JP2007035337A - Insulating polymer material composition and insulator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide excellent mechanical property and electrical property for a polymer product such as a high-voltage apparatus without impairing workability; and to contribute to global environment conservation with sufficient biodegradability. <P>SOLUTION: This insulating polymer material composition is provided by adding a phenol resin (of, for instance, 40-80 phr) as a curing agent to epoxidized linseed oil (of, for instance, 100 phr) to knead them, and by three-dimensionally cross-linking the kneaded substance by heat-treating it. The insulating polymer material composition is applied to a polymer product such as an insulator. For instance, imidazoles as a curing promotor is used or various kinds of additives are used in addition to the epoxidized linseed oil and the phenol resin as needed. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an insulating polymer material composition and an insulator, and is used, for example, in an insulating configuration of a high-voltage device including a switchgear such as a circuit breaker or a disconnector in a housing.

  For example, it is applied to insulation configurations (for example, parts that require insulation) of voltage equipment (high voltage equipment, etc.) equipped with switchgear such as circuit breakers and disconnectors in the housing (for example, directly exposed to the outdoors) A composition obtained by curing a polymer material mainly composed of petroleum-derived thermosetting resin (resin using petroleum as a starting material; epoxy resin, etc.), for example, a polymer material is cast. A product (mold cast product; hereinafter referred to as a polymer product) composed of the composition has been widely known.

  Along with the sophistication and concentration of society, there is a strong demand for high-voltage equipment, etc. with increased capacity, downsizing, and high reliability (for example, mechanical properties (such as dielectric breakdown electric field characteristics) and electrical properties). There have been demands for improvements in various properties of the polymer products.

Generally, as a main component of a polymer material, for example, a glass transition point (hereinafter referred to as Tg) 100 ° C. or higher heat-resistant epoxy resin or a bisphenol A type epoxy resin having relatively high mechanical properties (strength etc.) In consideration of the case where the above-mentioned polymer product is disposed (for example, due to the reason of life or failure), a high polymer material having biodegradability is known. Development of molecular products has been attempted (for example, Patent Document 1).
JP 2002-358829 A.

In various technical fields, attempts have been made to apply a composition obtained by curing a plant-derived polymer material (for example, to a printed wiring board) (for example, Patent Document 2), for example, in a room temperature atmosphere. In this case, it is known that sufficient mechanical properties can be obtained. However, the composition uses an aldehyde as a curing agent, and the mechanical properties are lowered in a high temperature atmosphere. It was not applied to.
Japanese Patent Laid-Open No. 2002-53699.

  As described above, a polymer product using a heat-resistant epoxy resin having a glass transition point (hereinafter referred to as Tg) of 100 ° C. or higher as a main component of the polymer material is hard and fragile, and has a severe temperature change. If used underneath, there is a risk of cracking. For this reason, for example, a solid epoxy resin (for example, a result of a crack resistance test using a metal conductor of −30 ° C. or lower) is used as the main component of the polymer material, or a large amount of filler is added to the polymer material. Attempts have been made to improve the crack resistance and the like by adding it, but the viscosity of the polymer material becomes extremely high. For example, the pot life (minimum required for industrial work) Time), and workability may be deteriorated.

  The bisphenol A type epoxy resin is widely used as an industrial product because of its high mechanical properties. However, the bisphenol A itself is considered to be harmful as an environmental hormone, It is beginning to be a concern from the point of view of sex. In a cured composition such as a polymer product, there is a report that bisphenol A rarely leaks out from the composition and is not harmful, but a very small amount (for example, ppm level, or Even if it is in the composition as described above, unreacted bisphenol A (low molecular weight component) is present in the composition. There is a concern that the bisphenol A may leak into the air.

  For example, in a polymer product manufacturing facility, in a limited environment such as a step of synthesizing a bisphenol A type epoxy resin and various additives, a step of casting a polymer material after the synthesis step, etc. There is a risk of a high concentration bisphenol A atmosphere. Even if each process of the production equipment is completely unmanned (the production line for polymer products is unmanned), ventilation equipment (equipment for purifying air in the use environment) is required in each process. For this reason (that is, a ventilation facility that was not assumed in the past is required), the product cost may increase.

  In the case of disposing of the above-mentioned polymer product (for example, disposing for reasons such as lifetime or failure), various treatment methods can be applied, but each has the following problems.

  In the case of polymer products made of polymer materials mainly composed of petroleum-derived substances (for example, epoxy resins, etc.), applying the method of incineration will emit a large amount of various harmful substances and carbon dioxide, resulting in environmental pollution, There was concern about the possibility of causing problems such as global warming. On the other hand, a method of simply landfilling the polymer product can be applied, but the final disposal sites related to the landfill process tend to decrease year by year. The remaining years of this final disposal site are estimated around 2008 by the former Ministry of Health. In addition, the former Economic Planning Agency predicts that the cost of waste disposal will rise around 2008, and the economic growth rate will be pushed down, based on the previous calculations by the former Ministry of Health and Welfare.

