TW201444903A - Fixing resin composition, rotor and motor vehicles, and method of producing rotor - Google Patents
Fixing resin composition, rotor and motor vehicles, and method of producing rotor Download PDFInfo
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Abstract
Description
本發明係關於一種用於轉子之固定用樹脂組成物、轉子、汽車、及轉子之製造方法。 The present invention relates to a method for producing a resin composition for a rotor, a rotor, an automobile, and a rotor.
近年來,於轉子之技術領域中,一直使用於設於轉子鐵芯中之孔部插入永久磁鐵,且於孔部與永久磁鐵之間填充液態樹脂,藉此將永久磁鐵固定於轉子鐵芯之技術。於該技術領域中,通常使用胺基甲酸酯樹脂或環氧樹脂等液態樹脂。此種技術例如記載於專利文獻1中。 In recent years, in the technical field of the rotor, a permanent magnet has been inserted into a hole portion provided in a rotor core, and a liquid resin is filled between the hole portion and the permanent magnet, thereby fixing the permanent magnet to the rotor core. technology. In the technical field, a liquid resin such as a urethane resin or an epoxy resin is usually used. Such a technique is described, for example, in Patent Document 1.
另外,於專利文獻2中,記載有用於密封馬達之馬達密封用環氧樹脂、以及將其硬化而成之成形品。據記載,該成形品可獲得作業環境性、生產性、耐熱性、導熱性、耐溶劑性、高濕耐水性及較低之線膨脹係數。因此,認為可將專利文獻2中所記載之成形品用於馬達之外殼。 Further, Patent Document 2 describes an epoxy resin for sealing a motor for sealing a motor and a molded article obtained by curing the epoxy resin. According to the description, the molded article can obtain work environment, productivity, heat resistance, thermal conductivity, solvent resistance, high moisture resistance, and a low coefficient of linear expansion. Therefore, it is considered that the molded article described in Patent Document 2 can be used for the outer casing of the motor.
另外,專利文獻3所記載之轉子具有下述結構:於收容永久磁鐵之第1孔部之側面,形成有與第1孔部連通且沿著轉子之旋轉方向的第2孔部。於該第2孔部中填充有樹脂或者配置有彈簧,藉此,於轉子之旋轉方向上永久磁 鐵自第1孔部之側壁受到之應力得到緩和。據記載,藉此可防止永久磁鐵破損。另外,作為於轉子鐵芯之孔部與磁鐵之間填充液態樹脂之方法,有預先填入法及塗敷法兩種。預先填入法包含以下步驟。首先,利用分注器將液態樹脂填充至轉子鐵芯之孔部。然後,於填充有液態樹脂之孔部插入磁鐵。預先填入法係記載於專利文獻4及5中。另一方面,塗敷法包含以下步驟。首先,利用毛刷將液態樹脂塗佈於磁鐵上,再將塗佈有液態樹脂之磁鐵插入至轉子鐵芯之孔部。塗敷法係記載於專利文獻6中。 Further, the rotor described in Patent Document 3 has a configuration in which a second hole portion that communicates with the first hole portion and is along the rotation direction of the rotor is formed on the side surface of the first hole portion in which the permanent magnet is housed. The second hole portion is filled with a resin or a spring is disposed, thereby permanently magnetizing in the rotation direction of the rotor. The stress that the iron receives from the side wall of the first hole portion is alleviated. According to the description, it is possible to prevent the permanent magnet from being damaged. Further, as a method of filling the liquid resin between the hole portion of the rotor core and the magnet, there are two methods of pre-filling and coating. The prefill method includes the following steps. First, a liquid resin is filled into the hole portion of the rotor core by a dispenser. Then, a magnet is inserted into the hole portion filled with the liquid resin. The pre-filling method is described in Patent Documents 4 and 5. On the other hand, the coating method comprises the following steps. First, a liquid resin is applied to a magnet by a brush, and a magnet coated with a liquid resin is inserted into a hole of the rotor core. The coating method is described in Patent Document 6.
[專利文獻] [Patent Literature]
[專利文獻1]日本專利特開2007-236020號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-236020
[專利文獻2]日本專利特開2009-13213號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-13213
[專利文獻3]日本專利特開2002-359942號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2002-359942
[專利文獻4]日本專利特開2005-304247號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2005-304247
[專利文獻5]日本專利特開平11-98735號公報 [Patent Document 5] Japanese Patent Laid-Open No. Hei 11-98735
[專利文獻6]日本專利特開2003-199303號公報 [Patent Document 6] Japanese Patent Laid-Open Publication No. 2003-199303
要將上述的填充液態樹脂之技術應用於將樹脂注入到轉子鐵芯之孔部與預先插入至該孔部之磁鐵之間的間隙中之注入方法較為困難。 It is difficult to apply the above-described technique of filling a liquid resin to a method of injecting a resin into a gap between a hole portion of a rotor core and a magnet previously inserted into the hole portion.
另外,專利文獻2所記載之環氧樹脂係以覆蓋整個馬 達為目的。因此,難以將專利文獻2所記載之樹脂用於固定永久磁鐵之目的。 Further, the epoxy resin described in Patent Document 2 covers the entire horse. For the purpose. Therefore, it is difficult to use the resin described in Patent Document 2 for the purpose of fixing a permanent magnet.
因此,本發明人等進行研究之結果發現,藉由採用嵌入成形(insert molding),可將樹脂填充於轉子鐵芯之孔部與預先插入至該孔部之磁鐵之間的間隙中。 As a result of research conducted by the inventors of the present invention, it has been found that by insert molding, the resin can be filled in the gap between the hole portion of the rotor core and the magnet previously inserted into the hole portion.
然而,於轉子鐵芯之孔部與磁鐵之間的間隙較窄之情況下,有無法向間隙中填充熔融樹脂之虞。因此,本發明人等認為,為了提高對間隙之填充特性,在固形樹脂之熔融黏度方面尚有改善之餘地。 However, when the gap between the hole portion of the rotor core and the magnet is narrow, there is a possibility that the gap cannot be filled with the molten resin. Therefore, the inventors of the present invention thought that there is still room for improvement in the melt viscosity of the solid resin in order to improve the filling characteristics of the gap.
根據本發明,可提供一種固定用樹脂組成物,其係用於構成轉子之固定構件者,該轉子包括:轉子鐵芯,其包含由多個板構件積層而成之積層體,固設於旋轉軸上,且於前述積層體中設置有沿著前述旋轉軸之周緣部配置之多個孔部;磁鐵,其係插入於前述孔部中;及前述固定構件,其係使填充於前述孔部與前述磁鐵之相隔部中的前述固定用樹脂組成物硬化而成;且上述固定用樹脂組成物包含:熱硬化性樹脂(A)5質量%以上40質量%以下,其含有於150℃之ICI黏度為3泊(poise)以下之環氧樹脂(A1)70質量%以上100質量%以下;硬化劑(B)3質量%以上35質量%以下,其於150℃之ICI黏度為2泊以下;及無機填充材料(C)50質量%以上93質量%以下;並且於模具溫度175℃、成形壓力6.9MPa、注入時間20秒之條件下,將前述固定用樹脂組成物注入至具有寬度3mm、厚度 80μm之剖面形狀的流路中時之狹縫流動長度(slit flow length)為75mm以上300mm以下。 According to the present invention, there is provided a fixing resin composition for a fixing member constituting a rotor, the rotor comprising: a rotor core including a laminated body formed by laminating a plurality of plate members, fixed to the rotation a plurality of hole portions disposed along a peripheral edge portion of the rotating shaft, a magnet inserted into the hole portion, and a fixing member filled in the hole portion The fixing resin composition in the partition portion of the magnet is cured, and the fixing resin composition contains the thermosetting resin (A) in an amount of 5 mass% or more and 40 mass% or less, and the ICI contained in the ICI at 150 ° C. The epoxy resin (A1) having a viscosity of 3 poise or less is 70% by mass or more and 100% by mass or less; the curing agent (B) is 3% by mass or more and 35% by mass or less, and the ICI viscosity at 150 ° C is 2 poise or less; And the inorganic filler (C) is 50% by mass or more and 93% by mass or less; and the fixing resin composition is injected to have a width of 3 mm and a thickness under the conditions of a mold temperature of 175 ° C, a molding pressure of 6.9 MPa, and an injection time of 20 seconds. The slit flow length in the flow path of the cross-sectional shape of 80 μm is 75 mm or more and 300 mm or less.
根據本發明,可提供一種填充特性優異的固形之固定用樹脂組成物及使用其之轉子。 According to the present invention, it is possible to provide a solid fixing resin composition excellent in filling characteristics and a rotor using the same.
100‧‧‧轉子 100‧‧‧Rotor
110‧‧‧轉子鐵芯 110‧‧‧Rotor core
112‧‧‧鋼板 112‧‧‧ steel plate
114‧‧‧端板 114‧‧‧End board
116‧‧‧槽部 116‧‧‧ slot department
118a‧‧‧端板 118a‧‧‧End plate
118b‧‧‧端板 118b‧‧‧End board
120‧‧‧磁鐵 120‧‧‧ magnet
121‧‧‧側壁 121‧‧‧ side wall
123‧‧‧側壁 123‧‧‧ side wall
130‧‧‧固定構件 130‧‧‧Fixed components
140‧‧‧填充部 140‧‧‧Filling Department
150‧‧‧孔部 150‧‧‧ hole department
151‧‧‧側壁 151‧‧‧ side wall
152‧‧‧孔部 152‧‧‧ Hole Department
153‧‧‧側壁 153‧‧‧ side wall
154a‧‧‧孔部 154a‧‧‧孔部
154b‧‧‧孔部 154b‧‧‧ Hole Department
156‧‧‧孔部 156‧‧‧ Hole Department
160‧‧‧鉚接部 160‧‧‧Riveting
170‧‧‧軸 170‧‧‧Axis
200‧‧‧上模 200‧‧‧上模
210‧‧‧罐 210‧‧‧ cans
220‧‧‧流路 220‧‧‧flow path
D1‧‧‧間隔寬度 D1‧‧‧ interval width
上述目的、以及其他目的、特徵及優點可藉由以下所述之較佳實施形態、及該實施形態所隨附的以下之圖式而更為明瞭。 The above and other objects, features and advantages of the present invention will become more apparent from
圖1係以示意方式表示本發明之實施形態之轉子的俯視圖。 Fig. 1 is a plan view schematically showing a rotor according to an embodiment of the present invention.
圖2係以示意方式表示本發明之實施形態中之嵌入成形用模具的俯視圖。 Fig. 2 is a plan view schematically showing a mold for insert molding in an embodiment of the present invention.
圖3係以示意方式表示本發明之實施形態之轉子之一部分的擴大圖。 Fig. 3 is a schematic enlarged view showing a part of a rotor according to an embodiment of the present invention.
圖4係以示意方式表示本發明之實施形態之轉子之一部分的剖面圖。 Fig. 4 is a cross-sectional view showing a part of a rotor according to an embodiment of the present invention in a schematic manner.
圖5係以示意方式表示本發明之實施形態之轉子的剖面圖。 Fig. 5 is a cross-sectional view showing the rotor of the embodiment of the present invention in a schematic manner.
圖6係表示本發明之實施形態之轉子之變化例的剖面圖。 Fig. 6 is a cross-sectional view showing a modification of the rotor according to the embodiment of the present invention.
圖7係以示意方式表示變化例之轉子的俯視圖。 Fig. 7 is a plan view showing a rotor of a modification in a schematic manner.
圖8係以示意方式表示變化例之轉子的俯視圖。 Fig. 8 is a plan view showing a rotor of a modification in a schematic manner.
圖9係以示意方式表示變化例之轉子的俯視圖。 Fig. 9 is a plan view showing a rotor of a modification in a schematic manner.
以下,使用圖式對本發明之實施形態進行說明。再者,於所有圖式中,均對相同構成要素標附相同符號,且適宜地省略說明。 Hereinafter, embodiments of the present invention will be described using the drawings. In the drawings, the same components are denoted by the same reference numerals, and the description is omitted as appropriate.
圖1係本發明之實施形態之轉子的俯視圖。圖3係本發明之實施形態之轉子之一部分的擴大圖。圖4係本發明之實施形態之轉子之一部分的剖面圖。圖5係表示轉子之構成的剖面圖。本實施形態之轉子100係包括:轉子鐵芯110、磁鐵120、及固定構件130。轉子鐵芯110包含由多個板構件(電磁鋼板)積層而成之積層體。轉子鐵芯110係固設於旋轉軸(軸170)上。另外,轉子鐵芯110中,於該積層體中設置有沿著旋轉軸之周緣部配置之多個孔部150。磁鐵120係插入於孔部150中。固定構件130係使填充於孔部150與磁鐵120之相隔部中的固定用樹脂組成物硬化而成。 Fig. 1 is a plan view of a rotor according to an embodiment of the present invention. Fig. 3 is an enlarged view of a portion of a rotor according to an embodiment of the present invention. Fig. 4 is a cross-sectional view showing a part of a rotor according to an embodiment of the present invention. Fig. 5 is a cross-sectional view showing the configuration of a rotor. The rotor 100 of the present embodiment includes a rotor core 110, a magnet 120, and a fixing member 130. The rotor core 110 includes a laminate in which a plurality of plate members (electromagnetic steel sheets) are laminated. The rotor core 110 is fixed to a rotating shaft (shaft 170). Further, in the rotor core 110, a plurality of holes 150 disposed along the peripheral edge portion of the rotating shaft are provided in the laminated body. The magnet 120 is inserted into the hole 150. The fixing member 130 is formed by curing the fixing resin composition filled in the space between the hole portion 150 and the magnet 120.
轉子鐵芯110係藉由將薄板狀之磁性體的電磁鋼板(鋼板112)積層多個而構成。轉子鐵芯110中設置有用以插入軸170之貫穿孔。該轉子鐵芯110例如可形成為筒狀。轉子鐵芯110於俯視下之形狀並無特別限定,例如可為圓形、多角形等。另外,多個電磁鋼板相互藉由鉚接部160而結合。另外,電磁鋼板係包含例如鐵或鐵合金等。又,於轉子鐵芯110之軸方向之端部,設置有端板114。再者,於端板114中,亦可設置鉚接部160以及用以避免與填充部140之開口部之干擾的槽部116。 The rotor core 110 is configured by laminating a plurality of thin magnetic steel sheets (steel sheets 112). A through hole for inserting the shaft 170 is provided in the rotor core 110. The rotor core 110 can be formed, for example, in a cylindrical shape. The shape of the rotor core 110 in plan view is not particularly limited, and may be, for example, a circle, a polygon, or the like. Further, a plurality of electromagnetic steel sheets are coupled to each other by the caulking portion 160. Further, the electromagnetic steel sheet contains, for example, iron or an iron alloy. Further, an end plate 114 is provided at an end portion of the rotor core 110 in the axial direction. Further, in the end plate 114, a caulking portion 160 and a groove portion 116 for avoiding interference with the opening portion of the filling portion 140 may be provided.
多個孔部150(或者包含多個孔部之孔部群)係以將旋轉軸之軸心作為中心而成為點對稱之方式配置於轉子鐵芯110中。孔部150之個數並無特別限定,例如為2n或3n個(n為自然數,例如設為2~5)。於各孔部150中插入有磁鐵120。孔部150只要依照磁鐵120之形狀而構成即可,例如亦可於磁鐵120之角部周圍具有空隙(margin:(間隙部)。 The plurality of hole portions 150 (or the hole portion group including the plurality of hole portions) are disposed in the rotor core 110 such that the axis of the rotating shaft is center-symmetric. The number of the hole portions 150 is not particularly limited, and is, for example, 2 n or 3 n (n is a natural number, for example, 2 to 5). A magnet 120 is inserted into each of the hole portions 150. The hole portion 150 may be configured in accordance with the shape of the magnet 120. For example, a void (gap portion) may be formed around the corner portion of the magnet 120.
孔部150之配置佈局並不限定於圖1所示之形態,例如亦可採用圖7~9所示之各種配置佈局。可將以2個或3個孔部150為一組的孔部群沿著旋轉軸之周緣部配置。如圖1所示,各孔部群可包含相互離開且配置為V字形的2個孔部。另外,如圖9所示,孔部群亦可包含孔部154a、154b、及形成於該等孔部154a、154b之間的孔部156。另外,如圖8所示,配置為V字形之孔部亦可連通而構成1個孔部152。再者,如圖7所示,多個孔部150亦可相互離開地配置於孔部150相對於軸之面垂直方向正交之位置。 The arrangement of the holes 150 is not limited to the configuration shown in FIG. 1. For example, various layouts shown in FIGS. 7 to 9 may be employed. A group of holes having a pair of two or three hole portions 150 may be disposed along a peripheral portion of the rotating shaft. As shown in Fig. 1, each of the hole groups may include two holes that are spaced apart from each other and arranged in a V shape. Further, as shown in FIG. 9, the hole group may include hole portions 154a and 154b and a hole portion 156 formed between the hole portions 154a and 154b. Further, as shown in FIG. 8, the hole portions arranged in a V shape may communicate with each other to constitute one hole portion 152. Further, as shown in FIG. 7, the plurality of hole portions 150 may be disposed apart from each other so that the hole portion 150 is orthogonal to the direction perpendicular to the surface of the shaft.
另外,磁鐵120只要固定於孔部150內部即可。例如,如圖3及圖4所示,可將磁鐵120固定於孔部150之側壁中位於轉子鐵芯110之外周圓側之側壁151上。亦即,可使磁鐵120之側壁121與孔部150之側壁151接觸。換言之,可將本發明之固定用樹脂組成物填充於孔部150之側壁151以外之側壁與磁鐵120之相隔部(填充部140)中。將該固定用樹脂組成物硬化,形成固定構件130。固定構 件130亦可設置於孔部150之角部與磁鐵120之間。此處,磁鐵120例如可使用釹磁鐵等永久磁鐵。 Further, the magnet 120 may be fixed inside the hole portion 150. For example, as shown in FIGS. 3 and 4, the magnet 120 may be fixed to the side wall 151 on the outer circumference side of the rotor core 110 in the side wall of the hole portion 150. That is, the side wall 121 of the magnet 120 can be brought into contact with the side wall 151 of the hole portion 150. In other words, the fixing resin composition of the present invention can be filled in the space between the side wall other than the side wall 151 of the hole portion 150 and the magnet 120 (filling portion 140). The fixing resin composition is cured to form a fixing member 130. Fixed structure The member 130 may also be disposed between the corner portion of the hole portion 150 and the magnet 120. Here, as the magnet 120, for example, a permanent magnet such as a neodymium magnet can be used.
於圖3及圖4中,側壁153係指孔部150之側壁中位於轉子鐵芯110之內周圓側者。另外,側壁123係指磁鐵120之側壁中與孔部150之側壁153相對向者。 In FIGS. 3 and 4, the side wall 153 means that the side wall of the hole portion 150 is located on the inner circumference side of the rotor core 110. In addition, the side wall 123 refers to the side wall of the magnet 120 facing the side wall 153 of the hole portion 150.
本實施形態中,如圖3或圖4所示,轉子鐵芯110中孔部150與磁鐵120於直徑方向上之間隙的間隔寬度D1係定義為自孔部150之側壁153至磁鐵120之側壁123的距離。於存在上述間隙之情況下,間隔寬度D1較佳為20μm以上、500μm以下。更佳為50μm以上、300μm以下。藉由將該間隔寬度D1設定於上述範圍內,可對轉子賦予良好之機械強度。 In the present embodiment, as shown in FIG. 3 or FIG. 4, the interval width D1 of the gap between the hole portion 150 and the magnet 120 in the radial direction of the rotor core 110 is defined as the side wall 153 of the hole portion 150 to the side wall of the magnet 120. 123 distance. When the gap is present, the interval width D1 is preferably 20 μm or more and 500 μm or less. More preferably, it is 50 micrometers or more and 300 micrometers or less. By setting the interval width D1 within the above range, it is possible to impart good mechanical strength to the rotor.
發明人等進行研究之結果判明,於寬度較窄之區域中,容易發生未填充有樹脂之情況。 As a result of research conducted by the inventors, it has been found that in a region having a narrow width, it is likely to be unfilled with a resin.
針對於此,藉由使用填充特性優異的本發明之固定用樹脂組成物,可抑制於寬度較窄之區域中發生未填充有樹脂之情況。藉此,可將固定構件130良好地填充於孔部150與磁鐵120之間隙中,故而可提高轉子100之剛性。因此,可減低自旋轉時之轉子產生之噪音。 On the other hand, by using the fixing resin composition of the present invention having excellent filling properties, it is possible to prevent the resin from being filled with a resin in a region having a narrow width. Thereby, the fixing member 130 can be well filled in the gap between the hole portion 150 and the magnet 120, so that the rigidity of the rotor 100 can be improved. Therefore, the noise generated by the rotor during spin rotation can be reduced.
