JP5322220B2 - 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, it is applied to insulation structures (parts that require insulation) of voltage equipment (high voltage equipment, etc.) equipped with switching devices such as circuit breakers and disconnectors in the housing (for example, directly exposed to the outdoors) An insulating material obtained by appropriately mixing various components such as a curing agent with an insulating polymer component such as an epoxy resin derived from a fossil raw material (petroleum, etc.) (hereinafter referred to as a fossil-derived epoxy resin). An insulating polymer material composition (hereinafter referred to as an insulating composition) obtained by heat-curing (three-dimensional crosslinking) the insulating material, for example, by casting the insulating material 2. Description of the Related Art Products (mold cast products; hereinafter referred to as insulating products) made of an insulating composition have been widely known.

  In addition, with the sophistication and concentration of society, the capacity, size, and high physical properties of voltage devices, etc. (for example, insulation (dielectric breakdown field characteristics, etc.), mechanical properties (bending strength, etc.)), etc. In addition to the strong demand, improvements in various characteristics have been demanded for the insulating products.

For example, many of the insulating products that are subject to disposal (for example, products that are disposed of due to lifetime, failure, etc.) were disposed of simply by landfilling methods, but the number of final disposal sites related to landfilling decreased year by year. Concerned about the tendency to continue, 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 estimated the waste treatment cost to rise around 2008 based on the above estimate. Since it was predicted that the growth rate would be pushed down, the development of insulating products considering global environmental conservation (energy saving, prevention of global warming by suppressing CO ₂ emissions, etc.) and reuse (recycling) has been promoted.

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

  In addition, there has been an attempt to apply a biodegradable resin (for example, polylactic acid-based resin) as an insulating polymer component (for example, Patent Document 1). Since it is a substance that is easily melted at a temperature (for example, melted at a temperature of about 100 ° C.), it has not been particularly suitable for application to a high voltage device (a high voltage device that can rise in temperature to about 100 ° C. during use).

  In recent years, attempts have been made to apply epoxidized vegetable oil as an insulating polymer component (for example, Patent Document 2). Epoxidized linseed oil, which is mentioned as an example of epoxidized vegetable oil, has been applied as a stabilizer for vinyl chloride, as is epoxidized soybean oil. This epoxidized vegetable oil itself is almost neutral and carbon neutral, and even if it is incinerated, almost no harmful substances (for example, environmental hormones), carbon dioxide, etc. are discharged and it can be said that it can contribute to environmental conservation. However, since it is less reactive than epoxy resins derived from fossil raw materials, it takes a long time to cure, and it is considered that mechanical properties are not sufficient in addition to low Tg, and it is applied to actual insulating products. There wasn't. In addition, there was no attempt to apply a non-fossil raw material-derived material to components other than the insulating polymer component.

  On the other hand, when a fossil-derived epoxy resin is used as an insulating polymer component, there has been an attempt to apply a non-fossil raw material-derived material to any other components (curing agents, etc.). The application ratio as a whole is very small, and most of them are occupied by components depending on the fossil raw material-derived substances (for example, Patent Documents 3 and 4).

  In addition, attempts to apply non-fossil raw material-derived materials have progressed in technical fields different from high-voltage devices, etc., for example, printed wiring boards, etc., to which a thermosetting crosslinked composition using biological materials is applied. Although known (for example, Patent Document 5), aldehydes are used as a curing agent, and it is difficult to obtain sufficient mechanical properties in a severe use environment such as a high-voltage device.

JP 2002-358829 A (for example, [0007] to [0012]) JP 2007-35337 A (for example, [0015]) JP-A-6-128360 (for example, [0013], [0014]) JP-A-7-10966 (for example, [0029] to [0031]) JP 2002-53699 A (for example, [0007] to [0011]).

  The inventor of the present application has paid attention to the following first to fourth problems in the insulating composition in accordance with the technical progress as described above.

  That is, as a first problem, simply applying a general curing agent or the like to epoxidized linseed oil is less reactive than an epoxy resin derived from a fossil raw material, so that the curing time is long and Tg is low. Although it was considered low and mechanical properties were not sufficient, it can be applied to actual insulating products.

  As a 2nd subject, handling of each component is made easy and workability | operativity is mentioned, for example.

  The third problem is not only to improve the characteristics of the insulating composition but also to improve the workability by, for example, relatively lowering the curing temperature.

  As a fourth problem, it is possible to moderate the blending ratio of the curing agent so that curing failure does not occur.

