JP5359008B2 - Method for producing insulating polymer material composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an insulating composition, which uses an insulating material comprised of an epoxy resin derived from a non-fossil, a filler, etc., not only to contribute to the global environmental maintenance but also to improve furthermore the characteristics (electrical properties and mechanical properties). <P>SOLUTION: The insulating material (nanocomposite) is formed by mixing each components of at least an epoxy resin derived from a non-fossil (epoxy linseed oil and the like), a hardener, a nanofiller and a modifying agent, and a product obtained byheat-curing the above insulating material is applied to the insulating constituent of voltage equipment. The above insulating material is not such one that each component is mixed collectively, but such one that at first a mixture is obtained which contains at least an epoxy resin derived from a non-fossil, a nanofiller and a modifying agent, and then the mixture is mill-treated with a roll mill and preheated (aged) in a given condition and thereafter added with a hardener, and furthermore mixed. Then, the above insulating material is casted in a given shaped metal mold and heat-cured to obtain a desired insulating composition. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

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.

  Applicable to insulation configurations (for example, parts that require insulation) of voltage equipment (heavy electrical equipment, etc.) equipped with switching devices such as circuit breakers and disconnectors in the housing (for example, directly exposed to the outdoors) As a thing, various components, such as a hardening | curing agent and a filler (for example, inorganic fillers, such as a silica and an alumina), etc. with respect to the epoxy resin (henceforth a fossil origin epoxy resin) derived from a fossil raw material (petroleum etc.) suitably. Polymer material composition (hereinafter referred to as insulating composition) obtained by heat-curing an insulating material obtained by mixing, for example, a product (mold casting) constituted by an insulating composition formed by casting the insulating material Products; hereinafter referred to as insulating products) have been widely known.

  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, in the past, many of the insulating products (for example, products that are disposed of due to lifetime, failure, etc.) to be disposed of have been disposed of simply by landfilling, but there is a final disposal site related to landfilling. Concerned about the declining trend year by year, the former Ministry of Health and Welfare estimated the remaining years of the final disposal site as around 2008, and the former Economic Planning Agency raised the waste disposal cost around 2008 based on the above estimate. However, because it was predicted that the economic growth rate would be pushed down, the development of insulating products that consider global environment conservation (energy saving, prevention of global warming by suppressing CO ₂ emissions, etc.) and reuse (recycling) has been promoted. It was.

However, the reuse method has not been established yet and is hardly performed. Exceptionally, 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 have been made to apply non-fossil raw material-derived substances (for example, a combination of an inorganic filler and an organic filler such as a wood resource as a filler) to each component of the insulating composition. The application ratio of the composition as a whole is small, and most of the composition is occupied by components depending on the fossil raw material-derived substances.

  In addition, an attempt to apply a biodegradable resin (for example, polylactic acid-based resin) as a resin that is one of the essential components of the insulating composition is known (for example, Patent Document 1). The decomposable resin is thermoplastic and is a substance that is relatively easy to melt (for example, melt at a temperature of about 100 ° C.). Therefore, it is particularly a high voltage device (a high voltage that can rise to about 100 ° C. during use). Application to equipment) is not suitable.

  In addition, although an attempt to apply a thermosetting cross-linking composition using a biological material is also known (for example, Patent Document 2), an aldehyde is used as a curing agent, and a temperature atmosphere of about room temperature. Although it has high mechanical properties under (for example, a temperature environment in a printed wiring board), it is difficult to obtain sufficient mechanical properties in a high-temperature atmosphere (for example, an environment in which a voltage device or the like is used).

  On the other hand, in consideration of heat resistance, for example, an insulating product using a heat-resistant epoxy resin having a glass transition point (hereinafter referred to as Tg) of 100 ° C. or higher is known, but such an insulating product is hard and brittle. There is a high cracking rate when used in an environment where the temperature changes drastically. For example, a solid epoxy resin (for example, a crack resistance test using a metal conductor with a result of −30 ° C. or lower) is used as the main component of the insulating material, or a large amount of filler is added to improve crack resistance. Attempts have been made, however, the viscosity of the insulating material has increased remarkably, and for example, sufficient pot life (pot life; minimum time required for industrial work) is ensured in casting work, etc. There was a risk that workability would deteriorate.

  Fossil-derived epoxy resins are widely known as materials that satisfy many of the various properties required from the viewpoint of industrial materials (electrical properties, mechanical properties, etc.). Attempts have been made to substitute three-dimensionally crosslinked epoxy resins (hereinafter referred to as non-fossil-derived epoxy resins). Epoxidized linseed oil, which is mentioned as an example of non-fossil-derived epoxy resin, has been applied as a stabilizer for vinyl chloride in the same way as epoxidized soybean oil, but is more reactive than epoxy resin derived from fossil raw materials. Therefore, the curing time is long, the Tg is low, and the mechanical properties are small, so that it has not been applied to insulating products.

