JP2009215375A - Hydrate-dispersed resin composition, and porous body and insulated electric wire using the same, and method for manufacturing insulated electric wire - Google Patents
Hydrate-dispersed resin composition, and porous body and insulated electric wire using the same, and method for manufacturing insulated electric wire Download PDFInfo
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Abstract
Description
本発明は、水和物分散樹脂組成物およびこれを用いた多孔質物並びに絶縁電線およびその製造方法に関する。 The present invention relates to a hydrate-dispersed resin composition, a porous material using the same, an insulated wire, and a method for producing the same.
近年、医療分野をはじめとする精密電子機器類や通信機器類の小型化や高密度実装化が進むなかで、これらに使用される電線・ケーブルもますます細径化が図られている。 In recent years, with the progress of miniaturization and high-density mounting of precision electronic devices and communication devices such as medical fields, the diameters of electric wires and cables used for these devices have been further reduced.
さらに信号線等では、伝送信号の一層の高速化を求める傾向が顕著であり、これに使用される電線の絶縁体層を薄くかつ可能な限り低誘電率化することにより伝送信号の高速化を図ることが望まれている。 Furthermore, in signal lines and the like, the tendency to further increase the speed of transmission signals is remarkable, and the speed of transmission signals can be increased by reducing the dielectric constant as much as possible and making the insulator layer of the wires used for this thin. It is desired to plan.
この絶縁体には従来、ポリエチレンやフッ素樹脂などの誘電率の低い絶縁材料を発泡させたものが使われている。発泡絶縁体層の形成には、予め発泡させたフィルムを導体上に巻き付ける方法や押出方式が知られており、特に押出方式が広く用いられている。 For this insulator, conventionally, an insulating material having a low dielectric constant such as polyethylene or fluororesin is used. For forming the foamed insulator layer, a method of winding a film previously foamed on a conductor and an extrusion method are known, and the extrusion method is particularly widely used.
発泡を形成する方法としては、大きく物理的な発泡方法と化学的な発泡方法に分けられる。 Methods for forming foaming can be broadly divided into physical foaming methods and chemical foaming methods.
物理的な発泡方法としては、液体フロンのような揮発性発泡用液体を溶融樹脂中に注入し、その気化圧により発泡させる方法や窒素ガス、炭酸ガスなど押出機中の溶融樹脂に直接気泡形成用ガスを圧入させることにより一様に分布した細胞状の微細な独立気泡体を樹脂中に発生させる方法などがある。 As a physical foaming method, a volatile foaming liquid such as liquid chlorofluorocarbon is injected into the molten resin and foamed by its vaporization pressure, or bubbles are formed directly in the molten resin in the extruder such as nitrogen gas or carbon dioxide gas. For example, there is a method of generating fine closed cells in the form of cells uniformly distributed by injecting a working gas into the resin.
化学的な発泡方法としては、樹脂中に発泡剤を分散混合した状態で成形し、その後熱を加えることにより発泡剤の分解反応を発生させ、分解により発生するガスを利用して発泡させることが良く知られている。 As a chemical foaming method, a foaming agent is dispersed and mixed in a resin, and after that, heat is applied to cause a decomposition reaction of the foaming agent, and foaming is performed using a gas generated by the decomposition. Well known.
なお、この出願の発明に関連する先行技術文献情報としては、次のものがある。 The prior art document information related to the invention of this application includes the following.
しかしながら、溶融樹脂中に揮発性発泡用液体を注入する方法では、気化圧が強く、気泡の微細形成が難しく薄肉成形に限界がある。また、揮発性発泡用液体の注入速度が遅いために、高速製造化が難しく、生産性に劣るという問題もある。さらに、押出機中で直接気泡形成用ガスを圧入する方法は、細径薄肉押出形成に限界があること、安全面で特別な設備や技術を必要とするため、生産性に劣ることや製造コストの上昇を招いてしまう問題がある。 However, in the method of injecting the volatile foaming liquid into the molten resin, the vaporization pressure is strong, and it is difficult to form fine bubbles, and there is a limit to thin-wall molding. Moreover, since the injection | pouring speed | velocity | rate of the volatile foaming liquid is slow, there also exists a problem that high-speed manufacture is difficult and it is inferior to productivity. Furthermore, the method of directly injecting the gas for forming bubbles in the extruder is limited in the formation of small-diameter and thin-walled extrusion, and requires special equipment and technology for safety, resulting in poor productivity and manufacturing costs. There is a problem that leads to an increase.