  In addition, there is an attempt to collect and reuse (recycle) the polymer product, but the reuse method has not been established and is hardly performed. Exceptionally, only members with relatively uniform quality (PE cable covering members used in polymer products) are recovered and used as thermal energy. However, since this thermal energy requires a combustion treatment step, Like this, there is a risk of causing problems such as environmental pollution and global warming.

  On the other hand, in the case of a polymer product made of a biodegradable polymer material, there is a risk of melting when used in an atmosphere at a temperature of 100 ° C. or higher. In the case of polymer products composed of biologically derived cross-linked compositions, aldehydes are used as cured products, and therefore have high mechanical properties under a normal temperature atmosphere (for example, a temperature environment in a printed wiring board). In a high temperature atmosphere (for example, an environment where a high voltage device or the like is used), sufficient mechanical properties may not be obtained.

  As described above, there is a demand for improving the various problems associated with the disposal of the polymer product while maintaining good properties (mechanical properties, electrical properties, etc.) of the polymer product.

  The present invention has been made on the basis of the above-mentioned problems, and can impart good mechanical and electrical properties to polymer products such as high-voltage equipment without deteriorating workability. An object of the present invention is to provide an insulating polymer material composition and an insulator that have degradability and excellent environmental properties.

  The present invention is intended to solve the above-described problems, and the invention according to claim 1 is used for an insulation structure of a voltage device, and includes kneading containing epoxidized linseed oil and a phenol resin. The kneaded material is three-dimensionally cross-linked by heat treatment.

  The invention described in claim 2 is the invention described in claim 1, characterized in that the kneaded material contains imidazoles.

  A third aspect of the invention is characterized in that, in the first or second aspect of the invention, the phenol resin is used in an amount of 40 to 80 phr with respect to 100 phr of the epoxidized linseed oil.

  The invention described in claim 4 is an insulator comprising the insulating polymer material composition according to any one of claims 1 to 3 and a metal insert.

  In the invention described in claim 1, for example, the kneaded material of each material is three-dimensionally cross-linked by heat treatment without using a large amount of filler or the like (for example, a large amount of filler or the like like conventional polymer products).

  In the invention of claim 2, imidazoles are the starting point for curing in the phenolic resin.

  In the invention according to claim 4, the difference between the linear expansion coefficient of the insulating polymer material composition and the linear expansion coefficient of the metal insert is small (for example, smaller than that of a conventional polymer product).

  As described above, according to the present invention, good mechanical properties and electrical properties can be obtained as a polymer product such as a high-voltage device without deteriorating workability (for example, ensuring sufficient pot life) and sufficient. It has a high biodegradability (for example, biodegradability when landfilled in soil) and can contribute to global environmental conservation.

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

  In this embodiment, for example, in an insulating polymer material composition applied to a portion of a polymer product that requires insulation, instead of using a petroleum-derived polymer material such as an epoxy resin, it is naturally derived and is tertiary. A polymer material that is originally crosslinked (that is, a polymer material having a natural material as a base material (starting material)) is used.

  That is, if the polymer material is as described above, sufficiently good electrical properties and mechanical properties can be obtained without deteriorating workability, and it can be applied to a high voltage device, and the polymer material itself is carbon neutral. Therefore, even if a composition made of the polymer material (polymer product, etc.) is incinerated, it can prevent or control the emission of harmful substances (eg, environmental hormones) and carbon dioxide, and it can be buried in the soil, for example. In this case, the focus is on biodegradability. In the composition composed of a naturally derived polymer material, an example applied to a printed wiring board is known, but there was no example applied to a polymer product such as a high voltage device.

  Specifically, as described above, epoxidized linseed oil is used as a polymer material that is naturally derived and three-dimensionally cross-linked. Conventionally, epoxidized linseed oil has been widely used as a stabilizer in vinyl chloride resin, for example, as with epoxidized soybean oil, but has low reactivity and requires a long time for curing compared to general industrial epoxy resin. However, since it has low Tg characteristics and mechanical properties, it has not been applied and studied as a polymer product for high voltage equipment.

  In this embodiment, in an insulating polymer material composition obtained by curing epoxidized linseed oil, a thermosetting resin such as a phenol resin is used as a curing agent (added to epoxidized linseed oil) to perform the above-described curing. As a result, Tg is improved, the insulation property of the insulating polymer material composition is improved, and better characteristics than the existing industrial epoxy resin products can be obtained (for example, the dielectric breakdown electric field characteristics are good). Is found.