如圖5所示,端板114係固定於軸170上,且於軸方向上夾持轉子鐵芯110。端板114係由鉚接部160固定於軸170上。但並不限定於此種形態,如圖6所示,亦可將端板118a、118b藉由熔接等而固定於軸170上。另外,於孔部150內,可不於磁鐵120之外周緣側之側壁上形成固 定構件130,但亦可如圖6所示般,於磁鐵120之外周緣側及內周緣側該兩側壁上形成固定構件130。 As shown in FIG. 5, the end plate 114 is fixed to the shaft 170 and sandwiches the rotor core 110 in the axial direction. The end plate 114 is fixed to the shaft 170 by a rivet portion 160. However, the present invention is not limited to this embodiment. As shown in FIG. 6, the end plates 118a and 118b may be fixed to the shaft 170 by welding or the like. Further, in the hole portion 150, the solid portion may not be formed on the side wall on the peripheral side of the magnet 120. Although the member 130 is fixed, as shown in FIG. 6, the fixing member 130 may be formed on the both side walls on the outer peripheral side and the inner peripheral side of the magnet 120.
以下,對構成本發明之轉子100之固定用樹脂組成物的各成分進行說明。 Hereinafter, each component constituting the fixing resin composition of the rotor 100 of the present invention will be described.
該固定用樹脂組成物可用於形成轉子以及形成包含轉子之車輛。亦即,該固定用樹脂組成物係用於將配置於包含電磁鋼板之轉子鐵芯內所形成之孔部中的磁鐵固定。 The fixing resin composition can be used to form a rotor and to form a vehicle including a rotor. That is, the fixing resin composition is used to fix a magnet disposed in a hole portion formed in a rotor core including an electromagnetic steel sheet.
本發明之固形之固定用樹脂組成物包含:含有環氧樹脂之熱硬化性樹脂(A)、硬化劑(B)、及無機填充材料(C)。該固定用樹脂組成物藉由環氧樹脂之150℃下之ICI黏度為3泊以下之事項而與其他固定用樹脂組成物相區別。另外,關於該固定用樹脂組成物,於模具溫度175℃、成形壓力6.9MPa、注入時間20秒之條件下,將固定用樹脂組成物注入至具有寬度3mm、厚度80μm之剖面形狀的流路中時之狹縫流動長度為75mm以上。再者,此時之狹縫流動長度較佳為75mm以上300mm以下,更佳為80mm以上300mm以下。 The solid-state fixing resin composition of the present invention comprises a thermosetting resin (A) containing an epoxy resin, a curing agent (B), and an inorganic filler (C). The fixing resin composition is distinguished from other fixing resin compositions by the fact that the ICI viscosity at 150 ° C of the epoxy resin is 3 poise or less. In addition, the fixing resin composition was injected into a flow path having a cross-sectional shape having a width of 3 mm and a thickness of 80 μm under the conditions of a mold temperature of 175 ° C, a molding pressure of 6.9 MPa, and an injection time of 20 seconds. The slit flow length is 75 mm or more. Further, the slit flow length at this time is preferably 75 mm or more and 300 mm or less, more preferably 80 mm or more and 300 mm or less.
首先,對熱硬化性樹脂(A)進行說明。 First, the thermosetting resin (A) will be described.
熱硬化性樹脂(A)並無特別限制,可使用:環氧樹脂(A1)、氧雜環丁烷樹脂、(甲基)丙烯酸酯樹脂、不飽和聚酯樹脂、鄰苯二甲酸二烯丙酯樹脂、順丁烯二醯亞胺樹脂等。其中,可較佳地使用硬化性及保存性、硬化物之 耐熱性、耐濕性、耐化學品優異之環氧樹脂(A1)。 The thermosetting resin (A) is not particularly limited, and an epoxy resin (A1), an oxetane resin, a (meth) acrylate resin, an unsaturated polyester resin, or a diene phthalate may be used. An ester resin, a maleimide resin, or the like. Among them, curability and preservability, and hardened materials can be preferably used. Epoxy resin (A1) excellent in heat resistance, moisture resistance and chemical resistance.
本發明之熱硬化性樹脂(A)含有環氧樹脂(A1)。該環氧樹脂(A1)可列舉一分子中具有2個以上環氧基者。 The thermosetting resin (A) of the present invention contains an epoxy resin (A1). The epoxy resin (A1) may be one having two or more epoxy groups in one molecule.
環氧樹脂之分子量或結構並無特別限定,較佳為使固定用樹脂組成物之黏度降低者。環氧樹脂(A1)之150℃下之ICI黏度的上限值為3泊以下,較佳為1.5泊以下。下限值並無特別限定,較佳為0泊以上,更佳為0.01泊以上。藉此,可提高固定用樹脂組成物之填充特性,即便於孔部與磁鐵之間隙較窄之情況下,亦可確保鋼板與磁鐵之接著面積充分,故而可賦予較高之機械強度。 The molecular weight or structure of the epoxy resin is not particularly limited, and it is preferred to lower the viscosity of the fixing resin composition. The upper limit of the ICI viscosity at 150 ° C of the epoxy resin (A1) is 3 poise or less, preferably 1.5 poise or less. The lower limit is not particularly limited, but is preferably 0 poise or more, and more preferably 0.01 poise or more. Thereby, the filling property of the fixing resin composition can be improved, and even when the gap between the hole portion and the magnet is narrow, the contact area between the steel sheet and the magnet can be ensured to be sufficient, so that high mechanical strength can be imparted.
另外,環氧樹脂(A1)例如可列舉:聯苯型環氧樹脂,具有伸聯苯基骨架之苯酚芳烷基型環氧樹脂、具有伸苯基骨架之苯酚芳烷基型環氧樹脂、具有伸苯基骨架之萘酚芳烷基型環氧樹脂、具有甲氧基萘骨架之苯酚芳烷基型環氧樹脂等苯酚芳烷基型環氧樹脂,苯酚酚醛清漆環氧樹脂、鄰甲酚酚醛清漆型環氧樹脂,雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、四甲基雙酚型環氧樹脂等雙酚型環氧樹脂,聯二萘酚型(bisnaphthol type)環氧樹脂、二環戊二烯型環氧樹脂、二氫蒽二醇型環氧樹脂、及三苯基甲烷型環氧樹脂。 Further, examples of the epoxy resin (A1) include a biphenyl type epoxy resin, a phenol aralkyl type epoxy resin having a biphenyl skeleton, and a phenol aralkyl type epoxy resin having a pendant phenyl skeleton. A phenol aralkyl type epoxy resin having a phenylene aralkyl type epoxy resin having a phenylene skeleton, a phenol aralkyl type epoxy resin having a methoxynaphthalene skeleton, a phenol novolac epoxy resin, and an adjacent Phenolic novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, tetramethyl bisphenol type epoxy resin and other bisphenol type epoxy resin, Bisnaphthol type epoxy resin, dicyclopentadiene type epoxy resin, dihydrothylene glycol type epoxy resin, and triphenylmethane type epoxy resin.
其中,環氧樹脂(A1)除了聯苯型環氧樹脂、雙酚型環氧樹脂等具有結晶性之環氧樹脂以外,較佳為具有伸苯基骨架之苯酚芳烷基型環氧樹脂、具有伸聯苯基骨架之苯酚芳烷基型環氧樹脂、三苯基甲烷型環氧樹脂。該等可單 獨使用亦可混合兩種以上而使用。 Among them, the epoxy resin (A1) is preferably a phenol aralkyl type epoxy resin having a pendant phenyl skeleton, in addition to a crystalline epoxy resin such as a biphenyl type epoxy resin or a bisphenol type epoxy resin. A phenol aralkyl type epoxy resin having a biphenyl skeleton and a triphenylmethane type epoxy resin. The order It can be used alone or in combination of two or more.
相對於固定用樹脂組成物之合計值100質量%,本發明之熱硬化性樹脂(A)之含量並無特別限定,較佳為5質量%以上40質量%以下,更佳為7質量%以上20質量%以下。 The content of the thermosetting resin (A) of the present invention is not particularly limited, and is preferably 5% by mass or more and 40% by mass or less, and more preferably 7% by mass or more, based on 100% by mass of the total of the fixing resin composition. 20% by mass or less.
於本發明之含有環氧樹脂(A1)之較佳形態中,該環氧樹脂之含量的下限值並無特別限定,相對於熱硬化性樹脂(A)100質量%較佳為70質量%以上100質量%以下,更佳為80質量%以上100質量%以下。 In a preferred embodiment of the epoxy resin (A1) of the present invention, the lower limit of the content of the epoxy resin is not particularly limited, and is preferably 70% by mass based on 100% by mass of the thermosetting resin (A). The above is 100% by mass or less, and more preferably 80% by mass or more and 100% by mass or less.
其次,對硬化劑(B)進行說明。硬化劑(B)係用以使熱硬化性樹脂(A)中所含之環氧樹脂(A1)產生三維交聯者。硬化劑(B)並無特別限定,較佳為使固定用樹脂組成物之黏度降低者。硬化劑(B)例如150℃下之ICI黏度的上限值較佳為2泊以下,更佳為1.8泊以下,進而較佳為1.7泊以下。下限值並無特別限定,較佳為0泊以上,更佳為0.01泊以上。 Next, the hardener (B) will be described. The hardener (B) is used to produce a three-dimensional crosslinker of the epoxy resin (A1) contained in the thermosetting resin (A). The curing agent (B) is not particularly limited, and it is preferred to lower the viscosity of the fixing resin composition. The upper limit of the ICI viscosity of the curing agent (B) at 150 ° C is preferably 2 poise or less, more preferably 1.8 poise or less, still more preferably 1.7 poise or less. The lower limit is not particularly limited, but is preferably 0 poise or more, and more preferably 0.01 poise or more.
另外,硬化劑(B)例如可採用:酚醛清漆型酚樹脂、具有伸苯基骨架之苯酚芳烷基樹脂、具有伸聯苯基骨架之苯酚芳烷基樹脂、具有伸苯基骨架之萘酚芳烷基樹脂、以羥基苯甲醛、甲醛及苯酚之反應產物為主的酚樹脂、以及三苯基甲烷型酚化合物與酚醛清漆型酚化合物之共聚物等酚樹脂。該等可單獨使用一種亦可併用兩種以上。利用如上所述之酚樹脂系硬化劑,可使抗燃性、耐濕性、電性特 性、硬化性、保存穩定性等之平衡達到良好。尤其是就硬化性方面而言,例如酚樹脂系硬化劑之羥基當量可設為90g/eq以上、250g/eq以下。 Further, the hardener (B) may be, for example, a novolac type phenol resin, a phenol aralkyl resin having a pendant phenyl skeleton, a phenol aralkyl resin having a pendant phenyl skeleton, and a naphthol having a pendant phenyl skeleton. A phenol resin such as a aralkyl resin, a phenol resin mainly composed of a reaction product of hydroxybenzaldehyde, formaldehyde, and phenol, and a copolymer of a triphenylmethane type phenol compound and a novolak type phenol compound. These may be used alone or in combination of two or more. By using the phenol resin-based hardener as described above, it is possible to impart flame resistance, moisture resistance, and electrical properties. The balance of sex, hardenability, storage stability, etc. is good. In particular, in terms of hardenability, for example, the hydroxyl group equivalent of the phenol resin-based curing agent can be 90 g/eq or more and 250 g/eq or less.
進而,作為可併用之硬化劑,例如可列舉聚加成型硬化劑、觸媒型硬化劑、縮合型硬化劑等。 Further, examples of the curing agent that can be used in combination include a polyaddition hardening agent, a catalyst type curing agent, and a condensation type curing agent.
作為聚加成型硬化劑,例如可列舉:包括二乙三胺(DETA)、三乙四胺(TETA)、間二甲苯二胺(MXDA)等脂肪族多胺,二胺基二苯基甲烷(DDM)、間苯二胺(MPDA)、二胺基二苯基碸(DDS)等芳香族多胺,此外二氰二胺(DICY)、有機酸二醯肼等的多胺化合物;包括六氫鄰苯二甲酸酐(HHPA)、甲基四氫鄰苯二甲酸酐(MTHPA)等脂環族酸酐,苯偏三酸酐(TMA)、焦蜜石酸二酐(PMDA)、二苯甲酮四羧酸二酐(BTDA)等芳香族酸酐等的酸酐;酚醛清漆型酚樹脂、酚聚合物等多酚化合物;多硫化物、硫酯、硫醚等多硫醇化合物;異氰酸酯預聚物、封端異氰酸酯等異氰酸酯化合物;含羧酸之聚酯樹脂等有機酸類等。 Examples of the polyaddition hardening agent include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and m-xylenediamine (MXDA), and diaminodiphenylmethane (diaminodiphenylmethane). DDM), an aromatic polyamine such as m-phenylenediamine (MPDA) or diaminodiphenyl hydrazine (DDS), a polyamine compound such as dicyandiamide (DICY) or an organic acid dioxane; Alicyclic anhydrides such as phthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA), trimellitic anhydride (TMA), pyromellitic dianhydride (PMDA), benzophenone IV An acid anhydride such as an aromatic acid anhydride such as carboxylic acid dianhydride (BTDA); a polyphenol compound such as a novolak type phenol resin or a phenol polymer; a polythiol compound such as a polysulfide, a thioester or a thioether; an isocyanate prepolymer and a seal An isocyanate compound such as a terminal isocyanate; an organic acid such as a carboxylic acid-containing polyester resin.
作為觸媒型硬化劑,例如可列舉:苄基二甲胺(BDMA)、2,4,6-三-二甲基胺基甲基苯酚(DMP-30)等三級胺化合物;2-甲基咪唑、2-乙基-4-甲基咪唑(EMI24)等咪唑化合物;BF3錯合物等路易斯酸等。 Examples of the catalyst-type hardener include a tertiary amine compound such as benzyldimethylamine (BDMA) or 2,4,6-tris-dimethylaminomethylphenol (DMP-30); An imidazole compound such as imidazole or 2-ethyl-4-methylimidazole (EMI24); a Lewis acid such as BF 3 complex or the like.
作為縮合型硬化劑,例如可列舉:可溶酚醛樹脂等具有羥甲基之酚樹脂;含羥甲基之尿素樹脂等尿素樹脂;含羥甲基之三聚氰胺樹脂等三聚氰胺樹脂等。 Examples of the condensing-type hardening agent include a phenol resin having a methylol group such as a resol resin, a urea resin such as a hydroxymethyl group-containing urea resin, and a melamine resin such as a hydroxymethyl group-containing melamine resin.
於併用上述其他硬化劑之情況下,相對於全部硬化劑(B),酚樹脂系硬化劑之含量的下限值較佳為20質量%以上,更佳為30質量%以上,特佳為50質量%以上。若調配比例在上述範圍內,則可保持抗燃性且表現出良好之流動性。另外,酚樹脂系硬化劑之含量的上限值並無特別限定,相對於全部硬化劑(B)較佳為100質量%以下。 When the other curing agent is used in combination, the lower limit of the content of the phenol resin-based curing agent is preferably 20% by mass or more, more preferably 30% by mass or more, and particularly preferably 50% based on the total amount of the curing agent (B). More than % by mass. If the blending ratio is within the above range, the flame resistance can be maintained and good fluidity can be exhibited. In addition, the upper limit of the content of the phenol resin-based curing agent is not particularly limited, and is preferably 100% by mass or less based on the total amount of the curing agent (B).
硬化劑(B)之含量之合計值相對於本發明之固定用樹脂組成物的下限值並無特別限定,較佳為相對於固定用樹脂組成物之合計值100質量%為3質量%以上,更佳為3.5質量%以上。若調配比例的下限值在上述範圍內,則可獲得良好之硬化性。另外,硬化劑(B)之含量之合計值相對於本發明之固定用樹脂組成物的上限值亦無特別限定,較佳為相對於全部固定用樹脂組成物之合計值100質量%為35質量%以下,更佳為15質量%以下。 The total value of the content of the curing agent (B) is not particularly limited, and the lower limit of the fixing resin composition of the present invention is preferably 3% by mass or more based on 100% by mass of the total of the fixing resin composition. More preferably, it is 3.5% by mass or more. When the lower limit of the blending ratio is within the above range, good curability can be obtained. In addition, the total value of the content of the curing agent (B) is not particularly limited as long as the upper limit of the fixing resin composition of the present invention, and is preferably 35% by mass based on the total value of all the fixing resin compositions. The mass% or less is more preferably 15% by mass or less.
再者,作為硬化劑(B)之酚樹脂與環氧樹脂較佳為以使全部熱硬化性樹脂(A)中之環氧基數(EP)、與全部酚樹脂中之酚性羥基數(OH)的當量比(EP)/(OH)為0.8以上、1.3以下之方式進行調配。若當量比在上述範圍內,則於將所得之固定用樹脂組成物成形時,可獲得充分之硬化特性。 Further, the phenol resin and the epoxy resin as the curing agent (B) are preferably such that the number of epoxy groups (EP) in the entire thermosetting resin (A) and the number of phenolic hydroxyl groups in the entire phenol resin (OH) The equivalence ratio (EP) / (OH) is adjusted to be 0.8 or more and 1.3 or less. When the equivalent ratio is in the above range, sufficient curing properties can be obtained when the obtained fixing resin composition is molded.
作為本發明之固定用樹脂組成物中所使用之無機填充材料(C),可使用固定用樹脂組成物之技術領域中通常使用的無機填充材料。例如可列舉:熔融碎裂矽石及熔融 球狀矽石等熔融矽石、結晶性矽石、氧化鋁、高嶺土、滑石、黏土、雲母、岩綿、矽灰石、玻璃粉、玻璃鱗片、玻璃珠、玻璃纖維、碳化矽、氮化矽、氮化鋁、碳黑、石墨、二氧化鈦、碳酸鈣、硫酸鈣、碳酸鋇、碳酸鎂、硫酸鎂、硫酸鋇、纖維素、芳族醯胺、木材、將酚樹脂成形材料或環氧樹脂成形材料之硬化物粉碎所得的粉碎粉末等。其中,較佳為熔融碎裂矽石、熔融球狀矽石、晶性矽石等矽石,更佳可使用熔融球狀矽石。又,其中碳酸鈣於成本方面而言較佳。無機填充材料(C)可使用一種,或者亦可併用兩種以上。 As the inorganic filler (C) used in the fixing resin composition of the present invention, an inorganic filler which is generally used in the technical field of the fixing resin composition can be used. For example, melting cracked vermiculite and melting Melted vermiculite such as globular vermiculite, crystalline vermiculite, alumina, kaolin, talc, clay, mica, rock wool, ash stone, glass powder, glass flakes, glass beads, glass fiber, tantalum carbide, tantalum nitride , aluminum nitride, carbon black, graphite, titanium dioxide, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, cellulose, aromatic guanamine, wood, forming a phenol resin molding material or epoxy resin The pulverized powder obtained by pulverizing the cured product of the material or the like. Among them, a vermiculite such as a molten fragmented vermiculite, a molten spherical vermiculite, or a crystalline vermiculite is preferable, and a molten spherical vermiculite is more preferably used. Also, among them, calcium carbonate is preferred in terms of cost. One type of the inorganic filler (C) may be used, or two or more types may be used in combination.
無機填充材料(C)之平均粒徑D50較佳為0.01μm以上、75μm以下,更佳為0.05μm以上、50μm以下。藉由使無機填充材料(C)之平均粒徑在上述範圍內,則本發明之固定用樹脂組成物對孔部與磁鐵之相隔部(填充部)之填充性可提高。另外,藉由將無機填充材料(C)之平均粒徑的上限值設定為75μm以下,填充性可進一步提高。 The average particle diameter D 50 of the inorganic filler (C) is preferably 0.01 μm or more and 75 μm or less, more preferably 0.05 μm or more and 50 μm or less. When the average particle diameter of the inorganic filler (C) is within the above range, the filling property of the fixing resin composition of the present invention with respect to the partition portion (filling portion) between the hole portion and the magnet can be improved. In addition, by setting the upper limit of the average particle diameter of the inorganic filler (C) to 75 μm or less, the filling property can be further improved.
平均粒徑D50係利用RODOS SR型雷射繞射型測定裝置(SYMPATEC HEROS&RODOS)所測定之體積換算平均粒徑。 The average particle diameter D 50 is a volume-converted average particle diameter measured by a RODOS SR-type laser diffraction type measuring device (SYMPATEC HEROS & RODOS).
