TWI512061B - Insulating coatings, insulated wires, and insulated wires - Google Patents
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Description
本發明係關於一種絕緣塗料、絕緣電線、及絕緣電線之製造方法。The present invention relates to an insulating coating, an insulated wire, and a method of manufacturing an insulated wire.
自先前以來，以絕緣皮膜被覆導體而成之絕緣電線被用於馬達或變壓器等各種電氣設備用電線圈。形成該電線圈之絕緣電線必須要具有對導體之密合性、電氣絕緣性及耐熱性。特別是近年來，對於宇宙用電氣設備、飛行器用電氣設備、原子力用電氣設備、能量用電氣設備、汽車用電氣設備要求小型化或輕量化並且高性能化。例如，於馬達等旋轉電機或變壓器中，必須具有較先前更高之輸出化。Insulated wires which are covered with an insulating film have been used for electric coils for various electrical equipment such as motors and transformers. The insulated wire forming the electric coil must have adhesion to the conductor, electrical insulation, and heat resistance. In particular, in recent years, it is required to reduce the size, weight, and performance of electrical equipment for the universe, electrical equipment for aircraft, electrical equipment for atomic power, electrical equipment for energy, and electrical equipment for automobiles. For example, in a rotating electrical machine or a transformer such as a motor, it is necessary to have a higher output than before.
進而，近年來，伴隨設備之小型化、輕量化之傾向，對於旋轉電機亦要求更小型、輕量且高性能者。為了滿足此要求，必須於馬達之芯捲繞更多之絕緣電線，但為於芯之槽(slot)中儘可能地塞入較多之絕緣電線，而提高絕緣電線之絕緣皮膜的高密合化要求。因此，必須抑制因暴露於高溫下後生成之氧化皮膜所致的密合力降低。Further, in recent years, with the trend toward miniaturization and weight reduction of equipment, it is required to be smaller, lighter, and higher in performance for a rotating electrical machine. In order to meet this requirement, it is necessary to wind more insulated wires in the core of the motor, but to increase the high density of the insulating film of the insulated wires in order to insert as many insulated wires as possible in the slots of the core. Claim. Therefore, it is necessary to suppress a decrease in the adhesion force due to the oxide film formed after exposure to a high temperature.
作為自先前以來一直用於製作絕緣皮膜之含有熱硬化性樹脂的絕緣塗料，大量報告有在將絕緣皮膜形成於導體上之步驟中提高絕緣皮膜的密合性者。然而，該等絕緣塗料雖可獲得初期之密合性，但於絕緣電線持續長時間暴露於高溫環境下之情形時，難以保持導體與絕緣皮膜之 密合性。進而，存在以下缺點：如上述先前之絕緣塗料所產生的密合性改良效果係僅限於絕緣塗料與導體直接接觸時才可顯現出之效果，若為了提高機械強度等對絕緣電線所要求之其他特性而欲鑽研皮膜結構，則其構成會受到限制。As an insulating coating material containing a thermosetting resin which has been used for producing an insulating film from the past, a large number of reports have been reported in which the adhesion of the insulating film is improved in the step of forming the insulating film on the conductor. However, although these insulating coatings can achieve initial adhesion, it is difficult to maintain the conductor and the insulating film when the insulated wire is exposed to a high temperature environment for a long time. Adhesion. Further, there is a drawback in that the adhesion improving effect produced by the above-mentioned prior insulating coating is limited to the effect that can be exhibited only when the insulating coating is in direct contact with the conductor, and other requirements for the insulated wire in order to improve mechanical strength and the like If the characteristics of the film structure are to be studied, the composition thereof may be limited.
因此，進行以下嘗試：將提高絕緣被膜之與金屬導體之密合性的成分(密合改良劑)添加於絕緣塗料，使絕緣被膜之機械強度提高，藉此亦改善絕緣電線之耐加工性(例如，參照專利文獻1~4)。密合改良劑通常相對於樹脂而添加數%。然而，此種絕緣電線雖可保持絕緣皮膜對金屬導體之密合力，但存在藉由添加密合改良劑而使絕緣皮膜自身之耐熱性變得不足之情況。因此，產生以下問題：因捲線時之加熱等熱歷程而使機械強度降低，因而使絕緣電線之耐加工性惡化，導致絕緣被膜之損傷，造成絕緣特性降低。Therefore, an attempt has been made to add a component (adhesion improver) which improves the adhesion between the insulating film and the metal conductor to the insulating coating material, thereby improving the mechanical strength of the insulating film, thereby improving the workability of the insulated wire ( For example, refer to Patent Documents 1 to 4). The adhesion improver is usually added in an amount of several % with respect to the resin. However, such an insulated wire can maintain the adhesion of the insulating film to the metal conductor, but the heat resistance of the insulating film itself may be insufficient by the addition of the adhesion improving agent. Therefore, there is a problem in that the mechanical strength is lowered due to a heat history such as heating at the time of winding, and thus the workability of the insulated wire is deteriorated, and the insulating film is damaged, resulting in a decrease in insulation properties.
如上所述，先前並無利用以下操作作為提高導體與絕緣皮膜之密合性之手段的情況：於將絕緣塗料燒附於導體上後，藉由皮膜所含之添加劑或殘留之溶劑成分而產生對導體之積極的化學反應。As described above, the following operation has not been used as a means for improving the adhesion between the conductor and the insulating film: after the insulating coating is baked on the conductor, it is produced by the additive or the residual solvent component contained in the film. A positive chemical reaction to the conductor.
[專利文獻1]日本特開平8-218007號公報[Patent Document 1] Japanese Patent Laid-Open No. Hei 8-218007
[專利文獻2]國際公開第2009/048102號[Patent Document 2] International Publication No. 2009/048102
[專利文獻3]日本特開2009-9824號公報[Patent Document 3] Japanese Patent Laid-Open Publication No. 2009-9824
[專利文獻4]日本特開2009-123403號公報[Patent Document 4] Japanese Patent Laid-Open Publication No. 2009-123403
本發明之課題在於提供一種具有對導體之密合性且可形成耐熱性優異之絕緣被膜的絕緣塗料。An object of the present invention is to provide an insulating coating material having an insulating film which is excellent in heat resistance and which has adhesion to a conductor.
進而，本發明之課題在於提供一種即便長時間暴露於高溫環境下，絕 緣皮膜之密合力亦不會降低之絕緣電線。Further, an object of the present invention is to provide a method that is exposed to a high temperature environment for a long time. The insulation of the edge film will not reduce the insulated wire.
進而，本發明之課題在於提供一種上述絕緣電線之製造方法。Further, an object of the present invention is to provide a method of manufacturing the above insulated electric wire.
本發明人等係鑒於上述課題，對如下絕緣電線之製造方法進行潛心研究：藉由使絕緣電線之絕緣皮膜含有特定之還原劑，而抑制導體表面之氧化皮膜之生成，即便於高溫環境下亦可保持絕緣皮膜對金屬導體之密合力。其結果發現：藉由使用含有下述特定還原劑之絕緣塗料來形成絕緣皮膜，而可利用燒附步驟後殘留於皮膜中之還原劑來防止熱處理後之導體之氧化，且無損絕緣皮膜之諸特性，可製作長期耐熱性優異之絕緣電線，該還原劑係均勻分散於構成絕緣皮膜之樹脂組成物的溶劑成分中，且其沸點夠高者。本發明係基於此見解而完成者。In view of the above problems, the present inventors have made intensive studies on the method for producing an insulated electric wire by suppressing the formation of an oxide film on the surface of the conductor by including a specific reducing agent in the insulating film of the insulated electric wire, even in a high temperature environment. The adhesion of the insulating film to the metal conductor can be maintained. As a result, it was found that the insulating film can be formed by using an insulating coating containing the specific reducing agent described below, and the reducing agent remaining in the film after the baking step can be used to prevent oxidation of the conductor after the heat treatment, and the insulating film is not impaired. The characteristics are such that an insulated wire excellent in long-term heat resistance can be produced, and the reducing agent is uniformly dispersed in a solvent component of a resin composition constituting the insulating film, and has a boiling point high enough. The present invention has been completed based on this finding.
根據本發明，提供下述手段。According to the present invention, the following means are provided.
(1)一種絕緣塗料，於含有可藉由塗佈、燒附而形成絕緣皮膜之樹脂的絕緣塗料中含有沸點為160℃以上之還原劑。(1) An insulating coating comprising a reducing agent having a boiling point of 160 ° C or more in an insulating coating containing a resin capable of forming an insulating film by coating or baking.
(2)如上述(1)之絕緣塗料，其中，上述還原劑之含量相對於樹脂固形物成分為1質量%以上30質量%以下。(2) The insulating coating material according to the above (1), wherein the content of the reducing agent is 1% by mass or more and 30% by mass or less based on the resin solid content.
(3)如上述(1)或(2)之絕緣塗料，其中，上述還原劑為具有還原性羥基之化合物。(3) The insulating coating according to (1) or (2) above, wherein the reducing agent is a compound having a reducing hydroxyl group.
(4)如上述(1)至(3)中任一項之絕緣塗料，其中，上述還原劑為1分子中之碳數為10以上的化合物。(4) The insulating coating material according to any one of the above (1), wherein the reducing agent is a compound having a carbon number of 10 or more in one molecule.
(5)如上述(1)至(4)中任一項之絕緣塗料，其中，上述還原劑為具有羥基之類萜。(5) The insulating coating according to any one of (1) to (4) above, wherein the reducing agent is a hydrazine having a hydroxyl group.
(6)如上述(1)或(2)之絕緣塗料，其中，上述還原劑選自由香茅醇、辛醇、氫醌、香葉醇、抗壞血酸、沉香醇、三縮四乙二醇(tetraethylene glycol)及十二烷硫醇(dodecanethiol)組成之群。(6) The insulating coating according to (1) or (2) above, wherein the reducing agent is selected from the group consisting of citronellol, octanol, hydroquinone, geraniol, ascorbic acid, linalool, tetraethylene glycol (tetraethylene) Glycol) and a group of dodecanethiol.
(7)一種絕緣電線，其係藉由將含有可形成絕緣皮膜之樹脂的絕緣塗 料塗佈、燒附於導體上而形成1層或2層以上之絕緣皮膜者，於該絕緣皮膜之至少1層中含有沸點為160℃以上之還原劑。(7) An insulated electric wire by which an insulating coating containing a resin capable of forming an insulating film is applied When the material is coated and fired on a conductor to form one or two or more insulating films, at least one layer of the insulating film contains a reducing agent having a boiling point of 160 ° C or higher.
(8)如上述(7)之絕緣電線，其中，上述還原劑之含量相對於樹脂固形物成分為1質量%以上30質量%以下。(8) The insulated electric wire according to the above (7), wherein the content of the reducing agent is 1% by mass or more and 30% by mass or less based on the resin solid content.
(9)如上述(7)或(8)之絕緣電線，其中，上述還原劑為具有還原性羥基之化合物。(9) The insulated electric wire according to the above (7) or (8), wherein the reducing agent is a compound having a reducing hydroxyl group.