一方、化学発泡方法は、予め樹脂中に発泡剤を混練し、分散混合し、成形加工後に熱により発泡剤を反応分解させて発生したガスにより発泡をさせるため、樹脂の成形加工温度を、発泡剤の分解温度より低く保持しなければならない問題がある。さらに、素線の径が細くなると、押出被覆では樹脂圧により断線が起こりやすく、高速化が難しくなるという別の問題もある。 On the other hand, in the chemical foaming method, the foaming agent is kneaded in advance in the resin, dispersed and mixed, and after the molding process, the foaming agent is reacted with heat to cause foaming by the generated gas. There is a problem that it must be kept below the decomposition temperature of the agent. Furthermore, when the diameter of the wire becomes thin, there is another problem that the extrusion coating tends to cause disconnection due to the resin pressure, and it is difficult to increase the speed.
そこで、本発明の目的は、前記の問題点を解決するために、容易に製造可能な水和物分散樹脂組成物およびこれを用いた多孔質物並びに絶縁電線およびその製造方法を提供することにある。 Therefore, an object of the present invention is to provide a hydrate-dispersed resin composition that can be easily manufactured, a porous material using the same, an insulated wire, and a method for manufacturing the same, in order to solve the above-described problems. .
本発明は上記目的を達成するために創案されたものであり、架橋硬化型樹脂組成物に水和物を分散させた水和物分散樹脂組成物であって、前記水和物はその化学式中の水分子の数が５個以上であり、前記水和物の平均粒径が１０μｍ以下である水和物分散樹脂組成物である。 The present invention was devised to achieve the above object, and is a hydrate-dispersed resin composition in which a hydrate is dispersed in a cross-linked curable resin composition, the hydrate having the chemical formula Is a hydrate-dispersed resin composition in which the number of water molecules is 5 or more and the average particle size of the hydrate is 10 μm or less.
また、前記架橋硬化型樹脂組成物が、紫外線又は熱によって硬化する組成物であるとよい。 The cross-linking curable resin composition may be a composition that is cured by ultraviolet rays or heat.
本発明は、前記水和物分散樹脂組成物を、架橋することにより硬化した後、加熱により水和物の水分を除去した多孔質物である。 The present invention is a porous product obtained by curing the hydrate-dispersed resin composition by crosslinking and then removing moisture from the hydrate by heating.
本発明は、前記水和物分散樹脂組成物を、導体の周囲に被覆して絶縁層とした後、前記絶縁層を架橋することにより前記水和物分散樹脂組成物を硬化し、加熱して水和物の水分を除去することで前記絶縁層の中に空孔を形成した絶縁電線である。 The present invention comprises coating the hydrate-dispersed resin composition around a conductor to form an insulating layer, and then curing the hydrate-dispersed resin composition by crosslinking the insulating layer, followed by heating. It is an insulated wire in which pores are formed in the insulating layer by removing moisture from the hydrate.
本発明は、前記水和物分散樹脂組成物を、導体の周囲に被覆して絶縁層とした後、前記絶縁層を架橋することにより前記水和物分散樹脂組成物を硬化し、加熱して水和物の水分を除去することで前記絶縁層の中に空孔を形成した絶縁電線の製造方法である。 The present invention comprises coating the hydrate-dispersed resin composition around a conductor to form an insulating layer, and then curing the hydrate-dispersed resin composition by crosslinking the insulating layer, followed by heating. This is a method for manufacturing an insulated wire in which pores are formed in the insulating layer by removing moisture from the hydrate.
また、前記加熱がマイクロ波加熱であるとよい。 The heating is preferably microwave heating.
本発明によれば、容易に多孔質物を形成できる材料を提供できる。 According to the present invention, a material capable of easily forming a porous material can be provided.
以下、本発明の好適な実施形態を添付図面にしたがって説明する。 Preferred embodiments of the present invention will be described below with reference to the accompanying drawings.
本実施形態に係る水和物分散樹脂組成物は、架橋硬化型樹脂組成物に水和物を分散させてなる。この水和物は、その化学式中の水分子の数が５個以上、水和物の平均粒径が１０μｍ以下であり、好ましくは平均粒径が５μｍ以下であると良い。 The hydrate-dispersed resin composition according to this embodiment is obtained by dispersing a hydrate in a cross-linked curable resin composition. This hydrate has 5 or more water molecules in its chemical formula, and the average particle size of the hydrate is 10 μm or less, preferably 5 μm or less.
水和物の水分子の数（化学式中の水分子の数）を５個以上とするのは、水和物の水分子の数が５個より少ないと、水和物の添加量に応じて水分子の脱水によって得られる空隙形成効果を得にくいためである。 The number of water molecules in the hydrate (the number of water molecules in the chemical formula) is set to 5 or more if the number of water molecules in the hydrate is less than 5, depending on the amount of hydrate added. This is because it is difficult to obtain a void forming effect obtained by dehydration of water molecules.
