TW202106889A - Solder paste and flux for solder paste - Google Patents

Solder paste and flux for solder paste Download PDF

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TW202106889A
TW202106889A TW109117353A TW109117353A TW202106889A TW 202106889 A TW202106889 A TW 202106889A TW 109117353 A TW109117353 A TW 109117353A TW 109117353 A TW109117353 A TW 109117353A TW 202106889 A TW202106889 A TW 202106889A
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mass
solder
flux
mass ppm
solder paste
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TW109117353A
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TWI817013B (en
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川浩由
白鳥正人
川又勇司
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日商千住金屬工業股份有限公司
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/26Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C13/00Alloys based on tin
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C13/00Alloys based on tin
    • C22C13/02Alloys based on tin with antimony or bismuth as the next major constituent

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)

Abstract

The present invention adoptes a solder paste containing a specific solder powder and a flux. The solder powder contains a solder alloy which has an alloy composition including: As: 10 mass ppm or more and less than 40 mass ppm, and at least one of Bi: 0 to 10,000 mass ppm, and Pb: 0 to 51,000 mass ppm, and Sb: 0 to 3,000 mass ppm, with the balance of Sn, and satisfies formulas (1) and (2). 300 ≤ 3As+Sb+Bi+Pb (1) 0.1 ≤ {(3As+Sb)/(Bi+Pb)} * 100 ≤ 200 (2) In the formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.

Description

焊料膏及焊料膏用助焊劑 Solder paste and flux for solder paste

本發明係關於焊料膏及焊料膏用助焊劑。本申請案係根據2019年5月27日於日本提出申請之日本特願2019-098936號主張優先權,並在此援引其內容。 The present invention relates to solder paste and flux for solder paste. This application claims priority based on Japanese Patent Application No. 2019-098936 filed in Japan on May 27, 2019, and its content is cited here.

近年來,對於CPU(Central Processing Unit:中央處理單元)等具有焊料接頭之電子裝置,係要求小型化、高性能化。伴隨於此,必須達到印刷電路板與電子裝置之電極的小型化。由於電子裝置係經由電極與印刷電路板連接,所以隨著電極的小型化,連接兩者之焊料接頭亦變小。 In recent years, electronic devices with solder joints such as CPUs (Central Processing Units) have been required to be miniaturized and high-performance. Along with this, it is necessary to achieve miniaturization of the electrodes of printed circuit boards and electronic devices. Since the electronic device is connected to the printed circuit board via the electrode, as the electrode becomes smaller, the solder joint connecting the two becomes smaller.

為了經由如此細微的電極來連接電子裝置與印刷電路板,一般是使用焊料膏。 In order to connect the electronic device and the printed circuit board via such fine electrodes, solder paste is generally used.

焊料膏係藉由印刷等來供給至印刷電路板的電極上。焊料膏的印刷係藉由將設置有開口部之金屬遮罩放置在印刷電路板上,使刮板壓抵於金屬遮罩同時進行移動,以將焊料膏從金屬遮罩的開口部一次性地塗佈於印刷電路板上的電極而進行。 The solder paste is supplied to the electrodes of the printed circuit board by printing or the like. The printing of solder paste is done by placing a metal mask with an opening on the printed circuit board, and pressing the squeegee against the metal mask while moving, so that the solder paste can be removed from the opening of the metal mask at once. It is applied to the electrodes on the printed circuit board.

此外,在購入焊料膏之情形下,通常不會一次印刷就用完全部量的焊料膏。因此,焊料膏必須以不會損及對基板的印刷性能之方式來維持於製造當時的適當黏度。 In addition, when the solder paste is purchased, the entire amount of solder paste is usually not used in one printing. Therefore, the solder paste must maintain the proper viscosity at the time of manufacture in a way that does not impair the printing performance on the substrate.

然而,近年來隨著電極之小型化的進展,焊料膏的印刷面積亦往狹小化進展,所購入之焊料膏至用畢為止的時間亦隨之長期化。焊料膏為焊料粉末與助焊劑經混煉而成者,在歷經長時間的保管期之情形下,視保管狀況,會有焊料膏的黏度上升,而會有無法發揮購入當時的印刷性能的情況。 However, with the progress of miniaturization of electrodes in recent years, the printing area of the solder paste has also been narrowed, and the time required for the purchased solder paste to be used up has also increased for a long time. Solder paste is a mixture of solder powder and flux. After a long storage period, depending on the storage conditions, the viscosity of the solder paste may increase, and the printing performance at the time of purchase may not be exhibited. .

因此,例如於專利文獻1中揭示一種焊料合金,其係為了抑制焊料膏的經時變化,而含有Sn以及選自由Ag、Bi、Sb、Zn、In及Cu所組成群組中的1種或2種以上,並且含有既定量的As。於同一文獻中,係顯示出於25℃下經過2週後的黏度與製作當時的黏度相比為未達140%之結果。 Therefore, for example, Patent Document 1 discloses a solder alloy that contains Sn and one selected from the group consisting of Ag, Bi, Sb, Zn, In, and Cu in order to suppress changes in solder paste over time. Two or more types, and contain a predetermined amount of As. In the same document, it is shown that the viscosity after 2 weeks at 25°C is less than 140% compared to the viscosity at the time of production.

另一方面,焊接(soldering,亦稱軟焊)所使用之助焊劑係具有:將存在於焊料及成為焊接對象之接合對象物的金屬表面之金屬氧化物予以化學性地去除,並使金屬元素可於兩者的交界上移動之效能。因此,藉由使用助焊劑來進行焊接,可於焊料與接合對象物的金屬表面之間形成金屬間化合物,而得到牢固的接合。 On the other hand, the flux used in soldering (also known as soldering) has the ability to chemically remove the metal oxides present on the solder and the metal surface of the joining object to be soldered, and to make the metal elements The ability to move on the boundary between the two. Therefore, by soldering using a flux, an intermetallic compound can be formed between the solder and the metal surface of the joining object, and a strong joint can be obtained.

於含有如此焊接用助焊劑與焊料粉末之焊料膏中,藉由助焊劑所含有之搖變減黏劑(thixotropic agent,又稱觸變劑)來賦予搖變減黏性。搖變減黏劑係於助焊劑中建構網狀結構而賦予搖變減黏性。 In the solder paste containing such soldering flux and solder powder, the thixotropic agent (also called thixotropic agent) contained in the flux is used to impart thixotropic viscosity reduction. The thixotropic viscosity-reducing agent builds a network structure in the flux to give the thixotropic viscosity-reducing property.

[先前技術文獻] [Prior Technical Literature]

[專利文獻] [Patent Literature]

[專利文獻1]日本特開2015-98052號公報 [Patent Document 1] JP 2015-98052 A

如上述般,專利文獻1所記載之發明為除了Sn及As之外可選擇性地含有6種元素之焊料合金。此外,於同一文獻中係顯示出當As含量較多時,則熔融性較差之結果。 As described above, the invention described in Patent Document 1 is a solder alloy that can optionally contain 6 types of elements in addition to Sn and As. In addition, the same literature shows that when the As content is large, the melting property is poor.

在此,咸認於專利文獻1中所評估之熔融性係相當於熔融焊料的潤濕性。於同一文獻中所揭示之熔融性係以顯微鏡來觀察熔融物的外觀,並藉由未完全熔融之焊料粉末的有無來進行評估。此係由於熔融焊料的潤濕性若是愈高,則變得愈難殘存未完全熔融的焊料粉末之故。 Here, it is believed that the meltability evaluated in Patent Document 1 corresponds to the wettability of molten solder. The meltability disclosed in the same document is observed by observing the appearance of the melt with a microscope, and evaluated by the presence or absence of solder powder that is not completely melted. This is because the higher the wettability of the molten solder, the more difficult it is for the solder powder that is not completely molten to remain.

一般而言,為了提升熔融焊料的潤濕性,必須使用高活性的助焊劑。於專利文獻1所記載之助焊劑中,為了抑制由As所造成之潤濕性的劣化,係考量使用高活性的助焊劑。但是,若使用高活性的助焊劑,則會由於焊料合金與活性劑之反應進行而導致膏的黏度上升。此外,有鑑於專利文獻1的記載,為了抑制黏度的上升,必須增加As含量。為了使專利文獻1所記載之焊料膏顯示出更低的黏度上升率及優異的潤濕性,必須持續增加助焊劑的活性力與As含量,因而導致惡性循環。 Generally speaking, in order to improve the wettability of molten solder, a highly active flux must be used. In the flux described in Patent Document 1, in order to suppress the deterioration of wettability caused by As, the use of a highly active flux is considered. However, if a highly active flux is used, the viscosity of the paste will increase due to the progress of the reaction between the solder alloy and the active agent. In addition, in view of the description of Patent Document 1, in order to suppress the increase in viscosity, it is necessary to increase the As content. In order for the solder paste described in Patent Document 1 to exhibit a lower rate of increase in viscosity and excellent wettability, it is necessary to continuously increase the activity of the flux and the As content, which leads to a vicious circle.

近來,對於焊料膏,係要求不受到使用環境和保管環境的影響而長期間維持穩定的性能者,此外,由於焊料接頭的細微化,亦要求更高的潤濕性。在欲使用專利文獻1所記載之焊料膏來對應近來的要求時,係如前述般地無法避免惡性循環。 Recently, solder pastes are required to maintain stable performance over a long period of time without being affected by the use environment and storage environment. In addition, due to the miniaturization of solder joints, higher wettability is also required. When it is desired to use the solder paste described in Patent Document 1 to meet recent demands, the vicious circle cannot be avoided as described above.