(10)如上述(7)至(9)中任一項之絕緣電線，其中，上述還原劑為1分子中之碳數為10以上的化合物。(10) The insulated electric wire according to any one of the above (7), wherein the reducing agent is a compound having a carbon number of 10 or more in one molecule.
(11)如上述(7)至(10)中任一項之絕緣電線，其中，上述還原劑為具有羥基之類萜。(11) The insulated electric wire according to any one of the above (7), wherein the reducing agent is a hydrazine having a hydroxyl group.
(12)如上述(7)或(8)之絕緣電線，其中，上述還原劑選自由香茅醇、辛醇、氫醌、香葉醇、抗壞血酸、沉香醇、三縮四乙二醇及十二烷硫醇組成之群。(12) The insulated wire according to the above (7) or (8), wherein the reducing agent is selected from the group consisting of citronellol, octanol, hydroquinone, geraniol, ascorbic acid, linalool, tetraethylene glycol, and ten A group consisting of dialkylthiols.
(13)如上述(7)至(12)中任一項之絕緣電線，其具有至少1層之絕緣皮膜，該絕緣皮膜係塗佈、燒附上述(1)至(6)中任一項之絕緣塗料而形成者。(13) The insulated electric wire according to any one of the above (7) to (12), which has at least one insulating film which is coated and baked by any one of the above (1) to (6). Formed by insulating paint.
(14)一種絕緣電線之製造方法，其包含下述步驟：將含有可藉由塗佈、燒附而形成絕緣皮膜之樹脂的絕緣塗料塗佈、燒附於導體上；於上述絕緣塗料中含有沸點為160℃以上之還原劑。(14) A method for producing an insulated electric wire, comprising the steps of: coating and baking an insulating coating containing a resin capable of forming an insulating film by coating and baking, on a conductor; and containing the insulating coating material A reducing agent having a boiling point of 160 ° C or higher.
(15)一種絕緣電線之製造方法，其係將含有可藉由塗佈、燒附而形成絕緣皮膜之樹脂的絕緣塗料塗佈、燒附於導體上，藉此而形成絕緣皮膜，並於絕緣皮膜上塗佈、燒附沸點為160℃以上之還原劑。(15) A method for producing an insulated electric wire by coating and baking an insulating coating material containing a resin capable of forming an insulating film by coating or baking, thereby forming an insulating film and insulating the film A reducing agent having a boiling point of 160 ° C or more is coated and baked on the film.
(16)一種絕緣電線之製造方法，其係將沸點為160℃以上之還原劑塗佈、燒附於導體上，進一步塗佈、燒附含有可藉由塗佈、燒附而形成絕緣皮膜之樹脂的絕緣塗料，藉此而形成絕緣皮膜。(16) A method for producing an insulated wire, which comprises applying and baking a reducing agent having a boiling point of 160 ° C or more on a conductor, further coating and baking, and forming an insulating film by coating and baking. An insulating coating of the resin, thereby forming an insulating film.
(17)如上述(14)至(16)中任一項之絕緣電線之製造方法，其中，上述還原劑為具有還原性羥基之化合物。(17) The method for producing an insulated electric wire according to any one of the above (14), wherein the reducing agent is a compound having a reducing hydroxyl group.
(18)如上述(14)至(17)中任一項之絕緣電線之製造方法，其中，上述還原劑為1分子中之碳數為10以上的化合物。(18) The method for producing an insulated electric wire according to any one of the above (14), wherein the reducing agent is a compound having a carbon number of 10 or more in one molecule.
(19)如上述(14)至(18)中任一項之絕緣電線之製造方法，其中，上述還原劑為具有羥基之類萜。(19) The method for producing an insulated electric wire according to any one of the above (14), wherein the reducing agent is a hydrazine having a hydroxyl group.
(20)如上述(14)至(16)中任一項之絕緣電線之製造方法，其中，上述還原劑選自由香茅醇、辛醇、氫醌、香葉醇、抗壞血酸、沉香醇、三縮四乙二醇及十二烷硫醇組成之群。(20) The method for producing an insulated electric wire according to any one of the above (14), wherein the reducing agent is selected from the group consisting of citronellol, octanol, hydroquinone, geraniol, ascorbic acid, linalool, and tris A group consisting of tetraethylene glycol and dodecanethiol.
根據本發明之絕緣塗料，可形成一種保持對導體之密合性且耐熱性優異之絕緣被膜。According to the insulating coating material of the present invention, an insulating film which maintains adhesion to a conductor and is excellent in heat resistance can be formed.
又，本發明之絕緣電線發揮如下優異之效果：即便長時間暴露於高溫環境下，絕緣皮膜對導體之密合力亦不降低。Moreover, the insulated wire of the present invention exhibits an excellent effect of not lowering the adhesion of the insulating film to the conductor even when exposed to a high temperature environment for a long period of time.
進而，本發明之絕緣電線之製造方法可提供一種即便長時間暴露於高溫環境下，絕緣皮膜對導體之密合力亦不降低的絕緣電線。Further, the method for producing an insulated electric wire according to the present invention can provide an insulated electric wire in which the adhesion force of the insulating film to the conductor is not lowered even when exposed to a high temperature environment for a long period of time.
又，於高於實際使用環境之溫度區域中實施熱處理來作為絕緣電線之耐熱試驗，本發明之絕緣電線可通過此種試驗。因此，根據本發明，可提供一種可靠性高之絕緣電線。Further, heat treatment is performed in a temperature region higher than the actual use environment as a heat resistance test of the insulated wire, and the insulated wire of the present invention can pass such a test. Therefore, according to the present invention, an insulated electric wire with high reliability can be provided.
1‧‧‧導體1‧‧‧conductor
2‧‧‧含有還原劑之絕緣皮膜2‧‧‧Insulation film containing reducing agent
3‧‧‧不含還原劑之絕緣層3‧‧‧Insulation without reducing agent
4‧‧‧含有密合改良劑之絕緣層4‧‧‧Insulation with adhesion modifier
10‧‧‧絕緣電線10‧‧‧Insulated wires
圖1係表示本發明之絕緣電線之一實施態樣之剖面圖。BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a cross-sectional view showing an embodiment of an insulated wire of the present invention.
圖2係表示本發明之絕緣電線之另一實施態樣之剖面圖。Fig. 2 is a cross-sectional view showing another embodiment of the insulated electric wire of the present invention.
圖3係表示本發明之絕緣電線之又一實施態樣之剖面圖。Fig. 3 is a cross-sectional view showing still another embodiment of the insulated electric wire of the present invention.
圖4係表示本發明之絕緣電線之又一實施態樣之剖面圖。Fig. 4 is a cross-sectional view showing still another embodiment of the insulated electric wire of the present invention.
圖5係表示本發明之絕緣電線之又一實施態樣之剖面圖。Fig. 5 is a cross-sectional view showing still another embodiment of the insulated electric wire of the present invention.
參照圖式，對本發明進行詳細說明。然而，本發明並不限於此。The invention will be described in detail with reference to the drawings. However, the invention is not limited thereto.
再者，於本說明書中，所謂「還原劑」係下述還原性物質之總稱：即便長時間地處於高溫環境下亦藉由還原反應抑制因與絕緣電線之金屬導體中的氧反應而生成之氧化膜的生成。本發明人等發現：藉由利用還原劑而一直將金屬導體之表面保持於正常之狀態，可於熱處理後亦使絕緣皮膜之密合力固定。In addition, in the present specification, the term "reducing agent" is a generic term for a reducing substance which is formed by a reaction of reducing oxygen in a metal conductor of an insulated wire by a reduction reaction even in a high temperature environment for a long period of time. Formation of an oxide film. The present inventors have found that the surface of the metal conductor can be kept in a normal state by using a reducing agent, and the adhesion of the insulating film can be fixed even after the heat treatment.
圖1~5係表示本發明之絕緣電線之較佳之一實施形態之概略剖面圖。如圖1~5所示，本發明之絕緣電線10於導體1之外周設置有含有還原劑之絕緣皮膜2。再者，含有還原劑之絕緣皮膜2既可如圖2、4及5所示直接設置於導體1之外周，亦可如圖3所示隔著含有密合改良劑之層4等其他層而設置於導體1上。進而，亦可如圖1~3及5所示，於導體1與含有還原劑之絕緣皮膜2之間、含有還原劑之絕緣皮膜2之外側等設置不含還原劑之絕緣皮膜3等。即，於本發明中，含有還原劑之層(皮膜)既可直接形成於導體上，亦可隔著其他層而設置於導體之外周。1 to 5 are schematic cross-sectional views showing a preferred embodiment of the insulated wire of the present invention. As shown in FIGS. 1 to 5, the insulated electric wire 10 of the present invention is provided with an insulating film 2 containing a reducing agent on the outer circumference of the conductor 1. Further, the insulating film 2 containing a reducing agent may be directly provided on the outer circumference of the conductor 1 as shown in Figs. 2, 4 and 5, or may be provided with another layer such as the layer 4 containing the adhesion improving agent as shown in Fig. 3 . It is disposed on the conductor 1. Further, as shown in FIGS. 1 to 3 and 5, an insulating film 3 containing no reducing agent or the like may be provided between the conductor 1 and the insulating film 2 containing a reducing agent, and the outside of the insulating film 2 containing a reducing agent. That is, in the present invention, the layer (film) containing the reducing agent may be formed directly on the conductor or may be provided on the outer circumference of the conductor via another layer.
本發明之絕緣塗料係使特定之還原劑均勻地分散於構成絕緣皮膜之樹脂組成物之溶劑成分中。作為用於本發明之溶劑成分，並無特別限制，例如可列舉：N-甲基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺等醯胺系溶劑；N,N-二甲基乙烯尿素、N,N-二甲基丙烯尿素、四甲基尿素等尿素系溶劑；γ-丁內酯、γ-己內酯等內酯系溶劑；丙烯碳酸酯等碳酸酯系溶劑；甲基乙基酮、甲基異丁乙基酮、環己酮等酮系溶劑；環丁碸等碸系溶劑等。該等之中，於高溶解性、高反應促進性等 方面較佳為醯胺系溶劑、尿素系溶劑，於不具有易於阻礙利用加熱之交聯反應之氫原子等方面，更佳為N-甲基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基乙烯尿素、N,N-二甲基丙烯尿素、四甲基尿素，特佳為N-甲基-2-吡咯啶酮。The insulating coating of the present invention uniformly disperses a specific reducing agent in the solvent component of the resin composition constituting the insulating film. The solvent component to be used in the present invention is not particularly limited, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide. Ammonium-based solvent; urea solvent such as N,N-dimethylethylene urea, N,N-dimethyl propylene urea, tetramethyl urea; lactone such as γ-butyrolactone and γ-caprolactone A solvent; a carbonate solvent such as propylene carbonate; a ketone solvent such as methyl ethyl ketone, methyl isobutyl ethyl ketone or cyclohexanone; an oxime solvent such as cyclobutyl hydrazine; and the like. Among these, high solubility, high reaction promotion, etc. In particular, it is preferably a guanamine-based solvent or a urea-based solvent, and is preferably a N-methyl-2-pyrrolidone or N,N-dimethyl group which does not easily hinder hydrogen atoms by a crosslinking reaction by heating. Ethyl acetamide, N,N-dimethylethylene urea, N,N-dimethyl propylene urea, tetramethyl urea, particularly preferably N-methyl-2-pyrrolidone.