水和物の平均粒径を１０μｍ以下とするのは、平均粒径が１０μｍより大きくなると、水和物を分散した架橋硬化型樹脂組成物からなる硬化物の機械的特性や薄膜形成時の外観などが著しく低下する問題があるためである。 The average particle size of the hydrate is set to 10 μm or less because when the average particle size is larger than 10 μm, the mechanical properties of the cured product composed of the cross-linked curable resin composition in which the hydrate is dispersed and the appearance when forming a thin film This is because there is a problem that the remarkably decreases.
架橋硬化型樹脂組成物とは、紫外線、熱、電子線、可視光などにより硬化するもので、特に限定するものではないが、好ましくは紫外線や熱、あるいは併用で架橋硬化する樹脂組成物が良く、さらに好ましくは紫外線架橋硬化型樹脂組成物が良い。架橋硬化型樹脂組成物としては、エチレン系、ウレタン系、シリコーン系、フッ素系、エポキシ系、ポリエステル系、ポリカーボネート系など公知の架橋硬化型樹脂組成物を選択できるが、架橋硬化型樹脂組成物の誘電率として４以下、好ましくは３以下のものが良い。 The cross-linking curable resin composition is cured by ultraviolet rays, heat, electron beam, visible light, etc., and is not particularly limited, but preferably a resin composition that is cross-linked and cured by ultraviolet rays, heat, or a combination thereof. More preferably, an ultraviolet crosslinking curable resin composition is used. As the cross-linking curable resin composition, known cross-linking curable resin compositions such as ethylene-based, urethane-based, silicone-based, fluorine-based, epoxy-based, polyester-based, and polycarbonate-based resins can be selected. The dielectric constant is 4 or less, preferably 3 or less.
水和物とは、水分子がほかの分子と結合して生成した形の構造を持つ分子化合物であり、化学式中に含まれる水分子の数に応じて、一水和物、二水和物などと呼ばれる。 Hydrates are molecular compounds with a structure in which water molecules are combined with other molecules, and depending on the number of water molecules contained in the chemical formula, monohydrates and dihydrates. And so on.
水分子を５個以上有する水和物としては、例えば、硝酸ビスマス、硝酸銅（II）、硫酸銅（II）、亜リン酸水素ナトリウム、珪酸マグネシウム、硫酸マンガン、チオ硫酸ナトリウムなどの五水和物、硫酸アンモニウムコバルト、硫酸アンモニウム銅、硫酸アンモニウム鉄、リン酸マグネシウムアンモニウム、ヨウ化コバルト（II）、硝酸ランタン、ヘキサフルオロ珪酸マグネシウム、チオ硫酸マグネシウム、硝酸セリウム、テトラフルオロホウ酸銅（II）、硫酸アンモニウムマンガン、硝酸ニッケル、硫酸ニッケル、テトラフルオロホウ酸ニッケル、ビベラジン、コハク酸ナトリウム、硝酸亜鉛、硝酸マンガンなどの六水和物、塩化セリウム（III）、硫酸コバルト（II）、硫酸第一鉄、硫酸鉄（II）、硫酸マグネシウム、リン酸水素二ナトリウム、亜硫酸ナトリウム、硫酸亜鉛、リン酸ナトリウム二塩基性などの七水和物、ホウ酸アンモニウム、水酸化バリウム、リン酸コバルト（II）、硫酸エルビウム（III）、リン酸マグネシウム第三、炭酸ネオジム、五ホウ酸カリウム、水酸化ストロンチウム、二塩化酸化ジルコニウム、フェノールスルホン酸亜鉛などの八水和物、硝酸アルミニウム、過塩素酸アルミニウム、硝酸第二鉄、硝酸鉄、メタケイ酸ナトリウム、硫化ナトリウム、硝酸鉄（III）、シュウ酸イットリウムなどの九水和物、シュウ酸エルビウム、シュウ酸サマリウム、炭酸ナトリウム、二リン酸ナトリウム、硫酸アトリウム、ピロリン酸ナトリウム、ヘキサシアノ鉄（II）酸ナトリウム、テトラホウ酸ナトリウム、セレン酸ナトリウム、シュウ酸ネオジム、シュウ酸テルビウムなどの十水和物、硫酸アルミニウムカリウム、硫酸アンモニウムクロム、硫酸アンモニウム鉄、リン酸ナトリウム三塩基性、硫酸第二鉄アンモニウム、リン酸ナトリウム、メソ−テトラ（４−スルフォナトフェニル）ポルフィン４ナトリウムなどの十二水和物があげられる。 Examples of hydrates having 5 or more water molecules include pentahydrate such as bismuth nitrate, copper (II) nitrate, copper (II) sulfate, sodium hydrogen phosphite, magnesium silicate, manganese sulfate, sodium thiosulfate, etc. Product, ammonium cobalt sulfate, copper ammonium sulfate, ammonium iron sulfate, magnesium ammonium phosphate, cobalt (II) iodide, lanthanum nitrate, magnesium hexafluorosilicate, magnesium thiosulfate, cerium nitrate, copper (II) tetrafluoroborate, manganese ammonium sulfate, Nickel nitrate, nickel sulfate, nickel