另外,於本發明之固定用樹脂組成物中,無機填充材料(C)可含有平均粒徑D50不同的兩種以上之球狀矽石。藉此,可同時實現提高流動性及填充性與抑制毛邊。 Further, in the fixing resin composition of the present invention, the inorganic filler (C) may contain two or more kinds of globular vermiculite having different average particle diameters D 50 . Thereby, it is possible to simultaneously improve fluidity and filling properties and suppress burrs.
相對於固定用樹脂組成物之合計值100質量%,無機填充材料(C)之含量較佳為50質量%以上,更佳為60 質量%以上,進而較佳為65質量%以上,特佳為75質量%以上。若下限值在上述範圍內,則可使所獲得之固定用樹脂組成物伴隨於硬化而產生的吸濕量之增加、或強度之下降減低。另外,無機填充材料(C)之量相對於固定用樹脂組成物之合計值100質量%較佳為93質量%以下,更佳為91質量%以下,進而較佳為90質量%以下。若上限值在上述範圍內,則所獲得之固定用樹脂組成物具有良好之流動性,並且具備良好之成形性。因此,轉子之製造穩定性提高,可獲得良率與耐久性的平衡優異之轉子。 The content of the inorganic filler (C) is preferably 50% by mass or more, and more preferably 60%, based on 100% by mass of the total of the fixing resin composition. The mass% or more is more preferably 65% by mass or more, and particularly preferably 75% by mass or more. When the lower limit is within the above range, the increase in the moisture absorption amount or the decrease in the strength due to the curing of the obtained fixing resin composition can be reduced. In addition, the amount of the inorganic filler (C) is preferably 93% by mass or less, more preferably 91% by mass or less, and still more preferably 90% by mass or less based on 100% by mass of the total of the fixing resin composition. When the upper limit is within the above range, the obtained fixing resin composition has good fluidity and good formability. Therefore, the manufacturing stability of the rotor is improved, and a rotor excellent in balance between the yield and the durability can be obtained.
另外,本發明人等進行研究之結果判明,藉由將無機填充材料(C)之含量設定為50質量%以上,可減小固定構件與電磁鋼板之線膨脹係數之差,可抑制電磁鋼板對應於溫度變化產生變形而使轉子之旋轉特性下降的情況。藉此,可實現耐久性之中尤其是旋轉特性的持續性優異之轉子。 In addition, as a result of the investigation by the inventors of the present invention, it has been found that by setting the content of the inorganic filler (C) to 50% by mass or more, the difference in linear expansion coefficient between the fixing member and the electromagnetic steel sheet can be reduced, and the electromagnetic steel sheet can be suppressed. The deformation of the temperature changes to cause the rotation characteristics of the rotor to decrease. Thereby, it is possible to realize a rotor excellent in durability, particularly in the durability of the rotation characteristics.
另外,於使用熔融碎裂矽石、熔融球狀矽石、晶性矽石等矽石作為無機填充材料(C)之情況下,矽石之含量相對於固定用樹脂組成物之合計值100質量%較佳為40質量%以上,更佳為60質量%以上。若下限值在上述範圍內,則流動性與熱膨脹係數之平衡良好。 In addition, in the case of using a vermiculite such as molten crushed vermiculite, molten globular vermiculite or crystalline vermiculite as the inorganic filler (C), the content of the vermiculite is 100 masses with respect to the total value of the fixing resin composition. % is preferably 40% by mass or more, and more preferably 60% by mass or more. When the lower limit is within the above range, the balance between fluidity and thermal expansion coefficient is good.
另外,將無機填充材料(C)與如後述之氫氧化鋁、氫氧化鎂等金屬氫氧化物、或硼酸鋅、鉬酸鋅、三氧化二銻等無機系阻燃劑併用之情況下,較理想為使該等無機系阻燃劑與上述無機填充材料之合計量在上述無機填充材料 (C)之含量之範圍內。 In addition, when the inorganic filler (C) is used in combination with a metal hydroxide such as aluminum hydroxide or magnesium hydroxide described later, or an inorganic flame retardant such as zinc borate, zinc molybdate or antimony trioxide, It is preferable that the total amount of the inorganic flame retardant and the inorganic filler is in the inorganic filler Within the range of the content of (C).
再者,於後述之本案實施例中,無機填充材料與氫氧化鋁等無機系阻燃劑之總計量係相對於固定用樹脂組成物之合計值100質量%為80質量%以上。然而,本發明中,為了根據轉子所使用之構件而適宜地調整流動性及線膨脹係數,亦可減低無機填充材料之含量,且增加樹脂材料之含量。 In the embodiment of the present invention, the total amount of the inorganic fillers and the inorganic flame retardant such as aluminum hydroxide is 80% by mass or more based on 100% by mass of the total of the fixing resin compositions. However, in the present invention, in order to appropriately adjust the fluidity and the coefficient of linear expansion according to the member used for the rotor, it is also possible to reduce the content of the inorganic filler and increase the content of the resin material.
本發明之固定用樹脂組成物亦可包含硬化促進劑(D)。硬化促進劑(D)只要為促進環氧樹脂之環氧基與酚樹脂系硬化劑(B)之羥基的反應者即可,可使用通常所用之硬化促進劑(D)。 The fixing resin composition of the present invention may further contain a curing accelerator (D). The curing accelerator (D) may be any one that promotes the reaction of the epoxy group of the epoxy resin with the hydroxyl group of the phenol resin-based curing agent (B), and a curing accelerator (D) which is usually used may be used.
作為硬化促進劑(D)之具體例,可列舉:有機膦、四取代鏻化合物、磷酸酯甜菜鹼化合物(phosphobetaine compound)、膦化合物與醌化合物之加成物、鏻化合物與矽烷化合物之加成物等含磷原子之化合物;以1,8-二氮雜雙環(5,4,0)十一烯-7、咪唑等脒系化合物、苄基二甲胺等三級胺或前述化合物之四級鎓鹽之脒鎓鹽(amidinium salt)、銨鹽等為代表的含氮原子之化合物。該等中,就硬化性之觀點而言,較佳為含磷原子之化合物,就流動性與硬化性之平衡之觀點而言,更佳為四取代鏻化合物、磷酸酯甜菜鹼化合物、膦化合物與醌化合物之加成物、鏻化合物與矽烷化合物之加成物等具有潛伏性之硬化促進劑。若考慮流動性方面,則特佳為四取代鏻化合物,另外,就耐 焊接性之觀點而言,特佳為磷酸酯甜菜鹼化合物、膦化合物與醌化合物之加成物,又,若考慮潛伏硬化性方面,則特佳為鏻化合物與矽烷化合物之加成物。另外,就連續成形性之觀點而言,較佳為四取代鏻化合物。又,考慮到成本方面,則有機膦、含氮原子之化合物亦可較佳地使用。 Specific examples of the curing accelerator (D) include an organic phosphine, a tetra-substituted fluorene compound, a phosphobetaine compound, an addition product of a phosphine compound and a hydrazine compound, and an addition of a hydrazine compound and a decane compound. a compound containing a phosphorus atom; a ruthenium compound such as 1,8-diazabicyclo(5,4,0)undecene-7, imidazole or the like, a tertiary amine such as benzyldimethylamine or the like A compound containing a nitrogen atom represented by an amidinium salt, an ammonium salt or the like. In the above, from the viewpoint of curability, a compound containing a phosphorus atom is preferred, and a tetrasubstituted fluorene compound, a phosphoric acid betaine compound, or a phosphine compound is more preferable from the viewpoint of balance between fluidity and hardenability. A latent hardening accelerator such as an adduct of a ruthenium compound, an adduct of a ruthenium compound and a decane compound. If considering the fluidity, it is especially a tetra-substituted ruthenium compound. From the viewpoint of weldability, a phosphate ester betaine compound, an addition product of a phosphine compound and a ruthenium compound, and an adduct of a ruthenium compound and a decane compound are particularly preferable in view of latent hardenability. Further, from the viewpoint of continuous moldability, a tetra-substituted fluorene compound is preferred. Further, in view of cost, an organic phosphine or a compound containing a nitrogen atom can also be preferably used.
作為本發明之固定用樹脂組成物中可使用之有機膦,例如可列舉:乙基膦、苯基膦等一級膦;二甲基膦、二苯基膦等二級膦;三甲基膦、三乙基膦、三丁基膦、三苯基膦等三級膦。 Examples of the organophosphine which can be used in the resin composition for fixing of the present invention include a primary phosphine such as ethylphosphine or phenylphosphine; a secondary phosphine such as dimethylphosphine or diphenylphosphine; and trimethylphosphine. A tertiary phosphine such as triethylphosphine, tributylphosphine or triphenylphosphine.
作為本發明之固定用樹脂組成物中可使用之四取代鏻化合物,例如可列舉下述通式(1)所表示之化合物等。 The tetrasubstituted fluorene compound which can be used in the resin composition for fixing of the present invention is, for example, a compound represented by the following formula (1).
通式(1)中,P表示磷原子,R1、R2、R3及R4分別獨立地表示芳香族基或烷基,A表示於芳香環上具有至少1個選自羥基、羧基、硫醇基中之任一官能基的芳香族有機酸之陰離子,AH表示於芳香環上具有至少1個選自羥基、羧基、硫醇基中之任一官能基的芳香族有機酸,x及y為1~3之整數,z為0~3之整數,且x=y。 In the formula (1), P represents a phosphorus atom, and R1, R2, R3 and R4 each independently represent an aromatic group or an alkyl group, and A represents at least one member selected from the group consisting of a hydroxyl group, a carboxyl group and a thiol group in the aromatic ring. An anion of an aromatic organic acid of any of the functional groups, AH represents an aromatic organic acid having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group and a thiol group on the aromatic ring, and x and y are 1~ An integer of 3, z is an integer from 0 to 3, and x = y.
通式(1)所表示之化合物例如可藉由以下方式而獲得,但並不限定於此。首先,將四取代鏻鹵化物、芳香族有機酸及鹼摻混於有機溶劑中均勻地混合,使該溶液體系 內產生芳香族有機酸陰離子。繼而,加入水即可使通式(1)所表示之化合物沈澱。對於通式(1)所表示之化合物,就合成時之取得率與硬化促進效果之平衡優異的觀點而言,較佳為與磷原子鍵結之R1、R2、R3及R4為苯基,且AH為於芳香環上具有羥基之化合物,即酚化合物,且A為該酚化合物之陰離子。再者,酚化合物之概念中包括單環之苯酚、甲酚、鄰苯二酚、間苯二酚或縮合多環式之萘酚、二羥基萘、具備多個芳香環之(多環式之)雙酚A、雙酚F、雙酚S、聯苯酚、苯基苯酚、苯酚酚醛清漆等,其中,較佳為使用具有2個羥基之酚化合物。 The compound represented by the formula (1) can be obtained, for example, by the following means, but is not limited thereto. First, a tetrasubstituted phosphonium halide, an aromatic organic acid, and a base are uniformly mixed in an organic solvent to prepare the solution system. An aromatic organic acid anion is produced internally. Then, the compound represented by the formula (1) can be precipitated by adding water. In view of the fact that the compound represented by the formula (1) is excellent in the balance between the yield at the time of synthesis and the curing acceleration effect, R1, R2, R3 and R4 bonded to the phosphorus atom are preferably a phenyl group, and AH is a compound having a hydroxyl group on an aromatic ring, that is, a phenol compound, and A is an anion of the phenol compound. Furthermore, the concept of phenolic compounds includes monocyclic phenol, cresol, catechol, resorcinol or condensed polycyclic naphthol, dihydroxynaphthalene, and multiple aromatic rings (multicyclic Bisphenol A, bisphenol F, bisphenol S, biphenol, phenylphenol, phenol novolac, and the like. Among them, a phenol compound having two hydroxyl groups is preferably used.
作為本發明之固定用樹脂組成物中可使用之磷酸酯甜菜鹼化合物,例如可列舉下述通式(2)所表示之化合物等。 The phosphate betained compound which can be used in the resin composition for fixing of the present invention is, for example, a compound represented by the following formula (2).
通式(2)中,X1表示碳數1~3之烷基,Y1表示羥基,a為0~5之整數,b為0~4之整數。 In the formula (2), X1 represents an alkyl group having 1 to 3 carbon atoms, Y1 represents a hydroxyl group, a is an integer of 0 to 5, and b is an integer of 0 to 4.
通式(2)所表示之化合物例如可藉由以下之方式而獲得。首先,使作為三級膦之三芳香族取代膦與重氮鎓鹽接觸,羥過使三芳香族取代膦與重氮鎓鹽所具有之重氮鎓基進行取代的步驟而獲得通式(2)所表示之化合物。但是並不限定於此。 The compound represented by the formula (2) can be obtained, for example, by the following method. First, a triarylphosphine triaryl substituted phosphine is contacted with a diazonium salt, and a hydroxy group is substituted by a triaromatic substituted phosphine with a diazonium group of a diazonium salt to obtain a formula (2). ) the compound represented. However, it is not limited to this.
作為本發明之固定用樹脂組成物中可使用之膦化合物與醌化合物之加成物,例如可列舉下述通式(3)所表示之化合物等。 The adduct of the phosphine compound and the hydrazine compound which can be used for the fixing resin composition of the present invention is, for example, a compound represented by the following formula (3).
通式(3)中,P表示磷原子,R5、R6及R7相互獨立地表示碳數1~12之烷基或碳數6~12之芳基,R8、R9及R10相互獨立地表示氫原子或碳數1~12之烴基,R8與R9亦可相互鍵結而形成環。 In the formula (3), P represents a phosphorus atom, and R5, R6 and R7 independently of each other represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R8, R9 and R10 independently represent a hydrogen atom. Or a hydrocarbon group having 1 to 12 carbon atoms, and R8 and R9 may be bonded to each other to form a ring.
作為膦化合物與醌化合物之加成物中所使用的膦化合物,例如較佳為三苯基膦、三(烷基苯基)膦、三(烷氧基苯基)膦、三萘基膦、三(苄基)膦等芳香環未羥取代或者存在烷基、烷氧基等取代基者,烷基、烷氧基等取代基可列舉具有1~6之碳數者。就獲得容易度之觀點而言,較佳為三苯基膦。 As the phosphine compound used in the adduct of the phosphine compound and the hydrazine compound, for example, triphenylphosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, trinaphthylphosphine, The aromatic ring such as tris(benzyl)phosphine is not hydroxy-substituted or a substituent such as an alkyl group or an alkoxy group is present, and examples of the substituent such as an alkyl group or an alkoxy group include those having a carbon number of 1 to 6. From the viewpoint of availability, triphenylphosphine is preferred.
又,作為膦化合物與醌化合物之加成物中所使用之醌化合物,可列舉鄰苯醌、對苯醌、蒽醌類,其中,就保存穩定性方面而言,較佳為對苯醌。 Further, examples of the ruthenium compound used in the adduct of the phosphine compound and the ruthenium compound include o-benzoquinone, p-benzoquinone, and anthracene. Among them, p-benzoquinone is preferred in terms of storage stability.
作為膦化合物與醌化合物之加成物之製造方法,可藉由在有機三級膦與苯醌類兩者均可溶解之溶劑中使其等接觸、混合而獲得加成物。作為溶劑,較佳為對加成物之溶 解性較低的丙酮或甲基乙基酮等酮類。但是並不限定於此。 As a method for producing an adduct of a phosphine compound and a hydrazine compound, an adduct can be obtained by contacting and mixing the organic trisphosphine and a benzoquinone in a solvent which can be dissolved. As a solvent, it is preferred to dissolve the adduct A ketone such as acetone or methyl ethyl ketone with low solubility. However, it is not limited to this.
通式(3)所表示之化合物中,就使固定用樹脂組成物之硬化物的熱時彈性模數降低方面而言,較佳與磷原子鍵結之R5、R6及R7為苯基,且R8、R9及R10為氫原子之化合物,即將1,4-苯醌與三苯基膦加成所得之化合物。 In the compound represented by the formula (3), in terms of lowering the thermal modulus of elasticity of the cured product of the fixing resin composition, R5, R6 and R7 which are preferably bonded to the phosphorus atom are phenyl groups, and A compound in which R8, R9 and R10 are a hydrogen atom, that is, a compound obtained by adding 1,4-benzoquinone and triphenylphosphine.
作為本發明之固定用樹脂組成物中可使用之鏻化合物與矽烷化合物之加成物,例如可列舉下述式(4)所表示之化合物等。 The adduct of the oxime compound and the decane compound which can be used for the fixing resin composition of the present invention is, for example, a compound represented by the following formula (4).
通式(4)中,P表示磷原子,Si表示矽原子。R11、R12、R13及R14相互獨立地表示具有芳香環或雜環之有機基、或者脂肪族基,X2係與基Y2及Y3鍵結之有機基。X3係與基Y4及Y5鍵結之有機基。Y2及Y3表示給質子基釋出質子所成之基,同一分子內之基Y2及Y3與矽原子鍵結而形成螯合物結構。Y4及Y5表示給質子基釋出質子所成之基,同一分子內之基Y4及Y5與矽原子鍵結而形成螯合物結構。X2、及X3相互可相同亦可不同,Y2、Y3、Y4、及Y5相互可相同亦可不同。Z1為具有芳香環或雜環之有機基、或者脂肪族基。 In the formula (4), P represents a phosphorus atom, and Si represents a germanium atom. R11, R12, R13 and R14 each independently represent an organic group having an aromatic ring or a heterocyclic ring or an aliphatic group, and X2 is an organic group bonded to the groups Y2 and Y3. X3 is an organic group bonded to the groups Y4 and Y5. Y2 and Y3 represent a group in which protons are released by protons, and groups Y2 and Y3 in the same molecule are bonded to a ruthenium atom to form a chelate structure. Y4 and Y5 represent a group in which a proton group is released, and a group Y4 and Y5 in the same molecule are bonded to a ruthenium atom to form a chelate structure. X2 and X3 may be the same or different from each other, and Y2, Y3, Y4, and Y5 may be the same or different from each other. Z1 is an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group.
通式(4)中,R11、R12、R13及R14例如可列舉苯 基、甲基苯基、甲氧基苯基、羥基苯基、萘基、羥基萘基、苄基、甲基、乙基、正丁基、正辛基及環己基等,該等之中,更佳為苯基、甲基苯基、甲氧基苯基、羥基苯基、羥基萘基等具有取代基之芳香族基或未經取代之芳香族基。 In the formula (4), R11, R12, R13 and R14 are, for example, benzene. Base, methylphenyl, methoxyphenyl, hydroxyphenyl, naphthyl, hydroxynaphthyl, benzyl, methyl, ethyl, n-butyl, n-octyl and cyclohexyl, among others, More preferably, it is a substituted aromatic group or an unsubstituted aromatic group such as a phenyl group, a methylphenyl group, a methoxyphenyl group, a hydroxyphenyl group or a hydroxynaphthyl group.
另外,通式(4)中,X2為與Y2及Y3鍵結之有機基。同樣地,X3為與基Y4及Y5鍵結之有機基。Y2及Y3為給質子基釋出質子所成之基,同一分子內之基Y2及Y3與矽原子鍵結而形成螯合物結構。同樣地,Y4及Y5為給質子基釋出質子所成之基,同一分子內之基Y4及Y5與矽原子鍵結而形成螯合物結構。基X2及X3相互可相同亦可不同,基Y2、Y3、Y4、及Y5相互可相同亦可不同。上述通式(4)中以-Y2-X2-Y3-、及-Y4-X3-Y5-表示之基係包含質子給予體釋出2個質子所成之基。質子給予體較佳為分子內具有至少2個羧基或羥基之有機酸,更佳為於構成芳香環之碳上具有至少2個羧基或羥基之芳香族化合物,進而更佳為於構成芳香環之鄰接之碳上具有至少2個羥基之芳香族化合物。例如,可列舉:鄰苯二酚、鄰苯三酚、1,2-二羥基萘、2,3-二羥基萘、2,2'-聯苯酚、1,1'-聯-2-萘酚、水楊酸、1-羥基-2-萘甲酸、3-羥基-2-萘甲酸、氯冉酸、單寧酸、2-羥基苄基醇、1,2-環己二醇、1,2-丙二醇及丙三醇等。該等之中,就獲得原料之容易程度與硬化促進效果之平衡的觀點而言,更佳為鄰苯二酚、1,2-二羥基萘、2,3-二羥基萘。 Further, in the formula (4), X2 is an organic group bonded to Y2 and Y3. Similarly, X3 is an organic group bonded to the groups Y4 and Y5. Y2 and Y3 are groups formed by proton-releasing protons, and the groups Y2 and Y3 in the same molecule are bonded to the ruthenium atom to form a chelate structure. Similarly, Y4 and Y5 are groups in which a proton is released to protons, and groups Y4 and Y5 in the same molecule are bonded to a ruthenium atom to form a chelate structure. The groups X2 and X3 may be the same or different from each other, and the groups Y2, Y3, Y4, and Y5 may be the same or different from each other. The group represented by -Y2-X2-Y3- and -Y4-X3-Y5- in the above formula (4) contains a group in which a proton donor releases two protons. The proton donor is preferably an organic acid having at least two carboxyl groups or hydroxyl groups in the molecule, more preferably an aromatic compound having at least two carboxyl groups or hydroxyl groups on the carbon constituting the aromatic ring, and more preferably forming an aromatic ring. An aromatic compound having at least two hydroxyl groups on the adjacent carbon. For example, catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2'-biphenol, 1,1'-bi-2-naphthol , salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chlorodecanoic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2 - Propylene glycol and glycerin, etc. Among these, catechol, 1,2-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene are more preferable from the viewpoint of obtaining a balance between the ease of the raw material and the hardening promoting effect.
