JP5229787B2 - Insulating polymer material composition - Google Patents

Description

  The present invention relates to an insulating polymer material composition, for example, an insulation configuration of a voltage device (for example, a high voltage device such as a heavy electrical device) provided with a switching device such as a circuit breaker or a disconnect device in a housing. It is used for.

  For example, applied to insulation structures (eg, parts that require insulation) of voltage equipment (heavy electrical equipment, etc.) with switchgear such as circuit breakers and disconnectors in the housing (for example, directly exposed to the outdoors) As a material, a thermosetting resin such as an epoxy resin derived from a fossil raw material (petroleum, etc.) (a resin starting from petroleum, etc.) is used as a matrix, and a curing agent or filler (for example, consuming a large amount of energy) A polymer material composition (hereinafter referred to as an insulating composition) obtained by heat-curing an insulating material obtained by appropriately mixing various components such as refined silica and alumina (inorganic fillers such as alumina). A product (mold cast product; hereinafter referred to as an insulating product) made of an insulating composition formed by casting has been widely known (for example, Patent Document 1). In addition, by appropriately preheating the components of the insulating material before the mixing step (for example, preheating the filler) or blending a dispersant (such as phosphate ester) (for example, Patent Document 2), the mixing property can be improved. It is known that the production efficiency can be improved by improving the quality (for example, reducing the viscosity of the mixture) or shortening the curing time in the subsequent curing process.

In addition, with the sophistication and concentration of society, the capacity of voltage devices, etc. has increased in size, size, and high physical properties (for example, electrical properties (such as dielectric breakdown electric field properties), mechanical properties (such as bending strength)), etc. In addition, there has been a strong demand for improvement in various characteristics of the insulating product. For example, because fossil raw material-derived materials (limited resources) have been widely used as thermosetting resins that influence the physical properties of insulating products, global environmental conservation (energy saving, prevention of global warming by reducing CO ₂ emissions, etc.) In view of the above, an attempt has been made to collect and reuse (recycle) an insulating product to be disposed of (for example, a product to be disposed of due to lifetime, failure, etc.).

However, the reuse method has not been established and is hardly performed. Exceptionally, only members with relatively uniform quality (PE cable covering members used in insulating products) are recovered and used as thermal energy. However, since this thermal energy requires a combustion treatment process, May harm the environment. Also, in the case of incineration, since various toxic substances and CO ₂ are discharged in large quantities, there is a risk of harming the global environment as described above.

  Attempts to apply a non-fossil raw material-derived substance (for example, a combination of an inorganic filler and an organic filler such as a wood resource as a filler) in each component of the insulating composition are known (for example, Patent Document 3), the application ratio of the entire insulating composition is very small, and most of it is occupied by components depending on the fossil raw material-derived material.

  In addition, an attempt to apply a biodegradable resin (for example, polylactic acid resin) as a thermosetting resin that is one of the essential components of the insulating composition is known (for example, Patent Document 4). Since the biodegradable resin is a substance that is relatively easily melted (for example, melted at a temperature of about 100 ° C.), particularly to a high-voltage device (a high-voltage device capable of increasing the temperature to about 100 ° C. during use). The application of is considered dangerous.

  Furthermore, although an attempt to apply a cross-linking composition using a biological material is also known (for example, Patent Document 5), an aldehyde is used as a curing agent, and a temperature atmosphere of about room temperature (for example, Although it has high mechanical properties in the temperature environment of a printed wiring board), it is difficult to obtain sufficient mechanical properties in a high-temperature atmosphere (for example, the usage environment of voltage devices or the like).

  Here, in an insulating composition to which a thermosetting resin generally referred to as an epoxy resin is applied, the most compounded component by volume ratio and weight ratio is a filler. From this, coal ash produced as a by-product of a thermal power plant or the like is applied as a filler for the epoxy resin (reuse of coal ash such as fly ash type I, type II, type III of JIS A6201-1999; For example, attempts to make patent documents 6 and non-patent documents 1) have begun.