  The inventor of the present application improves the Tg in epoxidized linseed oil, so that the cured product of the epoxidized linseed oil is excellent in insulation and has higher mechanical properties in a high-temperature atmosphere than the fossil-derived epoxy resin. I have already found that. If such non-fossil-derived epoxy resin can be substituted, sufficiently good electrical and mechanical properties can be obtained and applied to high-voltage equipment, and the non-fossil-derived epoxy resin itself has almost no harm and flaxseed oil is carbon. Since it is neutral, even if the insulating product is incinerated, emission of harmful substances (for example, environmental hormones) and carbon dioxide can be prevented or suppressed.

In order to meet the recent demand for higher efficiency and smaller size of insulating products, it is necessary to further improve the characteristics. For example, in order to reduce the raw material cost of the insulating composition and the thermal stress with the metal insert, an inorganic filler (silica or the like) having a particle size of micrometer level (for example, about several μm to several tens of μm) is used. Although utilized (for example, patent document 3), the examination example of the inorganic filler (henceforth a nano filler) of the nanometer level whose particle size is still smaller is also known (for example, patent document 4).
JP 2002-358829 A (for example, [0007] to [0012]) JP 2002-53699 A (for example, [0007] to [0011]) Japanese Unexamined Patent Application Publication No. 2007-270137 (for example, [0013] to [0016], [0025], [0026]). JP 2000-44226 A (for example, [0004], [0016], [0017], [0043])

  However, although nano fillers have been studied with insulating materials using a fossil-derived epoxy resin as a matrix (for example, Patent Document 4), there have been no studies with non-fossil-derived epoxy resins as a matrix.

  In addition, since the dispersibility with respect to the resin decreases as the particle size becomes smaller as in the case of the nano-filler, for example, the secondary agglomeration cannot be dispersed simply by mixing with the resin or the like, and the mechanical properties and the like may be decreased. . As a method for improving the dispersibility, in addition to a method of modifying the particle surface of the nano filler in advance with a modifier (for example, chemical modification with a silane coupling agent or the like), a thin film product such as a print or a film is used. It is conceivable to improve the dispersibility of primary particles by removing secondary aggregation by applying the ultrasonic dispersion method applied in the field of small volume production. In the production field such as wood, it is unsuitable from the viewpoint of production volume.

  As described above, it is required to further improve the characteristics of the insulating composition using an insulating material composed of a non-fossil-derived epoxy resin (epoxidized linseed oil, etc.), a filler, and the like. .

The present invention is for solving the above-mentioned problems, and the invention according to claim 1 is an epoxy resin derived from at least a non-fossil raw material, a filler having an average particle size of less than 1 μm (nanometer level) , A method for producing a composition used for an insulation structure of a voltage device, comprising a step of heat-curing an insulating material composed of each component of a modifier and a curing agent, wherein the insulating material comprises the components described above A mixture of at least non-fossil-derived epoxy resin, filler, and modifier excluding a curing agent is milled by a roll mill to obtain a mixture, and then the mixture is preheated and a curing agent is added and mixed. It is characterized by that.

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

  According to a third aspect of the present invention, in the first or second aspect of the present invention, the filler is silica.

  According to a fourth aspect of the present invention, in the first to third aspects of the present invention, the curing agent is a phenol resin.

  According to a fifth aspect of the present invention, in the first to fourth aspects of the present invention, the modifying agent is a silane coupling agent.

  The invention according to claim 6 is the invention according to claims 1 to 5, wherein the roll mill is a three-roll mill.

  As in the first to sixth aspects of the invention, by milling the mixture of each component excluding the curing agent, secondary aggregation is prevented and dispersibility is enhanced even in the primary particles, and heat curing is performed in that state. . Thereby, bending strength and insulation are improved, and an elastic modulus is also suppressed. In addition, when an insert (such as a metal insert embedded in an insulating product) is applied, the difference in linear expansion coefficient between the insert and the insulating composition is a general filler (for example, filling at a micrometer level). And at least the same level as that using the agent, and the generated stress due to thermal strain can be kept small.

  As described above, according to the first to sixth aspects of the invention, not only contributes to global environmental conservation, but also better mechanical properties (small elastic modulus, high bending strength, etc.), electrical properties ( High insulation properties). Moreover, even if an insert is applied, the generated stress due to thermal strain can be kept small, so that sufficient reliability as an insulating product can be obtained.