另外,通式(4)中之Z1表示具有芳香環或雜環之有 機基或脂肪族基,該等之具體例可列舉甲基、乙基、丙基、丁基、己基及辛基等脂肪族烴基,或苯基、苄基、萘基及聯苯基等芳香族烴基,縮水甘油氧基丙基、巰基丙基、胺基丙基及乙烯基等反應性取代基等,該等之中,就熱穩定性方面而言,更佳為甲基、乙基、苯基、萘基及聯苯基。 Further, Z1 in the formula (4) means having an aromatic ring or a heterocyclic ring Examples of the organic group or the aliphatic group include an aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group or an octyl group, or an aromatic group such as a phenyl group, a benzyl group, a naphthyl group or a biphenyl group. a reactive substituent such as a hydrocarbon group, a glycidoxypropyl group, a mercaptopropyl group, an aminopropyl group or a vinyl group, etc., among which, in terms of thermal stability, a methyl group, an ethyl group, and more preferably Phenyl, naphthyl and biphenyl.
鏻化合物與矽烷化合物之加成物之製造方法如下,於裝有甲醇之燒瓶中,加入苯基三甲氧基矽烷等矽烷化合物、2,3-二羥基萘等質子給予體且溶解,然後於室溫攪拌下滴加甲醇鈉一甲醇溶液。進而於室溫攪拌下向其中滴加預先準備的將四苯基溴化鏻等四取代鏻鹵化物溶解於甲醇中所得之溶液,此時析出結晶。對所析出之結晶進行過濾、水洗、真空乾燥,獲得鏻化合物與矽烷化合物之加成物。但是,並不限定於此。 The method for producing an adduct of a ruthenium compound and a decane compound is as follows. In a flask containing methanol, a proton donor such as phenyltrimethoxydecane or a proton donor such as 2,3-dihydroxynaphthalene is added and dissolved, and then dissolved in a chamber. A sodium methoxide-methanol solution was added dropwise with stirring. Further, a solution prepared by dissolving a tetrasubstituted phosphonium halide such as tetraphenylphosphonium bromide in methanol, which was prepared in advance, was added dropwise thereto under stirring at room temperature, at which time crystals were precipitated. The precipitated crystals were filtered, washed with water, and vacuum dried to obtain an adduct of a hydrazine compound and a decane compound. However, it is not limited to this.
本發明之固定用樹脂組成物中可使用之硬化促進劑(D)之含量的下限值相對於全部固定用樹脂組成物之合計值100質量%,較佳為0.1質量%以上。若硬化促進劑(D)之含量的下限值在上述範圍內,則可獲得充分之硬化性。另外,硬化促進劑(D)之含量的上限值相對於全部固定用樹脂組成物之合計值100質量%較佳為3%以下,更佳為1質量%以下。若硬化促進劑(D)之含量的上限值在上述範圍內,則可獲得充分之流動性。 The lower limit of the content of the curing accelerator (D) which can be used in the fixing resin composition of the present invention is preferably 0.1% by mass or more based on 100% by mass of the total of all the fixing resin compositions. When the lower limit of the content of the hardening accelerator (D) is within the above range, sufficient curability can be obtained. In addition, the upper limit of the content of the curing accelerator (D) is preferably 3% or less, and more preferably 1% by mass or less based on 100% by mass of the total of all the fixing resin compositions. When the upper limit of the content of the hardening accelerator (D) is within the above range, sufficient fluidity can be obtained.
本發明之固定用樹脂組成物中,亦可進而包含於構成芳香環之2個以上的鄰接之碳原子上分別鍵結有羥基之化合物(E)(以下,亦簡稱為「化合物(E)」)。藉由使 用於構成芳香環之2個以上的鄰接之碳原子上分別鍵結有羥基之化合物(E),則即便使用不具有潛伏性之含磷原子之硬化促進劑作為促進環氧樹脂(A1)與酚樹脂系硬化劑(B)的交聯反應之硬化促進劑(D)時,亦可抑制固定用樹脂組成物於熔融混練期間產生反應,可穩定地獲得固定用樹脂組成物。另外,化合物(E)亦具有降低固定用樹脂組成物之熔融黏度,提高流動性的效果。化合物(E)可使用下述通式(5)所表示之單環式化合物、或下述通式(6)所表示之多環式化合物等,且該等化合物亦可具有羥基以外之取代基。 Further, the fixing resin composition of the present invention may further contain a compound (E) in which a hydroxyl group is bonded to two or more adjacent carbon atoms constituting the aromatic ring (hereinafter, simply referred to as "compound (E)" ). By making The compound (E) having a hydroxyl group bonded to two or more adjacent carbon atoms constituting the aromatic ring, even if a curing accelerator containing no latent phosphorus atom is used as the promoting epoxy resin (A1) In the case of the curing accelerator (D) of the crosslinking reaction of the phenol resin-based curing agent (B), the reaction resin composition can be prevented from reacting during the melt-kneading, and the fixing resin composition can be stably obtained. Further, the compound (E) also has an effect of lowering the melt viscosity of the fixing resin composition and improving fluidity. The compound (E) may be a monocyclic compound represented by the following formula (5) or a polycyclic compound represented by the following formula (6), and the compounds may have a substituent other than a hydroxyl group. .
通式(5)中,R15及R19之任一者為羥基,當其中一者為羥基時,另一者為氫原子、羥基或羥基以外之取代基,R16、R17及R18為氫原子、羥基或羥基以外之取代基。 In the formula (5), any of R15 and R19 is a hydroxyl group, and when one of them is a hydroxyl group, the other is a substituent other than a hydrogen atom, a hydroxyl group or a hydroxyl group, and R16, R17 and R18 are a hydrogen atom and a hydroxyl group. Or a substituent other than a hydroxyl group.
通式(6)中,R20及R26之任一者為羥基,當其中一者為羥基時,另一者為氫原子、羥基或羥基以外之取代基,R21、R22、R23、R24及R25為氫原子、羥基或羥基以外之取代基。 In the formula (6), any one of R20 and R26 is a hydroxyl group, and when one of them is a hydroxyl group, the other is a substituent other than a hydrogen atom, a hydroxyl group or a hydroxyl group, and R21, R22, R23, R24 and R25 are a substituent other than a hydrogen atom, a hydroxyl group or a hydroxyl group.
作為通式(5)所表示之單環式化合物之具體例,例如可列舉:鄰苯二酚、鄰苯三酚、沒食子酸、沒食子酸酯或該等之衍生物。另外,作為通式(6)所表示之多環式化合物之具體例,例如可列舉:1,2-二羥基萘、2,3-二羥基萘及該等之衍生物。該等中,就流動性及硬化性之控制容易度而言,較佳為於構成芳香環之2個鄰接之碳原子上分別鍵結有羥基之化合物。另外,考慮到混練步驟中之揮發,更佳為母核為揮發性較低而稱量穩定性較高之萘環的化合物。此時,具體而言,可使化合物(E)例如為1,2-二羥基萘、2,3-二羥基萘及其衍生物等具有萘環之化合物。該等化合物(E)可單獨使用一種亦可將兩種以上併用。 Specific examples of the monocyclic compound represented by the formula (5) include catechol, pyrogallol, gallic acid, gallic acid ester, and the like. Further, specific examples of the polycyclic compound represented by the formula (6) include 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and the like. Among these, in terms of the ease of control of fluidity and hardenability, a compound in which a hydroxyl group is bonded to each of two adjacent carbon atoms constituting the aromatic ring is preferable. Further, in consideration of the volatilization in the kneading step, it is more preferable that the mother nucleus is a compound having a low volatility and a high stability of the naphthalene ring. In this case, specifically, the compound (E) can be, for example, a compound having a naphthalene ring such as 1,2-dihydroxynaphthalene or 2,3-dihydroxynaphthalene or a derivative thereof. These compounds (E) may be used alone or in combination of two or more.
化合物(E)之含量的下限值相對於全部固定用樹脂組成物之合計值100質量%較佳為0.01質量%以上,更佳為0.03質量%以上,特佳為0.05質量%以上。若化合物(E)之含量的下限值在上述範圍內,則可獲得使固定用樹脂組 成物之黏度充分降低與提高流動性之效果。另外,化合物(E)之含量的上限值相對於全部固定用樹脂組成物之合計值100質量%較佳為2質量%以下,更佳為0.8質量%以下,特佳為0.5質量%以下。若化合物(E)之含量的上限值在上述範圍內,則引起固定用樹脂組成物之硬化性降低或硬化物之物性下降的可能性較少。 The lower limit of the content of the compound (E) is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and particularly preferably 0.05% by mass or more based on 100% by mass of the total of all the fixing resin compositions. When the lower limit of the content of the compound (E) is within the above range, the resin group for fixation can be obtained. The viscosity of the product is sufficiently reduced and the effect of improving the fluidity. In addition, the upper limit of the content of the compound (E) is preferably 2% by mass or less, more preferably 0.8% by mass or less, and particularly preferably 0.5% by mass or less based on 100% by mass of the total of all the fixing resin compositions. When the upper limit of the content of the compound (E) is within the above range, the curing property of the fixing resin composition is lowered, and the physical properties of the cured product are less likely to decrease.
於本發明之固定用樹脂組成物中,可添加矽烷偶合劑等偶合劑(F)以提高環氧樹脂(A1)與無機填充材料(C)之密接性。作為偶合劑(F),只要為在環氧樹脂(A1)與無機填充材料(C)之間進行反應,使環氧樹脂(A1)與無機填充材料(C)之界面強度提高者即可,並無特別限定,例如可列舉環氧基矽烷、胺基矽烷、脲基矽烷、巰基矽烷等。另外,藉由將偶合劑(F)與前述之化合物(E)併用,亦可使化合物(E)的效果,即降低固定用樹脂組成物之熔融黏度、提高流動性的效果提高。 In the fixing resin composition of the present invention, a coupling agent (F) such as a decane coupling agent may be added to improve the adhesion between the epoxy resin (A1) and the inorganic filler (C). The coupling agent (F) may be a reaction between the epoxy resin (A1) and the inorganic filler (C) to improve the interface strength between the epoxy resin (A1) and the inorganic filler (C). The epoxy decane, amino decane, ureido decane, decyl decane, and the like are exemplified. Further, by using the coupling agent (F) in combination with the above-mentioned compound (E), the effect of the compound (E), that is, the effect of lowering the melt viscosity of the fixing resin composition and improving the fluidity can be improved.
作為環氧基矽烷,例如可列舉:γ-縮水甘油氧基丙基三乙氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基甲基二甲氧基矽烷、β-(3,4-環氧環己基)乙基三甲氧基矽烷等。另外,作為胺基矽烷,例如可列舉:γ-胺基丙基三乙氧基矽烷、γ-胺基丙基三甲氧基矽烷、N-β(胺基乙基)γ-胺基丙基三甲氧基矽烷、N-β(胺基乙基)γ-胺基丙基甲基二甲氧基矽烷、N-苯基-γ-胺基丙基三乙氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷、N-β(胺基乙基)γ-胺基丙基三乙氧基矽烷、N-6-(胺基己基)3-胺基丙基三甲氧 基矽烷、N-(3-(三甲氧基矽烷基丙基)-1,3-苯二甲胺等。另外,作為脲基矽烷,例如可列舉:γ-脲基丙基三乙氧基矽烷、六甲基二矽氮烷等。亦可以使胺基矽烷之一級胺基部位與酮或醛反應而加以保護之潛伏性胺基矽烷偶合劑的形式使用。另外,胺基矽烷亦可具有二級胺基。又,作為巰基矽烷,例如可列舉γ-巰基丙基三甲氧基矽烷、3-巰基丙基甲基二甲氧基矽烷,此外可列舉如雙(3-三乙氧基矽烷基丙基)四硫化物、雙(3-三乙氧基矽烷基丙基)二硫化物等藉由熱分解而表現與巰基矽烷偶合劑相同之功能的矽烷偶合劑等。另外,亦可調配使該等矽烷偶合劑預先進行水解反應所得者。該等矽烷偶合劑可單獨使用一種亦可將兩種以上併用。 Examples of the epoxy decane include γ-glycidoxypropyl triethoxy decane, γ-glycidoxypropyl trimethoxy decane, and γ-glycidoxy propyl methyl dimethyl oxide. Basear, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. Further, examples of the aminodecane include γ-aminopropyltriethoxydecane, γ-aminopropyltrimethoxydecane, and N-β(aminoethyl)γ-aminopropyltrimethyl. Oxydecane, N-β(aminoethyl)γ-aminopropylmethyldimethoxydecane, N-phenyl-γ-aminopropyltriethoxydecane, N-phenyl-γ -Aminopropyltrimethoxydecane, N-β(aminoethyl)γ-aminopropyltriethoxydecane, N-6-(aminohexyl)3-aminopropyltrimethoxy Pyridinium, N-(3-(trimethoxydecylpropyl)-1,3-xylylenediamine, etc. Further, as the ureido decane, for example, γ-ureidopropyltriethoxydecane may be mentioned. And hexamethyldiazepine or the like. It may also be used in the form of a latent amine decane coupling agent which is protected by reacting a primary amine moiety of an amino decane with a ketone or an aldehyde. Further, the amino decane may have two Further, examples of the mercaptodecane include γ-mercaptopropyltrimethoxydecane and 3-mercaptopropylmethyldimethoxydecane, and examples thereof include bis(3-triethoxydecylalkyl). a decane coupling agent which exhibits the same function as a mercaptodecane coupling agent by thermal decomposition, such as a tetrasulfide or a bis(3-triethoxydecylpropyl) disulfide, etc. The decane coupling agent may be subjected to a hydrolysis reaction in advance. The decane coupling agents may be used alone or in combination of two or more.
就連續成形性之觀點而言,較佳為巰基矽烷,就流動性之觀點而言,較佳為胺基矽烷,就密接性之觀點而言,較佳為環氧基矽烷。 From the viewpoint of continuous moldability, decyl decane is preferred, and from the viewpoint of fluidity, amino decane is preferred, and from the viewpoint of adhesion, epoxy decane is preferred.
作為本發明之固定用樹脂組成物中可使用之矽烷偶合劑等偶合劑(F)之含量的下限值,相對於全部固定用樹脂組成物之合計值100質量%較佳為0.01質量%以上,更佳為0.05質量%以上,特佳為0.1質量%以上。若矽烷偶合劑等偶合劑(F)之含量的下限值在上述範圍內,則環氧樹脂(A1)與無機填充材料(C)之界面強度不會降低,可獲得良好之抗振性。另外,作為矽烷偶合劑等偶合劑(F)之含量的上限值,相對於全部固定用樹脂組成物之合計值100質量%較佳為1質量%以下,更佳為0.8質量%以下, 特佳為0.6質量%以下。若矽烷偶合劑等偶合劑(F)之含量的上限值在上述範圍內,則環氧樹脂(A1)與無機填充材料(C)之界面強度不會降低,可獲得良好之抗振性。另外,若矽烷偶合劑等偶合劑(F)之含量在上述範圍內,則固定用樹脂組成物之硬化物的吸水性不會增大,可獲得良好之防銹性。 The lower limit of the content of the coupling agent (F) such as a decane coupling agent which can be used in the resin composition for fixing of the present invention is preferably 0.01% by mass or more based on 100% by mass of the total of all the fixing resin compositions. More preferably, it is 0.05% by mass or more, and particularly preferably 0.1% by mass or more. When the lower limit of the content of the coupling agent (F) such as a decane coupling agent is within the above range, the interface strength between the epoxy resin (A1) and the inorganic filler (C) is not lowered, and good vibration resistance can be obtained. In addition, the upper limit of the content of the coupling agent (F) such as a decane coupling agent is preferably 1% by mass or less, and more preferably 0.8% by mass or less based on 100% by mass of the total of all the fixing resin compositions. It is particularly preferably 0.6% by mass or less. When the upper limit of the content of the coupling agent (F) such as a decane coupling agent is within the above range, the interface strength between the epoxy resin (A1) and the inorganic filler (C) is not lowered, and good vibration resistance can be obtained. In addition, when the content of the coupling agent (F) such as a decane coupling agent is within the above range, the water absorbing property of the cured product of the fixing resin composition does not increase, and good rust resistance can be obtained.
本發明之固定用樹脂組成物中,亦可添加無機阻燃劑(G)以提高阻燃性。其中,藉由於燃燒時脫水、吸熱而阻礙燃燒反應之金屬氫氧化物、或複合金屬氫氧化物於可縮短燃燒時間方面較佳。作為金屬氫氧化物,可列舉:氫氧化鋁、氫氧化鎂、氫氧化鈣、氫氧化鋇、氫氧化鋯。複合金屬氫氧化物只要為含有兩種以上之金屬元素的水滑石化合物,至少一種金屬元素為鎂,且其他金屬元素為選自鈣、鋁、錫、鈦、鐵、鈷、鎳、銅、或鋅中之金屬元素的即可,作為此種複合金屬氫氧化物,可容易地以市售品獲得氫氧化鎂-鋅固溶體。其中,就連續成形性之觀點而言,較佳為氫氧化鋁、氫氧化鎂-鋅固溶體。無機阻燃劑(G)可單獨使用,亦可使用兩種以上。另外,自減低對連續成形性之影響之目的考慮,亦可利用矽烷偶合劑等矽化合物或蠟等脂肪族系化合物等進行表面處理後使用。 In the fixing resin composition of the present invention, an inorganic flame retardant (G) may be added to improve flame retardancy. Among them, the metal hydroxide or the composite metal hydroxide which hinders the combustion reaction due to dehydration and heat absorption at the time of combustion is preferable in terms of shortening the burning time. Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and zirconium hydroxide. The composite metal hydroxide is a hydrotalcite compound containing two or more metal elements, at least one metal element is magnesium, and the other metal elements are selected from the group consisting of calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper, or As the metal hydroxide in the zinc, a magnesium hydroxide-zinc solid solution can be easily obtained as a commercial metal hydroxide. Among them, from the viewpoint of continuous moldability, aluminum hydroxide or magnesium hydroxide-zinc solid solution is preferred. The inorganic flame retardant (G) may be used singly or in combination of two or more. In addition, for the purpose of reducing the influence on the continuous formability, it may be used after surface treatment with an antimony compound such as a decane coupling agent or an aliphatic compound such as a wax.
本發明之無機阻燃劑(G)之含量相對於本發明之固定用樹脂組成物之合計值100質量%較佳為1質量%以上、20質量%以下,更佳為3質量%以上、10質量%以下。 The content of the inorganic flame retardant (G) of the present invention is preferably 1% by mass or more and 20% by mass or less, more preferably 3% by mass or more, based on 100% by mass of the total of the fixing resin composition of the present invention. Below mass%.
本發明之固定用樹脂組成物中,離子性雜質之濃度的 上限值相對於固定用樹脂組成物較佳為500ppm以下,更佳為300ppm以下,進而較佳為200ppm以下。離子性雜質之濃度的下限值並無特別限定,例如,相對於本發明之固定用樹脂組成物為0ppb以上,更佳為10ppb以上,更佳為100ppb以上。藉此,將本發明之固定用樹脂組成物之硬化物使用於固定構件中時,即便於高溫、多濕條件下進行處理亦可保持較高之防銹性。 The concentration of the ionic impurities in the fixing resin composition of the present invention The upper limit is preferably 500 ppm or less, more preferably 300 ppm or less, still more preferably 200 ppm or less, based on the fixing resin composition. The lower limit of the concentration of the ionic impurities is not particularly limited, and is, for example, 0 ppb or more, more preferably 10 ppb or more, and still more preferably 100 ppb or more with respect to the fixing resin composition of the present invention. Therefore, when the cured product of the fixing resin composition of the present invention is used in a fixing member, it is possible to maintain high rust resistance even when it is treated under high temperature and high humidity conditions.