再者,為了接合細微的電極,必須提升焊料接頭的機械特性等。因元素的不同,當含量增多時,液相線溫度會上升,而液相線溫度與固相線溫度擴展,於凝固時會偏析而形成不均勻的合金組織。當焊料合金具有如此合金組織時,焊料接頭的拉伸強度等機械特性會劣化,而容易因來自外部的應力而斷裂。此問題係隨著近年來之電極的小型化而變得顯著。 Furthermore, in order to join fine electrodes, the mechanical properties of the solder joint must be improved. Due to the different elements, when the content increases, the liquidus temperature will rise, and the liquidus temperature and the solidus temperature will expand and segregate during solidification to form an uneven alloy structure. When the solder alloy has such an alloy structure, the mechanical properties such as the tensile strength of the solder joint will be deteriorated, and it will be easily broken due to external stress. This problem has become significant with the miniaturization of electrodes in recent years.

除此之外,對於焊料膏,係因應其使用條件或用途等而要求焊料之潤濕速度的提升、接合對象物之金屬表面(例如銅板)的腐蝕抑制、印刷性的提升、空隙(void)抑制等各種特性。 In addition, for solder paste, it is required to increase the wetting speed of the solder, the corrosion inhibition of the metal surface (for example, copper plate) of the joint object, the improvement of the printability, and the void in accordance with its use conditions or applications. Various characteristics such as suppression.

本發明係為了解決上述課題而成者,目的在於提供一種焊料膏,其係不易發生黏度上升等之經時變化,且潤濕性優異,具有高的機械特性,此外,還可以更為提高各種特性者。 The present invention was made in order to solve the above-mentioned problems, and its object is to provide a solder paste that is less prone to changes with time such as viscosity increase, has excellent wettability, and has high mechanical properties. In addition, it can improve various solder pastes. Characteristic.

在同時改善焊料膏之經時變化的抑制與優異的潤濕性時,需避免因使用具有高活性之助焊劑以及As含量的增加所造成之惡性循環。本發明者們係著眼於焊料粉末的合金組成,為了兼顧焊料膏之經時變化的抑制與優異的潤濕性而進行精心探討。 When improving the suppression of solder paste changes over time and excellent wettability at the same time, it is necessary to avoid the vicious circle caused by the use of high-activity fluxes and the increase in As content. The inventors of the present invention focused on the alloy composition of the solder powder, and conducted intensive studies in order to balance the suppression of the change over time of the solder paste and the excellent wettability.

首先,本發明者們係以先前使用作為焊料合金之Sn、SnCu、SnAgCu焊料合金作為基本組成,並探討於此基本組成中含有As之焊料粉末。然後,在使用此焊料粉末之情形下,著眼於抑制焊料膏之經時變化之理由所在,而探討As含量。 First, the inventors used Sn, SnCu, and SnAgCu solder alloys previously used as solder alloys as the basic composition, and explored the basic composition of solder powder containing As. Then, in the case of using this solder powder, the reason for suppressing the change over time of the solder paste is focused on, and the As content is discussed.

焊料膏的黏度之經時上升之理由,咸認係因為焊料粉末與助焊劑進行反應之故。然後,若將專利文獻1的表1之實施例4及比較例2的結果進行 比較,則As含量超過100質量ppm者係顯示出黏度上升率為低之結果。有鑑於此等結果而著眼於抑制焊料膏之經時變化之效果(以下,適當地稱為「增黏抑制效果」)之情形下,似乎可進一步增加As含量。惟於增加As含量之情形下,增黏抑制效果雖然會隨著As含量而略為增加,但所得到之增黏抑制效果並非對應於As含量的增加份額。咸認此係因為於焊料合金的表面所濃化之As量有其限度,因此即使含有既定量以上的As,也只是難以發揮增黏抑制效果之焊料合金內部的As量變多之故。此外,可確認到As含量過多時,焊料合金的潤濕性會惡化。 The reason why the viscosity of the solder paste increases over time is probably due to the reaction between the solder powder and the flux. Then, if the results of Example 4 and Comparative Example 2 in Table 1 of Patent Document 1 are compared By comparison, those with an As content exceeding 100 ppm by mass show a low rate of increase in viscosity. In view of these results, when focusing on the effect of suppressing the change over time of the solder paste (hereinafter, appropriately referred to as the "tackification suppression effect"), it seems that the As content can be further increased. However, in the case of increasing the As content, although the viscosity-increasing suppression effect will slightly increase with the As content, the resulting viscosity-increasing suppression effect does not correspond to the increase in the As content. It is believed that this is because there is a limit to the amount of As concentrated on the surface of the solder alloy. Therefore, even if it contains more than a predetermined amount of As, it is only because the amount of As inside the solder alloy that is difficult to exert the effect of suppressing the increase in viscosity increases. In addition, it can be confirmed that when the As content is too large, the wettability of the solder alloy deteriorates.

因此,本發明者們係想到在將As含量的範圍擴展至以往As含量較少而無法發揮增黏抑制效果的範圍為止之後,需添加As以外的發揮增黏抑制效果之元素,進而探討各種元素。其結果係偶然地發現Sb、Bi及Pb會發揮與As相同之效果。其原因雖尚未明確,但推測如下。 Therefore, the inventors thought that after extending the range of As content to the range where the As content was small and the effect of inhibiting the increase in viscosity would not be exhibited in the past, it was necessary to add elements other than As that exhibit the effect of inhibiting the increase in viscosity, and further explored various elements . As a result, it was accidentally discovered that Sb, Bi, and Pb exert the same effects as As. Although the reason is not clear, it is estimated as follows.

增黏抑制效果是藉由抑制與助焊劑之反應來發揮,所以可列舉出離子化傾向低之元素作為與助焊劑之反應性低的元素。一般而言,合金的離子化係視為合金組成的離子化傾向,亦即標準電極電位。例如含有相對於Sn為高電位的Ag之SnAg合金,較Sn更難以離子化。因此,含有較Sn為高電位的元素之合金難以離子化,而可推測焊料膏的增黏抑制效果為高。 The effect of suppressing thickening is exerted by suppressing the reaction with the flux. Therefore, an element with a low ionization tendency can be cited as an element with a low reactivity with the flux. Generally speaking, the ionization system of the alloy is regarded as the ionization tendency of the alloy composition, that is, the standard electrode potential. For example, SnAg alloys containing Ag, which has a higher potential than Sn, are more difficult to ionize than Sn. Therefore, an alloy containing an element having a higher potential than Sn is difficult to ionize, and it can be presumed that the effect of suppressing thickening of the solder paste is high.

在此,於專利文獻1中,除了Sn、Ag、Cu之外,亦揭示Bi、Sb、Zn及In作為等效元素,惟以離子化傾向來看,此等元素中係以Zn為最低階元素,係較Sn更低階之元素。也就是說,於專利文獻1中係記載有即使添加屬於低階元素之Zn,亦可得到增黏抑制效果之內容。因此,咸認以含有依循離子化 傾向而選擇之元素之焊料合金,係可得到相較於專利文獻1所記載之焊料合金為同等以上的增黏抑制效果。此外,如前述般,As含量增加時會使潤濕性劣化。 Here, in Patent Document 1, in addition to Sn, Ag, Cu, Bi, Sb, Zn, and In are also disclosed as equivalent elements, but in terms of ionization tendency, Zn is the lowest order among these elements. The element is a lower-order element than Sn. That is, Patent Document 1 describes that even if Zn, which is a low-order element, is added, the effect of suppressing thickening can be obtained. Therefore, it is believed to contain following ionization The solder alloy of the element that is tended to be selected can obtain an effect of suppressing viscosity increase which is equal to or higher than that of the solder alloy described in Patent Document 1. In addition, as described above, as the As content increases, the wettability deteriorates.

本發明者們係對發揮增黏抑制效果之Bi及Pb進行仔細探討。由於Bi及Pb會降低焊料合金的液相線溫度,所以在焊料合金的加熱溫度為恆定之情形下,會提升焊料合金的潤濕性。但是,由於其含量的不同會使固相線溫度顯著地降低,所以液相線溫度與固相線溫度之溫度差△T會變得過廣。△T變得過廣時,會致使於凝固時產生偏析,而導致機械強度等機械特性的降低。還發現到在同時添加有Bi及Pb之情形下,△T變廣之現象會顯著地顯現,故需進行嚴加管控。 The inventors carefully studied Bi and Pb, which exert the effect of suppressing viscosity increase. Since Bi and Pb lower the liquidus temperature of the solder alloy, when the heating temperature of the solder alloy is constant, the wettability of the solder alloy will be improved. However, due to the difference in its content, the solidus temperature will be significantly reduced, so the temperature difference ΔT between the liquidus temperature and the solidus temperature will become too wide. When ΔT becomes too wide, it will cause segregation during solidification, resulting in a decrease in mechanical properties such as mechanical strength. It has also been found that when Bi and Pb are added at the same time, the phenomenon of widening of ΔT will appear significantly, so strict control is required.

再者,本發明者們為了提升焊料合金的潤濕性而再次就Bi含量及Pb含量進行研討,惟當此等元素的含量增加時,△T會變廣。於是,本發明者們除了選擇離子化傾向相對於Sn為高電位的元素,還選擇Sb來作為改善焊料合金的潤濕性之元素,在確立Sb含量的容許範圍之前提下,詳細探討包含Sb在內之As、Bi、Pb及Sb各者的含量關係。其結果係偶然地發現到:此等元素之含量在滿足既定關係式的情形下,係增黏抑制效果優異,且潤濕性及△T之窄化於實用上皆不造成問題的程度。 Furthermore, the inventors of the present invention again discussed the Bi content and Pb content in order to improve the wettability of the solder alloy, but when the content of these elements increases, the ΔT becomes wider. Therefore, the inventors selected Sb as an element for improving the wettability of solder alloys in addition to the element whose ionization tendency is higher than that of Sn. Before establishing the allowable range of Sb content, the inventors discussed the inclusion of Sb in detail. The relationship among the contents of As, Bi, Pb and Sb. As a result, it was accidentally discovered that when the content of these elements satisfies the established relational formula, the viscosity increase and suppression effect is excellent, and the wettability and the narrowing of ΔT are not practically problematic.