By applying coal ash as a filler for the epoxy resin in this way, no new production energy is consumed in the filler, and no carbon dioxide is generated. Insulating compositions having mechanical properties can be safely applied and have the potential to contribute to global environmental conservation.
Japanese Patent No. 3359410 (for example, descriptions according to Tables 4 to 7) JP 2004-75817 A (for example, [0008] to [0011], [0018], [0024]) JP 2004-171799 A (for example, [0005] to [0007]) JP 2002-358829 A (for example, [0007] to [0012]) JP 2002-53699 A (for example, [0007] to [0011]) JP 2007-211252 A (for example, [0010] to [0017], [0038]) “COAL ASH widely used as a resource”, pamphlet, Japan Fly Ash Association, April 2004.

  In various components such as epoxy resins, curing agents, fillers, etc., the preheating performed before the mixing step in consideration of the improvement of manufacturing efficiency is set according to the characteristics of the epoxy resin, the heat curing conditions, etc. When the preheating temperature is high (for example, a temperature exceeding about 130 ° C.), among the various components, the epoxy resin and the curing agent can reduce the viscosity and contribute to shortening the curing time. In the case of using coal ash, the coal ash (at least a part) starts to solidify in a block form by pozzolanic reaction (for example, a part of the filled coal ash is solidified). As a result, coal ash cannot be uniformly dispersed in the epoxy resin, and the mechanical properties of the intended insulating composition are reduced. For example, when the preheating temperature is 150 ° C. or higher, the coal ash is solidified during the preheating step, and the mixing property may be lowered, and the molding itself may not be performed.

  When various components are preheated at a relatively low temperature (for example, about 130 ° C. or less) in consideration of the uniform dispersion and the like, coal ash does not start to solidify unless the preheating process is spent for a long time. If the viscosity is too high, the working time for the subsequent curing process becomes long, and the production efficiency deteriorates. Moreover, if the blending ratio of coal ash in the insulating material is reduced, the linear expansion coefficient of the insulating composition itself is increased. For example, when using an insert (such as a metal insert embedded in an insulating product), a sufficient amount of coal ash may be applied to reduce the difference in coefficient of linear expansion between the insert and the insulating composition. However, if the blending ratio is reduced as described above, the thermal physical properties increase due to the difference in the coefficient of linear expansion between the insert and the insulating composition, resulting in a decrease in mechanical properties.

  In Patent Document 2, in an insulating circuit board composition using an epoxy resin and an inorganic filler, an epoxy resin and a modifier (such as a phosphate ester) and a modifier (such as a silane coupling agent) are used. Although it is disclosed that the adhesiveness with the inorganic filler is improved and the inorganic filler is highly filled, the inorganic filler is limited to those containing aluminum nitride. Patent Document 6 discloses that in fly ash, ionic impurities are removed by pretreatment (such as a purification step) or surface treatment with a silane coupling agent is performed to increase affinity with an epoxy resin. However, the number of manufacturing processes increases.

  As described above, in an insulating composition using an insulating material composed of an epoxy resin, a curing agent, coal ash, etc., it not only contributes to the preservation of the global environment, but also provides an insulating property. There is a demand for imparting sufficient mechanical properties as a composition and enhancing the production efficiency of the insulating composition.

  The present invention is intended to solve the above-described problems, and uses an insulating material composed of epoxy resin, coal ash, filler, etc., and not only contributes to global environmental conservation, but is also sufficient as an insulating composition. An object of the present invention is to provide an insulating polymer material composition capable of imparting excellent mechanical properties and electrical properties and improving the production efficiency of the insulating composition.

Specifically, the invention described in claim 1 includes at least each component of epoxy resin, coal ash, curing agent, polyalkyl phosphate ester (for example, monoalkyl phosphate ester, dialkyl phosphate ester, trialkyl phosphate ester). It is a composition obtained by heat-curing an insulating material formed by mixing and used for an insulating structure of a voltage device. The coal ash is used in an amount of 500 phr to 600 phr with respect to 100 phr of an epoxy resin, and is 130 ° C. or lower. It is characterized by being mixed (mixed with other components) after preheating.

The invention described in claim 2 is characterized in that, in the invention described in claim 1 , the epoxy resin is epoxidized linseed oil.

The invention according to claim 3 is the invention according to claim 1 or 2 , characterized in that the coal ash is fly ash.

The invention according to claim 4 is the invention according to claims 1 to 3 , wherein the polyalkyl phosphate ester is used in an amount of 0.05 phr to 2 phr with respect to 100 phr of the epoxy resin.