本發明之離子性雜質並無特別限定,可列舉鹼金屬離子、鹼土金屬離子、鹵素離子等,更具體可列舉鈉離子、氯離子等。鈉離子之濃度的上限值相對於本發明之固定用樹脂組成物較佳為100ppm以下,更佳為70ppm以下,進而較佳為50ppm以下。另外,氯離子之濃度的上限值相對於本發明之固定用樹脂組成物較佳為100ppm以下,更佳為50ppm以下,進而較佳為30ppm以下。藉由設定為上述範圍內,可抑制電磁鋼板或磁鐵受到腐蝕。 The ionic impurities of the present invention are not particularly limited, and examples thereof include an alkali metal ion, an alkaline earth metal ion, and a halogen ion, and more specifically, a sodium ion or a chloride ion. The upper limit of the concentration of the sodium ion is preferably 100 ppm or less, more preferably 70 ppm or less, still more preferably 50 ppm or less, based on the fixing resin composition of the present invention. In addition, the upper limit of the concentration of the chloride ion is preferably 100 ppm or less, more preferably 50 ppm or less, and still more preferably 30 ppm or less, based on the fixing resin composition of the present invention. By setting it within the above range, it is possible to suppress corrosion of the electromagnetic steel sheet or the magnet.
本實施形態中,例如可藉由使用純度較高之環氧樹脂而減少離子性雜質。藉由以上所述,可獲得耐久性優異之轉子。 In the present embodiment, for example, ionic impurities can be reduced by using an epoxy resin having a high purity. According to the above, a rotor excellent in durability can be obtained.
離子性雜質之濃度可以如下方式求出。首先,將本發明之固定用樹脂組成物於175℃下進行180秒成形硬化後,利用粉碎機加以粉碎而獲得硬化物之粉末。將所獲得之硬化物粉末於純水中、120℃下進行24小時處理,將離子萃取至純水中後,使用ICP-MS(感應耦合電漿離子源質譜分析裝置)而可測定。 The concentration of the ionic impurities can be determined as follows. First, the fixing resin composition of the present invention is subjected to shape curing at 175 ° C for 180 seconds, and then pulverized by a pulverizer to obtain a powder of a cured product. The obtained cured product powder was treated in pure water at 120 ° C for 24 hours, and the ions were extracted into pure water, and then measured by ICP-MS (inductively coupled plasma ion source mass spectrometer).
本發明之固定用樹脂組成物中,氧化鋁之含量的上限值相對於固定用樹脂組成物之合計值100質量%較佳為10質量%以下,更佳為7質量%以下,更佳為5質量%以下。氧化鋁之含量的下限值並無特別限定,例如,相對於本發明之固定用樹脂組成物之合計值100質量%較佳為0質量%以上,更佳為0.01質量%以上,更佳為0.1質量%以上。藉由將氧化鋁之含量設定為上述上限值以下,可提高本發明之固定用樹脂組成物之流動性,並且可實現輕量化。再者,本實施形態中,0質量%係容許包含檢測極限之值。 In the resin composition for fixing of the present invention, the upper limit of the content of the alumina is preferably 10% by mass or less, more preferably 7% by mass or less, more preferably 7% by mass or less, more preferably the total value of the fixing resin composition. 5 mass% or less. The lower limit of the content of the alumina is not particularly limited. For example, the total value of the resin composition for fixing of the present invention is preferably 100% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.01% by mass or more. 0.1% by mass or more. By setting the content of the alumina to be equal to or less than the above upper limit value, the fluidity of the fixing resin composition of the present invention can be improved, and weight reduction can be achieved. Further, in the present embodiment, 0% by mass is allowed to include the value of the detection limit.
本發明之固定用樹脂組成物中,除了前述之成分以外,亦可適宜調配:水滑石類或選自鎂、鋁、鉍、鈦、鋯中的元素之水合氧化物等離子捕捉劑;碳黑、鐵丹、氧化鈦等著色劑;巴西棕櫚蠟等天然蠟;聚乙烯蠟等合成蠟;硬脂酸或硬脂酸鋅等高級脂肪酸及其金屬鹽類或者石蠟等脫模劑;聚丁二烯化合物、丙烯腈-丁二烯共聚化合物、聚矽氧油、聚矽氧橡膠等聚矽氧化合物等低應力劑。 In addition to the above-mentioned components, the fixing resin composition of the present invention may be suitably formulated with a hydrotalcite or a hydrated oxide ion scavenger of an element selected from the group consisting of magnesium, aluminum, lanthanum, titanium, and zirconium; carbon black, Colorants such as iron oxide and titanium oxide; natural waxes such as carnauba wax; synthetic waxes such as polyethylene wax; high-grade fatty acids such as stearic acid or zinc stearate, metal salts or paraffin wax release agents; polybutadiene A low stress agent such as a polyoxonium compound such as a compound, an acrylonitrile-butadiene copolymer compound, a polyoxyxene oil or a polyoxyxene rubber.
本發明之著色劑之含量相對於本發明之固定用樹脂組成物之合計值100質量%較佳為0.01質量%以上、1質量%以下,更佳為0.05質量%以上、0.8質量%以下。藉由將著色劑之含量設定為上述範圍內,則無需進行除去帶顏色之雜質的步驟,作業性提高。因此,可實現良率優異之轉子。 The content of the coloring agent of the present invention is preferably 0.01% by mass or more and 1% by mass or less, more preferably 0.05% by mass or more and 0.8% by mass or less based on 100% by mass of the total of the fixing resin composition of the present invention. By setting the content of the coloring agent within the above range, it is not necessary to carry out the step of removing the colored impurities, and the workability is improved. Therefore, a rotor excellent in yield can be achieved.
關於本發明之脫模劑之含量,相對於本發明之固定用樹脂組成物之合計值100質量%,本發明之脫模劑之含量的下限值並無特別限定,例如較佳為0.01質量%以上,更 佳為0.05質量%以上,另一方面,上限值例如較佳為1質量%以下,更佳為0.5質量%以下,進而較佳為0.2質量%以下,特佳為0.1質量%以下。眾所周知,通常於對半導體晶片進行轉移成形時,為了確保固定構件自模具中離開之脫模性係添加一定量之脫模劑。然而,若脫模劑之添加量過高,則有固定構件與電磁鋼板之密接性降低之虞。因此於本發明中,脫模劑之含量以較少為佳,尤佳為0.2質量%以下。藉此,可提高固定構件與電磁鋼板之密接性,故可實現耐久性優異之轉子。 The content of the release agent of the present invention is not particularly limited as long as the total value of the fixing resin composition of the present invention is 100% by mass, and the content of the releasing agent of the present invention is, for example, preferably 0.01% by mass. More than %, more The upper limit is preferably, for example, 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.2% by mass or less, and particularly preferably 0.1% by mass or less. As is well known, when a semiconductor wafer is subjected to transfer molding, a certain amount of a release agent is added to ensure a release property of the fixing member from the mold. However, if the amount of the releasing agent added is too high, the adhesion between the fixing member and the electromagnetic steel sheet may be lowered. Therefore, in the present invention, the content of the releasing agent is preferably as small as possible, and particularly preferably 0.2% by mass or less. Thereby, the adhesion between the fixing member and the electromagnetic steel sheet can be improved, so that the rotor excellent in durability can be realized.
本發明之低應力劑之含量相對於本發明之固定用樹脂組成物之合計值100質量%較佳為0.01質量%以上、3質量%以下,更佳為0.05質量%以上、2質量%以下。 The content of the low stress agent of the present invention is preferably 0.01% by mass or more and 3% by mass or less, more preferably 0.05% by mass or more and 2% by mass or less based on 100% by mass of the total of the fixing resin composition of the present invention.
藉由將本發明之固定用樹脂組成物設定為如上所說明之構成,可提高固定用樹脂組成物之填充特性。並且,即便於孔部與磁鐵之間隙較窄之情況下,亦可確保鋼板與磁鐵之接著面積充分。其結果,可對轉子賦予較高之機械強度。 By setting the fixing resin composition of the present invention to the above-described configuration, the filling characteristics of the fixing resin composition can be improved. Further, even when the gap between the hole portion and the magnet is narrow, the contact area between the steel sheet and the magnet can be ensured to be sufficient. As a result, a high mechanical strength can be imparted to the rotor.
另外,本發明之固定用樹脂組成物即便浸漬於自動變速器油(ATF,automatic transmission fluid)中,亦可將浸漬前後之重量變化率、體積變化率抑制為較小,故而具有對於用於汽車用途之轉子極為適宜之特性。將本發明之固定用樹脂組成物之成形品於150℃下、ATF中浸漬1000小時,ATF浸漬前後之重量變化率較佳為0.5%以下,更佳為0.35%以下。ATF浸漬前後之體積變化率較佳為1.0%以 下,更佳為0.90%。ATF浸漬前後之重量變化率及體積變化率例如可利用以下之方法得出。首先,使用成形機,於模具溫度175℃、注入壓力9.8MPa、硬化時間120秒之條件下對本發明之固定用樹脂組成物進行注入成形,獲得長度80mm、寬度10mm、厚度4mm之成形品(硬化物)。對所獲得之成形品於175℃下進行4小時加熱處理作為後硬化,將所得者作為試片,測定ATF浸漬前之重量X1、體積Y1。繼而,將該試片放入至耐壓容器中,於填充有ATF之狀態下、150℃下浸漬1000小時。然後,自耐壓容器中取出試片,拭除表面附著之ATF後,測定ATF浸漬後之重量X2、體積Y2,根據下式分別算出ATF浸漬前後之重量變化率及體積變化率。 Further, even if the resin composition for fixing of the present invention is immersed in an automatic transmission fluid (ATF), the weight change rate and the volume change rate before and after the immersion can be suppressed to be small, so that it can be used for automotive applications. The rotor is extremely suitable for its characteristics. The molded article of the fixing resin composition of the present invention is immersed in ATF at 150 ° C for 1,000 hours, and the weight change ratio before and after ATF immersion is preferably 0.5% or less, more preferably 0.35% or less. The volume change rate before and after ATF impregnation is preferably 1.0%. Next, it is preferably 0.90%. The weight change rate and the volume change rate before and after the ATF immersion can be obtained, for example, by the following method. First, the fixing resin composition of the present invention was injection-molded at a mold temperature of 175 ° C, an injection pressure of 9.8 MPa, and a curing time of 120 seconds to obtain a molded article having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm (hardening). ()). The obtained molded article was subjected to heat treatment at 175 ° C for 4 hours as post-hardening, and the obtained product was used as a test piece, and the weight X1 and volume Y1 before the ATF immersion were measured. Then, the test piece was placed in a pressure-resistant container, and immersed at 150 ° C for 1,000 hours in a state filled with ATF. Then, the test piece was taken out from the pressure-resistant container, and the surface-attached ATF was wiped off, and the weight X2 after the ATF immersion was measured, and the volume Y2 was measured, and the weight change rate and the volume change rate before and after the ATF immersion were calculated according to the following formula.
ATF浸漬前後之重量變化率[%]=(X2-X1)/X1×100 Weight change rate before and after ATF impregnation [%]=(X2-X1)/X1×100
ATF浸漬前後之體積變化率[%]=(Y2-Y1)/Y1×100 Volume change rate before and after ATF impregnation [%]=(Y2-Y1)/Y1×100
關於本發明之固定用樹脂組成物,於模具溫度175℃、成形壓力6.9MPa、注入時間20秒、硬化時間90秒之條件下,將固定用樹脂組成物注入至具有寬度3mm、厚度80μm之剖面形狀的流路中時之狹縫流動長度的下限值較佳為75mm以上,更佳為80mm以上,進而較佳為85mm以上,另一方面,上限值較佳為300mm以下。藉由使厚度80μm之狹縫長度為下限值以上,可提高對於寬度較窄之區域中之間隙的填充特性。另外,藉由使厚度80μm之狹縫長度為上限值以下,可抑制轉子上附著大量毛邊,且當使轉子旋轉時毛邊脫落而阻礙轉子旋轉的情況。 With respect to the fixing resin composition of the present invention, the fixing resin composition was injected into a section having a width of 3 mm and a thickness of 80 μm under the conditions of a mold temperature of 175 ° C, a molding pressure of 6.9 MPa, an injection time of 20 seconds, and a curing time of 90 seconds. The lower limit of the slit flow length in the flow path of the shape is preferably 75 mm or more, more preferably 80 mm or more, still more preferably 85 mm or more, and on the other hand, the upper limit is preferably 300 mm or less. By setting the slit length of 80 μm or more to the lower limit or more, the filling characteristics of the gap in the region having a narrow width can be improved. In addition, by setting the slit length of 80 μm or less to the upper limit or less, it is possible to suppress a large amount of burrs from adhering to the rotor, and the burrs are detached when the rotor is rotated to hinder the rotation of the rotor.
又,於本實施形態中,例如可藉由使填充材料之粒徑細小,降低環氧樹脂及/或硬化劑之軟化點,減少硬化促進劑之量等方法,而增加上述狹縫流動長度。 Further, in the present embodiment, for example, the slit flow length can be increased by making the particle diameter of the filler fine, reducing the softening point of the epoxy resin and/or the curing agent, and reducing the amount of the curing accelerator.
本發明之固定用樹脂組成物使用高化式黏度測定裝置於測定溫度175℃、荷重10kg下進行測定時之高化式黏度的下限值並無特別限定,較佳為3Pa‧s以上,更佳為5Pa‧s以上,進而較佳為6Pa‧s以上,另一方面,上限值並無特別限定,為50Pa‧s以下,更佳為30Pa‧s以下,進而較佳為15Pa‧s以下。若為上述下限值以上,則可抑制因成形時之內陷等而產生孔隙。若為上述上限值以下,則可獲得良好之填充性。藉此,可實現製造穩定性優異之轉子。 In the fixing resin composition of the present invention, the lower limit of the high-viscosity viscosity when the measurement is performed at a measurement temperature of 175 ° C and a load of 10 kg using a high-viscosity viscosity measuring device is not particularly limited, and is preferably 3 Pa ‧ s or more. The upper limit is not particularly limited, but is preferably 50 Pa‧s or less, more preferably 30 Pa‧s or less, and further preferably 15 Pa‧s or less. . When it is at least the above lower limit value, it is possible to suppress the occurrence of voids due to indentation or the like during molding. When it is at least the above upper limit value, good filling properties can be obtained. Thereby, a rotor excellent in manufacturing stability can be realized.
另外,於本實施形態中,例如可藉由降低環氧樹脂、硬化劑之軟化點,使用潛伏性之硬化促進劑,使用熔融球狀矽石作為填充材料等方法,而降低上述高化式黏度。 Further, in the present embodiment, for example, the high-viscosity viscosity can be lowered by reducing the softening point of the epoxy resin or the curing agent, using a latent hardening accelerator, and using a molten spherical vermiculite as a filler. .
本發明之固定用樹脂組成物於175℃下之凝膠時間較佳為10秒以上50秒以下,更佳為15秒以上45秒以下。若為上述下限值以上,則可提高填充性。若為上述上限值以下,則可加快成形週期。 The gel time of the fixing resin composition of the present invention at 175 ° C is preferably 10 seconds or more and 50 seconds or less, more preferably 15 seconds or more and 45 seconds or less. When it is more than the above lower limit value, the filling property can be improved. If it is less than or equal to the above upper limit, the molding cycle can be accelerated.
另外,於本實施形態中,例如可藉由增加硬化促進劑之量而降低上述凝膠時間。藉此,可實現製造穩定性優異之轉子。 Further, in the present embodiment, for example, the gel time can be lowered by increasing the amount of the curing accelerator. Thereby, a rotor excellent in manufacturing stability can be realized.
本發明之固定用樹脂組成物之螺旋流(spiral flow)較佳為50cm以上,更佳為60cm以上,進而較佳為80cm以上。若為上述下限值以上,則可提高填充性、尤其是對 垂直方向之填充性。上述螺旋流的上限值並無特別限定,較佳為250cm以下,更佳為220cm以下。藉此,可實現製造穩定性優異之轉子。 The spiral flow of the fixing resin composition of the present invention is preferably 50 cm or more, more preferably 60 cm or more, still more preferably 80 cm or more. If it is at least the above lower limit value, the filling property can be improved, especially Fillability in the vertical direction. The upper limit of the spiral flow is not particularly limited, but is preferably 250 cm or less, and more preferably 220 cm or less. Thereby, a rotor excellent in manufacturing stability can be realized.
另外,於本實施形態中,例如可藉由使用熔融球狀矽石作為填充材料,降低環氧樹脂、硬化劑之軟化點,減少硬化促進劑之量等方法而增加上述螺旋流。 Further, in the present embodiment, for example, the spiral flow can be increased by using a molten spherical vermiculite as a filler, reducing the softening point of the epoxy resin or the curing agent, and reducing the amount of the curing accelerator.
將本發明之固定用樹脂組成物使用硫化儀於測定溫度175℃下經時地測定硬化扭矩時測定開始60秒後之硬化扭矩值設為T60,至測定開始300秒後為止之最大硬化扭矩值設為Tmax時,測定開始60秒後之硬化扭矩值相對於至測定開始300秒後為止之最大硬化扭矩值的比T60/Tmax(%)較佳為40%以上,更佳為45%以上,進而較佳為50%以上。上述硬化扭矩值的比之上限值並無特別限定,較佳為100%以下,更佳為95%以下。若為上述下限值以上,則有望提高生產性。 When the curing resin composition of the present invention is subjected to measurement of the curing torque at a measurement temperature of 175 ° C using a vulcanizer, the curing torque value after 60 seconds from the start of the measurement is T 60 , and the maximum hardening torque is 300 seconds after the start of the measurement. When the value is T max , the ratio T 60 /T max (%) of the hardening torque value after 60 seconds from the start of the measurement to the maximum hardening torque value up to 300 seconds after the start of the measurement is preferably 40% or more, more preferably 45% or more, further preferably 50% or more. The upper limit of the hardening torque value is not particularly limited, but is preferably 100% or less, and more preferably 95% or less. If it is more than the above lower limit value, productivity is expected to be improved.
另外,於本實施形態中,例如可藉由增加硬化促進劑之量,而增大上述硬化扭矩值的比。藉此,可實現製造穩定性優異之轉子。 Further, in the present embodiment, for example, the ratio of the hardening torque value can be increased by increasing the amount of the curing accelerator. Thereby, a rotor excellent in manufacturing stability can be realized.
對本發明之固定用樹脂組成物,首先製作於模具溫度175℃、注入壓力9.8MPa、硬化時間120秒之硬化條件下,且依據JIS K7162而獲得之啞鈴形狀的前述固定用樹脂組成物之硬化物。將前述啞鈴形狀的前述固定用樹脂組成物之硬化物進而於175℃、4小時之條件下進行硬化而製作試片。對前述試片於溫度25℃、負荷速度1.0mm/min之條 件下進行拉伸試驗,得出斷裂能。再者,於ISO527-2中記載有與JIS K7162所記載之啞鈴形狀相同之形狀。 The fixing resin composition of the present invention is first produced in a dumbbell-shaped fixing resin composition obtained in accordance with JIS K7162 under a curing condition of a mold temperature of 175 ° C, an injection pressure of 9.8 MPa, and a curing time of 120 seconds. . The cured product of the above-mentioned dumbbell-shaped fixing resin composition was further cured at 175 ° C for 4 hours to prepare a test piece. For the above test piece at a temperature of 25 ° C, a load speed of 1.0 mm / min The tensile test was carried out under the test to obtain the fracture energy. Further, in ISO 527-2, the shape similar to the dumbbell shape described in JIS K7162 is described.
以下,將於溫度25℃、負荷速度1.0mm/min之條件下進行拉伸試驗所得出的斷裂能設為斷裂能a。另外,將於溫度150℃、負荷速度1.0mm/min之條件下進行拉伸試驗所得出的斷裂能設為斷裂能b。另外,將斷裂能a之測定條件下的斷裂強度設為斷裂強度a,斷裂能b之測定條件下的斷裂強度設為斷裂強度b。 Hereinafter, the fracture energy obtained by performing the tensile test under the conditions of a temperature of 25 ° C and a load speed of 1.0 mm/min is defined as the fracture energy a. Further, the fracture energy obtained by performing the tensile test under the conditions of a temperature of 150 ° C and a load speed of 1.0 mm/min was defined as the fracture energy b. In addition, the breaking strength under the measurement condition of the breaking energy a is the breaking strength a, and the breaking strength under the measurement condition of the breaking energy b is the breaking strength b.