又發現到藉由選擇調配於與上述焊料合金併用之助焊劑的成分,例如樹脂成分、活性成分或溶劑的種類,可更提高焊料之潤濕速度的提升、接合對象物之金屬表面(例如銅板)的腐蝕抑制、印刷性的提升、空隙抑制等各種特性。 It has also been found that by selecting the components of the flux used in combination with the above-mentioned solder alloys, such as resin components, active components, or solvent types, the wetting speed of the solder can be increased, and the metal surface of the joining object (such as copper plate) can be further improved. ) Corrosion inhibition, printability improvement, void suppression and other characteristics.

藉由此等見解所得到之本發明係如下所述。 The present invention based on these findings is as follows.

[1]一種焊料膏,其係含有焊料粉末與助焊劑, [1] A solder paste containing solder powder and flux,

前述焊料粉末含有焊料合金,該焊料合金係具有由As:10質量ppm以上且未達40質量ppm,以及Bi:0至10000質量ppm、Pb:0至5100質量ppm及Sb:0至3000質量ppm中的至少一種,以及剩餘部分為Sn所構成之合金組成,並滿足下述(1)式及(2)式; The aforementioned solder powder contains a solder alloy, the solder alloy has a composition of As: 10 mass ppm or more and less than 40 mass ppm, and Bi: 0 to 10,000 mass ppm, Pb: 0 to 5100 mass ppm, and Sb: 0 to 3000 mass ppm At least one of them, and the remainder is an alloy composition composed of Sn, and satisfies the following formulas (1) and (2);

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition.

[2]一種焊料膏,其係含有焊料粉末與助焊劑, [2] A solder paste containing solder powder and flux,

前述焊料粉末係含有焊料合金,該焊料合金係具有由As:10質量ppm以上且未達40質量ppm,以及Bi:超過0質量ppm且為10000質量ppm以下、Pb:超過0質量ppm且為5100質量ppm以下及Sb:超過0質量ppm且為3000質量ppm以下中的至少一種,以及剩餘部分為Sn所構成之合金組成,並滿足下述(1)式及(2)式。 The aforementioned solder powder system contains a solder alloy, which has a composition of As: 10 mass ppm or more and less than 40 mass ppm, Bi: more than 0 mass ppm and 10,000 mass ppm or less, and Pb: more than 0 mass ppm and 5100 Mass ppm or less and Sb: at least one of more than 0 mass ppm and 3000 mass ppm or less, and the remainder is an alloy composition composed of Sn, and satisfies the following formulas (1) and (2).

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition.

[3]一種焊料膏,其係含有焊料粉末與助焊劑, [3] A solder paste containing solder powder and flux,

前述焊料粉末係含有焊料合金,該焊料合金具有由As:10質量ppm以上且未達40質量ppm,以及Bi:50至10000質量ppm、Pb:超過0質量ppm且為 5100質量ppm以下及Sb:超過0質量ppm且為3000質量ppm以下中的至少一種,以及剩餘部分為Sn所構成之合金組成,並滿足下述(1)式及(2)式。 The aforementioned solder powder system contains a solder alloy, which has an As: 10 mass ppm or more and less than 40 mass ppm, and Bi: 50 to 10,000 mass ppm, and Pb: more than 0 mass ppm and is 5100 mass ppm or less and Sb: at least one of more than 0 mass ppm and 3000 mass ppm or less, and the remainder is an alloy composition composed of Sn, and satisfies the following formulas (1) and (2).

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition.

[4]一種焊料膏,其係含有焊料粉末與助焊劑, [4] A solder paste containing solder powder and flux,

前述焊料粉末係含有焊料合金,該焊料合金具有由As:10質量ppm以上且未達40質量ppm,以及Bi:超過0質量ppm且為10000質量ppm以下、Pb:50至5100質量ppm及Sb:超過0質量ppm且為3000質量ppm以下中的至少一種,以及剩餘部分為Sn所構成之合金組成,並滿足下述(1)式及(2)式。 The aforementioned solder powder system contains a solder alloy, which has As: 10 mass ppm or more and less than 40 mass ppm, Bi: more than 0 mass ppm and 10,000 mass ppm or less, Pb: 50 to 5100 mass ppm, and Sb: It exceeds 0 mass ppm and is at least one of 3000 mass ppm or less, and the remainder is an alloy composition composed of Sn, and satisfies the following formulas (1) and (2).

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition.

[5]一種焊料膏,其係含有焊料粉末與助焊劑, [5] A solder paste containing solder powder and flux,

前述焊料粉末係含有焊料合金,該焊料合金具有由As:10質量ppm以上且未達40質量ppm,以及Bi:超過0質量ppm且為10000質量ppm以下、Pb:超過0質量ppm且為5100質量ppm以下及Sb:50至3000質量ppm的至少一種,以及剩餘部分為Sn所構成之合金組成,並滿足下述(1)式及(2)式。 The aforementioned solder powder system contains a solder alloy having a composition of As: 10 mass ppm or more and less than 40 mass ppm, Bi: more than 0 mass ppm and 10,000 mass ppm or less, and Pb: more than 0 mass ppm and 5100 mass ppm ppm or less and Sb: at least one of 50 to 3000 mass ppm, and the remainder is an alloy composition composed of Sn, and satisfies the following equations (1) and (2).

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition.

[6]一種焊料膏,其係含有焊料粉末與助焊劑, [6] A solder paste containing solder powder and flux,

前述焊料粉末係含有焊料合金,該焊料合金係具有由As:10質量ppm以上且未達40質量ppm,以及Bi:50至10000質量ppm、Pb:50至5100質量ppm及Sb:超過0質量ppm且為3000質量ppm以下中的至少一種,以及剩餘部分為Sn所構成之合金組成,並滿足下述(1)式及(2)式。 The aforementioned solder powder system contains a solder alloy, the solder alloy system has As: 10 mass ppm or more and less than 40 mass ppm, and Bi: 50 to 10,000 mass ppm, Pb: 50 to 5100 mass ppm, and Sb: more than 0 mass ppm It is at least one of 3000 mass ppm or less, and the remainder is an alloy composition composed of Sn, and satisfies the following formulas (1) and (2).

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition.

[7]一種焊料膏,其係含有焊料粉末與助焊劑, [7] A solder paste containing solder powder and flux,

前述焊料粉末係含有焊料合金,該焊料合金係具有由As:10質量ppm以上且未達40質量ppm,以及Bi:超過0質量ppm且為10000質量ppm以下、Pb:50至5100質量ppm及Sb:50至3000質量ppm中的至少一種,以及剩餘部分為Sn所構成之合金組成,並滿足下述(1)式及(2)式。 The aforementioned solder powder system contains a solder alloy, and the solder alloy system is composed of As: 10 mass ppm or more and less than 40 mass ppm, Bi: more than 0 mass ppm and 10,000 mass ppm or less, Pb: 50 to 5100 mass ppm and Sb : At least one of 50 to 3000 mass ppm, and the remainder is an alloy composition composed of Sn, and satisfies the following equations (1) and (2).

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition.

[8]一種焊料膏,其係含有焊料粉末與助焊劑, [8] A solder paste containing solder powder and flux,

前述焊料粉末係含有焊料合金,該焊料合金係具有由As:10質量ppm以上且未達40質量ppm,以及Bi:50至10000質量ppm、Pb:超過0質量ppm且為5100質量ppm以下及Sb:50至3000質量ppm中的至少一種,以及剩餘部分為Sn所構成之合金組成,並滿足下述(1)式及(2)式。 The aforementioned solder powder system contains a solder alloy which has a composition consisting of As: 10 mass ppm or more and less than 40 mass ppm, Bi: 50 to 10,000 mass ppm, Pb: more than 0 mass ppm and less than 5100 mass ppm, and Sb : At least one of 50 to 3000 mass ppm, and the remainder is an alloy composition composed of Sn, and satisfies the following equations (1) and (2).

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition.

[9]一種焊料膏,其係含有焊料粉末與助焊劑, [9] A solder paste containing solder powder and flux,

前述焊料粉末係含有焊料合金,該焊料合金係具有由As:10質量ppm以上且未達40質量ppm,以及Bi:50至10000質量ppm、Pb:50至5100質量ppm及Sb:50至3000質量ppm中的至少一種,以及剩餘部分為Sn所構成之合金組成,並滿足下述(1)式及(2)式。 The aforementioned solder powder system contains a solder alloy having a composition of As: 10 mass ppm or more and less than 40 mass ppm, and Bi: 50 to 10,000 mass ppm, Pb: 50 to 5100 mass ppm, and Sb: 50 to 3000 mass ppm At least one of ppm and the remainder are alloy compositions composed of Sn, and satisfy the following formulas (1) and (2).

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition.

[10]如上述[1]至[9]中任一項所述之焊料膏,其中,前述助焊劑係含有樹脂成分、活性成分及溶劑。 [10] The solder paste according to any one of [1] to [9] above, wherein the flux system contains a resin component, an active component, and a solvent.

[11]如上述[10]所述之焊料膏,其中,前述助焊劑係含有受阻酚系化合物。 [11] The solder paste according to the above [10], wherein the flux system contains a hindered phenol compound.

[12]如上述[10]所述之焊料膏,其中,前述助焊劑係含有屬於氮化合物之金屬減活劑。 [12] The solder paste described in [10] above, wherein the flux contains a metal deactivator which is a nitrogen compound.

[13]如上述[10]所述之焊料膏,其中,前述助焊劑係含有酸改質松香。 [13] The solder paste according to the above [10], wherein the flux system contains acid-modified rosin.

[14]如上述[10]所述之焊料膏,其中,前述助焊劑係含有丙烯酸系樹脂。 [14] The solder paste according to [10] above, wherein the flux system contains acrylic resin.

[15]如上述[10]所述之焊料膏,其中,前述助焊劑係含有:選自由屬於單羧酸的反應物且為二聚物之二聚物酸、將氫添加於二聚物酸而得之氫化二聚物酸、屬於單羧酸的反應物且為三聚物之三聚物酸、以及將氫添加於三聚物酸而得之氫化三聚物酸所組成群組中之至少一種有機酸。 [15] The solder paste described in [10] above, wherein the flux system contains dimer acids selected from reactants belonging to monocarboxylic acids and dimers, and hydrogen is added to the dimer acid The resulting hydrogenated dimer acid, the trimeric acid that is a reactant of monocarboxylic acid and is a trimer, and the hydrogenated trimer acid obtained by adding hydrogen to the trimer acid are among the group consisting of At least one organic acid.