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

  This embodiment uses an insulating material (nanocomposite) formed by mixing at least non-fossil-derived epoxy resin, curing agent, nanofiller, and modifier, and heating the insulating material. It is an insulating composition obtained by curing and applied to an insulating structure of a voltage device. The insulating material is not simply a mixture of components, but first, obtain a mixture containing at least a non-fossil-derived epoxy resin, a nano-filler, and a modifier, and add a curing agent to the mixture and mix. It was obtained.

  Non-fossil-derived epoxy resins include those applied to general voltage equipment, and examples include those derived from plants 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-derived epoxy resins.

  Various nano fillers (such as silica) are known, and those having an average particle size of less than 1 μm are applied. Moreover, as a modifier, various things (for example, silane coupling agent) can be applied if it can improve the dispersibility when mixed with non-fossil-derived epoxy resin, nano-filler, and the like. it can. The blending ratio of nano fillers and modifiers may be set as appropriate according to the target insulating product. However, if there are too many nano fillers, the mixing / casting properties and dispersibility may be impaired. .

  For example, various curing agents such as amines, acid anhydrides, phenols and imidazoles that can react with non-fossil-derived epoxy resins can be applied, and plant-derived materials such as castor oil-based polyols can also be applied. . For example, the epoxy equivalent of the non-fossil-derived epoxy resin is calculated (calculated from the oxirane concentration in the case of epoxidized linseed oil), and the stoichiometric amount based on the epoxy equivalent is blended (for example, chemical (Mixed as 1.0 with respect to the 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 insulating product.

  In addition to the non-fossil-derived epoxy resin, nano-filler, modifier, and curing agent, for example, improvement of workability (for example, shortening of work time, etc.), moldability, Tg characteristics, mechanical / physical physical properties, Various additives can be used as appropriate for the purpose of improving electrical properties and the like. For example, curing accelerators (starting point of curing of curing agents; for example, organic peroxides, amines, imidazoles, etc.), reaction inhibition Agents, reaction aids (the purpose of controlling the reaction (Tg characteristics); peroxides, etc.) can be used in combination as appropriate.

  When peroxide is mixed and mixed, the viscosity of the mixture increases with time, and the productivity may decrease (for example, the mixability and moldability may decrease). If it is 60 minutes or more, for example, 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.

  The insulating material is a roll mill (3-roll mill) after mixing at least non-fossil-derived epoxy resin, nano-filler, and modifier (collective mixing, propeller stirring, etc.), except for the curing agent, among the components shown above. ), And the milled mixture is preheated (aged) at predetermined conditions (for example, 150 ° C. for 24 hours in the examples described later), and then added with a curing agent or the like (mixed with propeller). Etc.). And the target insulating composition is obtained by pouring the said insulating material into the metal mold | die of a predetermined shape, and heat-hardening.

  Conditions such as the preheating temperature and time, the roll interval of the roll mill, the roll speed, and the number of mill treatments are appropriately set according to the blending amount and type of each component of the insulating material. Moreover, the addition of the curing accelerator may be performed before or after the addition of the curing agent, for example, and an insulating composition having the same characteristics can be obtained. In addition, when bubbles or the like remain in the insulating material, it is preferable to perform a defoaming process (for example, before and after casting) in a reduced-pressure atmosphere, for example.

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

  First, as shown in Table 1 below, 100 g (phr) of an epoxidized linseed oil (Daicel Chemical Industries, Ltd., Daimac L-500) as a non-fossil-derived epoxy resin, and a phenol resin (Sumitomo Bakelite as a curing agent) Phenolformaldehyde type novolak (PR-HF-3) manufactured by the company (in this example, 61 g (phr) with respect to 100 phr of epoxy resin), silica having an average particle size of 15 μm as a general filler (Tatsumori) 550 g (phr), average particle diameter (primary particle diameter average diameter) 12 nm of silica (fumed silica (Aerosil # 200) manufactured by Nippon Aerosil Co., Ltd.) 6 g (phr) as nano filler, imidazole as curing accelerator 1 g (phr of 2-ethyl-4-methylimidazole (2E4MZ) manufactured by Shikoku Chemicals) , 0.6 g of silane coupling agent (KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.) (phr; 10 wt% with respect to the filler) was used as a modifier, and the components were mixed according to the following conditions 1 to 3. The insulating material obtained in this manner was heat-cured to obtain samples (10 mm × 5 mm × 200 mm) S1 to S3 of the insulating composition. The average particle diameter is a particle diameter corresponding to 50% of the cumulative distribution on a volume basis, and is measured by a wet particle size distribution measurement method in this example.