所謂斷裂能,係將拉伸試驗時之正向應力(stress)與正向應變(strein)之關係繪製成曲線(應力-應變曲線)而算出。 The fracture energy is calculated by plotting the relationship between the stress and the forward strain at the time of the tensile test as a curve (stress-strain curve).
具體而言,係將應變作為變數而算出的自拉伸試驗之開始點至斷裂點為止之應力之積分值。該斷裂能越大,則所獲得之轉子鐵芯具備越高之硬度及黏著強度,耐久性越優異。再者,斷裂能之單位為×10-4J/mm3。 Specifically, the integral value of the stress from the start point of the tensile test to the breaking point calculated by using the strain as a variable. The larger the fracture energy, the higher the hardness and the adhesion strength of the obtained rotor core, and the more excellent the durability. Further, the unit of the fracture energy is ×10 -4 J/mm 3 .
本發明之固定用樹脂組成物之硬化物(固定構件)的斷裂能a較佳為1.5×10-4J/mm3以上。藉由具有該範圍之斷裂能a,可獲得具備硬度及黏著強度的耐久性優異之轉子鐵芯。 The breaking energy a of the cured product (fixing member) of the fixing resin composition of the present invention is preferably 1.5 × 10 -4 J/mm 3 or more. By having the fracture energy a in this range, a rotor core excellent in durability and hardness and adhesion strength can be obtained.
另外,斷裂能a更佳為1.9×10-4J/mm3以上。藉由使斷裂能a在該範圍內,可實現即便於在高溫下長時間地高速旋轉之環境下,亦顯示充分之耐久性的轉子鐵芯。再者,對於上限值並無特別限制,只要為15.0×10-4J/mm3左右即充分。 Further, the breaking energy a is more preferably 1.9 × 10 -4 J/mm 3 or more. By setting the fracture energy a within this range, it is possible to realize a rotor core which exhibits sufficient durability even in an environment of high-speed rotation at a high temperature for a long period of time. In addition, the upper limit is not particularly limited, and it is sufficient as long as it is about 15.0 × 10 -4 J/mm 3 .
再者,斷裂能b較佳為1.2×10-4J/mm3以上。於較斷裂能a高之溫度下測定的斷裂能b在上述範圍內之情況下,可獲得亦可耐受溫度變化,且具備硬度及黏著強度的耐久性優異之轉子。另外,斷裂能b更佳為1.5×10-4J/mm3以上。藉由使斷裂能b在該範圍內,則高速旋轉時之耐久性更進一步提高。與斷裂能a同樣地,斷裂能b的上限值亦無特別限制,只要為8.0×10-4J/mm3左右即充分。 Further, the breaking energy b is preferably 1.2 × 10 -4 J/mm 3 or more. When the fracture energy b measured at a temperature higher than the fracture energy a is within the above range, a rotor excellent in durability and hardness and adhesion strength can be obtained. Further, the breaking energy b is more preferably 1.5 × 10 -4 J/mm 3 or more. When the fracture energy b is within this range, the durability at the time of high-speed rotation is further improved. Similarly to the fracture energy a, the upper limit of the fracture energy b is not particularly limited, and is sufficient as long as it is about 8.0 × 10 -4 J/mm 3 .
為了提高斷裂能a及b,以下方法較為有效。 In order to increase the fracture energy a and b, the following methods are effective.
首先,可藉由採用本發明之環氧樹脂與其硬化劑之組合,而提高樹脂成分之強度及黏著強度。除此以外,更佳為利用矽烷偶合劑將無機填充材料之表面改質,提高樹脂與無機填充材料之界面接著強度。另外,進而較佳為藉由調整無機填充材料之粒徑分佈,而形成於樹脂硬化體內部產生之微裂縫不容易發展之結構。 First, the strength and adhesion strength of the resin component can be improved by using the combination of the epoxy resin of the present invention and its hardener. In addition to this, it is more preferable to modify the surface of the inorganic filler by a decane coupling agent to improve the interface bonding strength between the resin and the inorganic filler. Further, it is more preferable to adjust the particle size distribution of the inorganic filler to form a structure in which microcracks generated inside the cured resin body are not easily developed.
藉由將本發明之固定用樹脂組成物之硬化物(固定構件)的斷裂強度a控制為50MPa以上之範圍內,本實施形態之轉子的耐久性可進一步提高。具體而言,藉由使斷裂強度a在該範圍內,高速旋轉時之耐久性更進一步提高。再者,斷裂強度a較佳為60MPa以上。對於上限值並無特別限制,只要為200MPa左右即充分。 The durability of the rotor of the present embodiment can be further improved by controlling the breaking strength a of the cured product (fixing member) of the fixing resin composition of the present invention to be within a range of 50 MPa or more. Specifically, by making the breaking strength a within this range, the durability at the time of high-speed rotation is further improved. Further, the breaking strength a is preferably 60 MPa or more. The upper limit is not particularly limited, and it is sufficient as long as it is about 200 MPa.
本發明之固定用樹脂組成物之硬化物的斷裂強度b亦與斷裂強度a同樣地,藉由將斷裂強度b控制為15MPa以上之範圍內,高速旋轉時之耐久性更進一步提高。再者,斷裂強度b較佳為20MPa以上。對於上限值並無特別限 制,只要為100MPa左右即充分。 In the same manner as the breaking strength a, the breaking strength b of the cured product of the fixing resin composition of the present invention is controlled by the breaking strength b within a range of 15 MPa or more, and the durability at the time of high-speed rotation is further improved. Further, the breaking strength b is preferably 20 MPa or more. There is no special limit on the upper limit The system is sufficient as long as it is about 100 MPa.
藉由將斷裂強度a及b設定於上述特定之範圍內,可提供耐久性優異之轉子。尤其可提供於轉子之高速旋轉使用時永久磁鐵的位置穩定性優異之轉子。 By setting the breaking strengths a and b within the above specific range, it is possible to provide a rotor excellent in durability. In particular, it is possible to provide a rotor excellent in positional stability of a permanent magnet when the rotor is rotated at a high speed.
對於本發明之固定用樹脂組成物,使用成形機,於模具溫度175℃、注入壓力9.8MPa、硬化時間120秒之條件下對上述固定用樹脂組成物進行注入成形,製作長度80mm、寬度10mm、厚度4mm的上述固定用樹脂組成物之成形體。進而,於175℃、4小時之條件下將上述成形體硬化而製作硬化物。然後,將該硬化物於ATF中、150℃下浸漬1000小時。將ATF浸漬前上述硬化物之重量設為X1,ATF浸漬後上述硬化物之重量設為X2時,可藉由(X2-X1)/X1×100算出重量變化率[%]。 In the fixing resin composition of the present invention, the fixing resin composition was injection-molded at a mold temperature of 175 ° C, an injection pressure of 9.8 MPa, and a curing time of 120 seconds to prepare a length of 80 mm and a width of 10 mm. A molded body of the above-mentioned fixing resin composition having a thickness of 4 mm. Further, the molded body was cured at 175 ° C for 4 hours to prepare a cured product. Then, the cured product was immersed in ATF at 150 ° C for 1,000 hours. The weight of the cured product before the ATF is immersed is X1, and when the weight of the cured product after the ATF is immersed is X2, the weight change rate [%] can be calculated by (X2-X1)/X1×100.
於此,ATF只要為通常所使用者則無特別限定,其係於基油中添加有各種添加劑。此處之基油通常為礦物油系基油、合成油系基油、或該等之混合物。添加劑成分可列舉黏度調節劑、摩擦調節劑等。 Here, the ATF is not particularly limited as long as it is a normal user, and various additives are added to the base oil. The base oil herein is typically a mineral oil based base oil, a synthetic oil based base oil, or a mixture of such. Examples of the additive component include a viscosity modifier, a friction modifier, and the like.
本實施形態中,重量變化率測定用之ATF例如可使用Matic Fluid D(日產汽車公司製造)、Auto Fluid Type T-IV(豐田汽車公司製造)、ATF DW-1(本田技研工業公司製造)等。 In the present embodiment, for the ATF for measuring the weight change rate, for example, Matic Fluid D (manufactured by Nissan Motor Co., Ltd.), Auto Fluid Type T-IV (manufactured by Toyota Motor Corporation), ATF DW-1 (manufactured by Honda Technik Co., Ltd.), or the like can be used. .
本發明之固定用樹脂組成物較佳為,將其硬化物(固定構件)於ATF中、150℃下浸漬1000小時之時的重量變化率為0.5%以下。更佳為0.2%以下。藉由使ATF浸漬前 後之重量變化率為上述上限值以下,則即便固定構件於高溫下長時間地接觸潤滑油,亦可抑制固定構件因潤滑油而大幅膨潤。 The fixing resin composition of the present invention preferably has a weight change ratio of 0.5% or less when the cured product (fixing member) is immersed in ATF at 150 ° C for 1,000 hours. More preferably, it is 0.2% or less. By impregnating ATF before When the weight change rate is less than or equal to the above upper limit value, even if the fixing member contacts the lubricating oil for a long period of time at a high temperature, the fixing member can be prevented from being largely swollen by the lubricating oil.
另外,本發明之固定用樹脂組成物較佳為,將其硬化物於ATF中、150℃下浸漬1000小時之時的重量變化率為-0.05%以上。更佳為-0.03%以上。藉由使ATF浸漬前後之重量變化率為上述下限值以上,則即便固定構件於高溫下長時間地接觸潤滑油,亦可抑制固定構件之一部分流出至潤滑油中。此外,藉由使ATF浸漬前後之重量變化率為上述下限值以上,可抑制潤滑油之特性降低。 Moreover, it is preferable that the fixing resin composition of the present invention has a weight change ratio of -0.05% or more when the cured product is immersed in ATF at 150 ° C for 1,000 hours. More preferably -0.03% or more. When the weight change rate before and after the immersion of the ATF is equal to or higher than the above lower limit value, even if the fixing member contacts the lubricating oil for a long period of time at a high temperature, it is possible to suppress a part of the fixing member from flowing out into the lubricating oil. Further, by changing the weight change rate before and after the ATF immersion to the above lower limit value, it is possible to suppress a decrease in the characteristics of the lubricating oil.
因此,藉由使ATF浸漬前後之重量變化率在上述範圍內,則即便於在高溫下長時間地高速旋轉之環境下,亦可將固定構件之尺寸維持為固定。其結果,可長時間地將磁鐵之位置維持為固定位置,因此可獲得長期可靠性優異之轉子。 Therefore, by setting the weight change rate before and after the ATF immersion within the above range, the size of the fixing member can be maintained constant even in an environment where the aluminum alloy is rotated at a high temperature for a long period of time. As a result, the position of the magnet can be maintained at a fixed position for a long period of time, so that a rotor excellent in long-term reliability can be obtained.
另外,將使本發明之固定用樹脂組成物的硬化物於ATF中、150℃下浸漬2000小時之時ATF浸漬後上述硬化物之重量設為X3時,藉由(X3-X1)/X1×100算出之重量變化率[%]較佳為-0.1%以上、0.6%以下。更佳為-0.07%以上、0.5%以下。藉由使於上述條件下測定之重量變化率在上述範圍內,可獲得即便於在高溫下長時間地高速旋轉之環境下,長期可靠性亦更優異之轉子。 In addition, when the cured product of the fixing resin composition of the present invention is immersed in ATF at 150 ° C for 2,000 hours, the weight of the cured product after the ATF immersion is X3, by (X3-X1) / X1 × The weight change rate [%] calculated at 100 is preferably -0.1% or more and 0.6% or less. More preferably, it is -0.07% or more and 0.5% or less. By setting the weight change rate measured under the above conditions within the above range, it is possible to obtain a rotor excellent in long-term reliability even in an environment where high-speed rotation is performed at a high temperature for a long period of time.
另外,將使本發明之固定用樹脂組成物的硬化物於ATF中、150℃下浸漬1000小時之時ATF浸漬前上述硬化 物之體積設為Y1,ATF浸漬後上述硬化物之體積設為Y2時,藉由(Y2-Y1)/Y1×100算出之體積變化率[%]較佳為-0.2%以上、1.5%以下。更佳為-0.1%以上、1%以下。藉由使於上述條件下測定之體積變化率在上述範圍內,可獲得即便於在高溫下長時間地高速旋轉之環境下,長期可靠性亦更優異之轉子。 Further, the cured product of the fixing resin composition of the present invention is immersed in ATF at 150 ° C for 1000 hours, and the above-mentioned hardening is performed before ATF immersion. When the volume of the object is Y1 and the volume of the cured product after the ATF is immersed is Y2, the volume change rate [%] calculated by (Y2-Y1)/Y1×100 is preferably -0.2% or more and 1.5% or less. . More preferably, it is -0.1% or more and 1% or less. By setting the volume change rate measured under the above conditions within the above range, it is possible to obtain a rotor excellent in long-term reliability even in an environment of high-speed rotation at a high temperature for a long period of time.
本發明之固定用樹脂組成物例如可藉由使用混合機等於常溫下混合均勻,然後視需要使用加熱輥、捏合機或擠出機等混練機進行熔融混練,繼而視需要加以冷卻、粉碎,而調整為所需之分散度或流動性等。 The fixing resin composition of the present invention can be uniformly mixed by using a mixer at room temperature, and then melt-kneaded by a kneading machine such as a heating roll, a kneader or an extruder, if necessary, and then cooled and pulverized as needed. Adjust to the required dispersion or fluidity, etc.
本發明之固定用樹脂組成物之製造方法並無特別限制,可藉由下述方式進行製造。 The method for producing the fixing resin composition of the present invention is not particularly limited, and it can be produced by the following method.
首先,將熱硬化性樹脂(A)、酚樹脂系硬化劑(B)及無機填充材料(C)、以及較佳為其他添加劑等調配規定量,獲得固定用樹脂組成物。繼而,將調配所得者使用例如混合機、噴射磨機、球磨機等於常溫下均勻地粉碎、混合後,使用加熱輥、捏合機或擠出機等混練機,一面加溫至90~120℃左右一面進行熔融、混練。繼而,將經混練後之固定用樹脂組成物冷卻、粉碎,可獲得顆粒或粉末狀的固形之固定用樹脂組成物。本發明之固定用樹脂組成物之粉末或顆粒的粒度例如較佳為5mm以下。藉由為5mm以下,可抑制打錠時產生填充不良而導致錠片(tablet)之質量不均勻增大的情況。 First, a thermosetting resin (A), a phenol resin-based curing agent (B), an inorganic filler (C), and preferably other additives are blended in a predetermined amount to obtain a fixing resin composition. Then, the blender is uniformly pulverized and mixed at a normal temperature using, for example, a mixer, a jet mill, or a ball mill, and then heated to a temperature of about 90 to 120 ° C using a kneading machine such as a heating roll, a kneader, or an extruder. Melt and knead. Then, the resin composition for fixing after kneading is cooled and pulverized to obtain a solid resin composition for fixing in the form of granules or powder. The particle size of the powder or granule of the fixing resin composition of the present invention is, for example, preferably 5 mm or less. When it is 5 mm or less, it is possible to suppress the occurrence of poor filling during the tableting and the unevenness in the quality of the tablet.
然後,藉由對所獲得之固定用樹脂組成物之粉末或顆 粒進行打錠成形,可獲得錠片。作為打錠成形所用之裝置,可使用單片式、或多片旋轉式之打錠機。錠片之形狀並無特別限定,較佳為圓柱狀。打錠機之陽模、陰模及環境之溫度並無特別限制,較佳為35℃以下。若大於35℃,則有固定用樹脂組成物產生反應因而黏度上升,流動性受損之虞。打錠壓力較佳為400×104Pa以上、3000×104Pa以下之範圍。藉由將打錠壓力設定為上述上限值以下,可抑制錠片剛壓成後產生破裂。另一方面,藉由將打錠壓力設定為上述下限值以上,可抑制因未獲得充分之凝聚力而錠片於輸送過程中產生破裂。打錠機之陽模、陰模之模具的材質、表面處理並無特別限定,可使用公知之材質的模具,作為表面處理之例,例如可列舉放電加工、塗佈脫模劑、鍍敷處理、研磨等。 Then, the tablet is obtained by tableting the powder or granules of the obtained fixing resin composition. As a device for forming an ingot, a one-piece type or a plurality of rotary type ingot machines can be used. The shape of the tablet is not particularly limited, and is preferably a columnar shape. The temperature of the male mold, the female mold and the environment of the tableting machine is not particularly limited, and is preferably 35 ° C or less. When it is more than 35 ° C, the fixing resin composition reacts and the viscosity increases, and the fluidity is impaired. The tableting pressure is preferably in the range of 400 × 10 4 Pa or more and 3000 × 10 4 Pa or less. By setting the tableting pressure to be equal to or lower than the above upper limit value, it is possible to suppress the occurrence of cracking immediately after the tablet is pressed. On the other hand, by setting the tableting pressure to be equal to or higher than the above lower limit value, it is possible to suppress cracking of the tablet during conveyance due to insufficient cohesive force. The material and surface treatment of the mold of the male mold and the female mold of the tableting machine are not particularly limited, and a mold of a known material can be used. Examples of the surface treatment include, for example, electric discharge machining, coating release agent, and plating treatment. , grinding, etc.
另外,本發明之固定構件之玻璃轉移溫度(Tg)較佳為130℃以上,更佳為140℃以上。若為上述下限值以上,則可靠性有望提高。上述玻璃轉移溫度(Tg)的上限值並無特別限定,較佳為200℃以下,更佳為190℃以下。藉此,可實現耐久性優異之轉子。 Further, the glass transition temperature (Tg) of the fixing member of the present invention is preferably 130 ° C or higher, more preferably 140 ° C or higher. If it is more than the above lower limit value, reliability is expected to increase. The upper limit of the glass transition temperature (Tg) is not particularly limited, but is preferably 200 ° C or lower, more preferably 190 ° C or lower. Thereby, a rotor excellent in durability can be realized.
另外,於本實施形態中,例如可藉由提高環氧樹脂、硬化劑之軟化點,而增大上述玻璃轉移溫度(Tg)。 Further, in the present embodiment, for example, the glass transition temperature (Tg) can be increased by increasing the softening point of the epoxy resin or the curing agent.
本發明之固定構件於150℃下之抗彎強度較佳為70MPa以上,更佳為100MPa以上。若為上述下限值以上,則不容易產生龜裂等,可靠性有望提高。上述抗彎強度的上限值並無特別限定,較佳為300MPa以下,更佳為250 MPa以下。藉此,可實現耐久性優異之轉子。 The flexural strength of the fixing member of the present invention at 150 ° C is preferably 70 MPa or more, more preferably 100 MPa or more. When it is more than the above lower limit value, cracks and the like are less likely to occur, and reliability is expected to increase. The upper limit of the above bending strength is not particularly limited, but is preferably 300 MPa or less, more preferably 250. Below MPa. Thereby, a rotor excellent in durability can be realized.
另外,於本實施形態中,例如可藉由利用偶合劑對填充材料之表面進行處理,而增大上述抗彎強度。 Further, in the present embodiment, for example, the surface of the filler can be treated with a coupling agent to increase the bending strength.
本發明之固定構件於150℃下之彎曲彈性模數的上限值較佳為1.6×104MPa以下,更佳為1.3×104MPa以下。若為上述上限值以下,則有望因應力緩和而可靠性提高。上述彎曲彈性模數的下限值並無特別限定,較佳為5000MPa以上,更佳為7000MPa以上。藉此,可實現耐久性優異之轉子。 The upper limit of the flexural modulus of the fixing member of the present invention at 150 ° C is preferably 1.6 × 10 4 MPa or less, more preferably 1.3 × 10 4 MPa or less. If it is less than or equal to the above upper limit value, it is expected that reliability is improved due to stress relaxation. The lower limit of the flexural modulus is not particularly limited, but is preferably 5,000 MPa or more, and more preferably 7,000 MPa or more. Thereby, a rotor excellent in durability can be realized.
另外,於本實施形態中,例如可藉由增加低應力劑之添加量,減少填充材料之調配量等方法而降低上述彎曲彈性模數。 Further, in the present embodiment, for example, the bending elastic modulus can be reduced by increasing the amount of the low stress agent added, reducing the amount of the filler to be added, and the like.