於本發明中，為了避免因為將絕緣塗料塗佈、燒附於導體上而造成還原劑完全地蒸發，使用沸點為160℃以上(較佳為180℃以上，更佳為210℃以上，較佳為290℃以下，更佳為250℃以下，較佳為180℃~290℃，更佳為210℃~250℃)者。於還原劑之沸點未滿160℃之情形時，成為如下之結果：因還原劑之反應性高，故於構成熱硬化性樹脂之低分子量成分彼此聚合、硬化之溫度區域，會因還原劑與該低分子量成分發生反應而阻礙熱硬化性樹脂之聚合反應，且利用燒附之硬化不足，故絕緣皮膜之強度降低。In the present invention, in order to avoid complete evaporation of the reducing agent by coating and baking the insulating coating on the conductor, the boiling point is 160 ° C or higher (preferably 180 ° C or higher, more preferably 210 ° C or higher, preferably. It is 290 ° C or less, more preferably 250 ° C or less, preferably 180 ° C to 290 ° C, more preferably 210 ° C to 250 ° C). When the boiling point of the reducing agent is less than 160 ° C, the reactivity of the reducing agent is high. Therefore, the temperature region in which the low molecular weight components constituting the thermosetting resin are polymerized and hardened is caused by the reducing agent and The low molecular weight component reacts to inhibit the polymerization reaction of the thermosetting resin, and the hardening by the sintering is insufficient, so that the strength of the insulating film is lowered.
若將還原劑之沸點設為160℃以上，則還原劑不會完全地蒸發、或不會與熱硬化性樹脂之成分發生反應，而可恰當地混入熱硬化性樹脂中。作為此種還原劑，只要為與可藉由塗佈、燒附而形成絕緣皮膜之樹脂相溶且抑制導體之氧化膜生成者，則並無特別限制，可列舉醇類、多元醇類、醛類、硫醇類、氫醌類、糖類等有機化合物。又，上述還原劑較佳為於150℃以上250℃以下之範圍內被氧化者。還原劑於標準狀態(23℃)下既可為固體狀，亦可為液體狀。When the boiling point of the reducing agent is 160° C. or more, the reducing agent does not completely evaporate or does not react with the components of the thermosetting resin, and can be appropriately mixed into the thermosetting resin. The reducing agent is not particularly limited as long as it is compatible with a resin which can form an insulating film by coating or baking, and suppresses generation of an oxide film of a conductor, and examples thereof include alcohols, polyols, and aldehydes. Organic compounds such as thiols, hydroquinones, and sugars. Further, the reducing agent is preferably oxidized in a range of from 150 ° C to 250 ° C. The reducing agent may be either solid or liquid in a standard state (23 ° C).
將一級醇、二級醇、一級硫醇、二級硫醇氧化，分別轉換成羧酸、羰基、亞磺酸、硫羰基，從而可進行導體之還原。該導體之還原係於置於熱環境時特別能促進反應，故可維持長時間暴露於高溫環境下時之導體與絕緣皮膜之間之密合力。The primary alcohol, the secondary alcohol, the primary thiol, and the secondary thiol are oxidized and converted into a carboxylic acid, a carbonyl group, a sulfinic acid, or a thiocarbonyl group, respectively, thereby allowing reduction of the conductor. The reduction of the conductor particularly promotes the reaction when placed in a hot environment, so that the adhesion between the conductor and the insulating film when exposed to a high temperature environment for a long period of time can be maintained.
作為可用於本發明之醇類，並無特別限制，可列舉：單萜(碳數：10)、倍半萜(碳數：15)、二萜(碳數：20)、二倍半萜(碳數：25)、 三萜(碳數：30)、四萜(碳數：40)等萜類中之具有羥基之類萜(例如，香葉醇、沉香醇、金合歡醇、印度防己毒、佛波醇而莽草毒素(phorbol anisatin)、沉香醇、甘草次酸、松脂醇、香葦醇(carveol)、香茅醇、松脂醇)；茴香醇、苄醇、二氫月桂烯醇、二甲基苯乙醇、二丙烯甘醇、十二烷醇、葑醇、3-甲氧基-3-甲基丁醇、辛醇、3-(5-異龍腦基(isocamphyl))-環己醇、四氫沉香醇、己醇、2-第三丁基環己醇等飽和醇；香茅醇、金合歡醇、橙花醇、2-苯乙烯醇、抗壞血酸、苯乙烯二甲基甲醇、2-甲基-4-(2,2,3-三甲基-3-環戊烯-1-基)-2-丁烯-1-醇、檀香醇、香葦醇、香茅醇、松脂醇、桂皮醇、順式-3-乙烯醇等不飽和醇等。於本發明中，既可單獨使用該等醇類中之1種，亦可組合2種以上而使用。The alcohol which can be used in the present invention is not particularly limited, and examples thereof include a monoterpene (carbon number: 10), a sesquiterpene (carbon number: 15), a diterpene (carbon number: 20), and a double quinone ( Carbon number: 25), Triterpenoids (carbon number: 30), tetraterpene (carbon number: 40), etc., which have hydroxyl groups such as geraniol, linalool, farnesol, indomethacin, phorbol and hydrazine Phorbol anisatin, linalool, glycyrrhetinic acid, rosinol, carveol, citronellol, rosinol; anisole, benzyl alcohol, dihydromyrcenol, dimethylphenylethanol, Dipropylene glycol, dodecanol, decyl alcohol, 3-methoxy-3-methylbutanol, octanol, 3-(5-isocamphylline)-cyclohexanol, tetrahydroagar a saturated alcohol such as alcohol, hexanol or 2-tert-butylcyclohexanol; citronellol, farnesol, nerol, 2-styryl alcohol, ascorbic acid, styrene dimethyl methanol, 2-methyl- 4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, sandalwood, camphorol, citronellol, rosinol, cinnamyl alcohol, An unsaturated alcohol such as cis-3-vinyl alcohol or the like. In the present invention, one of the alcohols may be used alone or two or more of them may be used in combination.
作為可用於本發明之多元醇類，並無特別限制，可列舉：乙二醇、二伸乙甘醇、三甘醇、三縮四乙二醇、1,2-丙二醇、二丙烯甘醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇-1,5-戊二醇及聚乙二醇等二醇類。於本發明中，既可單獨使用該等多元醇類中之1種，亦可組合2種以上而使用。更佳為該等多元醇類中之於兩末端具有羥基之二醇類，於熱硬化性樹脂之溶解力優異之方面，進而較佳為三縮四乙二醇。The polyhydric alcohol which can be used in the present invention is not particularly limited, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, triethylene glycol, 1,2-propylene glycol, and dipropylene glycol. Glycols such as 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol-1,5-pentanediol, and polyethylene glycol. In the present invention, one of the above polyols may be used alone or two or more of them may be used in combination. More preferably, the diol having a hydroxyl group at both terminals in the above-mentioned polyols is preferably triethylene glycol in terms of the solubility of the thermosetting resin.
作為可用於本發明之醛類，並無特別限制，可列舉紫蘇醛、香茅醛、香葉醇、橙花醛。該等之中，於存在氧之情況下之清漆穩定性、對溶劑之溶解性之方面更佳為香葉醇、橙花醛。既可單獨使用該等醛類中之1種，亦可組合2種以上而使用。The aldehyde which can be used in the present invention is not particularly limited, and examples thereof include perillaldehyde, citronellal, geraniol, and nerol. Among these, geranol and nerol are more preferable in terms of varnish stability and solubility in a solvent in the presence of oxygen. One type of these aldehydes may be used alone or two or more types may be used in combination.
作為可用於本發明之硫醇類，並無特別限制，可列舉：辛烷硫醇、癸烷硫醇、十二烷硫醇、十八烷硫醇等脂肪族硫醇類、雙(2-巰基乙基)硫醚、雙(2,3-二巰丙基)硫醚、1,2-雙(2-巰基乙基硫)乙烷、2-(2-巰基乙基硫)-1,3-二巰基丙烷、1,2-雙(2-巰基乙基硫)-3-巰基丙烷、4-巰基甲基-1,8-二巰基-3,6-二硫雜辛烷、2,4-雙(巰基甲基)-1,5- 二巰基-3-硫噴妥鈉(thiopentone)、4,8-雙(巰基甲基)-1,11-二巰基-3,6,9-三硫癸烷、4,7-雙(巰基甲基)-1,11-二巰基-3,6,9-三硫癸烷、5,7-雙(巰基甲基)-1,11-二巰基-3,6,9-三硫癸烷、1,2,7-三巰基-4,6-二硫雜庚烷(dithiaheptane)、1,2,9-三巰基-4,6,8-三硫雜壬烷(trithianonane)、1,2,8,9-四巰基-4,6-二硫雜壬烷(dithianonane)、1,2,10,11-四巰基-4,6,8-三硫癸烷、1,2,12,13-四巰基-4,6,8,10-四硫雜三癸烷、四(4-巰基-2-硫雜丁基)甲烷、四(7-巰基-2,5-二硫雜庚基)甲烷、1,5-二巰基-3-巰基甲基硫-2,4-二硫噴妥鈉、3,7-雙(巰基甲基硫)-1,9-二巰基-2,4,6,8-四硫雜壬烷(tetrathianonane)、1,1,3,3-四(巰基甲基硫)丙烷、2,5-雙(巰基甲基)-1,4-二硫、2,5-雙(2-巰基乙基)-1,4-二硫、2,5-雙(巰基甲基)-1-硫、2,5-雙(2-巰基乙基)-1-硫、雙(4-巰基苯基)硫醚、雙(4-巰基甲基苯基)硫醚、3,4-噻吩二硫醇等聚硫醇類、及該等之二聚物~二十聚物等之類的低聚物等硫醇類。該等之中，於對溶劑之溶解性、於空氣中不易劣化之方面更佳為十二烷硫醇、4,7-雙(巰基甲基)-1,11-二巰基-3,6,9-三硫癸烷。既可單獨使用該等硫醇類中之1種，亦可組合2種以上而使用。The thiol which can be used in the present invention is not particularly limited, and examples thereof include aliphatic thiols such as octane thiol, decane thiol, dodecane thiol and octadecane thiol, and bis (2- Mercaptoethyl) sulfide, bis(2,3-dimercaptopropyl) sulfide, 1,2-bis(2-mercaptoethylsulfanyl)ethane, 2-(2-mercaptoethylsulfanyl)-1, 3-dimercaptopropane, 1,2-bis(2-mercaptoethylsulfanyl)-3-mercaptopropane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2, 4-bis(decylmethyl)-1,5-dimercapto-3-thiopentone, 4,8-bis(indolylmethyl)-1,11-dimercapto-3,6,9- Trisulfide Decane, 4,7-bis(fluorenylmethyl)-1,11-dimercapto-3,6,9-trisulfide Decane, 5,7-bis(fluorenylmethyl)-1,11-dimercapto-3,6,9-trisulfide Decane, 1,2,7-trimercapto-4,6-dithiaheptane, 1,2,9-trimethyl-4,6,8-trithianonane, 1 , 2,8,9-tetradecyl-4,6-dithianonane, 1,2,10,11-tetradecyl-4,6,8-trisulfide Decane, 1,2,12,13-tetradecyl-4,6,8,10-tetrathiatrioxane, tetrakis(4-mercapto-2-thiabutyl)methane, tetrakis(7-fluorenyl)- 2,5-Dithiaheptyl)methane, 1,5-diamidino-3-indolylmethylsulfo-2,4-dithiopental, 3,7-bis(indolylmethylsulfan)-1, 9-diamidino-2,4,6,8-tetrathianonane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 2,5-bis(decylmethyl)- 1,4-disulfide 2,5-bis(2-mercaptoethyl)-1,4-disulfide 2,5-bis(decylmethyl)-1-sulfide 2,5-bis(2-mercaptoethyl)-1-sulfide Polythiols such as bis(4-mercaptophenyl) sulfide, bis(4-mercaptomethylphenyl) sulfide, 3,4-thiophene dithiol, and the likes of these dimers Mercaptans such as oligomers such as substances. Among these, it is more preferably dodecanethiol or 4,7-bis(indolylmethyl)-1,11-diindolyl-3,6 in terms of solubility to a solvent and difficulty in deterioration in air. 9-trisulfide Decane. One type of these thiols may be used alone or two or more types may be used in combination.