tetrafluoroborate, viverazine, sodium succinate, zinc nitrate, manganese nitrate hexahydrate, cerium (III) chloride, cobalt (II) sulfate, ferrous sulfate, iron sulfate ( II), magnesium sulfate, disodium hydrogen phosphate Sodium sulfite, zinc sulfate, sodium phosphate dibasic heptahydrate, ammonium borate, barium hydroxide, cobalt (II) phosphate, erbium (III) sulfate, magnesium phosphate tertiary, neodymium carbonate, five Octahydrates such as potassium borate, strontium hydroxide, zirconium dichloride oxide, zinc phenolsulfonate, aluminum nitrate, aluminum perchlorate, ferric nitrate, iron nitrate, sodium metasilicate, sodium sulfide, iron nitrate ( III), non-hydrates such as yttrium oxalate, erbium oxalate, samarium oxalate, sodium carbonate, sodium diphosphate, atrium sulfate, sodium pyrophosphate, sodium hexacyanoferrate (II), sodium tetraborate, selenate Sodium, neodymium oxalate, terbium oxalate Any decahydrate, potassium aluminum sulfate, chromium ammonium sulfate, ammonium iron sulfate, tribasic sodium phosphate, ammonium ferric sulfate, sodium phosphate, meso-tetra (4-sulfonatophenyl) porphine tetrasodium, etc. Dihydrate.
これらは必要に応じて二種以上、選択的に組み合わせて用いても良い。 These may be used in combination of two or more as required.
本実施形態に係る水和物分散樹脂組成物によれば、水和物分散樹脂組成物を硬化させた際に、水和物を利用して空孔を形成できるため、容易に多孔質物や多孔質被覆電線が得られる。 According to the hydrate-dispersed resin composition according to the present embodiment, when the hydrate-dispersed resin composition is cured, pores can be formed using the hydrate, so that a porous material or a porous material can be easily formed. A quality coated electric wire is obtained.
多孔質物は、水和物分散樹脂組成物を架橋することにより硬化させた後、その硬化させた水和物分散樹脂組成物を加熱して水和物の水分を除去して形成される。 The porous material is formed by curing the hydrate-dispersed resin composition by crosslinking and then heating the cured hydrate-dispersed resin composition to remove moisture from the hydrate.
次に、水和物分散樹脂組成物を用いた絶縁電線について説明する。 Next, an insulated wire using the hydrate-dispersed resin composition will be described.
図１に示すように、本実施形態に係る絶縁電線１は、導体２と、導体２の周囲に被覆された絶縁層３とからなる。
As shown in FIG. 1, the insulated wire 1 according to the present embodiment includes a conductor 2 and an
絶縁層３は、導体２に被覆された水和物分散樹脂組成物が、架橋することにより硬化された後、加熱により水和物の水分を除去され形成された空孔４を有する多孔質物で形成される。
The insulating
次に、本実施形態に係る絶縁電線１の製造方法を説明する。 Next, the manufacturing method of the insulated wire 1 which concerns on this embodiment is demonstrated.
導体２の外周に、架橋硬化型樹脂組成物に水和物を分散した水和物分散樹脂組成物を被覆して絶縁層３を形成する。この絶縁層３を加熱架橋することにより前記水和物分散樹脂組成物を硬化し、さらにマイクロ波加熱することにより、水和物の水分を除去することで絶縁層３の中に空孔４を形成すると絶縁電線１が得られる。
The
導体２の外周に架橋硬化型樹脂組成物を被覆して架橋硬化した後、加熱により脱水させるのは、脱水による体積収縮によって空隙率の低下が防止できるほか、膜厚や外径の変化を防止し、安定した絶縁電線を得ることができるためである。 The outer periphery of the conductor 2 is coated with a cross-linkable curable resin composition, cross-linked and cured, and then dehydrated by heating. In addition to preventing volume reduction due to dehydration, the porosity can be prevented from being decreased, and changes in film thickness and outer diameter can be prevented. This is because a stable insulated wire can be obtained.