本發明之固定構件於25℃以上、玻璃轉移溫度(Tg)以下之區域內的線膨脹係數(α1)較佳為10ppm/℃以上、25ppm/℃以下,更佳為15ppm/℃以上、20ppm/℃以下。若在上述範圍內,則與電磁鋼板之熱膨脹差較小且可防止磁鐵脫落。藉此,可實現耐久性優異之轉子。 The linear expansion coefficient (α1) of the fixing member of the present invention in a region of 25 ° C or more and a glass transition temperature (Tg) or less is preferably 10 ppm / ° C or more, 25 ppm / ° C or less, more preferably 15 ppm / ° C or more, 20 ppm / Below °C. If it is in the above range, the difference in thermal expansion from the electromagnetic steel sheet is small and the magnet can be prevented from coming off. Thereby, a rotor excellent in durability can be realized.
另外,於本實施形態中,例如可藉由增加填充材料之調配量,而減小上述線膨脹係數(α1)。 Further, in the present embodiment, for example, the linear expansion coefficient (α1) can be reduced by increasing the amount of the filling material.
本發明之固定構件於25℃以上、玻璃轉移溫度(Tg)以下之區域內的線膨脹係數(α2)較佳為10ppm/℃以上、100ppm/℃以下,更佳為20ppm/℃以上、80ppm/℃以下。若在上述範圍內,則與電磁鋼板之熱膨脹差較小且可防止磁鐵脫落。藉此,可實現耐久性優異之轉子。 The linear expansion coefficient (α2) of the fixing member of the present invention in a region of 25 ° C or more and a glass transition temperature (Tg) or less is preferably 10 ppm / ° C or more, 100 ppm / ° C or less, more preferably 20 ppm / ° C or more, 80 ppm / Below °C. If it is in the above range, the difference in thermal expansion from the electromagnetic steel sheet is small and the magnet can be prevented from coming off. Thereby, a rotor excellent in durability can be realized.
另外,於本實施形態中,例如可藉由增加填充材料之調配量,而減小上述線膨脹係數(α2)。 Further, in the present embodiment, for example, the linear expansion coefficient (α2) can be reduced by increasing the amount of the filling material.
(轉子之製造方法) (Manufacturing method of the rotor)
本實施形態之轉子100之製造方法包括以下步驟:準備轉子鐵芯110,該轉子鐵芯110中設置有沿著旋轉軸(軸170)貫穿於其中之貫穿孔的周緣部配置之多個孔部150;將磁鐵120插入至孔部150中;於孔部150與磁鐵120之相隔部填充固定用樹脂組成物;將樹脂組成物硬化,獲得固定構件130;於轉子鐵芯110之前述貫穿孔中插入軸170,並且將軸170固設於轉子鐵芯上。 The manufacturing method of the rotor 100 of the present embodiment includes the steps of preparing a rotor core 110 in which a plurality of holes arranged along a peripheral portion of a through hole through which a rotating shaft (shaft 170) is inserted is provided 150; inserting the magnet 120 into the hole portion 150; filling the fixing resin composition at a portion between the hole portion 150 and the magnet 120; curing the resin composition to obtain the fixing member 130; in the through hole of the rotor core 110 The shaft 170 is inserted and the shaft 170 is fixed to the rotor core.
作為本實施形態中填充固定用樹脂組成物之方法,較佳為嵌入成形。以下加以詳細說明。 The method of filling and fixing the resin composition in the present embodiment is preferably insert molding. The details will be described below.
首先,對嵌入成形裝置進行說明。 First, the insert molding apparatus will be described.
圖2係嵌入成形所使用之嵌入成形裝置之上模200的剖面圖。 Figure 2 is a cross-sectional view of the overmold 200 of the insert forming apparatus used for insert molding.
作為固定構件130之形成方法之一例,可採用使用錠片狀之固定用樹脂組成物進行嵌入成形的方法。該嵌入成形中使用嵌入成形裝置。該成形裝置係包括:上模200,其包含供給錠片狀之固定用樹脂組成物之罐210、及使熔融狀態之固定用樹脂組成物移動之流路220;下模;加熱器件,對該等上模及下模進行加熱;及擠出機構,將熔融狀態之固定用樹脂組成物擠出。嵌入成形裝置例如亦可具備搬送轉子鐵芯等之搬送功能。 As an example of the method of forming the fixing member 130, a method of insert molding using a tablet-shaped fixing resin composition can be employed. An insert molding device is used in the insert molding. The molding apparatus includes an upper mold 200 including a tank 210 for supplying a fixing resin composition in the form of an ingot, and a flow path 220 for moving the fixing resin composition in a molten state; a lower mold; and a heating device. The upper mold and the lower mold are heated, and the extrusion mechanism is used to extrude the resin composition for fixing in a molten state. The insert molding apparatus may have, for example, a conveying function of conveying a rotor core or the like.
本實施形態中,上模200及下模較佳為與轉子鐵芯110 之上表面及下表面(即,構成轉子鐵芯110之電磁鋼板之一表面)密接,且例如較佳為板狀。本實施形態之上模200及下模並不覆蓋轉子鐵芯110之整體,例如並不覆蓋側面之一部分,就該點而言,與半導體裝置之製造方法中使用的通常之轉移成形之模具不同。轉移成形之模具係構成為將半導體晶片整體配置於由上模與下模構成之模槽內。 In this embodiment, the upper mold 200 and the lower mold are preferably connected to the rotor core 110. The upper surface and the lower surface (i.e., one surface of the electromagnetic steel sheet constituting the rotor core 110) are in close contact with each other, and are preferably plate-shaped, for example. In the present embodiment, the upper mold 200 and the lower mold do not cover the entirety of the rotor core 110, and do not cover one of the side portions, for example, which is different from the usual transfer forming mold used in the manufacturing method of the semiconductor device. . The mold for transfer molding is configured such that the entire semiconductor wafer is placed in a cavity formed by an upper mold and a lower mold.
另外,罐210可具有兩條單獨之流路220,亦可具有Y字形之流路220。藉此,可自1個罐210中向2個孔部填充本發明之固定用樹脂組成物。再者,1個罐亦可具有向1個孔部填充固定用樹脂組成物之1條流路,亦可具有向3個以上之孔部填充固定用樹脂組成物之3條流路。其中,多個流路可相互獨立,亦可連續。 In addition, the tank 210 may have two separate flow paths 220, and may also have a Y-shaped flow path 220. Thereby, the fixing resin composition of the present invention can be filled into the two holes from one can 210. In addition, one tank may have one flow path for filling the fixing resin composition into one hole portion, or may have three flow paths for filling the fixing resin composition into three or more holes. Wherein, the plurality of flow paths can be independent of each other or continuous.
繼而,對本實施形態之嵌入成形進行說明。 Next, the insert molding of this embodiment will be described.
首先,將轉子鐵芯於烘箱中或熱板上等預熱後,固定於未圖示之成形裝置之下模上。繼而,於轉子鐵芯之孔部中插入磁鐵。然後,使下模上升,將上模200按壓於轉子鐵芯之上表面。藉此,以上模200與下模夾持轉子鐵芯110之上表面及下表面。此時,上模200中之流路220之前端部係配置於孔部與磁鐵之相隔部上。另外,轉子鐵芯由於自成形裝置之下模及上模200之熱傳導而受到加熱。成形裝置之下模及上模200的溫度例如係調整為150℃~200℃左右,以使轉子鐵芯達到適合於固定用樹脂組成物成形、硬化之溫度。於該狀態下將錠片狀之固定用樹脂組成物供給至上模200的罐210內。供給至上模200的罐210內的 錠片狀之固定用樹脂組成物在罐210內受到加熱而成為熔融狀態。 First, the rotor core is preheated in an oven or a hot plate, and then fixed to a lower mold of a forming device (not shown). Then, a magnet is inserted into the hole portion of the rotor core. Then, the lower mold is raised to press the upper mold 200 against the upper surface of the rotor core. Thereby, the upper mold 200 and the lower mold sandwich the upper surface and the lower surface of the rotor core 110. At this time, the front end portion of the flow path 220 in the upper mold 200 is disposed on the space between the hole portion and the magnet. In addition, the rotor core is heated by the heat conduction from the lower mold of the forming apparatus and the upper mold 200. The temperature of the lower mold and the upper mold 200 of the forming apparatus is adjusted, for example, to about 150 ° C to 200 ° C so that the rotor core can reach a temperature suitable for forming and hardening the fixing resin composition. In this state, the tablet-shaped fixing resin composition is supplied into the can 210 of the upper mold 200. Supplied into the can 210 of the upper mold 200 The ingot-shaped fixing resin composition is heated in the can 210 to be in a molten state.
繼而,利用柱塞(擠出機構)將熔融狀態之固定用樹脂組成物自罐210中擠出。如此,固定用樹脂組成物於流路220中移動而填充至孔部與磁鐵之相隔部中。於此期間,轉子鐵芯因自模具(下模及上模200)之熱傳導而受到加熱,藉此使所填充之固定用樹脂組成物硬化,形成固定構件。此時,溫度條件例如可設為150℃~200℃。另外,硬化時間例如可設為30秒~180秒。藉此,插入於孔部150之內部的磁鐵120由固定構件130固定。然後,使上模200自轉子鐵芯之上表面離開。繼而,於轉子鐵芯110之貫穿孔中插入軸170,並且將軸170固設於轉子鐵芯上。 Then, the fixing resin composition in a molten state is extruded from the can 210 by a plunger (extrusion mechanism). In this manner, the fixing resin composition moves in the flow path 220 and is filled in the space between the hole portion and the magnet. During this period, the rotor core is heated by heat conduction from the mold (the lower mold and the upper mold 200), whereby the filled fixing resin composition is cured to form a fixing member. At this time, the temperature condition can be, for example, 150 ° C to 200 ° C. Further, the hardening time can be, for example, 30 seconds to 180 seconds. Thereby, the magnet 120 inserted inside the hole portion 150 is fixed by the fixing member 130. Then, the upper mold 200 is separated from the upper surface of the rotor core. Then, the shaft 170 is inserted into the through hole of the rotor core 110, and the shaft 170 is fixed to the rotor core.
藉由以上所述,獲得本實施形態之轉子。 According to the above, the rotor of this embodiment is obtained.
此處,本實施形態之嵌入成形方法不需要進行拆模,就該點而言,與製造半導體裝置所使用之轉移成形方法不同。 Here, the insert molding method of the present embodiment does not require mold removal, and this point is different from the transfer molding method used for manufacturing a semiconductor device.
於嵌入成形方法中,係於轉子鐵芯110之上表面與上模200密接之狀態下,通過上模200之流路而向轉子鐵芯110之孔部填充樹脂。因此,不會於轉子鐵芯110之上表面與上模200之間填充大量之樹脂,上模200與上表面之裝卸變得容易。 In the insert molding method, the resin is filled into the hole portion of the rotor core 110 through the flow path of the upper mold 200 in a state where the upper surface of the rotor core 110 is in close contact with the upper mold 200. Therefore, a large amount of resin is not filled between the upper surface of the rotor core 110 and the upper mold 200, and the upper mold 200 and the upper surface are easily attached and detached.
另一方面,於轉移成形方法中,係於半導體晶片與模具之間的模槽中填充樹脂,故而必須熟練地將模具自成形品拆除。因此,密封半導體晶片之樹脂會特別要求模具與 成形品之脫模性。 On the other hand, in the transfer molding method, since the resin is filled in the cavity between the semiconductor wafer and the mold, it is necessary to skillfully remove the mold from the molded article. Therefore, the resin that seals the semiconductor wafer will specifically require the mold and The release property of the molded article.
本實施形態之轉子100可搭載於混合動力車、燃料電池車及電動車等電動車輛、火車及船舶等交通工具中。 The rotor 100 of the present embodiment can be mounted on a vehicle such as an electric vehicle such as a hybrid vehicle, a fuel cell vehicle, or an electric vehicle, or a train or a ship.
[實施例] [Examples]
以下,參照實施例詳細地說明本發明,但本發明並不受該等實施例的記載之任何限定。只要未特別說明,則以下所記載之「份」係表示「質量份」,「%」係表示「質量%」。 Hereinafter, the present invention will be described in detail with reference to examples but the present invention is not limited to the description of the examples. Unless otherwise stated, the "parts" described below indicate "parts by mass" and "%" means "mass%".
將各實施例及各比較例中使用之原料成分示於下述。 The raw material components used in the respective examples and comparative examples are shown below.
(熱硬化性樹脂(A)) (thermosetting resin (A))
環氧樹脂1:聯苯型環氧樹脂(三菱化學製造,YX4000K,150℃下之ICI黏度:0.11泊) Epoxy resin 1: biphenyl type epoxy resin (manufactured by Mitsubishi Chemical Corporation, YX4000K, ICI viscosity at 150 ° C: 0.11 poise)
環氧樹脂2:四甲基雙酚F型環氧樹脂(新日鐵化學製造,YSLV-80XY,150℃下之ICI黏度:0.03泊) Epoxy Resin 2: Tetramethylbisphenol F-type epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., YSLV-80XY, ICI viscosity at 150 °C: 0.03 poise)
環氧樹脂3:鄰甲酚酚醛清漆型環氧樹脂(DIC製造,EPICLON N-665,150℃下之ICI黏度:3.06泊) Epoxy Resin 3: o-cresol novolac type epoxy resin (manufactured by DIC, EPICLON N-665, ICI viscosity at 150 ° C: 3.06 poise)
環氧樹脂4:具有伸苯基骨架之苯酚芳烷基型環氧樹脂(日本化藥製造,NC-2000,150℃下之ICI黏度:1.20泊) Epoxy Resin 4: Phenol aralkyl type epoxy resin having a phenyl stretch structure (manufactured by Nippon Kayaku Co., Ltd., NC-2000, ICI viscosity at 150 ° C: 1.20 poise)
環氧樹脂5:具有伸聯苯基骨架之苯酚芳烷基型環氧樹脂(日本化藥製造,NC3000,150℃下之ICI黏度:0.85泊) Epoxy Resin 5: Phenol aralkyl type epoxy resin having a biphenyl skeleton (manufactured by Nippon Kayaku Co., Ltd., NC3000, ICI viscosity at 150 ° C: 0.85 poise)
環氧樹脂6:三苯基甲烷型環氧樹脂(日本化藥製造,E-1032H-60,150℃下之ICI黏度:1.30泊) Epoxy resin 6: Triphenylmethane type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., E-1032H-60, ICI viscosity at 150 ° C: 1.30 poise)
環氧樹脂7:鄰甲酚酚醛清漆型環氧樹脂(DIC製造,EPICLON N-670,150℃下之ICI黏度:4.28泊) Epoxy Resin 7: o-cresol novolac type epoxy resin (manufactured by DIC, EPICLON N-670, ICI viscosity at 150 ° C: 4.28 poise)
再者,150℃下之熔融黏度(ICI黏度)係使用錐-板型黏度計CV-1S(東亞工業股份有限公司製造)而測定。 Further, the melt viscosity (ICI viscosity) at 150 ° C was measured using a cone-plate type viscometer CV-1S (manufactured by Toayama Kogyo Co., Ltd.).
(硬化劑(B)) (hardener (B))
酚樹脂系硬化劑1:酚醛清漆型酚樹脂(Sumitomo Bakelite製造,PR-HF-3,150℃下之ICI黏度:1.08泊) Phenolic resin-based hardener 1: Novolak-type phenol resin (manufactured by Sumitomo Bakelite, PR-HF-3, ICI viscosity at 150 ° C: 1.08 poise)
酚樹脂系硬化劑2:具有伸苯基骨架之苯酚芳烷基樹脂(明和化成製造,MEH-7800-4S,150℃下之ICI黏度:0.73泊) Phenolic resin-based hardener 2: Phenol aralkyl resin having a phenyl stretch structure (manufactured by Minghe Chemical Co., Ltd., MEH-7800-4S, ICI viscosity at 150 ° C: 0.73 poise)
酚樹脂系硬化劑3:具有伸聯苯基骨架之苯酚芳烷基樹脂(明和化成製造,MEH-7851SS,150℃下之ICI黏度:0.68泊) Phenolic resin-based hardener 3: phenol aralkyl resin having a biphenyl skeleton (manufactured by Megumi Kasei, MEH-7851SS, ICI viscosity at 150 ° C: 0.68 poise)
酚樹脂系硬化劑4:以2-羥基苯甲醛、甲醛及苯酚之反應產物為主的酚樹脂(Air Water製造,HE910-20,150℃下之ICI黏度:1.5泊) Phenolic resin-based hardener 4: a phenol resin mainly composed of a reaction product of 2-hydroxybenzaldehyde, formaldehyde and phenol (manufactured by Air Water, HE910-20, ICI viscosity at 150 ° C: 1.5 poise)
酚樹脂系硬化劑5:酚醛清漆型酚樹脂(Sumitomo Bakelite製造,PR-51714,150℃下之ICI黏度:1.64泊) Phenolic resin-based hardener 5: Novolak-type phenol resin (manufactured by Sumitomo Bakelite, PR-51714, ICI viscosity at 150 ° C: 1.64 poise)
(無機填充材料(C)) (Inorganic Filling Material (C))
球狀矽石1(電氣化學工業製造,FB-950,平均粒徑D50為23μm) Spherical vermiculite 1 (manufactured by the electrical and chemical industry, FB-950, average particle diameter D 50 is 23 μm)
球狀矽石2(電氣化學工業製造,FB-35,平均粒徑D50為10μm) Spherical vermiculite 2 (manufactured by the electrical and chemical industry, FB-35, average particle diameter D 50 is 10 μm)
球狀矽石3(Admatechs製造,SO-25R,平均粒徑D50 為0.5μm) Spherical vermiculite 3 (manufactured by Admatechs, SO-25R, average particle diameter D 50 is 0.5 μm)
氧化鋁(電氣化學工業製造,DAW-45,平均粒徑D50為43μm) Alumina (manufactured by the electrical and chemical industry, DAW-45, average particle diameter D 50 is 43 μm)
(硬化促進劑(D)) (hardening accelerator (D))
硬化促進劑1:三苯基膦 Hardening accelerator 1: triphenylphosphine
硬化促進劑2:以下述式(7)所表示之硬化促進劑 Hardening accelerator 2: a hardening accelerator represented by the following formula (7)
硬化促進劑3:以下述式(8)所表示之硬化促進劑 Hardening accelerator 3: a hardening accelerator represented by the following formula (8)
硬化促進劑4:以下述式(9)所表示之硬化促進劑 Hardening accelerator 4: a hardening accelerator represented by the following formula (9)
硬化促進劑5:以下述式(10)所表示之硬化促進劑 Hardening accelerator 5: a hardening accelerator represented by the following formula (10)
(偶合劑(F)) (coupler (F))
偶合劑1:苯基胺基丙基三甲氧基矽烷(Dow Corning Toray股份有限公司製造,CF4083) Coupler 1: Phenylaminopropyltrimethoxydecane (manufactured by Dow Corning Toray Co., Ltd., CF4083)
偶合劑2:γ-縮水甘油氧基丙基三甲氧基矽烷(信越化學工業股份有限公司製造,KBM-403) Coupler 2: γ-glycidoxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)
(無機阻燃劑(G)) (Inorganic flame retardant (G))
氫氧化鋁(住友化學製造,CL-303) Aluminum hydroxide (manufactured by Sumitomo Chemical, CL-303)
(其他添加劑) (other additives)
離子捕捉劑:水滑石(協和化學工業製造,商品名DHT-4H) Ion trapping agent: hydrotalcite (manufactured by Kyowa Chemical Industry, trade name DHT-4H)
著色劑:碳黑(三菱化學製造,MA600) Colorant: carbon black (Mitsubishi Chemical, MA600)
脫模劑:褐煤酸酯蠟(Hoechst製造,Hoechst Wax E) Release agent: montanic acid ester wax (Hoechst Wax E, Hoechst)
低應力劑1:聚矽氧樹脂(信越化學工業股份有限公司製造,KMP-594) Low stress agent 1: Polyoxyl resin (manufactured by Shin-Etsu Chemical Co., Ltd., KMP-594)
低應力劑2:聚矽氧油(Dow Corning Toray股份有限公司製造,TZ-8120) Low stress agent 2: Polyoxygenated oil (manufactured by Dow Corning Toray Co., Ltd., TZ-8120)
(實施例) (Example)
於實施例及比較例中,將根據表1及表2所示之調配量調配各成分所得者,使用混合機於常溫下進行混合,獲得粉末狀中間體。將所獲得之粉末狀中間體裝填於自動供 給裝置(料斗)中,定量供給至80℃~100℃之加熱輥進行熔融混練。然後進行冷卻,繼而加以粉碎,獲得固定用樹脂組成物。藉由使用成形裝置對所獲得之固定用樹脂組成物進行打錠成形而獲得錠片。 In the examples and the comparative examples, those obtained by blending the respective components according to the amounts shown in Tables 1 and 2 were mixed at room temperature using a mixer to obtain a powdery intermediate. Filling the obtained powdered intermediate in automatic supply In the feeding device (hopper), the heating roller which is quantitatively supplied to 80 ° C to 100 ° C is melt-kneaded. Then, it is cooled and then pulverized to obtain a fixing resin composition. The tablet was obtained by ingot forming the obtained fixing resin composition by using a molding device.