作為可用於本發明之氫醌類，並無特別限制，可列舉：氫醌、單甲基氫醌、單乙基氫醌、2,3-二甲基氫醌、2,5-二甲基氫醌、2,6-二甲基氫醌、及氫醌化合物(例如，3-甲基-4-羥基苯基戊酸酯、3-甲基-4-羥基苯基癸酸酯、3-甲基-4-羥基苯基油酸酯、3-乙基-4-羥基苯基辛酸酯、3-乙基-4-羥基苯基油酸酯、3-丙基-4-羥基苯基肉豆蔻酸酯(myristate)、3-丙基-4-羥基苯基棕櫚油酸(palmitoleate)、3-異丙基-4-羥基苯基棕櫚酸酯、3-異丙基-4-羥基苯基肉豆蔻酸酯(myristoleate)、3-丁基-4-羥基苯基月桂酸酯、3-丁基-4-羥基苯基亞麻油酸酯、3-異丁基-4-羥基苯基戊酸酯、3-異丁基-4-羥基苯基亞 麻酸酯(linolenate)、3-第二丁基-4-羥基苯基硬脂酸酯、3-第二丁基-4-羥基苯基肉豆蔻酸酯、3-第三丁基-4-羥基苯基戊酸酯、3-第三丁基-4-羥基苯基癸酸酯、3-第三丁基-4-羥基苯基油酸酯、3-戊基-4-羥基苯基辛酸酯、3-戊基-4-羥基苯基亞麻酸酯)。該等之中，就對溶劑之溶解性之觀點而言，更佳為氫醌、單乙基氫醌。既可單獨使用該等氫醌類中之1種，亦可組合2種以上而使用。The hydroquinone which can be used in the present invention is not particularly limited, and examples thereof include hydroquinone, monomethylhydroquinone, monoethylhydroquinone, 2,3-dimethylhydroquinone, and 2,5-dimethyl group. Hydroquinone, 2,6-dimethylhydroquinone, and hydroquinone compounds (for example, 3-methyl-4-hydroxyphenylvalerate, 3-methyl-4-hydroxyphenyl phthalate, 3- Methyl-4-hydroxyphenyl oleate, 3-ethyl-4-hydroxyphenyl octanoate, 3-ethyl-4-hydroxyphenyl oleate, 3-propyl-4-hydroxyphenyl Myristate, 3-propyl-4-hydroxyphenyl palmitoleic acid (palmitoleate), 3-isopropyl-4-hydroxyphenyl palmitate, 3-isopropyl-4-hydroxybenzene Myristoleate, 3-butyl-4-hydroxyphenyllaurate, 3-butyl-4-hydroxyphenyllinoleate, 3-isobutyl-4-hydroxyphenylpenta Acid ester, 3-isobutyl-4-hydroxyphenyl Linolenate, 3-t-butyl-4-hydroxyphenyl stearate, 3-t-butyl-4-hydroxyphenyl myristate, 3-tert-butyl-4- Hydroxyphenyl valerate, 3-tert-butyl-4-hydroxyphenyl phthalate, 3-tert-butyl-4-hydroxyphenyl oleate, 3-pentyl-4-hydroxyphenyl octate Acid ester, 3-pentyl-4-hydroxyphenyl linolenate). Among these, from the viewpoint of solubility of the solvent, hydroquinone or monoethylhydroquinone is more preferable. One type of these hydroquinones may be used alone or two or more types may be used in combination.
作為可用於本發明之糖類，可列舉單糖類及多糖類。具體而言，可列舉阿洛糖、阿卓糖、葡萄糖、果糖、乳糖、甘露糖、古洛糖、艾杜糖、半乳糖、塔羅糖等。於本發明中，既可單獨使用該等糖類中之1種，亦可組合2種以上而使用。該等糖類中，就為通用之物質且較為廉價之觀點而言，較佳為使用葡萄糖。Examples of the saccharide which can be used in the present invention include monosaccharides and polysaccharides. Specific examples thereof include allose, altrose, glucose, fructose, lactose, mannose, gulose, idose, galactose, talose, and the like. In the present invention, one type of these saccharides may be used alone or two or more types may be used in combination. Among these saccharides, glucose is preferably used from the viewpoint of being a general-purpose substance and being relatively inexpensive.
作為可用於本發明之羧酸，並無特別限制，可列舉若於高溫下分解則轉換成具有甲醯基(醛)之甲酸的草酸、或具有羥基之抗壞血酸。The carboxylic acid which can be used in the present invention is not particularly limited, and examples thereof include oxalic acid which is converted into formic acid having a formazan group (aldehyde) or ascorbic acid having a hydroxyl group when it is decomposed at a high temperature.
作為用於本發明之還原劑，較佳為於180℃以上之高溫活躍地表現還原作用。就此種觀點而言，作為用於本發明之還原劑，較佳為具有還原性羥基之化合物。As the reducing agent used in the present invention, it is preferred to actively exhibit a reduction at a high temperature of 180 ° C or higher. From this point of view, as the reducing agent used in the present invention, a compound having a reducing hydroxyl group is preferred.
又，作為用於本發明之還原劑，較佳為具有某種程度之分子量之化合物，以使即便將絕緣塗料塗佈、燒附於導體上還原劑亦不會完全地分解、蒸發。就此種觀點而言，作為用於本發明之還原劑，較佳為還原劑1分子中之碳數為10以上(較佳為15以下，更佳為12以下，較佳為10~15，更佳為10~12)之化合物。Further, as the reducing agent used in the present invention, a compound having a certain molecular weight is preferable so that the insulating agent is not completely decomposed and evaporated even if the reducing agent is applied and baked on the conductor. In this regard, as the reducing agent used in the present invention, it is preferred that the number of carbon atoms in the molecule of the reducing agent is 10 or more (preferably 15 or less, more preferably 12 or less, preferably 10 to 15, more preferably A compound of 10 to 12).
進而，作為可用於本發明之有機系還原劑，較佳為高沸點、且熱硬化性樹脂低聚物之溶解能充分。就此種觀點而言，作為用於本發明之還原劑，較佳為下述具有羥基之類萜：因為具有不飽和烴基故揮發性高，且變為氣體方顯示出還原性之。Further, the organic reducing agent which can be used in the present invention preferably has a high boiling point and is sufficiently soluble in the thermosetting resin oligomer. From such a viewpoint, as the reducing agent used in the present invention, it is preferred to have a hydrazine such as a hydroxyl group which has a high volatility because of having an unsaturated hydrocarbon group, and exhibits a reducing property when it becomes a gas.
於本發明中，既可單獨使用上述還原劑中之1種，亦可組合2種以上而使用。In the present invention, one type of the above-mentioned reducing agents may be used alone or two or more types may be used in combination.
本發明之絕緣塗料中之還原劑之含量可根據還原劑之種類適當設定，但相對於樹脂固形物成分為1質量%以上(較佳為2質量%以上)30質量%以下(較佳為15質量%以下，更佳為10質量%)、或1~30質量%，較佳為1~15質量%，更佳為2~10質量%。若還原劑之含量相對於樹脂固形物成分過少，則於燒附時所有還原劑蒸發，不易表現效果。另一方面，若還原劑之含量相對於樹脂固形物成分過多，則樹脂固形物成分之溶解能降低，熱硬化性樹脂之硬化反應不易進行，產生熱硬化性樹脂之析出等，清漆之穩定性變差，絕緣皮膜之強度降低。The content of the reducing agent in the insulating coating material of the present invention can be appropriately set depending on the type of the reducing agent, but it is 1% by mass or more (preferably 2% by mass or more) and 30% by mass or less (preferably 15%) based on the resin solid content. The mass% or less, more preferably 10% by mass), or 1 to 30% by mass, more preferably 1 to 15% by mass, still more preferably 2 to 10% by mass. If the content of the reducing agent is too small relative to the resin solid content, all of the reducing agent evaporates at the time of baking, and the effect is hard to be expressed. On the other hand, when the content of the reducing agent is too large relative to the resin solid content component, the solubility of the resin solid content component is lowered, the hardening reaction of the thermosetting resin is hard to proceed, and precipitation of the thermosetting resin occurs, and the stability of the varnish is stabilized. The variation is made, and the strength of the insulating film is lowered.
作為用於本發明之可形成絕緣皮膜之樹脂，並無特別限制，就耐熱性之觀點而言，較佳地使用聚酯樹脂、聚醯亞胺樹脂、聚酯醯亞胺樹脂、聚醯胺醯亞胺樹脂等熱硬化性樹脂。於本發明中，熱硬化性樹脂既可單獨使用1種，亦可混合2種以上而使用。The resin which can be used for forming the insulating film of the present invention is not particularly limited, and from the viewpoint of heat resistance, a polyester resin, a polyimide resin, a polyesterimide resin, a polyamine is preferably used. A thermosetting resin such as a quinone imide resin. In the present invention, the thermosetting resin may be used singly or in combination of two or more.
作為可用於本發明之聚酯樹脂，並無特別限制，可列舉藉由在芳香族聚酯中添加酚樹脂等而改質者。具體而言，可列舉耐熱等級(class)為H種之聚酯樹脂。作為市售之H種聚酯樹脂，可列舉Isone1200(商品名，Schenectady International公司製)等。The polyester resin which can be used in the present invention is not particularly limited, and those which are modified by adding a phenol resin or the like to the aromatic polyester may be mentioned. Specifically, a polyester resin having a heat resistance class of H type can be cited. As a commercially available H type polyester resin, Isone 1200 (trade name, manufactured by Schenectady International Co., Ltd.), etc. are mentioned.