By using a polyalkyl phosphate ester as in the first to fourth aspects of the invention, the compatibility between the epoxy resin and coal ash is improved. For this reason, it is not necessary to pre-process the coal ash (such as a refining process) or reduce the blending ratio, and the coal ash can be easily dispersed uniformly in the epoxy resin. In addition, when an insert (such as a metal insert incorporated in an insulating product) is used, the difference in linear expansion coefficient between the insert and the insulating composition is reduced.

Moreover, in the invention of Claim 2, the mixture ratio of the non-fossil raw material origin substance increases. Furthermore, in the invention described in claim 4 , it is possible to prevent the insulating property of the insulating composition from being too low and to prevent the action similar to that of the plasticizer from being too great.

As described above, according to the first to fourth aspects of the invention, not only contributes to the preservation of the global environment while imparting electrical properties, but also imparts sufficient mechanical properties and electrical properties as an insulating composition, It becomes possible to increase the production efficiency of the insulating composition. Moreover, in invention of Claim 2, it becomes possible to contribute more to the said global environment conservation. Furthermore, the invention according to claim 4 can impart better mechanical properties and electrical properties.

  Hereinafter, the insulating polymer material composition in the embodiment of the present invention will be described in detail.

  This embodiment uses an insulating material obtained by mixing an epoxy resin, coal ash, and a curing agent, and at least a component containing a phosphate ester, and is obtained by heating and curing the insulating material. It is an insulating composition applied to the insulation structure of a voltage apparatus. For example, it has been known to use a phosphate ester only in the case of an inorganic filler containing aluminum nitride as in Patent Document 2, but an anion against coal ash such as fly ash as in this embodiment. The use of system surfactants has not been known.

  When phosphate ester is used as an anionic surfactant, the compatibility between coal ash and epoxy resin is increased, and the viscosity of the insulating material is reduced. If the amount of phosphate ester is too large, it is an ionic material, so that the insulation of the insulating composition is lowered, or the action similar to that of a plasticizer is increased, resulting in a decrease in strength and an increase in linear expansion coefficient. Therefore, it is preferable to adjust the blending amount.

  Examples of the epoxy resin include those applied to general voltage equipment, and examples include those derived from plants (derived from non-fossil raw materials) such as epoxidized linseed oil and epoxidized soybean oil. In addition, epoxidized products composed of animal and vegetable oils that are unsaturated fatty acids can also be applied as non-fossil raw material-derived substances.

  As coal ash which is a filler, for example, coal ash produced as a by-product of a thermal power plant or the like can be applied (recycle coal ash). Specifically, fly ash as shown in Non-Patent Document 1 (for example, Type I, type II, type III). Although there are some differences in the physical properties of the target polymer composition depending on the type of fly ash, they are common in that they are excellent in environmental performance, economy and the like. The blending ratio of the filler may be appropriately set according to the target polymer composition, but if it is too large, the mixing / casting property may be impaired.

  As a hardening | curing agent, various things, such as amines, acid anhydrides, phenols, imidazoles, etc. which can react with an epoxy resin, for example, can apply the thing derived from plants, such as a castor oil-type polyol.

  For example, an epoxy equivalent of the epoxy resin is calculated, and a stoichiometric amount based on the epoxy equivalent is added (for example, 1.0 as a stoichiometric ratio). The blending ratio of such a curing agent can be appropriately set depending on, for example, the priority order of physical properties required for the target polymer product.

  In addition to the epoxy resin, coal ash, and curing agent, for example, workability is improved (for example, shortening of work time, etc.), moldability, Tg characteristics, mechanical / physical properties, electrical properties, and the like are improved. For the purpose, various additives can be appropriately used. For example, curing accelerators (starting point of curing of the curing agent; for example, organic peroxides, amines, imidazoles, etc.), reaction inhibitors, reaction aids (reaction ( The purpose of controlling (Tg characteristics); peroxide, etc.) can be used in combination as appropriate.

  When peroxide is mixed with polymer components, etc., the mixture increases in viscosity over time, and the productivity may decrease (for example, the mixability and moldability may decrease). If the time (pot life) is, for example, 60 minutes or more, it can be regarded as having good productivity.