  The thermosetting resin such as the phenol resin, for example, first calculates the epoxy equivalent based on the oxirane concentration of the epoxidized linseed oil, and the stoichiometric amount based on the epoxy equivalent (for example, 0 to the stoichiometric ratio). 0.5-2.0). Moreover, you may use imidazole as a starting point (role of a hardening accelerator) in the said thermosetting resin.

  In the present embodiment, for example, workability is improved (for example, work time is shortened), formability, Tg characteristics, mechanical / physical properties (for example, hardness, elastic modulus, linear expansion coefficient, thermal conductivity, etc.) In addition to using the epoxidized linseed oil, thermosetting resin, etc. as a matrix (for example, epoxidized linseed oil, phenolic resin, imidazole in the examples described later) for the purpose of improving electrical properties, etc. These additives (for example, fillers and coupling agents (for example, for chemically bonding the matrix and the filler)) can be used as appropriate.

  For example, when the insulating polymer material composition of the present embodiment is applied to an insulator, the insulating polymer material composition includes silica powder, alumina powder, and dolomite powder for the purpose of improving the physical properties of the matrix. A filler such as graphite powder is used. The insulator is generally known to have a structure in which a metal insert is embedded in the insulating polymer material composition.

  In the case of the insulator as described above, if there is a large difference between the linear expansion coefficient of the insulating polymer material composition and the linear expansion coefficient of the metal insert, there is a size corresponding to the use environment of the insulator between them. Thermal stress is generated, and cracks and the like may occur. Therefore, for example, when using the above-mentioned filler, in order to prevent the difference in the linear expansion coefficient from increasing in the type, amount of addition, particle size, particle size distribution, etc. of the filler, It is preferable to set appropriately considering the shape, the material of the metal insert, the shape and the like.

  As a specific example, about 50 vol% is used as a target with the silica powder as a filler. Further, when a filler having a particle size on the order of nanometers (a so-called nanoparticle filler) is used, a filler for a surface area effect (for example, a resin (epoxidized linseed oil or the like in the present embodiment)). (Effects of increasing the contact point (surface area)) in a smaller amount (for example, an addition amount of about 1/10 or less) than when a filler having a general particle size (for example, micro milliorder) is used. It is possible to improve the physical properties of the matrix.

  In addition, although it is preferable to use the filler as described above as appropriate, from the viewpoint of improving the physical properties of the matrix by the filler, a general-purpose filler (for example, a filler having a general particle size) is epoxidized vegetable oil. This is the same as when added to polyphenol. Also, in the coupling agent, it is preferable to use the same as in the case of the above-mentioned filler. However, for example, from the viewpoint of chemically bonding the matrix and the filler, the same as in the case of using a general-purpose coupling agent. It is.

  As said coupling agent, what has a functional group which reacts with resin (hydrophobic group) or a filler (hydrophilic group) is applicable, for example. When silica is used as the filler, for example, a silane coupling agent, a titanate coupling agent, or the like can be effectively applied.

[Example]
Next, examples of the insulating polymer material composition in the present embodiment will be described. First, in this example, 100 phr of epoxidized linseed oil (in this example, epoxidized linseed oil (product name: Daimac L-500) manufactured by Daicel Chemical Industries, Ltd.) was used as a curing agent. In the example, phenol formaldehyde type novolak (product name; PR-HF-3) manufactured by Sumitomo Bakelite Co., Ltd., 40-80 phr, imidazoles as a curing accelerator (in this example, 2-ethyl- manufactured by Shikoku Kasei Kogyo Co., Ltd.) 4-methylimidazole (product name: 2E4MZ)) 1 phr, silica powder (silica powder (product name: MFC-4) manufactured by Tatsumori in this example) 420-480 phr as a filler is added and kneaded (for example, added amount) Kneading under the appropriate conditions) and casting the kneaded product, a 24 kV insulator (JIS C3851 EIE20A; insulator high) To prepare a sample S1~S5 of 255mm).

  In this example, first, phenolic resin and silica powder heated in the same manner (heated to 50 to 150 ° C.) with respect to the epoxidized linseed oil heated (heated to 50 to 150 ° C.). After further adding imidazoles, the mixture was sufficiently mixed and stirred, and the resulting kneaded product was defoamed under reduced pressure. Thereafter, the kneaded product is poured into a predetermined mold (mold for producing an insulator for 24 kV) (in the air), defoamed again under a reduced pressure atmosphere, and heated at a temperature of 150 to 200 ° C. Each sample was produced by heating and curing for ~ 20 hours.