<Condition 1; Example>
First, a non-fossil-derived epoxy resin, a nano filler, a modifier, and a curing accelerator are mixed at once, and a mixture is obtained by stirring with a propeller to obtain a three-roll mill (DR-35 type manufactured by Kanada Rika Kogyo Co., Ltd .; roll size 63 .5Φ × 150 Lmm) milling (roll interval 0.2 mm, low speed side roll speed 80 rpm, high speed side roll speed 200 rpm) was performed three times. This mixture was preheated, further added with a curing agent, stirred with a propeller, and defoamed in a reduced pressure atmosphere of about 0.01 MPa. Then, the sample was poured into a mold, defoamed again in a reduced pressure atmosphere of about 0.001 MPa, and then heat-cured to obtain a sample S1 of an insulating composition.

<Condition 2; Comparative Example>
First, based on the integral blend method, a non-fossil-derived epoxy resin, a general filler, a modifier, a curing agent, and a curing accelerator are mixed together and a propeller is stirred to obtain a mixture. Defoaming was performed under a reduced-pressure atmosphere. This mixture was poured into a mold, defoamed again in a reduced pressure atmosphere of about 0.001 MPa, and then heat-cured to obtain a sample S2 of an insulating composition.

<Condition 3; Comparative Example>
First, based on the integral blend method, non-fossil-derived epoxy resin, nano-filler, modifier, curing agent, curing accelerator are mixed at once, and a mixture is obtained by stirring with a propeller to obtain a reduced pressure atmosphere of about 0.01 MPa. The defoaming treatment was performed below. This mixture was poured into a mold, defoamed again under a reduced pressure atmosphere of about 0.001 MPa, and then heat-cured to obtain a sample S3 of an insulating composition.

In each of the above samples S1 to S3, the bending strength (MPa), bending elastic modulus, volume resistivity (Ω · cm), and linear expansion coefficient (10 ⁻⁶ / ° C.) by TMA in a room temperature atmosphere by a three-point bending method are obtained. Each was measured and the results are shown in Table 2 below.

  As shown in Table 2, it was confirmed that the sample S2 exhibited a sufficiently large bending strength and volume resistivity, and the linear expansion coefficient was sufficiently small, but the elastic modulus was too large. Moreover, although the sample S3 showed the sufficiently large volume resistivity and the elasticity modulus was suppressed small, it was confirmed that the bending strength was too small and the linear expansion coefficient was too large. On the other hand, it was confirmed that Sample S1 exhibited sufficiently large bending strength and volume resistivity, and that the elastic modulus and linear expansion coefficient were sufficiently small.

  Therefore, according to the insulating composition obtained by obtaining a mixture containing at least a non-fossil-derived epoxy resin, a nanofiller, and a modifier, preheating the mixture, adding a curing agent, and the like, as in sample S1. Compared with insulating compositions such as Samples 2 and 3, they exhibit sufficiently good values in all of bending strength, flexural modulus, volume resistivity, and linear expansion coefficient, and can further improve characteristics. I can read that.

  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 types and blending amounts of non-fossil-derived epoxy resins, nanofillers, modifiers, curing agents and other various additives. However, the present invention is not limited to the contents shown in this embodiment. In addition to the non-fossil-derived epoxy resin, nano-filler, modifier, curing agent, etc., various additives (for example, implementations) within a range that does not impair the properties of the target insulating composition. It is apparent that the same effects as those shown in this example can be obtained even when additives other than the examples are appropriately blended.

Claims (6)

A composition used for the insulation structure of a voltage device, including a step of heat-curing an insulating material composed of at least an epoxy resin derived from a non-fossil raw material, a filler having an average particle size of less than 1 μm , a modifier, and a curing agent. A method of manufacturing a product,
The insulating material is obtained by milling a mixture of at least a non-fossil-derived epoxy resin, a filler, and a modifier, excluding the curing agent, by a roll mill, and then preheating the mixture. A method for producing an insulating polymer material composition, comprising adding a curing agent and mixing.   The method for producing an insulating polymer material composition according to claim 1, wherein the epoxy resin is epoxidized linseed oil.   The method for producing an insulating polymer material composition according to claim 1, wherein the filler is silica.   The method for producing an insulating polymer material composition according to claim 1, wherein the curing agent is a phenol resin.   The method for producing an insulating polymer material composition according to claim 1, wherein the modifier is a silane coupling agent.   The method for producing an insulating polymer material composition according to any one of claims 1 to 5, wherein the roll mill is a three-roll mill.