  Crosslinking in the insulating composition of the present embodiment is essentially due to the curing agent, and the crosslinking structure is affected by the curing conditions and the presence or absence of the curing accelerator, reaction inhibitor, reaction aid, etc. There is no.

  For example, the curing conditions (temperature, time, etc.) are appropriately set (for example, appropriately set according to the type and blending amount of the curing accelerator) in order to obtain the desired physical properties of the insulating composition. Even if the curing conditions are different, there is no great difference in the physical properties themselves. Moreover, the reaction accelerator and reaction inhibitor are appropriately applied for the purpose of improving the workability and productivity by increasing the reactivity or making it safe (suppressed). Even if the kind and the blending ratio are different, there is no great difference in the physical properties themselves. Further, the reaction aid is appropriately applied to adjust the reactivity (for example, adjustment of Tg characteristics in the case of peroxide) in the same manner as the reaction accelerator and reaction inhibitor (for example, curing conditions and acceleration of curing). This is applied as appropriate according to the type and blending amount of the agent and the like, and even if the kind and blending amount of the reaction aid is different, there is no significant difference in the physical properties themselves.

[Example]
Next, examples of the insulating composition in the present embodiment will be described.

  First, as shown in Table 1 below, 100 phr of epoxidized linseed oil (Daimac Chemicals Daimac L-500), which is a non-fossil raw material-derived material, is used as an epoxy resin, and phenol resin (PR, manufactured by Sumitomo Bakelite Co., Ltd.) as a curing agent. -HF-3) in a stoichiometric amount (61 phr with respect to 100 phr of epoxy resin in this example), fly ash as a coal ash that is an inorganic filler (Fly ash type II manufactured by TEPCO Environmental Engineering Co., Ltd. (JIS A6201-1999)) ), 500 phr to 600 phr, 1 phr of imidazole (2E4MZ manufactured by Shikoku Kasei Co., Ltd.) as a curing accelerator, and 0.05 phr to 5.0 phr of polyalkyl phosphoric acid (ADEKA COL CS-1361E manufactured by ADEKA) as a surfactant, Preheat these various components at 130 ℃ Mixture to obtain a variety of insulating materials S1-S9.

  Also, the same epoxidized linseed oil, phenolic resin, fly ash, and imidazole as the insulating materials S1 to S9 are used in 100 phr, stoichiometric amount (61 phr with respect to 100 phr of epoxy resin in this embodiment), 300 phr to 450 phr, and 1 phr, respectively. Various components were preheated at a temperature of 100 ° C. to 130 ° C. and then mixed to obtain various insulating materials P1 to P7. In the case of samples P1 to P7, fly ash was preheated after surface treatment with 1 wt% of silane coupling agent (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) (1 wt% with respect to fly ash) by an integral blend method.

Then, the mixing / casting properties (relative evaluation) and the viscosity (P · s) of each of the insulating materials S1 to S9 and P1 to P7 produced as described above were measured, and the results are shown in Table 2 below. Moreover, samples of various insulating compositions (10 mm × 5 mm) were obtained by casting the insulating materials S1 to S9 and P1 to P7, respectively, and performing heat treatment (three-dimensional crosslinking) at a temperature of 150 ° C. for 20 hours. × 200 mm sample) was prepared, the bending strength (MPa) in a room temperature atmosphere by a three-point bending method, and the linear expansion coefficient (10 ⁻⁶ ) by TMA were measured, and the results are shown in Table 2 below. In addition, in the mixing / castability column of Table 2 below, the symbol “○” indicates excellent results, the symbol “×” indicates that the desired molding was not possible, and the symbol “Δ” indicates “x”. If the result is better but insufficient, it shall be indicated.

<Insulating materials P1 to P7>
From the results shown in Table 2, in the case of an insulating material surface-treated by the integral blend method, if the preheating temperature of the fly ash is relatively high like the insulating material P7, the fly ash is solidified during mixing by the preheating. It can be read that casting is no longer possible.