[16]如上述[10]所述之焊料膏,其中,前述助焊劑含有以下述通式(1)所表示之化合物, [16] The solder paste described in [10] above, wherein the flux contains a compound represented by the following general formula (1),

Figure 109117353-A0202-12-0011-143
Figure 109117353-A0202-12-0011-143

式(1)中,R1、R2、R3及R4各自獨立地表示氫原子或碳數1至4的烷基。 In formula (1), R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[17]如上述[10]所述之焊料膏,其中,前述助焊劑含有唑(Azole)類。 [17] The solder paste according to the above [10], wherein the soldering flux contains Azoles.

[18]如上述[10]所述之焊料膏,其中,前述助焊劑含有芳香族胍化合物。 [18] The solder paste according to the above [10], wherein the flux contains an aromatic guanidine compound.

[19]如上述[10]所述之焊料膏,其中,前述助焊劑含有屬於醯胺化合物之醯胺系搖變減黏劑。 [19] The solder paste according to the above [10], wherein the flux contains an amide-based thixotropic agent which is an amide compound.

[20]如上述[10]所述之焊料膏,其中,前述助焊劑含有屬於山梨醇(sorbitol)化合物之山梨醇系搖變減黏劑。 [20] The solder paste described in [10] above, wherein the flux contains a sorbitol-based thixotropic agent which is a sorbitol compound.

[21]如上述[10]所述之焊料膏,其中,前述助焊劑一併具有二醇(glycol)系溶劑與有機酸酯。 [21] The solder paste according to the above [10], wherein the soldering flux includes a glycol-based solvent and an organic acid ester.

[22]如上述[10]所述之焊料膏,其中,前述助焊劑一併具有二醇系溶劑與碳數16至18的一元醇。 [22] The solder paste according to the above [10], wherein the flux includes a glycol solvent and a monohydric alcohol having 16 to 18 carbon atoms.

[23]如上述[1]至[22]中任一項所述之焊料膏,其係更含有氧化鋯粉末。 [23] The solder paste described in any one of [1] to [22] above, which further contains zirconia powder.

[24]一種焊料膏用助焊劑,其係使用在焊料膏之助焊劑,前述焊料膏係含有包含焊料合金之焊料粉末,該焊料合金具有由As:10質量ppm以上且未達40質量ppm,以及Bi:0至10000質量ppm、Pb:0至5100質量ppm及Sb:0至3000質量ppm中的至少一種,以及剩餘部分為Sn所構成之合金組成,並且滿足下述(1)式及(2)式。 [24] A flux for solder paste, which is a flux used in solder paste, said solder paste containing solder powder containing a solder alloy, the solder alloy having As: 10 mass ppm or more and less than 40 mass ppm, And Bi: at least one of 0 to 10000 mass ppm, Pb: 0 to 5100 mass ppm, and Sb: 0 to 3000 mass ppm, and the remainder is an alloy composition composed of Sn, and satisfies the following formula (1) and ( 2) Type.

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition.

[25]一種焊料膏用助焊劑,其係使用在焊料膏之助焊劑,前述焊料膏係含有包含焊料合金之焊料粉末,該焊料合金具有由As:10質量ppm以上且未達40質量ppm,以及Bi:超過0質量ppm且為10000質量ppm以下、Pb: 超過0質量ppm且為5100質量ppm以下及Sb:超過0質量ppm且為3000質量ppm以下中的至少一種,以及剩餘部分為Sn所構成之合金組成,並且滿足下述(1)式及(2)式。 [25] A flux for solder paste, which is a flux used in solder paste, said solder paste containing solder powder containing a solder alloy, the solder alloy having As: 10 mass ppm or more and less than 40 mass ppm, And Bi: more than 0 mass ppm and less than 10000 mass ppm, Pb: More than 0 mass ppm and less than 5100 mass ppm and Sb: at least one of more than 0 mass ppm and less than 3000 mass ppm, and the remainder is an alloy composition composed of Sn, and satisfies the following formula (1) and (2) )formula.

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition.

根據本發明,可提供一種焊料膏及焊料膏用助焊劑,該焊料膏不易發生黏度上升等之經時變化,潤濕性優異,具有高的機械特性,除此之外,可更提高各種特性。 According to the present invention, it is possible to provide a solder paste and a flux for solder paste, which are less prone to changes with time such as increase in viscosity, are excellent in wettability, and have high mechanical properties. In addition, various properties can be improved. .

以下詳細說明本發明。 The present invention will be described in detail below.

於本說明書中,與焊料合金組成相關之「ppm」在未特別指定時為「質量ppm」。「%」在未特別指定時為「質量%」。 In this manual, "ppm" related to solder alloy composition is "mass ppm" unless otherwise specified. "%" is "mass%" when it is not specified.

<焊料膏> <Solder Paste>

本實施型態之焊料膏係含有特定的焊料粉末與助焊劑。 The solder paste of this embodiment contains specific solder powder and flux.

《焊料粉末》 "Solder Powder"

使用在本實施型態之焊料膏之焊料粉末係含有焊料合金,該焊料合金具有由As:10質量ppm以上且未達40質量ppm,以及Bi:0至10000質量ppm、 Pb:0至5100質量ppm及Sb:0至3000質量ppm中的至少一種,以及剩餘部分為Sn所構成之合金組成,並滿足下述(1)式及(2)式。 The solder powder of the solder paste used in this embodiment contains a solder alloy, which has As: 10 mass ppm or more and less than 40 mass ppm, and Bi: 0 to 10,000 mass ppm, Pb: at least one of 0 to 5100 ppm by mass and Sb: 0 to 3000 ppm by mass, and the remainder is an alloy composition composed of Sn, and satisfies the following equations (1) and (2).

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition.

1.合金組成 1. Alloy composition

(1)As:10質量ppm以上且未達40質量ppm (1) As: 10 mass ppm or more and less than 40 mass ppm

As為可抑制焊料膏的黏度之經時變化之元素。 As is an element that can suppress the change in the viscosity of the solder paste over time.

由於As係與助焊劑之反應性低且相對於Sn為高電位的元素,故推測其可發揮增黏抑制效果。As未達10質量ppm時,無法充分地發揮增黏抑制效果。As含量的下限為10質量ppm以上,較佳為14質量ppm以上。 Since As is an element with low reactivity with flux and a high potential relative to Sn, it is speculated that it can exert an effect of suppressing viscosity increase. When As is less than 10 mass ppm, the effect of suppressing thickening cannot be sufficiently exhibited. The lower limit of the As content is 10 mass ppm or more, preferably 14 mass ppm or more.

另一方面,As過多時,會由於助焊劑的活性而使得焊料合金之潤濕性劣化。As含量的上限為未達40質量ppm,較佳為38質量ppm以下,更佳為未達25質量ppm,又更佳為24質量ppm以下,特佳為18質量ppm以下。 On the other hand, when there is too much As, the wettability of the solder alloy will deteriorate due to the activity of the flux. The upper limit of the As content is less than 40 mass ppm, preferably 38 mass ppm or less, more preferably less than 25 mass ppm, still more preferably 24 mass ppm or less, and particularly preferably 18 mass ppm or less.

(2)Bi:0至10000質量ppm、Pb:0至5100質量ppm及Sb:0至3000質量ppm中的至少一種 (2) Bi: at least one of 0 to 10000 mass ppm, Pb: 0 to 5100 mass ppm, and Sb: 0 to 3000 mass ppm

Sb係與助焊劑之反應性低並顯示出增黏抑制效果之元素。 Sb is an element that has low reactivity with flux and exhibits an effect of suppressing viscosity increase.

於本發明中,焊料合金含有Sb的情況下,Sb含量的下限為0質量ppm以上,可超過0質量ppm,亦可為50質量ppm以上。此外,Sb含量較佳為82質量ppm以上,更佳為123質量ppm以上,又更佳為150質量ppm以上。 In the present invention, when the solder alloy contains Sb, the lower limit of the Sb content is 0 mass ppm or more, may exceed 0 mass ppm, or may be 50 mass ppm or more. In addition, the Sb content is preferably 82 mass ppm or more, more preferably 123 mass ppm or more, and still more preferably 150 mass ppm or more.

另一方面,當Sb含量過多時,潤濕性會劣化,故需設為適當的含量。Sb含量的上限為3000質量ppm以下,較佳為1000質量ppm以下,更佳為700質量ppm以下,又更佳為300質量ppm以下。 On the other hand, when the Sb content is too large, the wettability deteriorates, so it needs to be set to an appropriate content. The upper limit of the Sb content is 3000 mass ppm or less, preferably 1000 mass ppm or less, more preferably 700 mass ppm or less, and still more preferably 300 mass ppm or less.

Bi及Pb係與Sb同樣為與助焊劑之反應性低並顯示出增黏抑制效果之元素。此外,Bi及Pb係降低焊料合金的液相線溫度,同時使熔融焊料的黏性降低,故為可抑制由As所致之潤濕性的劣化之元素。若存在有Sb、Bi及Pb的至少一種,則可抑制由As所致之潤濕性的劣化。 Bi and Pb are elements that have low reactivity with flux and exhibit a viscosity-inhibiting effect like Sb. In addition, Bi and Pb are elements that lower the liquidus temperature of the solder alloy and at the same time reduce the viscosity of the molten solder, so that the deterioration of the wettability caused by As can be suppressed. If at least one of Sb, Bi, and Pb is present, the deterioration of wettability due to As can be suppressed.