  Further, as a comparative example of the samples S1 to S5, the silica 450 phr and acid anhydride (in this example, phthalic anhydride (product name: HN2200) manufactured by Hitachi Chemical) 60 phr with respect to 100 phr of the epoxidized linseed oil. , Tertiary amine (DMP-30 (product name: L-86) manufactured by Meiden Chemical in this example) 1 phr was added and kneaded, and the kneaded product was cast to obtain an insulator similar to samples S1 to S5. Sample P1 was manufactured (manufactured under the same conditions as Samples S1 to S5). Further, 100 phr of a bisphenol A type epoxy resin (in this example, an epoxy resin (product name: CT200A) manufactured by Bantico), 60 phr of the phenol resin, 450 phr of silica, and 1 phr of a tertiary amine were added and kneaded, and the kneaded product. Was cast to produce an insulator sample P2 similar to the samples S1 to S5 (produced under the same conditions as the samples S1 to S5).

  Then, the load at the time of insulator bending fracture (Pw0 (N)) is measured as the mechanical properties of each of the samples S1 to S5, P1, and P2, and the lightning impulse (V50 (kV)) is measured as the electrical properties. The measurement results are shown in Table 1 below. The load at the time of the insulator bending fracture was measured in accordance with JIS-C 3851. Further, the lightning impulse was measured by a lifting method with a step width of 5 kV (only the positive polarity was measured because the positive electrode has a small value).

  As shown in Table 1, each of the samples S1 to S5 has a sufficient load (lightning at the time of bending bending of the insulator), as well as the sample P2 using the petroleum-derived bisphenol A type epoxy resin (especially good in the sample S3). Impulse was measured. Similarly to the sample S3, the sample P1 using epoxidized linseed oil and the acid anhydride as the curing agent has a lower load at the time of bending bending and lightning impulse compared to the samples S1 to S5. It was done.

  Therefore, according to the insulating polymer material composition composed of a kneaded material containing epoxidized linseed oil as the polymer material as in each of the samples S1 to S5, the existing petroleum-derived bisphenol A type epoxy resin is used. Similar to the insulating polymer material composition used, sufficient mechanical and electrical properties can be obtained in a polymer product (for example, an insulator made of the insulating polymer material composition and a metal insert). It could be confirmed. In addition, by using a phenol resin as a curing agent for the epoxidized linseed oil, compared with the case where an acid anhydride or the like is used as the curing agent, the polymer product has better mechanical and electrical properties. It was confirmed that it was obtained. Further, it was confirmed that imidazoles and silica can be applied as a curing accelerator and a filler, respectively.

  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 can be made 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, in this embodiment, epoxidized linseed oil is used as a polymer material that is naturally derived and three-dimensionally cross-linked, a phenol resin is used as a curing agent, imidazoles are used as a curing accelerator, and silica powder is used as a filler. An example of an insulating polymer material composition obtained by casting (heat-treating) the kneaded material was given, but the scope of the technical idea of the present invention was limited to the above-mentioned types of materials (manufacturers, grades, etc.) It can be applied to various materials as long as it is essentially a reaction between an epoxidized vegetable oil such as epoxidized linseed oil and a polyphenol (a reaction between an aromatic ring and a substance having a hydroxyl group). It is.

  The curing of the kneaded material in the casting (heat treatment) is one of the steps for adapting to the physical properties of the target insulating polymer material composition. It can be appropriately set (for example, set to a curing temperature / time other than the example) depending on (for example, the target polymer product) and the material used. In the examples, an example of a manufacturing method in which casting is performed in the air has been given. For example, in consideration of a molding cycle, casting in a reduced-pressure atmosphere (for example, casting in which the defoaming step can be omitted), transfer molding, It is also possible to apply injection molding or the like.

  Furthermore, in the blending amount of each material, in the present embodiment, an example of a 24 kV insulator using phenol resin 40 to 80 phr, imidazoles 1 phr, and silica powder 420 to 480 phr with respect to 100 phr epoxidized linseed oil is given. The blending amounts of these materials can be appropriately changed according to the mechanical properties, electrical properties, etc. of the target polymer product.

  Furthermore, in the present embodiment, for the purpose of improving workability (for example, workability at the time of kneading of each material), reactivity, productivity, safety, etc. when producing an insulating polymer material composition, Even when various additives not listed are appropriately added according to the intended polymer product, it is apparent that the same effects as those of the examples can be obtained.

Claims (4)

Used for the insulation structure of voltage equipment,
It consists of a kneaded product containing epoxidized linseed oil and phenolic resin,
An insulating polymer material composition, wherein the kneaded material is three-dimensionally crosslinked by heat treatment.   The insulating polymer material composition according to claim 1, wherein the kneaded material contains imidazoles.   The insulating polymer material composition according to claim 1 or 2, wherein the phenol resin is used in an amount of 40 to 80 phr with respect to 100 phr of the epoxidized linseed oil.   An insulator comprising the insulating polymer material composition according to any one of claims 1 to 3 and a metal insert.