作為可用於本發明之聚醯亞胺樹脂，並無特別限制，可列舉熱硬化性芳香族聚醯亞胺等通常之聚醯亞胺樹脂，例如藉由下述方法而熱硬化者：使用將芳香族四羧酸二酐與芳香族二胺類於極性溶劑中反應而獲得之聚醯胺酸溶液，藉由形成絕緣皮膜時之燒附時的加熱處理而醯亞胺化，藉此。作為市售之聚醯亞胺樹脂，可列舉U清漆(商品名、宇部興產公司製)、U醯亞胺清漆(商品名、Unitika公司製)等。The polyimine resin which can be used in the present invention is not particularly limited, and examples thereof include a general polyimine resin such as a thermosetting aromatic polyimide, which is thermally cured by, for example, the following method: A polyphthalic acid solution obtained by reacting an aromatic tetracarboxylic dianhydride with an aromatic diamine in a polar solvent is imidized by heat treatment at the time of firing at the time of forming an insulating film. The commercially available polyimine resin may, for example, be a U varnish (trade name, manufactured by Ube Industries, Ltd.), a U-imine varnish (trade name, manufactured by Unitika Co., Ltd.), or the like.
作為可用於本發明之聚醯胺醯亞胺樹脂，並無特別限制，可列舉於極 性溶劑中使三羧酸酐與二異氰酸酯類直接反應而得者、於極性溶劑中將二胺類混合於三羧酸酐中並藉由二異氰酸酯類而醯胺化所得者。作為市售之聚醯胺醯亞胺樹脂，可列舉HI406(商品名、日立化成公司製)等。The polyamidoximine resin which can be used in the present invention is not particularly limited and can be exemplified by In the solvent, a tricarboxylic acid anhydride and a diisocyanate are directly reacted, and a diamine is mixed with a tricarboxylic acid anhydride in a polar solvent and amidated by a diisocyanate. HI406 (product name, manufactured by Hitachi Chemical Co., Ltd.) and the like are exemplified as the commercially available polyamidoximine resin.
作為可用於本發明之聚酯樹脂，並無特別限制，作為市售之聚酯醯亞胺樹脂，可列舉Neoheat 8200K2、Neoheat 8600、LITON 3300(商品名、東特塗料公司製)等。The polyester resin which can be used in the present invention is not particularly limited, and examples of the commercially available polyester phthalimide resin include Neoheat 8200K2, Neoheat 8600, and LITON 3300 (trade name, manufactured by Tote Paint Co., Ltd.).
亦可於無損本發明之效果之範圍內，於本發明之絕緣塗料中，摻合結晶化成核劑、結晶化促進劑、氣泡化成核劑、抗氧化劑、抗靜電劑、抗紫外線劑、光穩定劑、螢光增白劑、顏料、染料、相容劑、潤滑劑、強化劑、難燃劑、交聯劑、交聯助劑、塑化劑、增黏劑、減黏劑及彈性體等各種添加劑、或三聚氰胺樹脂、環氧樹脂等密合改良劑、用以提高皮膜強度之無機氧化物填料、樹脂填料、滑石等礦物。In the insulating coating of the present invention, the crystallization nucleating agent, the crystallization accelerator, the bubble nucleating agent, the antioxidant, the antistatic agent, the ultraviolet ray inhibitor, and the light stabilizer may be blended in the insulating coating of the present invention. Agents, fluorescent brighteners, pigments, dyes, compatibilizers, lubricants, enhancers, flame retardants, crosslinkers, cross-linking aids, plasticizers, tackifiers, viscosity reducers, elastomers, etc. Various additives, such as adhesion modifiers such as melamine resin and epoxy resin, inorganic oxide fillers for improving film strength, resin fillers, and minerals such as talc.
作為用於本發明之絕緣電線之導體1，例如可列舉銅、銅合金、鋁、鋁合金或其等之組合等通常用作絕緣電線之導體者。又，導體1之剖面形狀亦無特別限制，既可如圖1~4所示為圓形狀，亦可如圖5所示為矩形且角變圓者。The conductor 1 used for the insulated electric wire of the present invention may, for example, be generally used as a conductor of an insulated electric wire, such as copper, a copper alloy, aluminum, an aluminum alloy, or the like. Further, the cross-sectional shape of the conductor 1 is not particularly limited, and may be a circular shape as shown in FIGS. 1 to 4, or a rectangular shape as shown in FIG.
本發明之絕緣電線係藉由將含有可形成絕緣皮膜的樹脂之絕緣塗料塗佈、燒附於導體上而形成1層或2層以上之絕緣皮膜者，於該絕緣皮膜之至少1層中含有沸點為160℃以上之還原劑。絕緣皮膜中所含有之還原劑藉由抑制於高溫環境下在導體產生之氧化膜之成長，而保持絕緣皮膜對導體之密合性。因此，本發明之絕緣電線發揮以下優異之效果：耐熱性及機械特性優異，並且即便長時間暴露於高溫環境下時絕緣被膜之密合性亦不降低。The insulated electric wire of the present invention is formed by coating and baking an insulating coating containing a resin capable of forming an insulating film on a conductor to form one or two or more insulating films, and at least one layer of the insulating film is contained in the insulating film. A reducing agent having a boiling point of 160 ° C or higher. The reducing agent contained in the insulating film maintains the adhesion of the insulating film to the conductor by suppressing the growth of the oxide film generated in the conductor in a high temperature environment. Therefore, the insulated electric wire of the present invention exhibits an excellent effect of excellent heat resistance and mechanical properties, and does not deteriorate the adhesion of the insulating film even when exposed to a high temperature environment for a long period of time.
作為可形成用於本發明之絕緣電線之絕緣皮膜的樹脂及還原劑之具體例，與用於上述絕緣塗料者相同，且較佳之範圍亦相同。又，關於還原劑 之含量之較佳範圍，亦與上述絕緣塗料之較佳範圍相同。Specific examples of the resin and the reducing agent which can form the insulating film for the insulated electric wire of the present invention are the same as those used for the above insulating coating, and the preferred range is also the same. Also, about reducing agents The preferred range of the content is also the same as the preferred range of the above insulating coating.
作為本發明之絕緣電線之製造方法，只要為包含於絕緣皮膜中具有160℃以上之沸點之還原劑之方法則並無特別限制。作為本發明之絕緣電線中之絕緣被膜之形成方法，可列舉：將本發明之絕緣塗料塗佈、燒附於導體上之方法；於將不含還原劑之絕緣塗料塗佈、燒附於導體上後或於燒附中，吹送氣體狀之還原劑之方法；藉由將含有可形成絕緣皮膜的樹脂之絕緣塗料塗佈、燒附於導體上而形成絕緣皮膜，並於絕緣皮膜上塗佈、燒附還原劑之方法；將還原劑塗佈、燒附於導體上，進而塗佈、燒附含有可形成絕緣皮膜的樹脂之絕緣塗料之方法等。藉由該等方法，即便於長時間暴露於高溫環境下時，亦可保持絕緣電線之導體與絕緣被膜之間之密合力。The method for producing the insulated electric wire of the present invention is not particularly limited as long as it is a reducing agent having a boiling point of 160 ° C or higher contained in the insulating film. The method for forming the insulating film in the insulated electric wire of the present invention includes a method of applying and baking the insulating coating material of the present invention on a conductor, and coating and baking the insulating coating material containing no reducing agent on the conductor. a method of blowing a gaseous reducing agent after being applied to or after burning; forming an insulating film by coating and baking an insulating coating containing a resin capable of forming an insulating film on a conductor, and coating the insulating film on the insulating film A method of baking a reducing agent; a method of coating and baking a reducing agent on a conductor, and further coating and baking an insulating coating containing a resin capable of forming an insulating film. By these methods, the adhesion between the conductor of the insulated wire and the insulating film can be maintained even when exposed to a high temperature environment for a long period of time.
於將還原劑塗佈、燒附於導體上或絕緣皮膜上之情形時，既可對導體或絕緣皮膜噴霧還原劑單體或還原劑組成物，亦可將導體或連同設置有絕緣皮膜之導體浸漬於還原劑組成物中。於該情形時，對於還原劑組成物中之還原劑之濃度，並無特別限制，但較佳為30重量%以上，以使還原劑組成物之溶劑易於藉由燒附而蒸發。作為上述溶劑，只要可溶解還原劑則並無特別限制，例如較佳為使用乙基甲基酮、丙酮、乙酸乙酯、乙酸甲酯、甲苯、四氫呋喃、甲醇、乙醇、異丙醇、氯仿、二氯亞甲基(dichloromethylene)等揮發性相對較高者。When the reducing agent is coated and fired on the conductor or on the insulating film, the conductor or the insulating film may be sprayed with a reducing agent monomer or a reducing agent composition, or the conductor or a conductor provided with an insulating film may be used. Immersed in the reducing agent composition. In this case, the concentration of the reducing agent in the reducing agent composition is not particularly limited, but is preferably 30% by weight or more so that the solvent of the reducing agent composition is easily evaporated by baking. The solvent is not particularly limited as long as it can dissolve the reducing agent. For example, ethyl methyl ketone, acetone, ethyl acetate, methyl acetate, toluene, tetrahydrofuran, methanol, ethanol, isopropanol, chloroform, or the like is preferably used. Dichloromethylene and other relatively high volatility.
用於本發明之絕緣電線之還原劑即便不將含有還原劑之絕緣塗料塗佈、燒附於導體上或塗佈、燒附成其他層，亦可表現其效果。於本發明中，亦可將沸點為160℃以上之還原劑直接塗佈於導體上，並於其上，形成不含還原劑之熱硬化性樹脂層。對於還原劑之塗佈方法並無特別限制，既可於塗佈熱硬化性樹脂清漆前，將還原劑溶液噴霧塗佈於導體上，亦可使導體浸漬於還原劑溶液中。或者，既可將不含還原劑之絕緣層形成 於導體上，並於其上噴霧塗佈還原劑溶液，亦可浸漬於還原劑溶液中。The reducing agent used for the insulated electric wire of the present invention can exhibit the effect even if the insulating coating material containing the reducing agent is not coated or baked on a conductor or coated or baked into another layer. In the present invention, a reducing agent having a boiling point of 160 ° C or higher may be directly applied onto a conductor, and a thermosetting resin layer containing no reducing agent may be formed thereon. The coating method of the reducing agent is not particularly limited, and the reducing agent solution may be spray-coated on the conductor before the application of the thermosetting resin varnish, or the conductor may be immersed in the reducing agent solution. Alternatively, an insulating layer containing no reducing agent can be formed The reducing agent solution is sprayed onto the conductor and sprayed thereon, or may be immersed in the reducing agent solution.