在本發明之焊料合金含有Bi之情形下,Bi含量的下限為0質量ppm以上,可超過0質量ppm,亦可為50質量ppm以上。Bi含量較佳為82質量ppm以上,更佳為123質量ppm以上,又更佳為150質量ppm以上。 When the solder alloy of the present invention contains Bi, the lower limit of the Bi content is 0 mass ppm or more, may exceed 0 mass ppm, or may be 50 mass ppm or more. The Bi content is preferably 82 mass ppm or more, more preferably 123 mass ppm or more, and still more preferably 150 mass ppm or more.

在本發明之焊料合金含有Pb之情形下,Pb含量的下限為0質量ppm以上,可超過0質量ppm,亦可為50質量ppm以上。Pb含量較佳為82質量ppm以上,更佳為123質量ppm以上,又更佳為150質量ppm以上,最佳為250質量ppm以上。 When the solder alloy of the present invention contains Pb, the lower limit of the Pb content is 0 mass ppm or more, may exceed 0 mass ppm, or may be 50 mass ppm or more. The Pb content is preferably 82 mass ppm or more, more preferably 123 mass ppm or more, still more preferably 150 mass ppm or more, and most preferably 250 mass ppm or more.

另一方面,此等元素的含量過多時,由於固相線溫度顯著地降低,所以液相線溫度與固相線溫度之溫度差的△T變得過廣。△T變得過廣時,於熔融焊料的凝固過程中Bi或Pb的含量少之高熔點的結晶相析出,使液相的Bi或Pb濃縮。之後在熔融焊料的溫度進一步降低時,Bi或Pb的濃度高之低熔點的結晶相產生偏析。因此,焊料合金的機械強度等產生劣化,可靠度變差。尤其是Bi濃度高之結晶相硬且易碎,於焊料合金中產生偏析時,可靠度顯著的降低。 On the other hand, when the content of these elements is too large, the solidus temperature decreases significantly, so the ΔT of the temperature difference between the liquidus temperature and the solidus temperature becomes too wide. When ΔT becomes too wide, during the solidification process of the molten solder, a high melting point crystal phase with a small content of Bi or Pb is precipitated, and the liquid phase of Bi or Pb is concentrated. Then, when the temperature of the molten solder is further reduced, a crystal phase with a high Bi or Pb concentration and a low melting point segregates. Therefore, the mechanical strength of the solder alloy is deteriorated, and the reliability is deteriorated. In particular, the crystalline phase with high Bi concentration is hard and fragile, and when segregation occurs in the solder alloy, the reliability is significantly reduced.

從此觀點來看,在本發明之焊料合金含有Bi之情形下,Bi含量的上限為10000質量ppm以下,較佳為5000質量ppm以下,更佳為1000質量ppm以下,又更佳為300質量ppm以下。 From this point of view, when the solder alloy of the present invention contains Bi, the upper limit of the Bi content is 10000 mass ppm or less, preferably 5000 mass ppm or less, more preferably 1000 mass ppm or less, and still more preferably 300 mass ppm the following.

在本發明之焊料合金含有Pb之情形下,Pb含量的上限為5100質量ppm以下,較佳為5000質量ppm以下,更佳為1000質量ppm以下,又更佳為500質量ppm以下,特佳為350質量ppm以下,最佳為300質量ppm以下。 In the case where the solder alloy of the present invention contains Pb, the upper limit of the Pb content is 5100 mass ppm or less, preferably 5000 mass ppm or less, more preferably 1000 mass ppm or less, still more preferably 500 mass ppm or less, particularly preferably 350 mass ppm or less, preferably 300 mass ppm or less.

(3)(1)式 (3)(1)

本發明之焊料合金必須滿足下述(1)式。 The solder alloy of the present invention must satisfy the following formula (1).

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

上述(1)式中,As、Sb、Bi及Pb各自表示合金組成中的含量(質量ppm)。 In the above formula (1), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.

As、Sb、Bi及Pb皆為顯示出增黏抑制效果之元素,此等之合計必須為300質量ppm以上。 As, Sb, Bi, and Pb are all elements exhibiting a thickening suppression effect, and the total of these must be 300 mass ppm or more.

於(1)式中,將As含量設為3倍者係在含有Sb、Bi及Pb的至少一種之情形下,由於As含量係較此等的含量少,而且,與Sb、Bi和Pb相比,As之增黏抑制效果較高。 In the formula (1), the As content is set to 3 times when it contains at least one of Sb, Bi, and Pb, because the As content is less than these, and it is in phase with Sb, Bi, and Pb. Compared with, As has a higher viscosity increasing and inhibiting effect.

(1)式在未達300時,係未充分地發揮增黏抑制效果。(1)式的下限為300以上,較佳為318以上,更佳為360以上,又更佳為392以上,特佳為464以上,最佳為714以上。另一方面,從增黏抑制效果之觀點來看,(1)式的上限雖無特別限定,惟從將△T設為適合的範圍之觀點來看,較佳為18214以下,更佳為15130以下,又更佳為11030以下,特佳為6214以下。 When the formula (1) is less than 300, the viscosity increase suppression effect is not sufficiently exhibited. The lower limit of the formula (1) is 300 or more, preferably 318 or more, more preferably 360 or more, still more preferably 392 or more, particularly preferably 464 or more, and most preferably 714 or more. On the other hand, from the viewpoint of the thickening suppression effect, the upper limit of the formula (1) is not particularly limited, but from the viewpoint of setting ΔT in a suitable range, it is preferably 18214 or less, more preferably 15130 Hereinafter, it is more preferably 11030 or less, and particularly preferably 6,214 or less.

又,由於As含量的上限未達40質量ppm,所以本發明之焊料合金係含有合計多於180質量ppm之Sb、Bi及Pb的至少一種。如此,於本發明 中雖然As含量少,但Sb、Bi及Pb的含量設定為較多而發揮充分的增黏抑制效果。在皆不含有Sb、Bi及Pb之情形下,焊料膏的黏度會立即增加。從上述的較佳樣態中適當地選擇之上限者係下述(1a)式。 In addition, since the upper limit of the As content is less than 40 mass ppm, the solder alloy of the present invention contains at least one of Sb, Bi, and Pb in a total of more than 180 mass ppm. So, in the present invention Although the As content is small, the content of Sb, Bi, and Pb is set to be large to exhibit a sufficient viscosity increase inhibitory effect. In the absence of Sb, Bi, and Pb, the viscosity of the solder paste will increase immediately. The upper limit appropriately selected from the above-mentioned preferable aspects is the following formula (1a).

300≦3As+Sb+Bi+Pb≦18214 (1a) 300≦3As+Sb+Bi+Pb≦18214 (1a)

上述(1a)式中,As、Sb、Bi及Pb各自表示合金組成中的含量(質量ppm)。 In the above formula (1a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.

(4)(2)式 (4)(2)

本發明之焊料合金必須滿足下述(2)式。 The solder alloy of the present invention must satisfy the following formula (2).

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(2)式中,As、Sb、Bi及Pb各自表示合金組成中的含量(質量ppm)。 In the above formula (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.

當As及Sb之含量多時,焊料合金之潤濕性會劣化。另一方面,Bi及Pb雖會抑制因含有As所致之潤濕性劣化,惟當含量過多時,△T會變廣,所以必須嚴加管控。尤其在同時含有Bi及Pb之合金組成中,△T係容易變廣。也就是說,如欲增加Bi及Pb之含量以過度改善潤濕性,則會導致△T變廣。另一方面,如欲增加As、Sb之含量以改善增黏抑制效果,則會導致潤濕性劣化。於是,在本發明中,係分為As及Sb之群組、和Bi及Pb之群組,而當兩群組之合計量在合適的既定範圍內時,係同時滿足增黏抑制效果、△T之窄化、及潤濕性的全部。 When the content of As and Sb is high, the wettability of the solder alloy will deteriorate. On the other hand, although Bi and Pb can suppress the deterioration of wettability due to the content of As, when the content is too large, the ΔT will become wider, so strict control must be exercised. Especially in an alloy composition containing both Bi and Pb, the ΔT system tends to become wider. In other words, if you want to increase the content of Bi and Pb to improve the wettability too much, ΔT will become wider. On the other hand, if the content of As and Sb is to be increased to improve the effect of inhibiting viscosity increase, the wettability will deteriorate. Therefore, in the present invention, it is divided into the group of As and Sb, and the group of Bi and Pb, and when the total amount of the two groups is within an appropriate predetermined range, the viscosity increase suppression effect, △ All of the narrowing and wettability of T.

(2)式未達0.1時,Bi及Pb之含量的合計與As及Sb之含量的合計相比,係變得相對較多,故△T會變廣。(2)式之下限為0.1以上,較佳為0.2以上,更佳為0.3以上,又更佳為0.5以上,特佳為0.8以上,最佳為10.3以上。 (2) When the formula is less than 0.1, the sum of the contents of Bi and Pb becomes relatively larger than the sum of the contents of As and Sb, so ΔT becomes wider. (2) The lower limit of the formula is 0.1 or more, preferably 0.2 or more, more preferably 0.3 or more, still more preferably 0.5 or more, particularly preferably 0.8 or more, and most preferably 10.3 or more.

另一方面,當(2)式超過200時,As及Sb之含量的合計與Bi及Pb之含量的合計相比,係變得相對較多,故潤濕性會劣化。(2)之上限為200以下,較 佳為192.7以下,更佳為158.5以下,又更佳為143.9以下,再更佳為102.0以下,特佳為96.0以下。 On the other hand, when the formula (2) exceeds 200, the total content of As and Sb becomes relatively larger than the total content of Bi and Pb, and therefore the wettability deteriorates. (2) The upper limit is 200 or less, compared with It is preferably 192.7 or less, more preferably 158.5 or less, still more preferably 143.9 or less, still more preferably 102.0 or less, particularly preferably 96.0 or less.

又,(2)式之分母為「Bi+Pb」,若未含此等元素,則(2)式不成立。亦即,本發明中之合金必含有Bi及Pb中之至少一種。未含有Bi及Pb之合金組成係如前述般,為潤濕性差。 In addition, the denominator of formula (2) is "Bi+Pb". If these elements are not included, formula (2) does not hold. That is, the alloy in the present invention must contain at least one of Bi and Pb. The alloy composition that does not contain Bi and Pb is as described above, and has poor wettability.