The present invention is a technical idea created to solve the above-described problems, and the inventions of claims 1 to 6 are not only obtained by heat curing, respectively, but the intended insulating composition is obtained, For example, sufficient Tg characteristics and volume resistivity can be obtained even when applied as an insulating configuration of a high voltage device, and the first problem is solved. According to a fifth aspect of the invention, has low skin irritation, it solves the second problem to improve the workability. According to a sixth aspect of the invention, because of the low melting point of the derivative solves the third problem to improve the workability. The invention according to claim 3 can set the blending ratio of the curing agent so that curing failure does not occur, and solves the fourth problem.

More specifically, the invention described in claim 1 is a composition obtained by heat-curing and three-dimensionally crosslinking an insulating material comprising at least epoxidized linseed oil and a curing agent, and used for an insulating structure of a voltage device. the curing agent, Ri comprising the derivative of the plant-derived polyphenols 1 or more, as the derivative, characterized that you containing gallic acid derivatives and / or tannin derivative.

The invention described in claim 2 is characterized in that, in the invention described in claim 1 , the derivative in the curing agent is contained in an amount of 10 wt% to 150 wt% with respect to the epoxidized linseed oil .

The invention described in claim 3 is characterized in that, in the invention described in claim 1 , the derivative in the curing agent is contained in an amount of 50 wt% to 150 wt% with respect to the epoxidized linseed oil .

The invention according to claim 4 is characterized in that, in the inventions according to claims 1 to 3 , the gallic acid derivative contains one or more benzophenones .

The invention according to claim 5 is the invention according to claims 1 to 3 , wherein as the gallic acid derivative , pyrogallol, methyl gallate, ethyl gallate, propyl gallate, isopropyl gallate, pentyl gallate, isopentyl gallate, gallic acid The gallic acid derivative containing at least one of hexadecyl acid, heptadecyl gallate, and octadecyl gallate has 8 or more carbon atoms in the alkyl group.

The invention described in claim 6 is characterized in that, in the invention described in claims 1 to 3 , the gallic acid derivative has an alkyl group having 8 or more carbon atoms .

As described above, according to the first to sixth aspects of the invention, it is possible not only to contribute to global environment conservation but also to obtain sufficiently good heat resistance, insulation, mechanical properties, etc. in the insulating composition.

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

  This embodiment is an insulating composition obtained by heat-curing an insulating material composed of an insulating polymer component or the like and three-dimensionally crosslinking it, and can be applied, for example, to an insulating configuration of a high-voltage device. Insulating materials do not simply apply epoxidized linseed oil as an insulating polymer component, but contain derivatives of plant-derived polyphenols such as gallic acid and tannin (hereinafter referred to as plant-derived derivatives) as curing agents. Apply what consists of.

  Even when epoxidized linseed oil is applied in this way, according to the insulating material to which the curing agent made of a plant-derived derivative is applied, an insulating composition can be obtained by three-dimensional crosslinking by heat curing, even if it is a high voltage device. Even when applied to the above-described insulation configuration, many of the various characteristics (heat resistance, insulation, mechanical properties, etc.) required for the high-voltage equipment are sufficiently satisfied, and further, it can contribute to the preservation of the global environment.

[Epoxidized linseed oil]
Epoxidized linseed oil includes epoxidized linseed oil composed of glycerides such as linolenic acid, linoleic acid and oleic acid.

[Curing agent]
Plant-derived polyphenols used as raw materials for curing agents are known to have a plurality of phenolic hydroxy groups (hydroxy groups bonded to aromatic rings such as benzene rings and naphthalene rings) in the molecule. Yes, it is a substance synthesized during photosynthesis of plants. Specific examples of the plant-derived polyphenols include gallic acid, tannin, flavonol, isoflavone, catechin, quercetin, anthocyanin and the like.

  Among the plant-derived derivatives, gallic acid derivatives are based on gallic acid and introduce functional groups, oxidize, reduce, and replace atoms to such an extent that the structure and properties of gallic acid itself do not change significantly. And the like. Specific examples thereof include pyrogallol, methyl gallate, ethyl gallate, propyl gallate, isopropyl gallate, pentyl gallate, isopentyl gallate, octyl gallate, decyl gallate, dodecyl gallate, tridecyl gallate, gallic acid Examples include tetradecyl, pentadecyl gallate, hexadecyl gallate, heptadecyl gallate, and octadecyl gallate. 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 3,4,4′-pentahydroxybenzophenone, 2,3,3 ′, 4 And benzophenones such as 4 ′, 5′-hexahydroxybenzophenone. The above-mentioned plant-derived derivatives exist in various products and grades as commercial products. As a hardening | curing agent, what consists of any one of the said plant-derived derivatives may be sufficient, and what consists of multiple types may be sufficient.