於本發明中，還原劑既可以單體直接塗佈，亦可以揮發性良好之有機溶劑(例如，乙酸乙酯、甲醇、丙酮、甲基乙基酮、氯仿、甲苯、己烷、環己烷、四氫呋喃等)稀釋而使用。對於還原劑之濃度並無特別限制，於可抑制還原劑之強烈味道之方面，較佳為5%~80體積%。In the present invention, the reducing agent may be directly coated with a monomer or an organic solvent having good volatility (for example, ethyl acetate, methanol, acetone, methyl ethyl ketone, chloroform, toluene, hexane, cyclohexane). , tetrahydrofuran, etc.) are diluted and used. The concentration of the reducing agent is not particularly limited, and is preferably from 5% to 80% by volume in terms of suppressing the strong taste of the reducing agent.
本發明之絕緣電線較佳為具有至少1層塗佈、燒附本發明之絕緣塗料而形成之絕緣皮膜。此種絕緣皮膜既可直接設置於導體上，亦可隔著其他層而設置於導體之外周。The insulated wire of the present invention preferably has at least one layer of an insulating film formed by coating and baking the insulating coating of the present invention. Such an insulating film may be provided directly on the conductor or may be provided on the outer circumference of the conductor via another layer.
亦可於本發明之絕緣電線中，形成與導體之密合性優異之含有密合改良劑之密合層。密合層可藉由在導體上塗佈密合層用熱硬化性樹脂清漆，並進行燒附硬化而形成。藉由形成此種密合層，可提高特別是初期之密合性、即於導體上形成絕緣皮膜之步驟中的絕緣皮膜之密合性。Further, in the insulated electric wire of the present invention, an adhesion layer containing an adhesion improver excellent in adhesion to a conductor can be formed. The adhesion layer can be formed by applying a thermosetting resin varnish for the adhesion layer to the conductor and baking and hardening. By forming such an adhesion layer, it is possible to improve the adhesion of the insulating film in the initial step, that is, the step of forming an insulating film on the conductor.
作為可用於密合層之熱硬化性樹脂，例如可列舉聚醯亞胺、聚胺酯(polyurethane)、聚醯胺醯亞胺、聚酯、聚苯并咪唑、聚酯醯亞胺、三聚氰胺樹脂、環氧樹脂等。Examples of the thermosetting resin which can be used for the adhesion layer include polyimine, polyurethane, polyamidoximine, polyester, polybenzimidazole, polyester phthalimide, melamine resin, and ring. Oxygen resin, etc.
作為密合改良劑，例如可使用矽烷氧化物系密合改良劑(矽烷偶合劑)、烷氧化鈦、醯化鈦、鈦螯合物等鈦系密合改良劑、三系密合改良劑、咪唑系密合改良劑、三聚氰胺系密合改良劑、碳二醯亞胺系密合改良劑、硫醇系密合改良劑等通常用作絕緣電線之密合改良劑者。As the adhesion improving agent, for example, a decane oxide-based adhesion improving agent (decane coupling agent), a titanium-based adhesion improving agent such as a titanium alkoxide, a titanium telluride or a titanium chelate compound, or the like can be used. An adhesion improver, an imidazole-based adhesion improver, a melamine-based adhesion improver, a carbodiimide-based adhesion improver, a thiol-based adhesion improver, etc., which are generally used as an adhesion improver for insulated wires. .
對於密合改良劑之添加量並無特別限制，較佳為相對於樹脂固形物成分為0.01質量%以上，更佳為10質量%以下，進而較佳為0.01~10質量%左右。又，對於密合層之厚度並無特別限制，較佳為1 μm以上。The amount of the adhesion improving agent to be added is not particularly limited, but is preferably 0.01% by mass or more, more preferably 10% by mass or less, and still more preferably about 0.01% by mass to 10% by mass based on the resin solid content. Further, the thickness of the adhesion layer is not particularly limited, but is preferably 1 μm or more.
於本發明中，因使用沸點為160℃以上且於約150~250℃時特別容易氧化之還原劑，故當於上述範圍或其以上之溫度範圍內暴露絕緣電線之情形時，可抑制下述氧化膜之生成：因與由還原劑所造成之被含有 於導體中之氧反應而生成者。In the present invention, since a reducing agent which is particularly susceptible to oxidation at a boiling point of 160 ° C or higher and at about 150 to 250 ° C is used, when the insulated electric wire is exposed in a temperature range of the above range or higher, the following can be suppressed. Oxide film formation: due to being contained by a reducing agent Produced by the reaction of oxygen in the conductor.
當於絕緣電線之被膜中含有密合改良劑之情形時，為表現密合力而於密合改良劑與導體金屬之間形成配位鍵，故必須使含有密合改良劑之密合層直接接觸於導體。進而，利用該密合改良劑之反應係僅於固體或液體之狀態下發生。相對於此，用於本發明之還原劑於例如導體為銅之情形時，作用於在液體或氣體狀態下生成於導體表面之氧化銅，而將其還原成銅。因此，即便還原劑單體或含有還原劑之絕緣層不直接接觸於導體表面，但只要成為氣體之還原劑穿透構成絕緣皮膜之樹脂內部並到達至導體表面即可。用於本發明之還原劑於約140℃左右開始氣化反應。藉此，可抑制導體表面之氧化銅之成長。又，利用還原劑之還原反應係暴露絕緣電線之溫度越高越容易進行。When the adhesion improving agent is contained in the film of the insulated wire, a bonding bond is formed between the adhesion improving agent and the conductor metal in order to express the adhesion force, so that the adhesion layer containing the adhesion improving agent must be directly contacted. For conductors. Further, the reaction using the adhesion improver occurs only in a solid or liquid state. On the other hand, in the case where the conductor is copper, for example, the reducing agent used in the present invention acts on copper oxide which is formed on the surface of the conductor in a liquid or gas state, and is reduced to copper. Therefore, even if the reducing agent monomer or the insulating layer containing the reducing agent does not directly contact the surface of the conductor, it is sufficient that the reducing agent that becomes the gas penetrates the inside of the resin constituting the insulating film and reaches the surface of the conductor. The reducing agent used in the present invention starts the gasification reaction at about 140 °C. Thereby, the growth of copper oxide on the surface of the conductor can be suppressed. Further, the reduction reaction by the reducing agent makes it easier to carry out the temperature at which the insulated electric wire is exposed.
進而，絕緣塗料之燒附即便於以500℃以上進行之情形時，於絕緣塗料中所含之溶劑蒸發期間，絕緣皮膜之溫度不會上升至上述溫度，亦不滿300℃。因此，考慮到此方面，於本發明之絕緣電線中，只要以於燒附後絕緣皮膜中亦殘留還原劑之方式適當設定燒附溫度、燒附時間、還原劑之種類、還原劑之沸點、還原劑之含量等即可。Further, even when the insulating coating is baked at 500 ° C or higher, the temperature of the insulating film does not rise to the above temperature during the evaporation of the solvent contained in the insulating coating, and is less than 300 ° C. Therefore, in consideration of this aspect, in the insulated electric wire of the present invention, the baking temperature, the baking time, the kind of the reducing agent, the boiling point of the reducing agent, and the boiling point of the reducing agent are appropriately set so that the reducing agent remains in the insulating film after the baking. The content of the reducing agent or the like may be used.
以下，基於實施例，進一步詳細地說明本發明，但本發明並不限定於該等實施例。Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the examples.
(實施例1)(Example 1)
於2 L可分離式燒瓶中，逐量添加熱硬化性聚酯樹脂清漆(商品名：Neoheat 8200K2，東特塗料公司製，樹脂固形物成分：40%)2000 g作為熱硬化性樹脂清漆，並添加N,N'-二甲基乙醯胺670 g作為溶劑。於室溫下進行攪拌，獲得暗褐色透明之接觸於導體之層用絕緣樹脂清漆。In a 2 L separable flask, 2000 g of a thermosetting polyester resin varnish (trade name: Neoheat 8200K2, manufactured by Tote Paint Co., Ltd., resin solid content: 40%) was added as a thermosetting resin varnish. 670 g of N,N'-dimethylacetamide was added as a solvent. Stirring was carried out at room temperature to obtain an insulating resin varnish which was dark brown and transparent to the layer of the conductor.
於另一2 L可分離式燒瓶中，逐量添加熱硬化性聚酯樹脂清漆(商品 名：Neoheat 8200K2，東特塗料公司製，樹脂固形物成分：40%)2000 g作為熱硬化性樹脂清漆。進而添加香茅醇19.2 g，於室溫下進行攪拌，獲得暗紅色透明之含有還原劑之絕緣塗料(外層用)。Add thermosetting polyester resin varnish to another 2 L separable flask Name: Neoheat 8200K2, manufactured by Dongte Coatings Co., Ltd., resin solid content: 40%) 2000 g as a thermosetting resin varnish. Further, 19.2 g of citronellol was added, and the mixture was stirred at room temperature to obtain a dark red transparent insulating coating containing a reducing agent (for the outer layer).
於導體(導體直徑1 mm之銅線)上，塗佈接觸於上述導體之層用清漆，並藉由大約10 m之熱風循環式豎型爐而於520℃下以通過時間10~20秒進行塗佈、燒附，形成厚度8 μm之層。進而，於其上，使用上述含有還原劑之絕緣塗料，藉由大約10 m之熱風循環式豎型爐於520℃下以通過時間10~20秒進行塗佈、燒附，形成還原劑層，製作絕緣皮膜之厚度為30 μm之絕緣電線。On the conductor (copper wire with a conductor diameter of 1 mm), the layer is coated with a varnish for contact with the above conductor, and is passed through a hot air circulating vertical furnace of about 10 m at 520 ° C for a passage time of 10 to 20 seconds. Coating and baking were carried out to form a layer having a thickness of 8 μm. Further, on the above, using the above-mentioned insulating coating material containing a reducing agent, a reducing agent layer is formed by coating and baking at 520 ° C for 10 to 20 seconds in a hot air circulating vertical furnace of about 10 m. An insulated wire having an insulating film thickness of 30 μm was produced.
將該實施例1之絕緣電線之剖面圖示於圖1中。A cross-sectional view of the insulated wire of this embodiment 1 is shown in Fig. 1.
(實施例2)(Example 2)
於2 L可分離式燒瓶中，逐量添加聚醯胺醯亞胺樹脂清漆(商品名：HI-406series，日立化成公司製，樹脂固形物成分：32%)2000 g作為熱硬化性樹脂清漆。進而添加辛醇19.2 g，於室溫下進行攪拌，獲得暗褐色透明之含有還原劑之絕緣塗料。In a 2 L separable flask, 2000 g of a polyamidoximine resin varnish (trade name: HI-406series, manufactured by Hitachi Chemical Co., Ltd., resin solid content: 32%) was added in an amount of 2000 g as a thermosetting resin varnish. Further, 19.2 g of octanol was added, and the mixture was stirred at room temperature to obtain a dark brown transparent insulating coating containing a reducing agent.
於另一2 L可分離式燒瓶中，逐量添加聚醯胺醯亞胺樹脂清漆(商品名：HI-406series，日立化成公司製，樹脂固形物成分：32%)2000 g作為熱硬化性樹脂清漆，進而添加NMP(N-甲基-2-吡咯啶酮)135 g作為稀釋溶劑。於室溫下進行攪拌，獲得暗褐色透明之外層用絕緣塗料。In another 2 L separable flask, a polyamidoximine resin varnish (trade name: HI-406series, manufactured by Hitachi Chemical Co., Ltd., resin solid content: 32%) was added in an amount of 2000 g as a thermosetting resin. The varnish was further added with 135 g of NMP (N-methyl-2-pyrrolidone) as a diluent solvent. Stirring was carried out at room temperature to obtain an insulating coating for a dark brown transparent outer layer.