從上述的較佳樣態中適當地選擇之上限者係下述(2a)式。 The upper limit appropriately selected from the above-mentioned preferred aspects is the following formula (2a).

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦158.5 (2a) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦158.5 (2a)

上述(2a)式中,As、Sb、Bi及Pb各自表示合金組成中的含量(質量ppm)。 In the above formula (2a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the alloy composition.

(5)Ni:0至600質量ppm、Fe:0至100質量ppm (5) Ni: 0 to 600 mass ppm, Fe: 0 to 100 mass ppm

Fe與Ni為可抑制金屬間化合物的生長之任意元素。 Fe and Ni are arbitrary elements that can inhibit the growth of intermetallic compounds.

在本發明之焊料合金接合Cu電極之情形下、或是如後述般含有Cu之情形下,Ni可將接合界面上所形成之Cu6Sn5層轉化為(Cu,Ni)6Sn5層,而薄化金屬間化合物層的膜厚。此外,Fe於熔融焊料的凝固時可促進晶核的生成而抑制Cu6Sn5、Cu3Sn、Ag3Sn等金屬間化合物相的生長。若此等元素的含量於既定範圍內,則液相線溫度不會過度地上升,△T會位在容許範圍內,而能夠維持高的機械特性。 In the case where the solder alloy of the present invention is joined to Cu electrodes, or when Cu is contained as described later, Ni can convert the Cu 6 Sn 5 layer formed on the joint interface into a (Cu,Ni) 6 Sn 5 layer, And thin the film thickness of the intermetallic compound layer. In addition, Fe can promote the formation of crystal nuclei during the solidification of molten solder and inhibit the growth of intermetallic compound phases such as Cu 6 Sn 5 , Cu 3 Sn, and Ag 3 Sn. If the content of these elements is within the predetermined range, the liquidus temperature will not rise excessively, ΔT will be within the allowable range, and high mechanical properties can be maintained.

在本發明之焊料合金含有Ni之情形下,Ni含量的上限較佳為600質量ppm以下,更佳為500質量ppm以下,又更佳為100質量ppm以下,特佳為50質量ppm以下。 When the solder alloy of the present invention contains Ni, the upper limit of the Ni content is preferably 600 mass ppm or less, more preferably 500 mass ppm or less, still more preferably 100 mass ppm or less, and particularly preferably 50 mass ppm or less.

在本發明之焊料合金含有Fe之情形下,Fe含量的上限較佳為100質量ppm以下,更佳為80質量ppm以下,又更佳為50質量ppm以下。 In the case where the solder alloy of the present invention contains Fe, the upper limit of the Fe content is preferably 100 mass ppm or less, more preferably 80 mass ppm or less, and still more preferably 50 mass ppm or less.

Ni與Fe之含量的下限並無特別限定,惟為了充分地發揮抑制金屬間化合物的生長之效果,Ni含量的下限較佳為10質量ppm以上,更佳為40質量ppm以上。Fe含量的下限較佳為10質量ppm以上,更佳為20質量ppm以上。 The lower limit of the content of Ni and Fe is not particularly limited, but in order to fully exhibit the effect of inhibiting the growth of intermetallic compounds, the lower limit of the content of Ni is preferably 10 mass ppm or more, more preferably 40 mass ppm or more. The lower limit of the Fe content is preferably 10 mass ppm or more, more preferably 20 mass ppm or more.

(6)In:0至1200質量ppm (6) In: 0 to 1200 mass ppm

In為Sn的固溶強化型元素體,故為可維持高的機械特性之任意元素。若In含量於既定範圍內,則△T會位在容許範圍內,而能夠維持高的機械特性。 In is a solid solution strengthening element body of Sn, so it is an arbitrary element that can maintain high mechanical properties. If the In content is within the predetermined range, ΔT will be within the allowable range, and high mechanical properties can be maintained.

在本發明之焊料合金含有In之情形下,In含量的上限較佳為1200質量ppm以下,更佳為100質量ppm以下。 In the case where the solder alloy of the present invention contains In, the upper limit of the In content is preferably 1200 ppm by mass or less, more preferably 100 ppm by mass or less.

In含量的下限並無特別限定,惟為了充分地形成固溶體,較佳為20質量ppm以上,更佳為30質量ppm以上,又更佳為50質量ppm以上。 The lower limit of the In content is not particularly limited, but in order to sufficiently form a solid solution, it is preferably 20 mass ppm or more, more preferably 30 mass ppm or more, and still more preferably 50 mass ppm or more.

(7)Ni:0至600質量ppm、Fe:0至100質量ppm及In:0至1200質量ppm中的至少兩種 (7) At least two of Ni: 0 to 600 mass ppm, Fe: 0 to 100 mass ppm, and In: 0 to 1200 mass ppm

若Ni、Fe及In的各含量於既定範圍內,則△T容易位於容許範圍內,而可維持高的機械特性。於本發明中,係可在既定範圍內含有此等中的至少兩種以上,亦可同時含有三種。 If the contents of Ni, Fe, and In are within a predetermined range, ΔT is easily within the allowable range, and high mechanical properties can be maintained. In the present invention, at least two or more of these may be contained within a predetermined range, or three of them may be contained at the same time.

(8)Ni:0至600質量ppm及Fe:0至100質量ppm,以及(3)式 (8) Ni: 0 to 600 mass ppm and Fe: 0 to 100 mass ppm, and (3) formula

本發明之焊料合金較佳係含有既定量的Ni及Fe,並且滿足下述(3)式。 The solder alloy of the present invention preferably contains a predetermined amount of Ni and Fe, and satisfies the following formula (3).

0≦Ni/Fe≦50 (3) 0≦Ni/Fe≦50 (3)

(3)式中,Ni及Fe各自表示合金組成中的含量(質量ppm)。 (3) In the formula, Ni and Fe each represent the content (mass ppm) in the alloy composition.

Fe與Ni可抑制金屬間化合物的生長,惟Ni可抑制接合界面之金屬間化合物層的生長,Fe可抑制焊料合金中之金屬間化合物相的生長。為了抑 制焊料接頭全體之金屬間化合物的生長,兩元素的含量較佳係具有某種程度的均衡。 Fe and Ni can inhibit the growth of intermetallic compounds, but Ni can inhibit the growth of the intermetallic compound layer at the joint interface, and Fe can inhibit the growth of the intermetallic compound phase in the solder alloy. In order to restrain For the growth of the intermetallic compound in the entire solder joint, the content of the two elements is preferably balanced to a certain extent.

本發明之焊料合金除了含有既定量的Ni及Fe之外,較佳係滿足(3)式。為了發揮此效果,(3)式的下限較佳為0以上,更佳為0.1以上,又更佳為2以上,特佳為7.5以上。(3)式的上限較佳為50以下,更佳為10以下,又更佳為8.0以下。 The solder alloy of the present invention preferably satisfies formula (3) in addition to containing a predetermined amount of Ni and Fe. In order to exert this effect, the lower limit of the formula (3) is preferably 0 or more, more preferably 0.1 or more, still more preferably 2 or more, and particularly preferably 7.5 or more. The upper limit of the formula (3) is preferably 50 or less, more preferably 10 or less, and still more preferably 8.0 or less.

本發明之焊料合金係為了抑制金屬間化合物的生長,並且液相線溫度不會過度地上升,使△T位於容許範圍內而維持高的機械特性,較佳係更滿足下述(4)式。 In order to suppress the growth of intermetallic compounds, the solder alloy of the present invention does not increase the liquidus temperature excessively, keeps ΔT within the allowable range and maintains high mechanical properties, and preferably satisfies the following formula (4) .

0≦Ni+Fe≦680 (4) 0≦Ni+Fe≦680 (4)

(4)式中,Ni及Fe各自表示合金組成中的含量(質量ppm)。 (4) In the formula, Ni and Fe each represent the content (mass ppm) in the alloy composition.

為了抑制金屬間化合物的生長,(4)式的下限較佳為0以上,更佳為20以上,又更佳為40以上,特佳為50以上,最佳為60以上。 In order to suppress the growth of intermetallic compounds, the lower limit of the formula (4) is preferably 0 or more, more preferably 20 or more, still more preferably 40 or more, particularly preferably 50 or more, and most preferably 60 or more.

此外,為了不使液相線溫度過度地上升,(4)式的上限較佳為680以下,更佳為500以下,又更佳為200以下,特佳為150以下,最佳為110以下。 In addition, in order not to increase the liquidus temperature excessively, the upper limit of the formula (4) is preferably 680 or less, more preferably 500 or less, still more preferably 200 or less, particularly preferably 150 or less, and most preferably 110 or less.

(9)Ag:0至4質量%及Cu:0至0.9質量%中的至少一種 (9) At least one of Ag: 0 to 4% by mass and Cu: 0 to 0.9% by mass

Ag為於結晶界面形成Ag3Sn而能夠提升焊料合金的可靠性之任意元素。此外,Ag為離子化傾向相對於Sn為高電位之元素,藉由使As、Pb及Bi共存,可助長此等之增黏抑制效果。 Ag is an arbitrary element that forms Ag 3 Sn at the crystal interface and can improve the reliability of the solder alloy. In addition, Ag is an element that tends to ionize and has a higher potential than Sn. Coexistence of As, Pb, and Bi can contribute to these thickening inhibitory effects.

Ag含量的下限較佳為0質量%以上,更佳為0.5質量%以上,又更佳1.0質量%以上。Ag含量的上限較佳為4質量%以下,更佳為3.5質量%以下,又更佳為3.0質量%以下。 The lower limit of the Ag content is preferably 0% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more. The upper limit of the Ag content is preferably 4% by mass or less, more preferably 3.5% by mass or less, and still more preferably 3.0% by mass or less.