另一方面,使用包括圖2所示之上模200的嵌入成形裝置,根據下述要領製作轉子。首先,將轉子鐵芯固定於成形裝置之下模上,繼而於轉子鐵芯之孔部中插入釹磁鐵後,使下模上升而將上模200按壓於轉子鐵芯之上表面。繼而,將錠片狀之固定用樹脂組成物供給至上模200的罐210中。繼而,利用柱塞,將熔融狀態之固定用樹脂組成物自罐210中擠出,將固定用樹脂組成物填充於孔部與釹磁鐵之相隔部。繼而,對所填充之固定用樹脂組成物進行加熱硬化而形成固定構件,獲得轉子。此時之成形條件係設定為轉子鐵芯溫度:160℃、硬化時間:120秒。 On the other hand, using the insert molding apparatus including the upper mold 200 shown in Fig. 2, the rotor was fabricated in accordance with the following procedure. First, the rotor core is fixed to the lower mold of the forming apparatus, and then the neodymium magnet is inserted into the hole portion of the rotor core, and the lower mold is raised to press the upper mold 200 against the upper surface of the rotor core. Then, the tablet-shaped fixing resin composition is supplied to the can 210 of the upper mold 200. Then, the fixing resin composition in a molten state is extruded from the can 210 by a plunger, and the fixing resin composition is filled in a portion where the hole portion and the neodymium magnet are separated. Then, the filled fixing resin composition is heat-cured to form a fixing member, and a rotor is obtained. The molding conditions at this time were set to rotor core temperature: 160 ° C, and hardening time: 120 seconds.
對所獲得之固定用樹脂組成物及轉子進行下述所示之測定及評價。將其結果示於表1及表2中。實施例之轉子的強度優異。 The measurement and evaluation of the obtained resin composition and the rotor described below were carried out. The results are shown in Tables 1 and 2. The rotor of the embodiment is excellent in strength.
(評價項目) (evaluation project)
螺旋流:將低壓轉移成形機(Kohtaki Precision Machine股份有限公司製造,KTS-15)轉用於嵌入成形,於175℃、注入壓力6.9MPa、保壓時間120秒之條件下,將固定用樹脂組成物注入至依據ANSI/ASTM D 3123-72之螺旋流測定用模具中,測定流動長度。螺旋流為流動性之參數,數值越大則流動性越佳。表1、2中的螺旋流之單 位為cm。 Spiral flow: a low-pressure transfer molding machine (manufactured by Kohtaki Precision Machine Co., Ltd., KTS-15) was used for insert molding, and the fixing resin was composed at 175 ° C, an injection pressure of 6.9 MPa, and a dwell time of 120 seconds. The material was injected into a mold for spiral flow measurement according to ANSI/ASTM D 3123-72, and the flow length was measured. The spiral flow is a parameter of fluidity, and the larger the value, the better the fluidity. Single spiral flow in Tables 1, 2 The bit is cm.
凝膠時間:將固定用樹脂組成物載置於控制為175℃之熱板上,使用刮勺以約1次/sec.之擊打進行揉練。測定固定用樹脂組成物因熱而溶解後至硬化為止之時間,作為凝膠時間。表1、2中的凝膠時間之單位為秒。 Gel time: The fixing resin composition was placed on a hot plate controlled at 175 ° C, and punched with a spatula at about 1 time/sec. The time until the fixing resin composition was dissolved by heat and hardened was measured as the gel time. The unit of gel time in Tables 1 and 2 is seconds.
高化式黏度:將約2.5g之固定用樹脂組成物形成錠片狀(直徑11mm、高度約15mm)後,利用高化式黏度測定裝置(島津製作所股份有限公司製造,CFT-500D)於測定溫度175℃、荷重10kg之條件下,使用直徑0.5mm、長度1.0mm之噴嘴(模嘴)進行測定。表1、2中的高化式黏度之單位為Pa‧s。 The high-viscosity viscosity is determined by a high-viscosity viscosity measuring device (manufactured by Shimadzu Corporation, CFT-500D), which is formed into a tablet shape (diameter: 11 mm, height: about 15 mm). The measurement was carried out using a nozzle (die) having a diameter of 0.5 mm and a length of 1.0 mm under the conditions of a temperature of 175 ° C and a load of 10 kg. The unit of the elevated viscosity in Tables 1 and 2 is Pa‧s.
硫化扭矩比:將使用硫化儀(Orientec股份有限公司製造,IVPS型JSR硫化儀),於測定溫度175℃下經時地測定固定用樹脂組成物之硬化扭矩時測定開始60秒後之硬化扭矩值設為T60,至測定開始300秒後為止之最大硬化扭矩值設為Tmax。求出測定開始60秒後之硬化扭矩值相對於至測定開始300秒後為止之最大硬化扭矩值的比T60/Tmax(%)作為硫化扭矩比。硫化儀之扭矩為熱剛性之參數。因此,硫化扭矩比越大,則硬化性越佳。 Vulcanization torque ratio: The curing torque value after 60 seconds from the start of the measurement of the curing torque of the fixing resin composition at a measurement temperature of 175 ° C using a vulcanizer (manufactured by Orientec Co., Ltd., IVPS type JSR vulcanizer) When T 60 is set, the maximum hardening torque value up to 300 seconds after the start of measurement is set to T max . The ratio T 60 /T max (%) of the hardening torque value after 60 seconds from the start of the measurement to the maximum hardening torque value up to 300 seconds after the start of the measurement was determined as the vulcanization torque ratio. The torque of the vulcanizer is a parameter of thermal rigidity. Therefore, the greater the vulcanization torque ratio, the better the hardenability.
狹縫流動長度:於模具溫度175℃、成形壓力6.9MPa、注入時間20秒、硬化時間90秒之條件下,於放射狀地設置有前端開放之特定厚度之槽(狹縫)的模具中,對固定用樹脂組成物進行注入成形,用游標卡尺測定流出至寬度3mm、厚度80μm之狹縫中之樹脂的長度。單位 為mm。 Slit flow length: in a mold in which a groove (slit) having a specific thickness opened at the front end is radially provided under the conditions of a mold temperature of 175 ° C, a molding pressure of 6.9 MPa, an injection time of 20 seconds, and a hardening time of 90 seconds. The fixing resin composition was subjected to injection molding, and the length of the resin flowing out into the slit having a width of 3 mm and a thickness of 80 μm was measured with a vernier caliper. unit Is mm.
轉子成形性:於視作電磁鋼板之模具(孔部之寬度為30mm,厚度為4mm,深度為75mm)中插入視作磁鐵之金屬片(寬度28mm,厚度3.8mm,長度74mm),將所得者設置於成形機中之後,於模具達到170℃之時對固定用樹脂組成物進行注入成形,於硬化時間120秒後將模具自成形機中取出。用肉眼觀察成形品之外觀,確認是否有孔隙等異常,將無孔隙等異常者評價為○,將存在孔隙等異常者評價為×。 Rotor formability: A metal piece (width 28 mm, thickness 3.8 mm, length 74 mm) which is regarded as a magnet is inserted into a mold which is regarded as an electromagnetic steel plate (the width of the hole portion is 30 mm, the thickness is 4 mm, and the depth is 75 mm). After being placed in a molding machine, the fixing resin composition was injection-molded at a temperature of 170 ° C, and the mold was taken out from the molding machine after a curing time of 120 seconds. The appearance of the molded article was visually observed to confirm whether or not there was an abnormality such as a void, and an abnormality such as no void was evaluated as ○, and an abnormality such as void was evaluated as ×.
玻璃轉移溫度:將低壓轉移成形機(Kohtaki Precision Machine股份有限公司製造,KTS-30)轉用於嵌入成形,於模具溫度175℃、注入壓力9.8MPa、硬化時間2分鐘之條件下對固定用樹脂組成物進行注入成形,獲得4mm×4mm×15mm之試片。將所獲得之試片於175℃下進行4小時後硬化之後,使用熱機械分析裝置(精工電子工業股份有限公司製造,TMA100),於測定溫度範圍0℃至320℃之溫度區域內以升溫速度5℃/min進行測定,根據此時所得之圖,確定玻璃轉移溫度以下之區域中的線膨脹係數(α1)及相當於橡膠狀之區域中的線膨脹係數(α2)。此時,將α1及α2之延長線之交點作為玻璃轉移溫度。表1、2中,玻璃轉移溫度之單位為℃,線膨脹係數(α1、α2)之單位為ppm/℃。 Glass transfer temperature: A low-pressure transfer molding machine (manufactured by Kohtaki Precision Machine Co., Ltd., KTS-30) was used for insert molding, and the fixing resin was applied under the conditions of a mold temperature of 175 ° C, an injection pressure of 9.8 MPa, and a hardening time of 2 minutes. The composition was subjected to injection molding to obtain a test piece of 4 mm × 4 mm × 15 mm. After the obtained test piece was hardened at 175 ° C for 4 hours, it was subjected to a thermomechanical analysis device (manufactured by Seiko Instruments Inc., TMA100) at a temperature increase rate in a temperature range of 0 ° C to 320 ° C. The measurement was performed at 5 ° C / min, and the linear expansion coefficient (α1) in the region below the glass transition temperature and the linear expansion coefficient (α2) in the rubber-like region were determined based on the graph obtained at this time. At this time, the intersection of the extension lines of α1 and α2 was taken as the glass transition temperature. In Tables 1 and 2, the unit of the glass transition temperature is °C, and the unit of the linear expansion coefficient (α1, α2) is ppm/°C.
抗燃性:將低壓轉移成形機(Kohtaki Precision Machine股份有限公司製造,KTS-30)轉用於嵌入成形, 於模具溫度175℃、注入壓力9.8MPa、注入時間15秒、硬化時間120秒之條件下對固定用樹脂組成物進行注入成形,製作127mm×12.7mm×3.2mm厚之抗燃試片。使用該等試片,依據UL94垂直法之標準進行抗燃試驗,判斷抗燃性。示出抗燃等級等。於本發明中,阻燃性並非必要條件,故而阻燃性只要適宜調整即可。 Flame resistance: The low pressure transfer molding machine (manufactured by Kohtaki Precision Machine Co., Ltd., KTS-30) was used for insert molding. The fixing resin composition was injection molded under the conditions of a mold temperature of 175 ° C, an injection pressure of 9.8 MPa, an injection time of 15 seconds, and a curing time of 120 seconds to prepare a flame resistant test piece of 127 mm × 12.7 mm × 3.2 mm thick. Using these test pieces, the fire resistance test was carried out in accordance with the standard of the UL94 vertical method to judge the flame resistance. The fire resistance rating and the like are shown. In the present invention, the flame retardancy is not a requirement, and therefore the flame retardancy may be appropriately adjusted.
斷裂能a及b:對依據JIS K7162而成形為啞鈴形之轉子固定用樹脂組成物之硬化物(以下記載為試片),於25℃或150℃、負荷速度1.0mm/min之條件下進行拉伸試驗。於該拉伸試驗中,拉伸試驗機使用Orientec公司製造之Tensilon UCT-30T型,應變計使用共和電業公司製造之KFG-2-120-D16-11L1M2R型。 The breaking energy a and b: a cured product (hereinafter referred to as a test piece) of a resin composition for fixing a rotor which is formed into a dumbbell shape according to JIS K7162, and is subjected to a condition of a load rate of 1.0 mm/min at 25 ° C or 150 ° C. Stretching test. In the tensile test, the Tensilon UCT-30T type manufactured by Orientec Co., Ltd. was used for the tensile tester, and the strain gauge was KFG-2-120-D16-11L1M2R type manufactured by Kyowa Electric Co., Ltd.
將拉伸試驗時之正向應力(stress)與正向應變(strein)之關係繪製成曲線(應力-應變曲線)。繼而,將應變作為變數,算出自拉伸試驗之開始點至斷裂點為止之應力之積分值。再者,單位為×10-4J/mm3。 The relationship between the stress and the forward strain at the time of the tensile test is plotted as a curve (stress-strain curve). Then, using strain as a variable, the integral value of the stress from the start point of the tensile test to the breaking point was calculated. Furthermore, the unit is ×10 -4 J/mm 3 .
耐油性:使用成形機(Kohtaki Precision Machine股份有限公司製造,KTS-30),於模具溫度175℃、注入壓力9.8MPa、硬化時間120秒之條件下對固定用樹脂組成物進行注入成形,獲得長度80mm、寬度10mm、厚度4mm之成形品(硬化物)。對所獲得之成形品於175℃下進行4小時加熱處理作為後硬化,以所得者作為試片,依據JIS K 6911,於25℃環境下測定抗彎強度及彎曲彈性模數。繼而,將該試片放入至耐壓容器中,於在耐壓容器中填充有 ATF油(Nissan Matic Fluid D)之狀態下、150℃之溫度下浸漬1000小時後,以與上述相同之方法測定抗彎強度及彎曲彈性模數。將相對於ATF油浸漬前之初始值,變化率在10%以內者評價為○,超過10%者評價為×。 Oil resistance: The molding resin composition was injection-molded at a mold temperature of 175 ° C, an injection pressure of 9.8 MPa, and a curing time of 120 seconds using a molding machine (manufactured by Kohtaki Precision Machine Co., Ltd.) to obtain a length. A molded article (cured product) of 80 mm, a width of 10 mm, and a thickness of 4 mm. The obtained molded article was subjected to heat treatment at 175 ° C for 4 hours for post-hardening, and the obtained product was used as a test piece, and the flexural strength and the flexural modulus were measured in an environment of 25 ° C in accordance with JIS K 6911. Then, the test piece is placed in a pressure-resistant container, and the pressure-resistant container is filled with After immersing for 1000 hours at a temperature of 150 ° C in the state of ATF oil (Nissan Matic Fluid D), the flexural strength and the flexural modulus were measured in the same manner as above. The initial value before the immersion of the ATF oil was evaluated as ○ within 10% of the change rate, and × when it was more than 10%.
ATF浸漬試驗(1000小時):使用成形機(Kohtaki Precision Machine股份有限公司製造,KTS-30),於模具溫度175℃、注入壓力9.8MPa、硬化時間120秒之條件下對固定用樹脂組成物進行注入成形,獲得長度80mm、寬度10mm、厚度4mm之成形品(硬化物)。對所獲得之成形品於175℃下進行4小時加熱處理作為後硬化,以所得者作為試片,測定ATF浸漬前之重量X1、體積Y1。繼而,將該試片放入至耐壓容器中,於填充有ATF之狀態下、150℃下浸漬1000小時。然後,自耐壓容器中取出試片,拭除表面附著之ATF後,測定ATF浸漬後之重量X2、體積Y2,根據下式分別算出ATF浸漬前後之重量變化率及體積變化率。 ATF immersion test (1000 hours): The fixing resin composition was subjected to a molding machine (manufactured by Kohtaki Precision Machine Co., Ltd., KTS-30) at a mold temperature of 175 ° C, an injection pressure of 9.8 MPa, and a curing time of 120 seconds. Injection molding was carried out to obtain a molded article (cured product) having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm. The obtained molded article was subjected to heat treatment at 175 ° C for 4 hours as post-hardening, and the obtained product was used as a test piece, and the weight X1 and volume Y1 before the ATF immersion were measured. Then, the test piece was placed in a pressure-resistant container, and immersed at 150 ° C for 1,000 hours in a state filled with ATF. Then, the test piece was taken out from the pressure-resistant container, and the surface-attached ATF was wiped off, and the weight X2 after the ATF immersion was measured, and the volume Y2 was measured, and the weight change rate and the volume change rate before and after the ATF immersion were calculated according to the following formula.
ATF浸漬前後之重量變化率[%]=(X2-X1)/X1×100 Weight change rate before and after ATF impregnation [%]=(X2-X1)/X1×100
ATF浸漬前後之體積變化率[%]=(Y2-Y1)/Y1×100 Volume change rate before and after ATF impregnation [%]=(Y2-Y1)/Y1×100
再者,ATF係分別使用Matic Fluid D(日產汽車公司製造)、Auto Fluid Type T-IV(豐田汽車公司製造)、ATF DW-1(本田技研工業公司製造)。 Further, the ATF system used Matic Fluid D (manufactured by Nissan Motor Co., Ltd.), Auto Fluid Type T-IV (manufactured by Toyota Motor Corporation), and ATF DW-1 (manufactured by Honda Technik Co., Ltd.).
ATF浸漬試驗(2000小時):除了將在ATF中之浸漬時間變更為2000小時以外,與上述ATF浸漬試驗(1000小時)同樣地分別算出ATF浸漬前後之重量變化率及體積 變化率。 ATF immersion test (2000 hours): The weight change rate and volume before and after ATF immersion were calculated in the same manner as the above ATF immersion test (1000 hours) except that the immersion time in ATF was changed to 2000 hours. Rate of change.
無機填充材料之脫離:於上述ATF浸漬試驗後,過濾ATF油,用顯微鏡確認濾紙上有無無機填充材料。 Detachment of the inorganic filler: After the ATF immersion test described above, the ATF oil was filtered, and the presence or absence of the inorganic filler on the filter paper was confirmed by a microscope.
根據實施列1~6可知,可獲得填充特性、機械特性、耐油性優異,於ATF浸漬試驗中亦表現出良好之特性的固定用樹脂組成物。 According to the first to sixth embodiments, it is possible to obtain a fixing resin composition which is excellent in filling characteristics, mechanical properties, and oil resistance, and which exhibits excellent characteristics in the ATF immersion test.
另外,於環氧樹脂之ICI黏度大於3之比較例1~2中,80μm狹縫流動長度均未達75。如此,比較例1~2中無法獲得具有充分之填充特性的固定用樹脂組成物。 Further, in Comparative Examples 1 to 2 in which the ICI viscosity of the epoxy resin was more than 3, the 80 μm slit flow length was less than 75. Thus, in Comparative Examples 1 and 2, the fixing resin composition having sufficient filling characteristics could not be obtained.
再者,上述實施形態以及多個變化例當然可於其內容不相對立之範圍內加以組合。另外,上述實施形態以及變化例中對各部之結構等進行了具體說明,但其結構等可於滿足本案發明之範圍內進行各種變更。 Furthermore, it is needless to say that the above-described embodiments and a plurality of modifications can be combined in a range in which the contents are not opposed to each other. In the above-described embodiments and modifications, the configuration of each unit and the like are specifically described. However, the configuration and the like can be variously modified within the scope of the present invention.
100‧‧‧轉子 100‧‧‧Rotor
110‧‧‧轉子鐵芯 110‧‧‧Rotor core
120‧‧‧磁鐵 120‧‧‧ magnet
130‧‧‧固定構件 130‧‧‧Fixed components
140‧‧‧填充部 140‧‧‧Filling Department
150‧‧‧孔部 150‧‧‧ hole department
160‧‧‧鉚接部 160‧‧‧Riveting
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI673938B (en) * | 2017-01-11 | 2019-10-01 | 日商豐田自動車股份有限公司 | Rotary electric-machine rotor |
TWI720804B (en) * | 2020-01-31 | 2021-03-01 | 東元電機股份有限公司 | Rotor assembly of permanent magnet motor and rotor end plate |
TWI788709B (en) * | 2019-10-08 | 2023-01-01 | 日商日本製鐵股份有限公司 | Rotor, rotor design method and rotor manufacturing method |
TWI828114B (en) * | 2021-04-14 | 2024-01-01 | 日商日本製鐵股份有限公司 | Subsequent laminated iron core manufacturing method and subsequent laminated iron core manufacturing apparatus |
-
2013
- 2013-05-22 TW TW102118066A patent/TW201444903A/en unknown
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI673938B (en) * | 2017-01-11 | 2019-10-01 | 日商豐田自動車股份有限公司 | Rotary electric-machine rotor |
TWI788709B (en) * | 2019-10-08 | 2023-01-01 | 日商日本製鐵股份有限公司 | Rotor, rotor design method and rotor manufacturing method |
TWI720804B (en) * | 2020-01-31 | 2021-03-01 | 東元電機股份有限公司 | Rotor assembly of permanent magnet motor and rotor end plate |
TWI828114B (en) * | 2021-04-14 | 2024-01-01 | 日商日本製鐵股份有限公司 | Subsequent laminated iron core manufacturing method and subsequent laminated iron core manufacturing apparatus |
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