使用所調製之含有還原劑之絕緣塗料，藉由大約10 m之熱風循環式豎型爐於520℃下以通過時間10~20秒對導體直徑1 mm之銅線進行塗佈、燒附，形成厚度為8 μm之還原劑層。進而，於其上，與還原劑層同樣地塗佈、燒附上述外層用絕緣塗料，形成厚度為22 μm之外層，製作絕緣皮膜之厚度為30 μm之絕緣電線。Using a prepared insulating coating containing a reducing agent, a copper wire having a conductor diameter of 1 mm is coated and sintered by a hot air circulating vertical furnace of about 10 m at a temperature of 520 ° C for 10 to 20 seconds. A reducing agent layer having a thickness of 8 μm. Furthermore, the above-mentioned outer layer insulating coating material was applied and baked in the same manner as the reducing agent layer, and a layer having a thickness of 22 μm was formed to form an insulating wire having an insulating film thickness of 30 μm.
將該實施例2之絕緣電線之剖面圖示於圖2中。A cross-sectional view of the insulated wire of this embodiment 2 is shown in Fig. 2 .
(實施例3、4、6及8~12、以及比較例2~4)(Examples 3, 4, 6 and 8 to 12, and Comparative Examples 2 to 4)
將熱硬化性樹脂、還原劑、及相對於熱硬化性樹脂之固形物成分之還原劑的含量如表1~3般變更，除此以外係與實施例2同樣地製作絕緣電線。An insulated wire was produced in the same manner as in Example 2 except that the content of the thermosetting resin, the reducing agent, and the reducing agent of the solid component of the thermosetting resin was changed as shown in Tables 1 to 3.
將該等實施例及比較例之絕緣電線之剖面圖示於圖2中。A cross-sectional view of the insulated wires of the examples and comparative examples is shown in Fig. 2 .
(實施例5)(Example 5)
於2 L可分離式燒瓶中，逐量添加聚醯胺醯亞胺樹脂清漆(商品名：HI-406series，日立化成公司製，樹脂固形物成分：32%)2000 g作為熱硬化性樹脂清漆。進而添加抗壞血酸6.4 g，於室溫下進行攪拌，獲得暗褐色透明之接觸於導體之層用的含有還原劑之絕緣塗料。In a 2 L separable flask, 2000 g of a polyamidoximine resin varnish (trade name: HI-406series, manufactured by Hitachi Chemical Co., Ltd., resin solid content: 32%) was added in an amount of 2000 g as a thermosetting resin varnish. Further, 6.4 g of ascorbic acid was added, and the mixture was stirred at room temperature to obtain an insulating coating containing a reducing agent for a dark brown transparent contact layer with a conductor.
於另一2 L可分離式燒瓶中，逐量添加聚醯胺醯亞胺樹脂清漆(商品名：HI-406series，日立化成公司製，樹脂固形物成分：32%)2000 g作為熱硬化性樹脂清漆，進而添加NMP 135g、及抗壞血酸6.4 g作為稀釋溶劑，於室溫下進行攪拌，獲得暗褐色透明之外層用的含有還原劑之絕緣塗料。In another 2 L separable flask, a polyamidoximine resin varnish (trade name: HI-406series, manufactured by Hitachi Chemical Co., Ltd., resin solid content: 32%) was added in an amount of 2000 g as a thermosetting resin. The varnish was further added with 135 g of NMP and 6.4 g of ascorbic acid as a diluent solvent, and stirred at room temperature to obtain an insulating coating containing a reducing agent for a dark brown transparent outer layer.
使用所調製之接觸於導體之層用的含有還原劑之絕緣塗料，藉由大約10 m之熱風循環式豎型爐於520℃下以通過時間10~20秒對銅線進行塗佈、燒附，形成還原劑層。進而，於其上，塗佈、燒附外層用塗料，形成外層，製作絕緣皮膜之厚度為30 μm之絕緣電線。The copper wire is coated and baked at 520 ° C for 10 to 20 seconds in a hot air circulating vertical furnace of about 10 m using an insulating coating containing a reducing agent for the layer of the contact with the conductor. Forming a reducing agent layer. Further, a coating material for the outer layer was applied and baked to form an outer layer, and an insulating wire having an insulating film thickness of 30 μm was produced.
將該實施例5之絕緣電線之剖面圖示於圖2中。A cross-sectional view of the insulated wire of this embodiment 5 is shown in Fig. 2.
(實施例7)(Example 7)
將還原劑、及相對於熱硬化性樹脂之固形物成分之還原劑之含量如表1般變更，除此以外係與實施例5同樣地製作絕緣電線。An insulated wire was produced in the same manner as in Example 5 except that the content of the reducing agent and the reducing agent of the solid content component of the thermosetting resin was changed as shown in Table 1.
將該實施例7之絕緣電線之剖面圖示於圖2中。A cross-sectional view of the insulated electric wire of this Example 7 is shown in Fig. 2 .
(實施例13)(Example 13)
於2 L可分離式燒瓶中，逐量添加聚醯胺醯亞胺樹脂清漆(商品名：HI-406series，日立化成公司製，樹脂固形物成分：32%)2000 g作為熱硬 化性樹脂清漆，並添加三聚氰胺樹脂(商品名：Super Beckamine，DIC公司製)24 g作為密合改良劑。於室溫下進行攪拌，獲得暗褐色透明之含有密合改良劑之絕緣樹脂清漆。In a 2 L separable flask, a polyamidoximine resin varnish (trade name: HI-406series, manufactured by Hitachi Chemical Co., Ltd., resin solid content: 32%) was added in an amount of 2000 g as a heat hardener. A resin varnish was added, and 24 g of a melamine resin (trade name: Super Beckamine, manufactured by DIC Corporation) was added as an adhesion improver. Stirring was carried out at room temperature to obtain a dark brown transparent insulating resin varnish containing an adhesion improver.
於另一2 L可分離式燒瓶中，逐量添加聚醯胺醯亞胺樹脂清漆(商品名：HI-406series，日立化成公司製，樹脂固形物成分：32%)2000 g作為熱硬化性樹脂清漆。進而添加沉香醇19.2 g，於室溫下進行攪拌，獲得暗紅色透明之含有還原劑之絕緣塗料(中間層用)。In another 2 L separable flask, a polyamidoximine resin varnish (trade name: HI-406series, manufactured by Hitachi Chemical Co., Ltd., resin solid content: 32%) was added in an amount of 2000 g as a thermosetting resin. Varnish. Further, 19.2 g of agar alcohol was added, and the mixture was stirred at room temperature to obtain a dark red transparent insulating coating containing a reducing agent (for the intermediate layer).
於又一2 L可分離式燒瓶中，逐量添加聚醯胺醯亞胺樹脂清漆(商品名：HI-406series，日立化成公司製，樹脂固形物成分：32%)2000 g作為熱硬化性樹脂清漆，進而添加NMP 135g作為稀釋溶劑。於室溫下進行攪拌，獲得暗褐色透明之最外層用絕緣樹脂清漆。In a further 2 L separable flask, a polyamidoximine resin varnish (trade name: HI-406series, manufactured by Hitachi Chemical Co., Ltd., resin solid content: 32%) was added in an amount of 2000 g as a thermosetting resin. The varnish was further added with 135 g of NMP as a diluent solvent. Stirring was carried out at room temperature to obtain an insulating resin varnish for the outermost layer of dark brown transparent.
使用上述含有密合改良劑之絕緣樹脂清漆，藉由大約10 m之熱風循環式豎型爐於520℃下以通過時間10~20秒對導體直徑1 mm之銅線進行塗佈、燒附，形成厚度為6 μm之密合層。進而，於其上，與密合層同樣地塗佈、燒附上述含有還原劑之絕緣塗料，形成還原劑層，進而於其上，與還原劑層同樣地塗佈、燒附上述最外層用絕緣樹脂清漆，形成最外層，製作絕緣皮膜之厚度為30 μm之絕緣電線。Using the above-mentioned insulating resin varnish containing the adhesion improving agent, a copper wire having a conductor diameter of 1 mm is coated and baked at 520 ° C by a hot air circulating vertical furnace of about 10 m for 10 to 20 seconds. A tight layer having a thickness of 6 μm was formed. In addition, the insulating coating material containing a reducing agent is applied and baked in the same manner as the adhesive layer to form a reducing agent layer, and the outermost layer is coated and baked in the same manner as the reducing agent layer. An insulating resin varnish is formed to form the outermost layer, and an insulating wire having a thickness of 30 μm is formed.
將該實施例13之絕緣電線之剖面圖示於圖3中。A cross-sectional view of the insulated wire of this Example 13 is shown in Fig. 3.
(實施例14)(Example 14)
將聚醯亞胺樹脂清漆(商品名：U-清漆，宇部興產公司製，樹脂固形物成分：20%)作為熱硬化性樹脂塗佈於導體上，藉由10 m之熱風循環式豎型爐於520℃下以通過時間10~20秒對導體直徑1 mm之銅線進行塗佈、燒附，製作絕緣皮膜之厚度為30 μm之絕緣電線。進而，將上述絕緣電線浸漬於以乙酸乙酯500 g稀釋香茅醇150 g所得之還原劑溶液中1秒左右，藉由空氣乾燥而去除乙酸乙酯。A polyimide resin varnish (trade name: U-varnish, manufactured by Ube Industries, Ltd., resin solid content: 20%) was applied as a thermosetting resin to a conductor, and a 10 m hot air circulation type vertical type was used. The furnace was coated and fired at 520 ° C for 10 to 20 seconds with a conductor diameter of 1 mm to produce an insulated wire having an insulating film thickness of 30 μm. Further, the insulated wire was immersed in a reducing agent solution obtained by diluting 150 g of citronellol with 500 g of ethyl acetate for about 1 second, and the ethyl acetate was removed by air drying.
將該實施例14之絕緣電線之剖面圖示於圖4中。A cross-sectional view of the insulated wire of this Example 14 is shown in Fig. 4.
(實施例15)(Example 15)
代替將絕緣電線浸漬於還原劑溶液中，而將以乙酸乙酯500 g稀釋香茅醇150 g所得之還原劑溶液直接使用噴霧塗佈於導體上，除此以外係以與實施例14相同之方式獲得絕緣皮膜之厚度為30 μm之絕緣電線。Instead of immersing the insulated wire in the reducing agent solution, the reducing agent solution obtained by diluting 150 g of citronellol with 500 g of ethyl acetate was directly spray-coated on the conductor, except that it was the same as in Example 14. An insulated wire having an insulating film thickness of 30 μm was obtained.
將該實施例15之絕緣電線之剖面圖示於圖4中。A cross-sectional view of the insulated wire of this Example 15 is shown in Fig. 4.