Cu為可提升焊料接頭的接合強度之任意元素。此外,Cu為離子化傾向相對於Sn為高電位之元素,藉由使As、Pb及Bi共存,可助長此等之增黏抑制效果。 Cu is an arbitrary element that can improve the bonding strength of solder joints. In addition, Cu is an element that tends to ionize and has a higher potential than Sn. Coexistence of As, Pb, and Bi can contribute to these thickening inhibitory effects.

Cu含量的下限較佳為0質量%以上,更佳為0.1質量%以上,又更佳為0.2質量%以上。Cu含量的上限較佳為0.9質量%以下,更佳為0.8質量%以下,又更佳為0.7質量%以下。 The lower limit of the Cu content is preferably 0% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.2% by mass or more. The upper limit of the Cu content is preferably 0.9% by mass or less, more preferably 0.8% by mass or less, and still more preferably 0.7% by mass or less.

(10)剩餘部分:Sn (10) Remaining part: Sn

本發明之焊料合金的剩餘部分為Sn。除了前述元素之外,可含有無可避免的雜質。即使含有無可避免的雜質,亦不會影響前述效果。此外,如後述般,即使包含本發明中未含有之元素作為無可避免的雜質,亦不會影響前述效果。 The remainder of the solder alloy of the present invention is Sn. In addition to the aforementioned elements, it may contain inevitable impurities. Even if it contains unavoidable impurities, it will not affect the aforementioned effects. In addition, as described later, even if an element not contained in the present invention is included as an inevitable impurity, the aforementioned effect will not be affected.

2.焊料粉末 2. Solder powder

本發明之焊料粉末係使用在後述焊料膏,較佳為球狀粉末。藉由成為球狀粉末,可提升焊料合金的流動性。本發明之焊料粉末於JIS Z 3284-1:2014中之粉末大小的分類(表2)中,較佳係滿足符合記號1至8之大小(粒度分布),更佳為滿足符合記號4至8之大小(粒度分布),又更佳為滿足符合記號5至8之大小(粒度分布)。粒徑滿足此條件時,粉末的表面積不會過大而抑制黏度的上升,此外,有時會抑制細微粉末的凝聚而抑制黏度的上升。因此可對更細微的零件進行焊接。 The solder powder of the present invention is used in the solder paste described later, and is preferably a spherical powder. By becoming spherical powder, the fluidity of the solder alloy can be improved. According to the classification of powder size in JIS Z 3284-1:2014 (Table 2), the solder powder of the present invention preferably satisfies the size (particle size distribution) that meets the marks 1 to 8, and more preferably satisfies the mark 4 to 8. The size (particle size distribution) is more preferably to meet the size (particle size distribution) of marks 5 to 8. When the particle size satisfies this condition, the surface area of the powder will not be too large to suppress the increase in viscosity. In addition, the aggregation of fine powder may be suppressed to suppress the increase in viscosity. Therefore, it is possible to weld finer parts.

焊料粉末的球形度較佳為0.90以上,更佳為0.95以上,最佳為0.99以上。於本發明中,球狀粉末的球形度係使用採用最小區域中心法(MZC法)之CNC圖像測定系統(Mitutoyo公司製的ULTRA QUICK VISION ULTRA QV350-PRO測定裝置)來測定。 The sphericity of the solder powder is preferably 0.90 or more, more preferably 0.95 or more, and most preferably 0.99 or more. In the present invention, the sphericity of the spherical powder is measured using a CNC image measuring system (ULTRA QUICK VISION ULTRA QV350-PRO measuring device manufactured by Mitutoyo) using the minimum zone center method (MZC method).

於本發明中,所謂真球度係表示與真球之偏差,例如為將500個球之各球的直徑除以長徑時所算出之算術平均值,值愈接近於上限的1.00,表示愈接近於真球。 In the present invention, the so-called true sphericity means the deviation from the real ball, for example, the arithmetic average calculated when the diameter of each ball of 500 balls is divided by the major diameter. The closer the value is to the upper limit of 1.00, the more Close to a real ball.

《助焊劑》 "Flux"

本實施型態之焊料膏所使用之助焊劑例如可列舉出含有樹脂成分與活性成分與溶劑者。 The flux used in the solder paste of this embodiment includes, for example, one containing a resin component, an active component, and a solvent.

樹脂成分例如可列舉出:松香系樹脂、丙烯酸系樹脂、胺甲酸乙酯系樹脂、聚酯系樹脂、苯氧樹脂、乙烯醚系樹脂、萜(Terpene)樹脂、改質萜樹脂(例如芳香族改質萜樹脂、氫化萜樹脂、氫化芳香族改質萜樹脂等)、萜酚樹脂、改質萜酚樹脂(例如氫化萜酚樹脂等)、苯乙烯樹脂、改質苯乙烯樹脂(例如苯乙烯丙烯酸樹脂、苯乙烯順丁烯二酸樹脂等)、二甲苯樹脂、改質二甲苯樹脂(例如酚改質二甲苯樹脂、烷基酚改質二甲苯樹脂、酚改質可溶酚醛型二甲苯樹脂、多元醇改質二甲苯樹脂、聚環氧乙烷加成二甲苯樹脂等)。 Examples of resin components include rosin resins, acrylic resins, urethane resins, polyester resins, phenoxy resins, vinyl ether resins, terpene resins, modified terpene resins (such as aromatic Modified terpene resin, hydrogenated terpene resin, hydrogenated aromatic modified terpene resin, etc.), terpene phenol resin, modified terpene phenol resin (such as hydrogenated terpene phenol resin, etc.), styrene resin, modified styrene resin (such as styrene Acrylic resin, styrene maleic acid resin, etc.), xylene resin, modified xylene resin (e.g. phenol modified xylene resin, alkylphenol modified xylene resin, phenol modified resol xylene Resin, polyol modified xylene resin, polyethylene oxide addition xylene resin, etc.).

在此所謂「丙烯酸系樹脂」,意指除了丙烯酸樹脂之外,還包含甲基丙烯酸樹脂、此等之酯和其他衍生物之概念。 The term "acrylic resin" here means not only acrylic resin, but also methacrylic resin, these esters, and other derivatives.

例如,松香系樹脂可列舉出:脂松香(gum rosin)、木松香及妥爾油松香(tall oil rosin)等原料松香,以及從該原料松香所得到之衍生物。該衍生物可列舉出:精製松香、氫化松香、歧化松香、聚合松香及α,β不飽和羧酸改質物(丙烯酸化松香、順丁烯二酸化松香、反丁烯二酸化松香等),以及該聚合松香的精製物、氫化物及歧化物,以及該α,β不飽和羧酸改質物的精製物、氫化物及歧化物等。 For example, rosin-based resins include raw rosins such as gum rosin, wood rosin, and tall oil rosin, and derivatives derived from the raw rosin. The derivatives can include: refined rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, and α, β unsaturated carboxylic acid modifiers (acrylated rosin, maleated rosin, fumarated rosin, etc.), and the polymerization Refined products, hydrides, and disproportions of rosin, and refined products, hydrides, and disproportions of the modified α,β unsaturated carboxylic acid, etc.

活性成分例如可列舉出:有機酸、胺、胺氫鹵酸鹽、有機鹵素化合物、搖變減黏劑、金屬減活劑、界面活性劑、抗氧化劑、矽烷偶合劑、著色劑等。 Examples of active ingredients include organic acids, amines, amine hydrohalides, organic halogen compounds, thixotropic agents, metal deactivators, surfactants, antioxidants, silane coupling agents, colorants, and the like.

有機酸例如可列舉出:戊二酸、己二酸、壬二酸、二十烷二酸、檸檬酸、乙醇酸、琥珀酸、柳酸、二乙醇酸、二2-吡啶甲酸、二丁基苯胺二乙醇酸、辛二酸、癸二酸、硫代乙醇酸、對苯二甲酸、十二烷二酸、對羥基苯基乙酸、2-吡啶甲酸、苯基琥珀酸、鄰苯二甲酸、反丁烯二酸、順丁烯二酸、丙二酸、月桂酸、苯甲酸、酒石酸、異三聚氰酸三(2-羧基乙基)酯、甘胺酸、1,3-環己烷二羧酸、2,2-雙(羥基甲基)丙酸、2,2-雙(羥基甲基)丁酸、2,3-二羥基苯甲酸、2,4-二乙基戊二酸、2-喹啉羧酸、3-羥基苯甲酸、蘋果酸、對大茴香酸(p-anisic acid)、硬脂酸、12-羥基硬脂酸、油酸、亞麻油酸(linoleic acid)、亞麻仁油酸(linolenic acid)、二聚物酸、三聚物酸、將氫添加於二聚物酸而成氫化物的氫化二聚物酸、將氫添加於三聚物酸而成氫化物的氫化三聚物酸等。 Examples of organic acids include glutaric acid, adipic acid, azelaic acid, eicosandioic acid, citric acid, glycolic acid, succinic acid, salicylic acid, diglycolic acid, di-2-picolinic acid, dibutyl Aniline diglycolic acid, suberic acid, sebacic acid, thioglycolic acid, terephthalic acid, dodecanedioic acid, p-hydroxyphenylacetic acid, 2-picolinic acid, phenylsuccinic acid, phthalic acid, Fumaric acid, maleic acid, malonic acid, lauric acid, benzoic acid, tartaric acid, tris(2-carboxyethyl) isocyanurate, glycine, 1,3-cyclohexane Dicarboxylic acid, 2,2-bis(hydroxymethyl)propionic acid, 2,2-bis(hydroxymethyl)butanoic acid, 2,3-dihydroxybenzoic acid, 2,4-diethylglutaric acid, 2-quinolinecarboxylic acid, 3-hydroxybenzoic acid, malic acid, p-anisic acid, stearic acid, 12-hydroxystearic acid, oleic acid, linoleic acid, flax Linolenic acid, dimer acid, trimer acid, hydrogenated dimer acid formed by adding hydrogen to dimer acid, hydrogenated dimer acid formed by adding hydrogen to trimer acid Hydrogenated trimer acid and so on.