  Among the aforementioned plant-derived derivatives, octyl gallate, decyl gallate, dodecyl gallate, tridecyl gallate, tetradecyl gallate, pentadecyl gallate and the like have a considerable amount of skin irritation. It is preferable to handle. For this reason, pyrogallol, methyl gallate, ethyl gallate, propyl gallate, isopropyl gallate, pentyl gallate, isopentyl gallate, hexadecyl gallate, heptadecyl gallate, octadecyl gallate, etc., which have little skin irritation, It can be said that it is more preferable from the viewpoint of workability.

  In addition, each plant-derived derivative improves compatibility with epoxidized linseed oil as the number of alkyl groups in the plant-derived derivative increases. For example, the melting point of gallic acid itself is around 260 ° C., but the gallic acid derivative has an alkyl group with 8 or more carbon atoms (octyl gallate, decyl gallate, dodecyl gallate, tridecyl gallate, tetradecyl gallate) And pentadecyl gallate, hexadecyl gallate, heptadecyl gallate, octadecyl gallate, etc.) have a melting point of around 100 ° C. and can be set at a low curing temperature, which is preferable from the viewpoint of workability.

  Although the amount of the curing agent varies depending on the amount of the active ingredient contained in the curing agent (in this embodiment, the plant-derived derivative that contributes to the crosslinking action), the intended insulating composition is within the range where curing failure does not occur. It is preferable to use appropriately depending on the product. For example, in the case of a curing agent composed solely of a plant-derived derivative as in the examples described later, the blending amount of the curing agent itself is appropriately set (in the examples described later, 10 wt% to 150 wt% with respect to epoxidized linseed oil, Preferably, 50 wt% to 150 wt% may be added), but when components other than plant-derived derivatives (for example, various additives) are included, the content of plant-derived derivatives in the curing agent is taken into consideration. Is preferably set.

[Other ingredients]
For example, various additives can be appropriately used for the purpose of further improving workability (for example, shortening of work time, etc.), moldability, Tg characteristics, mechanical properties, electrical properties, etc., and a curing accelerator. (Starting point of curing of the curing agent; for example, organic peroxides, amines (tertiary amine, aromatic amine, etc.), imidazoles), fillers (for example, inorganic fillers such as silica, alumina), reaction inhibitors , Reaction aids (the purpose of controlling the reaction (Tg characteristics); peroxides, etc.) can be used in combination as appropriate.

[Production method]
The insulating material can be obtained by appropriately blending the various components shown above and mixing them by, for example, milling or stirring. And the target insulating composition is shape | molded by casting the said insulating material to the metal mold | die of a predetermined shape, and heat-hardening. In addition, conditions, such as the said mill process and stirring process, are suitably set according to the compounding quantity, kind, etc. of the various components of an insulating material. The molding conditions can be set as appropriate, and various molding methods such as vacuum casting, pressure casting, transfer casting, injection molding, and the like can be applied.

  In addition, the blending ratio of each component of the insulating material of the present embodiment may be appropriately set according to the target insulating product, but for example, when a filler or the like is blended, the dispersibility and moldability are not impaired. It is preferable to set so. Moreover, it is generally known that the blending ratio in the case of reacting an epoxy resin and a phenol resin is determined stoichiometrically from the epoxy equivalent and the hydroxyl equivalent. On the other hand, when the epoxidized linseed oil is applied as in this embodiment, the epoxy group is present in the molecular chain and the reactivity is poor, so the blending ratio is not necessarily determined stoichiometrically. It can be appropriately set according to each component of the insulating material.

  The crosslinking in the insulating composition is essentially due to the curing agent, and the crosslinking structure is not affected by the curing conditions and the presence or absence of the curing accelerator, reaction inhibitor, reaction aid and the like.

  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 properties of the insulating composition, that is, optimal. The solutions are different, and even if the curing conditions are different, the physical properties themselves do not vary greatly.

  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, for epoxidized linseed oil (ADEKA Sizer O-180A manufactured by ADEKA), various curing agents (curing agents A to J described later) and 2-ethyl-4-methyl-imidazole (Shikoku Chemicals) as a curing accelerator. Various insulating materials were prepared by blending 1 phr of Curesol 2E4MZ) manufactured by Kogyo Co., Ltd.