水和物の水を加熱脱水するのにマイクロ波加熱を利用するのは、水はマイクロ波により、急速に加熱されるため周囲の樹脂などに影響をあたえることなく、短時間で加熱脱水ができ効率よく空孔形成ができるためである。また、導波管型マイクロ波加熱炉を用いることで、連続的に加熱脱水ができる。 Microwave heating is used to heat and dehydrate hydrated water because water is rapidly heated by microwaves, so heat dehydration can be performed in a short time without affecting the surrounding resin. This is because holes can be formed efficiently. Further, by using a waveguide type microwave heating furnace, heat dehydration can be performed continuously.
絶縁電線１によれば、電線の細径化や、伝送信号の高速化が図れる。 According to the insulated wire 1, the wire diameter can be reduced and the transmission signal speed can be increased.
また、絶縁電線１の製造方法によれば、水和物分散樹脂組成物を硬化させた後、マイクロ波加熱により脱水することで、容易に多孔質被覆電線が得られる。 Moreover, according to the manufacturing method of the insulated wire 1, after hardening a hydrate dispersion resin composition, it spin-dry | dehydrates by a microwave heating, and a porous covering electric wire is easily obtained.
（実施例１）
ポリブタジエンアクリレートオリゴマ（ＴＥＡＩ−１０００、日本曹達（株）製）１００質量部、ジシクロペンタニルメタクリレート５０質量部、イソボニルメタクリレート３０質量部、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド（ＤＡＲＯＣＵＲ ＴＰ０、チバスペシャルティケミカルズ製）５質量部、１−ヒドロキシシクロヘキシルフェニルケトン（ＩＲＧＡＣＵＲＥ １８４、チバスペシャルティケミカルズ製）１質量部からなる架橋硬化型樹脂組成物に、リン酸マグネシウムアンモニウム六水和物（ＮＨ4ＭｇＰＯ4・６Ｈ2Ｏ、和光純薬製）の平均粒径３μｍとしたものを１２４質量部撹拌分散した水和物分散樹脂組成物−実施例１（樹脂組成物−実施例１）を得た。なお、マイクロトラック粒度分布測定装置ＭＴ３０００II（Ｍｉｃｒｏｔｒａｃ Ｉｎｃ．製）を用いて粒度分布の５０％値を平均粒径とした。
Example 1
100 parts by mass of polybutadiene acrylate oligomer (TEAI-1000, manufactured by Nippon Soda Co., Ltd.), 50 parts by mass of dicyclopentanyl methacrylate, 30 parts by mass of isobornyl methacrylate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (DAROCUR TP0 , Ciba Specialty Ltd. Chemicals) 5 parts by weight, 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184, manufactured by Ciba Specialty Chemicals) to the cross-linkable resin composition comprising 1 part by weight of magnesium ammonium phosphate hexahydrate (NH 4 MgPO A hydrate-dispersed resin composition-Example 1 (resin composition-Example 1) obtained by stirring and dispersing 124 parts by mass of 4 · 6H 2 O (manufactured by Wako Pure Chemical Industries, Ltd.) having an average particle size of 3 μm was obtained. A 50% value of the particle size distribution was defined as an average particle size using a microtrack particle size distribution measuring device MT3000II (manufactured by Microtrac Inc.).
樹脂組成物−実施例１を、ガラス板上に４ＭＩＬのブレードを用いて、幅１００ｍｍ、長さ２００ｍｍの塗膜を形成し、窒素雰囲気下で、紫外線照射コンベア装置を用いて紫外線照射量５００ｍＪ／ｃｍ2を照射し硬化させ、膜厚約５０μｍのフィルムを作製した。 Resin composition-Example 1 was formed by using a 4 MIL blade on a glass plate to form a coating film having a width of 100 mm and a length of 200 mm, and using an ultraviolet irradiation conveyor device in a nitrogen atmosphere, an ultraviolet irradiation amount of 500 mJ / A film having a thickness of about 50 μm was prepared by irradiating and curing cm 2 .
次に樹脂組成物−実施例１を、加圧塗布槽でより導体４８ＡＷＧ（７／０．０１３ Ｓ−ＭＦ−ＡＧ合金線、日立電線製）上に速度５０ｍ／ｍｉｎで被覆し、これを紫外線照射炉（アイグラフィックス製、６ｋＷ）２灯に通して硬化させた後、導波管型マイクロ加熱炉を通して加熱脱水処理して、被覆厚５０μｍの電線を作製した。 Next, the resin composition-Example 1 was coated on a conductor 48AWG (7 / 0.013 S-MF-AG alloy wire, manufactured by Hitachi Cable Co., Ltd.) at a speed of 50 m / min with a pressure coating tank, and this was coated with ultraviolet rays. After passing through two irradiation furnaces (made by iGraphics, 6 kW) and curing, heat dehydration treatment was performed through a waveguide type micro heating furnace to produce an electric wire with a coating thickness of 50 μm.