(比較例1)(Comparative Example 1)
於2 L可分離式燒瓶中，逐量添加聚醯胺醯亞胺樹脂清漆(商品名：HI-406series，日立化成公司製，樹脂固形物成分：32%)2000 g作為熱硬化性樹脂清漆，進而添加NMP 135g作為稀釋溶劑。於室溫下進行攪拌，獲得暗褐色透明之絕緣塗料。In a 2 L separable flask, a polyamidoximine resin varnish (trade name: HI-406series, manufactured by Hitachi Chemical Co., Ltd., resin solid content: 32%) was added in an amount of 2000 g as a thermosetting resin varnish. Further, 135 g of NMP was added as a diluent solvent. Stirring was carried out at room temperature to obtain a dark brown transparent insulating coating.
使用絕緣塗料，藉由大約10 m之熱風循環式豎型爐於520℃下以通過時間10~20秒對導體直徑1 mm之銅線進行塗佈、燒附。進而，於其上，使用相同之絕緣塗料形成外層，製作絕緣皮膜之厚度為30 μm之絕緣電線。Using an insulating coating, a copper wire having a conductor diameter of 1 mm was coated and fired at 520 ° C with a hot air circulating vertical furnace of about 10 m for 10 to 20 seconds. Further, on the above, an outer layer was formed using the same insulating coating material, and an insulating wire having an insulating film thickness of 30 μm was produced.
(比較例5)(Comparative Example 5)
使用聚醯亞胺(商品名：U-清漆，宇部興產公司製，樹脂固形物成分：20%)作為熱硬化性樹脂，除此以外係以與比較例1相同之方式製作絕緣皮膜之厚度為30 μm之絕緣電線。The thickness of the insulating film was produced in the same manner as in Comparative Example 1, except that the polyimide resin (trade name: U-varnish, manufactured by Ube Industries, Ltd., resin solid content: 20%) was used as the thermosetting resin. It is an insulated wire of 30 μm.
對實施例1~15及比較例1~5之絕緣電線，進行下述試驗。將試驗結果示於表1~3中。The following tests were performed on the insulated wires of Examples 1 to 15 and Comparative Examples 1 to 5. The test results are shown in Tables 1-3.
<可撓性><flexibility>
以JIS C3003中記載之瓷漆線試驗方法為基準，對可撓性進行試驗。當自實施例1~15及比較例1~5之絕緣電線切取3個適當長度之試驗片，對於各者以於試驗片自身之周圍線與線接觸之方式緊密地捲繞10次時，藉由目視而觀察皮膜中是否產生能觀察到導體之龜裂。將未產生龜裂者判斷為 可撓性良好(GOOD)，將產生龜裂者判斷為可撓性不良(BAD)。The flexibility was tested based on the enamel line test method described in JIS C3003. When three test pieces of appropriate length were cut out from the insulated wires of Examples 1 to 15 and Comparative Examples 1 to 5, each of them was tightly wound 10 times in such a manner that the surrounding line of the test piece itself was in contact with the line. It was visually observed whether or not cracks in the film were observed in the film. Judging that no cracks have occurred Good flexibility (GOOD), and the occurrence of cracks is judged to be poor in flexibility (BAD).
<剝離撚回><peeling back>
對於210℃、24小時之熱處理前後之絕緣電線，取長度為30 cm之試驗片，將單側固定於旋轉機，另一側亦固定。自固定之試驗片之圓周上之一點向線之行進方向賦予傷痕，轉動旋轉機，測定至切斷絕緣皮膜為止之次數。次數越多，表示絕緣電線之絕緣被膜之密合力越高。For the insulated wire before and after the heat treatment at 210 ° C for 24 hours, a test piece having a length of 30 cm was taken, and the one side was fixed to the rotating machine, and the other side was also fixed. A point on the circumference of the self-fixed test piece was given a flaw in the traveling direction of the wire, and the number of times until the insulating film was cut was measured by rotating the rotary machine. The more the number of times, the higher the adhesion of the insulating film of the insulated wire.
<熱處理後之剝離強度><Peel strength after heat treatment>
使用拉伸試驗機(依據JIS B7721)，進行絕緣電線之180°剝離試驗。以壓製機破壞210℃、24小時之熱處理前後之絕緣電線，對絕緣皮膜施以1 mm寬之狹縫。將狹縫部之絕緣皮膜固定於拉伸試驗機，以25℃、20 mm/分鐘之速度測定剝離強度。強度越大，表示絕緣電線之絕緣被膜之密合力越強。A 180° peel test of the insulated wire was carried out using a tensile tester (according to JIS B7721). The insulated wire before and after the heat treatment at 210 ° C for 24 hours was destroyed by a press machine, and a slit of 1 mm width was applied to the insulating film. The insulating film of the slit portion was fixed to a tensile tester, and the peel strength was measured at a rate of 25 ° C and 20 mm / minute. The greater the strength, the stronger the adhesion of the insulating film of the insulated wire.
<伸長切斷><elongation cut>
對於210℃、24小時之熱處理前後之絕緣電線，取長度為40 cm之試驗片，於其中央部標記長度250 mm之標線。使用拉伸試驗機(依據JIS B7721)，以25℃、200 mm/分鐘之速度拉伸直至切斷，測定切斷時之標線之移位作為絕緣電線之伸長之標準。進而，觀測藉由切斷時之絕緣皮膜之收縮而露出之導體之長度作為絕緣電線之絕緣被膜之密合力。再者，對於導體之露出，於伸長之情形時，將密合之部位較少且變成筒狀者判斷為不良(NG)。For the insulated wire before and after the heat treatment at 210 ° C for 24 hours, a test piece having a length of 40 cm was taken, and a mark having a length of 250 mm was marked at the center portion thereof. Using a tensile tester (according to JIS B7721), the film was stretched at a speed of 25 ° C and 200 mm/min until cutting, and the displacement of the mark at the time of cutting was measured as a standard of elongation of the insulated wire. Further, the length of the conductor exposed by the shrinkage of the insulating film at the time of cutting was observed as the adhesion force of the insulating film of the insulated wire. Further, in the case of elongation of the conductor, in the case of elongation, it is judged to be defective (NG) when the portion to be adhered is small and becomes a tubular shape.
<還原法氧化膜厚測定><Reduction method for measuring oxide film thickness>
對210℃、24小時之熱處理前後之絕緣電線施以寬0.5 mm之狹縫，並浸漬於0.1 mol/L之氯化鉀水溶液中，流通5 mA之電流。測定之記錄速度係設為20 mm/min。此時，根據用於導體之還原之電力，測定絕緣電線之氧化皮膜之厚度。A slit of 0.5 mm in width was applied to the insulated wire before and after heat treatment at 210 ° C for 24 hours, and immersed in a 0.1 mol/L potassium chloride aqueous solution to circulate a current of 5 mA. The recording speed of the measurement was set to 20 mm/min. At this time, the thickness of the oxide film of the insulated wire was measured in accordance with the electric power for reduction of the conductor.
再者，於表1~3中，PAI、PEsI及PI係表示如下者。In addition, in Tables 1-3, PAI, PEsI, and PI are the following.
PAI：聚醯胺醯亞胺樹脂清漆(商品名：HI-406series，日立化成公司製，樹脂固形物成分：32%)PAI: Polyamidoximine resin varnish (trade name: HI-406series, manufactured by Hitachi Chemical Co., Ltd., resin solid content: 32%)
PEsI：熱硬化性聚酯樹脂清漆(商品名：Neoheat 8200K2，東特塗料公司製，樹脂固形物成分：40%)PEsI: Thermosetting polyester resin varnish (trade name: Neoheat 8200K2, manufactured by Dongte Coatings Co., Ltd., resin solid content: 40%)
PI：聚醯亞胺樹脂清漆(商品名：U-清漆，宇部興產公司製，樹脂固形物成分：20%)PI: Polyimide resin varnish (trade name: U-varnish, manufactured by Ube Industries, Ltd., resin solid content: 20%)
如表1及2所示，於實施例1~15中，機械特性優異，即便於長時間之熱處理後亦可防止導體之氧化，絕緣皮膜之密合力之降低得到抑制。As shown in Tables 1 and 2, in Examples 1 to 15, the mechanical properties were excellent, and the oxidation of the conductor was prevented even after the heat treatment for a long period of time, and the decrease in the adhesion force of the insulating film was suppressed.
相對於此，如表3所示，於比較例1及比較例5中，因絕緣皮膜中不含還原劑，故無法抑制於高溫環境下產生於導體上之氧化膜之成長，因而絕緣皮膜之密合性降低。於比較例2及比較例3中，還原劑之沸點較低，熱硬化性樹脂之低分子量成分於硬化之溫度區域與還原劑發生反應，阻礙燒附後之分子量降低之熱硬化性樹脂之硬化反應，因而燒附後之絕緣皮膜之強度降低。於比較例4中，因使用無還原力之具有酚性之羥基之甲酚，故導體與絕緣層密合之部位較少，於加熱處理後，產生起源於某些機械特性之密合不良。On the other hand, as shown in Table 3, in Comparative Example 1 and Comparative Example 5, since the insulating film does not contain a reducing agent, growth of the oxide film which is generated on the conductor in a high-temperature environment cannot be suppressed, and thus the insulating film is The adhesion is lowered. In Comparative Example 2 and Comparative Example 3, the boiling point of the reducing agent was low, and the low molecular weight component of the thermosetting resin reacted with the reducing agent in the hardened temperature region, and hardened by the thermosetting resin which inhibited the molecular weight after the sintering. The reaction is such that the strength of the insulating film after firing is lowered. In Comparative Example 4, since the phenol having a phenolic hydroxyl group having no reducing power was used, the portion where the conductor and the insulating layer were in close contact with each other was small, and after the heat treatment, adhesion defects originating from certain mechanical properties were caused.
1‧‧‧導體1‧‧‧conductor
2‧‧‧含有還原劑之絕緣皮膜2‧‧‧Insulation film containing reducing agent
3‧‧‧不含還原劑之絕緣層3‧‧‧Insulation without reducing agent
10‧‧‧絕緣電線10‧‧‧Insulated wires
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05230400A (en) * | 1992-02-20 | 1993-09-07 | Kao Corp | Electrically conductive paste and electrically conductive coating film |
| JPH111105A (en) * | 1997-06-13 | 1999-01-06 | Bridgestone Corp | Pneumatic tire |
| CN1317806A (en) * | 2000-03-31 | 2001-10-17 | 钟渊化学工业株式会社 | Self-melting adhered insulating wire and self-melting adhered twisted wire using same |
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2013
- 2013-02-20 TW TW102105814A patent/TWI512061B/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05230400A (en) * | 1992-02-20 | 1993-09-07 | Kao Corp | Electrically conductive paste and electrically conductive coating film |
| JPH111105A (en) * | 1997-06-13 | 1999-01-06 | Bridgestone Corp | Pneumatic tire |
| CN1317806A (en) * | 2000-03-31 | 2001-10-17 | 钟渊化学工业株式会社 | Self-melting adhered insulating wire and self-melting adhered twisted wire using same |
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