  As the curing agent, propyl gallate (hereinafter referred to as curing agent A), tannic acid (hereinafter referred to as curing agent B), and octadecyl gallate (hereinafter referred to as curing agent C) manufactured by Fuji Chemical Industry Co., Ltd. 1 and 2 were used. In addition, pyrogallol (hereinafter referred to as curing agent D), methyl gallate (hereinafter referred to as curing agent E), ethyl gallate (hereinafter referred to as curing agent F), 2,3,4-trihydroxybenzophenone (hereinafter referred to as “hardening agent D”) manufactured by Iwate Chemical Co., Ltd. , Curing agent G), 2,3,4,4′-tetrahydroxybenzophenone (hereinafter referred to as curing agent H), 2,2 ′, 3,4,4′-pentahydroxybenzophenone (hereinafter referred to as curing agent I), 2 , 3,3 ′, 4,4 ′, 5′-hexahydroxybenzophenone (hereinafter referred to as curing agent J) was used as shown in Tables 1 and 2 below.

  Each of the insulating materials is heat-cured into a predetermined shape (temperature 170 ° C., 16 hours) to obtain various insulating compositions, and each Tg characteristic (° C.) and volume resistivity (Ω / cm) The results are shown in Tables 1 and 2. The Tg characteristic was measured from the inflection point of the linear expansion coefficient based on the TMA method by cutting the insulating composition into a cylindrical shape (4 mmφ × 15 mm) to produce a sample piece. Moreover, the volume resistivity was measured by applying a DC voltage of 1000 V to the insulating composition according to JIS K 6911. The symbol “-” in the table indicates a case where a plurality of insulating compositions are produced and at least one defective curing occurs.

  In the results shown in Tables 1 and 2, the target insulating composition can be obtained by heating and curing, respectively. For example, sufficient Tg characteristics and volume resistivity can be obtained even when applied as an insulating configuration of high voltage equipment. I was able to confirm that

  When the amount of the curing agent is small, the crosslinking action by the curing agent is small, so that a curing failure tends to occur. However, when the amount of the curing agent is 50 wt% or more, the curing failure was not observed at all. In addition, it was found that an insulating composition in which curing failure did not occur at all can provide good Tg characteristics (above room temperature) and volume resistivity even when applied as an insulating configuration of a high voltage device, for example.

  From the results shown above, epoxidized linseed oil is applied as an insulating polymer component, and a curing agent containing a plant-derived derivative such as gallic acid or tannin is applied (for example, 10 wt% with respect to epoxidized linseed oil) By applying a curing agent containing a plant-derived derivative of ˜150 wt%, more preferably 50 wt% to 150 wt%, the non-fossil raw material-derived substance is simply added to the insulating polymer component as in Patent Document 2, for example. It has been found that it can contribute to global environmental protection compared to the case where it is applied, and provides sufficiently good insulation, heat resistance, and mechanical properties as an insulation configuration for high-voltage equipment exposed to harsh usage environments, for example. did.

  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 determined according to the type and blending amount of the epoxidized linseed oil and various components (curing agent, curing accelerator, etc.) in order to obtain the target insulating composition. It is set and is not limited to the contents shown in the present embodiment.

  In addition to the epoxidized linseed oil, curing agent, and curing accelerator, various additives (for example, components other than the examples) are appropriately added 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 (6)

A composition obtained by heat-curing an insulating material comprising at least epoxidized linseed oil and a curing agent and three-dimensionally cross-linking, and used for an insulating structure of a voltage device
The curing agent, Ri comprising the derivative of the plant-derived polyphenols 1 or more,
As the derivatives, insulating polymer material composition which is characterized that you containing gallic acid derivatives and / or tannin derivative. The insulating polymer material composition according to claim 1, wherein the derivative in the curing agent is contained in an amount of 10 wt% to 150 wt% with respect to the epoxidized linseed oil . The derivatives in the curing agent is an insulating polymer material composition of claim 1, wherein the containing 50wt% ~150wt% relative epoxidized linseed oil. The insulating polymer material composition according to any one of claims 1 to 3, wherein the gallic acid derivative contains one or more benzophenones . As the gallic acid derivative , one or more of pyrogallol, methyl gallate, ethyl gallate, propyl gallate, isopropyl gallate, pentyl gallate, isopentyl gallate, hexadecyl gallate, heptadecyl gallate, and octadecyl gallate insulating polymer material composition as claimed in any one of claims 1 to 3, characterized in that it contains. The insulating polymer material composition according to any one of claims 1 to 3, wherein the gallic acid derivative has an alkyl group having 8 or more carbon atoms .