（実施例２）
ポリブタジエンアクリレートオリゴマ（ＴＥＡＩ−１０００、日本曹達（株）製）１００質量部、ジシクロペンタニルメタクリレート５０質量部、イソボニルメタクリレート３０質量部、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド（ＤＡＲＯＣＵＲ ＴＰ０、チバスペシャルティケミカルズ製）５質量部、１−ヒドロキシシクロヘキシルフェニルケトン（ＩＲＧＡＣＵＲＥ １８４、チバスペシャルティケミカルズ製）１質量部からなる架橋硬化型樹脂組成物に、メタケイ酸ナトリウム九水和物（Ｎａ2ＳｉＯ3・９Ｈ2Ｏ、和光純薬製）の平均粒径３μｍとしたものを１２４重量部撹拌分散した水和物分散樹脂組成物−実施例２（樹脂組成物−実施例２）を得た。
(Example 2)
100 parts by mass of polybutadiene acrylate oligomer (TEAI-1000, manufactured by Nippon Soda Co., Ltd.), 50 parts by mass of dicyclopentanyl methacrylate, 30 parts by mass of isobornyl methacrylate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (DAROCUR TP0 , Manufactured by Ciba Specialty Chemicals) and 1 mass part of 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184, manufactured by Ciba Specialty Chemicals) in a cross-linked curable resin composition, sodium metasilicate nonahydrate (Na 2 SiO 3) A hydrate-dispersed resin composition-Example 2 (resin composition-Example 2) obtained by stirring and dispersing 124 parts by weight of 9H 2 O (manufactured by Wako Pure Chemical Industries, Ltd.) having an average particle size of 3 μm was obtained.
樹脂組成物−実施例２を用いて実施例１と同様にフィルムおよび電線を作製した。 Using the resin composition-Example 2, a film and an electric wire were produced in the same manner as in Example 1.
（実施例３）
両末端スチレン変性オリゴフェニレンエーテル（ＯＰＥ−２Ｓｔ、三菱ガス化学製）１００質量部、ジシクロペンタニルメタクリレート３０質量部、Ｎ−ビニルピロリドン２０質量部、イソボニルメタクリレート３０質量部、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド５質量部、１−ヒドロキシシクロヘキシルフェニルケトン１質量部からなる架橋硬化型樹脂組成物に、炭酸ナトリウム十水和物（Ｎａ2ＣＯ3・１０Ｈ2Ｏ、和光純薬製）の平均粒径８μｍとしたものを１２４質量部撹拌分散した水和物分散樹脂組成物−実施例３（樹脂組成物−実施例３）を得た。
(Example 3)
100 parts by mass of styrene-modified oligophenylene ether at both ends (OPE-2St, manufactured by Mitsubishi Gas Chemical), 30 parts by mass of dicyclopentanyl methacrylate, 20 parts by mass of N-vinylpyrrolidone, 30 parts by mass of isobornyl methacrylate, 2, 4, 6 -A crosslinked curable resin composition consisting of 5 parts by weight of trimethylbenzoyldiphenylphosphine oxide and 1 part by weight of 1-hydroxycyclohexyl phenyl ketone, sodium carbonate decahydrate (Na 2 CO 3 · 10H 2 O, manufactured by Wako Pure Chemical Industries, Ltd.) Hydrate dispersion resin composition-Example 3 (resin composition-Example 3) was obtained by stirring and dispersing 124 parts by mass of an average particle diameter of 8 μm).
樹脂組成物−実施例３を用いて実施例１と同様にフィルムおよび電線を作製した。 A film and an electric wire were produced in the same manner as in Example 1 using the resin composition-Example 3.
