHPA curing agent were mixed and stirred. Insulators were prepared under the same conditions.

2. Property evaluation method and result

The following items were evaluated for the insulators prepared in the above Examples and Comparative Examples, and the results of the measurements are shown in Table 1 below.

(1) Hardness

The hardness was measured by the test method specified in ASTM D-2240. When the hardness is high, there is a problem that the thermal shock resistance is deteriorated. When the hardness is low, there is a problem that the dielectric breakdown voltage is lowered, and it is preferable that the hardness is represented by 60 to 75.

(2) Accelerated load test

The reliability test was conducted to determine the deterioration of the insulation of the cured product for a long period of time. Twenty samples were prepared for each composition and heat treated at 120 ° C for 33 hours.

(3) Surface contact angle

After a certain amount of water was dropped on the insulating material, the contact angle was evaluated using a contact angle meter (CAX-150) after 5 minutes.

[Table 1]

The insulation prepared according to the examples showed excellent hardness, excellent reliability in long-time use, and excellent hydrophobicity on the surface of the cured product. On the contrary, the insulating materials prepared in Comparative Examples 1 and 2 do not contain an epoxy compound as an additive in the resin composition, or the content of the component deviates from the range suggested in the present invention. In this case, the hardness is relatively weak as compared with the insulator produced according to the embodiment, and it can be confirmed that the insulation breakdown has occurred. In addition, in the case of Comparative Examples 1 and 2, it can be seen that the hydrophobicity on the surface of the cured product is relatively lower than the hydrophobicity on the surface of the cured product of the examples.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It is to be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

S110: Production of epoxy compound
S120: Epoxy resin, curing agent and additive mixture
S130: Preparation of insulation after curing

Claims (8)

delete delete delete delete delete (a) reacting 6-perfluorobutyl hexanol and epichlorohydrin (ECH) to produce an epoxy compound;
(b) 50 to 80% by weight of an alicyclic epoxy resin and 19 to 40% by weight of a curing agent comprising methylhexahydrophthalic anhydride (MEHHPA) and hexahydophthalic anhydride (HHPA) 1 to 10% by weight of an additive including an epoxy compound is added and stirred; And
(c) curing the result of step (b) in a mold at 120 to 140 ° C for 30 minutes to 3 hours, and then separating the resultant from the mold to prepare an insulator,
The epoxy compound of step (a) is prepared at 80 to 110 ° C under a sodium hydroxide catalyst, and is hydrophobic including fluoro,
Wherein the surface contact angle of the insulator is 110 °. delete delete

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