Further, when the fly ash preheating temperature is relatively low as in the insulating materials P1 to P6, the fly ash is not solidified as described above, and the fly ash is mixed in a relatively small amount. Although the viscosity of the insulating material itself is suppressed and mixing / casting properties are improved, the coefficient of linear expansion is relatively high (an insert (iron: copper: aluminum = 12 × incorporated in a general insulating product). 10 ⁻⁶ : 17 × 10 ⁻⁶ : 22 × 10 ⁻⁶ ratio insert) is higher than the linear expansion coefficient (for example, the linear expansion coefficient of 33 × 10 ⁻⁶ is too large). ).

  Further, when the preheat temperature of fly ash is relatively low as in the insulating materials P1 to P6, the bending strength of the insulating composition increases and the linear expansion coefficient decreases as the blending ratio of the fly ash increases. Although the tendency was observed, the tendency for the viscosity of the insulating material itself to increase was also observed. That is, in the case of the insulating materials P1 to P6, when the fly ash is highly filled (for example, highly filled like the insulating materials S1 to S9 described later), the viscosity becomes too high, and the desired molding can be performed. I can read that it disappears.

  Therefore, in the case of applying fly ash that is simply surface-treated, it is difficult to produce an insulating composition unless the fly ash preheating temperature is set to a relatively low temperature or the blending ratio of the fly ash is reduced. It has been found that the mechanical properties and the like are low even if the insulating composition can be produced.

<When insulating materials S1 to S9 are used>
On the other hand, in the case of an insulating material using polyalkyl phosphoric acid, even if the preheating temperature is set to a relatively low temperature as in the insulating materials S1 to S9 and the fly ash is highly filled, the viscosity of the insulating material itself can be suppressed. It can be seen that mixing and casting properties are good. Further, it can be seen that the bending strength of the insulating composition is sufficient and the linear expansion coefficient is relatively low. In particular, it can be read that when the polyalkyl phosphoric acid is set to 2.0 phr or less (for example, 0.05 phr to 2 phr in this embodiment), a better bending strength can be obtained and the linear expansion coefficient becomes lower. . When the linear expansion coefficient is small as in the case of using the insulating materials S1 to S9, the difference in the linear expansion coefficient between the insert and the insulating composition is also reduced, so that the thermal stress can be suppressed, for example, stress in a low temperature atmosphere. It can be seen that destruction can be prevented. In addition, when the insulating properties of the samples using the insulating materials S1 to S9 were examined, it was confirmed that they were 1.0 × 10 ¹⁵ Ω · cm or more, respectively.

  Therefore, when the phosphate ester is used as in the insulating materials S1 to S9, the epoxy resin is preheated at a relatively low temperature (for example, the main material, for example, without performing a pretreatment such as a purification process in coal ash). Highly filled (for example, 500 phr to 600 phr filling with respect to 100 phr epoxy resin as in this embodiment) while uniformly dispersing coal ash preheated at 130 ° C. or less as in the embodiment, and good production efficiency It was found that sufficient mechanical and electrical properties can be imparted. It was also found that mechanical properties and electrical properties were improved by restricting the amount of phosphate ester.

  Although the present invention has been described in detail only for the specific examples described above, it is obvious to those skilled in the art that various changes and modifications are possible within the scope of the technical idea of the present invention. Such variations and modifications are naturally within the scope of the claims.

  For example, the mixing conditions and curing conditions of the insulating material are appropriately set according to the type and blending amount of epoxy resin, curing agent, coal ash, and other various additives, and the contents shown in this example It is not limited to. In addition to the epoxy resin, curing agent, coal ash, etc., various additives (for example, additives other than Examples) are appropriately used within a range that does not impair the properties of the target insulating composition. Even when blended, it is clear that the same effects as those shown in this example can be obtained.

Claims (4)

A composition obtained by heat-curing an insulating material formed by mixing at least components of epoxy resin, coal ash, curing agent, and polyalkyl phosphate ester, and used for an insulation structure of a voltage device,
An insulating polymer material composition, wherein the coal ash is used in an amount of 500 phr to 600 phr with respect to 100 phr of an epoxy resin and mixed after preheating at 130 ° C. or less .   The insulating polymer material composition according to claim 1, wherein the epoxy resin is epoxidized linseed oil.   The insulating polymer material composition according to claim 1, wherein the coal ash is fly ash.   The insulating polymer material composition according to any one of claims 1 to 3, wherein 0.05 to 2 phr of the polyalkyl phosphate ester is used with respect to 100 phr of the epoxy resin.