（実施例４）
ポリブタジエンアクリレートオリゴマ（ＴＥＡＩ−１０００、日本曹達（株）製）１００質量部、ジシクロペンタニルメタクリレート５０質量部、イソボニルメタクリレート３０質量部、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド（ＤＡＲＯＣＵＲ ＴＰ０、チバスペシャルティケミカルズ製）５質量部、１−ヒドロキシシクロヘキシルフェニルケトン（ＩＲＧＡＣＵＲＥ １８４、チバスペシャルティケミカルズ製）１質量部からなる架橋硬化型樹脂組成物に、珪酸マグネシウム五水和物（Ｍｇ2Ｓｉ3Ｏ8・５Ｈ2Ｏ、和光純薬製）の平均粒径１０μｍとしたものを１２４質量部撹拌分散した水和物分散樹脂組成物−実施例４（樹脂組成物−実施例４）を得た。
Example 4
100 parts by mass of polybutadiene acrylate oligomer (TEAI-1000, manufactured by Nippon Soda Co., Ltd.), 50 parts by mass of dicyclopentanyl methacrylate, 30 parts by mass of isobornyl methacrylate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (DAROCUR TP0 , Manufactured by Ciba Specialty Chemicals) and 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184, manufactured by Ciba Specialty Chemicals), a crosslinked curable resin composition containing magnesium silicate pentahydrate (Mg 2 Si 3 O A hydrate-dispersed resin composition-Example 4 (resin composition-Example 4) obtained by stirring and dispersing 124 parts by mass of an average particle size of 10 Hm (8.5H 2 O, manufactured by Wako Pure Chemical Industries, Ltd.) was obtained.
樹脂組成物−実施例４を用いて実施例１と同様にフィルムおよび電線を作製した。 A film and an electric wire were produced in the same manner as in Example 1 using the resin composition-Example 4.
（比較例１）
ポリブタジエンアクリレートオリゴマ（ＴＥＡＩ‐１０００、日本曹達（株）製）１００質量部、ジシクロペンタニルメタクリレート５０質量部、イソボニルメタクリレート３０質量部、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド（ＤＡＲＯＣＵＲ ＴＰ０、チバスペシャルティケミカルズ製）５質量部、１−ヒドロキシシクロヘキシルフェニルケトン（ＩＲＧＡＣＵＲＥ １８４、チバスペシャルティケミカルズ製）１質量部からなる架橋硬化型樹脂組成物に、リン酸水素カルシウム二水和物（ＣａＨＰＯ4・２Ｈ2Ｏ、和光純薬製）の平均粒径５μｍとしたものを１２４質量部撹拌分散した水和物分散樹脂組成物−比較例１（樹脂組成物−比較例１）を得た。
(Comparative Example 1)
100 parts by mass of polybutadiene acrylate oligomer (TEAI-1000, manufactured by Nippon Soda Co., Ltd.), 50 parts by mass of dicyclopentanyl methacrylate, 30 parts by mass of isobornyl methacrylate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (DAROCUR TP0 , Manufactured by Ciba Specialty Chemicals Co., Ltd.) and 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184, manufactured by Ciba Specialty Chemicals Co., Ltd.), a crosslinked curable resin composition containing calcium hydrogen phosphate dihydrate (CaHPO 4. A hydrate-dispersed resin composition-comparative example 1 (resin composition-comparative example 1) obtained by stirring and dispersing 124 parts by mass of 2H 2 O (manufactured by Wako Pure Chemical Industries, Ltd.) having an average particle size of 5 μm was obtained.
樹脂組成物−比較例１を用いて実施例と同様にフィルムおよび電線を作製した。 Using the resin composition-Comparative Example 1, films and electric wires were produced in the same manner as in the Examples.
（比較例２）
ポリブタジエンアクリレートオリゴマ（ＴＥＡＩ−１０００、日本曹達（株）製）１００質量部、ジシクロペンタニルメタクリレート５０質量部、イソボニルメタクリレート３０質量部、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド（ＤＡＲＯＣＵＲ ＴＰ０、チバスペシャルティケミカルズ製）５質量部、１−ヒドロキシシクロヘキシルフェニルケトン（ＩＲＧＡＣＵＲＥ １８４、チバスペシャルティケミカルズ製）１質量部からなる架橋硬化型樹脂組成物に、リン酸マンガン（II）塩基性四水和物（Ｍｎ（Ｈ2ＰＯ4）2・４Ｈ2０、和光純薬製）の平均粒径１１μｍとしたものを１２４質量部撹拌分散した水和物分散樹脂組成物−比較例２（樹脂組成物−比較例２）を得た。
(Comparative Example 2)
100 parts by mass of polybutadiene acrylate oligomer (TEAI-1000, manufactured by Nippon Soda Co., Ltd.), 50 parts by mass of dicyclopentanyl methacrylate, 30 parts by mass of isobornyl methacrylate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (DAROCUR TP0 , Manufactured by Ciba Specialty Chemicals Co., Ltd.) and 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184, manufactured by Ciba Specialty Chemicals Co., Ltd.). (Mn (H 2 PO 4) 2 · 4H 2 0, manufactured by Wako pure Chemical Industries, Ltd.) average particle size 11μm and the ones 124 parts by stirring the dispersed hydrate dispersed resin composition - Comparative example 2 (resin composition - Comparative Example 2) was obtained.
樹脂組成物−比較例２を用いて実施例と同様にフィルムおよび電線を作製した。 Using the resin composition-Comparative Example 2, films and electric wires were produced in the same manner as in the Examples.
（比較例３）
両末端スチレン変性オリゴフェニレンエーテル（ＯＰＥ−２Ｓｔ、三菱ガス化学製）１００質量部、ジシクロペンタニルメタクリレート３０質量部、Ｎ−ビニルピロリドン２０質量部、イソボニルメタクリレート３０質量部、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド５質量部、１−ヒドロキシシクロヘキシルフェニルケトン１質量部からなる架橋硬化型樹脂組成物に、炭酸ナトリウム十水和物（Ｎａ2ＣＯ3・１０Ｈ2Ｏ、和光純薬製）の平均粒径２０μｍとしたものを１２４質量部撹拌分散した水和物分散樹脂組成物−比較例３（樹脂組成物−比較例３）を得た。
(Comparative Example 3)
100 parts by mass of styrene-modified oligophenylene ether at both ends (OPE-2St, manufactured by Mitsubishi Gas Chemical), 30 parts by mass of dicyclopentanyl methacrylate, 20 parts by mass of N-vinylpyrrolidone, 30 parts by mass of isobornyl methacrylate, 2, 4, 6 -A crosslinked curable resin composition consisting of 5 parts by weight of trimethylbenzoyldiphenylphosphine oxide and 1 part by weight of 1-hydroxycyclohexyl phenyl ketone, sodium carbonate decahydrate (Na 2 CO 3 · 10H 2 O, manufactured by Wako Pure Chemical Industries, Ltd.) ) Dispersion having a mean particle size of 20 μm was obtained by stirring and dispersing 124 parts by mass of the hydrate-dispersed resin composition-Comparative Example 3 (resin composition-Comparative Example 3).
樹脂組成物−比較例３を用いて実施例と同様にフィルムおよび電線を作製した。 Using the resin composition-Comparative Example 3, films and electric wires were produced in the same manner as in the Examples.
実施例１〜４および比較例１〜３で作製したフィルムおよび電線について、評価した結果を表１に示す。空隙率は、マイクロ波加熱前後の硬化膜の質量および体積を求め算出した。 Table 1 shows the evaluation results of the films and electric wires produced in Examples 1 to 4 and Comparative Examples 1 to 3. The porosity was calculated by determining the mass and volume of the cured film before and after microwave heating.
表１に示すように、実施例１〜４に対し、水和物の水分子の数が少ない比較例１又は２は、得られる空隙率が小さく、水和物の添加量による空隙形成効率が低いことが分かる。水和物の平均粒径が１０μｍの実施例４に対して、平均粒径が１０μｍを超える比較例２又は３は、フィルムや電線において、平滑な表面が得られないほか、比較例３では電線被覆において、加圧塗布槽内のダイス部に水和物が詰まりやすく、断線が発生してしまうのに対して、実施例３ではそうした問題は全くない。 As shown in Table 1, with respect to Examples 1 to 4, Comparative Example 1 or 2 in which the number of water molecules in the hydrate is small has a small porosity, and the void formation efficiency due to the amount of hydrate added is small. It turns out that it is low. In contrast to Example 4 in which the average particle size of the hydrate is 10 μm, in Comparative Example 2 or 3 in which the average particle size exceeds 10 μm, a smooth surface cannot be obtained in a film or an electric wire. In the coating, the hydrate is likely to be clogged in the die part in the pressure application tank, and disconnection occurs. In Example 3, there is no such problem.
１ 絶縁電線
２ 導体
３ 絶縁層
４ 空孔
1 Insulated wire 2
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| JP2008058318A JP2009215375A (en) | 2008-03-07 | 2008-03-07 | Hydrate-dispersed resin composition, and porous body and insulated electric wire using the same, and method for manufacturing insulated electric wire |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015532763A (en) * | 2012-08-10 | 2015-11-12 | ジェネラル・ケーブル・テクノロジーズ・コーポレーション | Surface modified overhead conductor |
| JP2018076466A (en) * | 2016-11-11 | 2018-05-17 | 日立化成株式会社 | Curable resin composition, and cured product and resin foam produced therewith |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015532763A (en) * | 2012-08-10 | 2015-11-12 | ジェネラル・ケーブル・テクノロジーズ・コーポレーション | Surface modified overhead conductor |
| US10586633B2 (en) | 2012-08-10 | 2020-03-10 | General Cable Technologies Corporation | Surface modified overhead conductor |
| JP2018076466A (en) * | 2016-11-11 | 2018-05-17 | 日立化成株式会社 | Curable resin composition, and cured product and resin foam produced therewith |
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