胺例如可列舉出:乙胺、三乙胺、乙二胺、三乙四胺、2-甲基咪唑、2-十一基咪唑、2-十七基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苯甲基-2-甲基咪唑、1-苯甲基-2-苯基咪唑、1-氰基乙基-2-甲基咪唑、1-氰基乙基-2-十一基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-十一基咪唑鎓偏苯三酸酯、1-氰基乙基-2-苯基咪唑鎓偏苯三酸酯、2,4-二胺基-6-[2'-甲基咪唑基-(1')]-乙基-均三嗪、2,4-二胺基-6-[2'-十一基咪唑基-(1')]-乙基-均三嗪、2,4-二胺基-6-[2'-乙基-4'-甲基咪唑基-(1')]-乙基-均三嗪、2,4-二胺基-6-[2'-甲基咪唑基-(1')]-乙基-均三嗪異三聚氰酸加成物、2-苯基咪唑異三聚氰酸加成物、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲 基-5-羥基甲基咪唑、2,3-二氫-1H-吡咯[1,2-a]苯并咪唑、氯化1-十二基-2-甲基-3-苯甲基咪唑鎓、2-甲基咪唑啉、2-苯基咪唑啉、2,4-二胺基-6-乙烯基-均三嗪、2,4-二胺基-6-乙烯基-均三嗪異三聚氰酸加成物、2,4-二胺基-6-甲基丙烯醯氧基乙基-均三嗪、環氧基咪唑加成物、2-甲基苯并咪唑、2-辛基苯并咪唑、2-戊基苯并咪唑、2-(1-乙基戊基)苯并咪唑、2-壬基苯并咪唑、2-(4-噻唑基)苯并咪唑、苯并咪唑、2-(2'-羥基-5'-甲基苯基)苯并三唑、2-(2'-羥基-3'-三級丁基-5'-甲基苯基)-5-氯苯并三唑、2-(2'-羥基-3',5'-二(三級戊基)苯基)苯并三唑、2-(2'-羥基-5'-三級辛基苯基)苯并三唑、2,2'-亞甲基雙[6-(2H-苯并三唑-2-基)-4-三級辛基酚]、6-(2-苯并三唑基)4-三級辛基-6'-三級丁基-4'-甲基-2,2'-亞甲基雙酚、1,2,3-苯并三唑、1-[N,N-雙(2-乙基己基)胺基甲基]苯并三唑、羧基苯并三唑、1-[N,N-雙(2-乙基己基)胺基甲基]甲基苯并三唑、2,2'-[[(甲基-1H-苯并三唑-1-基)甲基]亞胺基]雙乙醇、1-(1',2'-二羧基乙基)苯并三唑、1-(2,3-二羧基丙基)苯并三唑、1-[(2-乙基己基胺基)甲基]苯并三唑、2,6-雙[(1H-苯并三唑-1-基)甲基]-4-甲基酚、5-甲基苯并三唑、5-苯基四唑等。 Examples of the amine include ethylamine, triethylamine, ethylenediamine, triethylenetetramine, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole , 2-Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-benzene Ylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1- Cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazole -(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-ss Triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isotriazine Polycyanic acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl 5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrole[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride , 2-methylimidazoline, 2-phenylimidazoline, 2,4-diamino-6-vinyl-s-triazine, 2,4-diamino-6-vinyl-s-triazine isotriazine Polycyanic acid adduct, 2,4-diamino-6-methacryloxyethyl-s-triazine, epoxy imidazole adduct, 2-methylbenzimidazole, 2-octyl Benzimidazole, 2-pentylbenzimidazole, 2-(1-ethylpentyl)benzimidazole, 2-nonylbenzimidazole, 2-(4-thiazolyl)benzimidazole, benzimidazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tertiary butyl-5'-methylphenyl)-5-chlorobenzene Triazole, 2-(2'-hydroxy-3',5'-bis(tertiary pentyl) phenyl) benzotriazole, 2-(2'-hydroxy-5'-tertiary octyl phenyl) )Benzotriazole, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tertiary octylphenol], 6-(2-benzotriazolyl ) 4-tertiary octyl-6'-tertiary butyl-4'-methyl-2,2'-methylene bisphenol, 1,2,3-benzotriazole, 1-(N,N -Bis(2-ethylhexyl)aminomethyl]benzotriazole, carboxybenzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]methylbenzotriazole Azole, 2,2'-[[(methyl-1H-benzotriazol-1-yl)methyl]imino]diethanol, 1-(1',2'-dicarboxyethyl)benzo Triazole, 1-(2,3-dicarboxypropyl)benzotriazole, 1-[(2-ethylhexylamino)methyl]benzotriazole, 2,6-bis[(1H-benzene Triazol-1-yl)methyl]-4-methylphenol, 5-methylbenzotriazole, 5-phenyltetrazole and the like.

胺氫鹵酸鹽為胺與鹵化氫進行反應之化合物。胺氫鹵酸鹽中的胺可列舉出:乙胺、乙二胺、三乙胺、二苯基胍、二甲苯基胍、甲基咪唑、2-乙基-4-甲基咪唑等,鹵化氫可列舉出氯、溴、碘的氫化物。 Amine hydrohalides are compounds in which amines react with hydrogen halides. The amines in the amine hydrohalides include ethylamine, ethylenediamine, triethylamine, diphenylguanidine, xylylguanidine, methylimidazole, 2-ethyl-4-methylimidazole, etc., halogenated Examples of hydrogen include hydrides of chlorine, bromine, and iodine.

有機鹵素化合物例如可列舉出:反式-2,3-二溴-2-丁烯-1,4-二醇、六溴化異三聚氰酸三烯丙酯、1-溴-2-丁醇、1-溴-2-丙醇、3-溴-1-丙醇、3-溴-1,2丙二醇、1.4-二溴-2-丁醇、1,3-二溴-2-丙醇、2,3-二溴-1-丙醇、2,3-二溴-1,4-丁二醇、2,3-二溴-2-丁烯-1,4-二醇等。 Examples of organic halogen compounds include: trans-2,3-dibromo-2-butene-1,4-diol, triallyl hexabromoisocyanurate, 1-bromo-2-butane Alcohol, 1-bromo-2-propanol, 3-bromo-1-propanol, 3-bromo-1,2propanediol, 1.4-dibromo-2-butanol, 1,3-dibromo-2-propanol , 2,3-dibromo-1-propanol, 2,3-dibromo-1,4-butanediol, 2,3-dibromo-2-butene-1,4-diol, etc.

搖變減黏劑例如可列舉出蠟系搖變減黏劑、醯胺系搖變減黏劑、山梨醇系搖變減黏劑等。 Examples of the thixotropic agent include wax-based thixotropic agents, amide-based thixotropic agents, and sorbitol-based thixotropic agents.

蠟系搖變減黏劑例如可列舉出酯化合物,具體上可列舉出蓖麻硬化油。 Examples of the wax-based thixotropic agent include ester compounds, and specifically, castor oil is exemplified.

醯胺系搖變減黏劑例如可列舉出單醯胺系搖變減黏劑、雙醯胺系搖變減黏劑、聚醯胺系搖變減黏劑,具體上可列舉出:月桂醯胺、棕櫚醯胺、硬脂醯胺、山萮醯胺、羥基硬脂醯胺、飽和脂肪醯胺、油醯胺、芥子醯胺、不飽和脂肪醯胺、對甲苯醯胺、對甲苯甲烷醯胺、芳香族醯胺、六亞甲基羥基硬脂醯胺、取代醯胺、羥甲基硬脂醯胺、羥甲基醯胺、脂肪酸酯醯胺等單醯胺;亞甲基雙硬脂醯胺、乙烯雙月桂醯胺、乙烯雙羥基脂肪(脂肪酸的碳數C6至C24)醯胺、乙烯雙羥基硬脂醯胺、飽和脂肪雙醯胺、亞甲基雙油醯胺、不飽和脂肪雙醯胺、間二甲苯雙硬脂醯胺、芳香族雙醯胺等雙醯胺;飽和脂肪酸聚醯胺、不飽和脂肪酸聚醯胺、芳香族聚醯胺、1,2,3-丙烷三羧酸三(2-甲基環己基醯胺)、環狀醯胺低聚物、非環狀醯胺低聚物等聚醯胺。 Examples of the amide-based thixotropic agent include monoamide-based thixotropic agent, bis-amide-based thixotropic agent, and polyamide-based thixotropic agent. Specific examples include: Laurel Amine, palmitoylamine, stearylamine, behenylamide, hydroxystearylamine, saturated fatty amide, oleamide, mustard amide, unsaturated fatty amide, p-toluamide, p-tolylmethane Monoamines such as amines, aromatic amides, hexamethylene hydroxystearyl amides, substituted amides, hydroxymethyl stearyl amides, hydroxymethyl amides, fatty acid ester amides, etc.; methylene bis-hardened Tallow amide, ethylene bis-lauric amide, ethylene bishydroxy fat (the carbon number of fatty acid is C6 to C24) amide, ethylene bishydroxystearyl amide, saturated fatty bis-amide, methylene bis-oleamide, unsaturated Fatty bisamide, meta-xylene bisstearylamide, aromatic bisamide and other bisamides; saturated fatty acid polyamide, unsaturated fatty acid polyamide, aromatic polyamide, 1,2,3-propane Polyamides such as tricarboxylic acid tris(2-methylcyclohexylamide), cyclic amide oligomers, and non-cyclic amide oligomers.

前述環狀醯胺低聚物可列舉出:二羧酸與二胺經環狀縮聚之醯胺低聚物、三羧酸與二胺經環狀縮聚之醯胺低聚物、二羧酸與三胺經環狀縮聚之醯胺低聚物、三羧酸與三胺經環狀縮聚之醯胺低聚物、二羧酸及三羧酸與二胺經環狀縮聚之醯胺低聚物、二羧酸及三羧酸與三胺經環狀縮聚之醯胺低聚物、二羧酸與二胺及三胺經環狀縮聚之醯胺低聚物、三羧酸與二胺及三胺經環狀縮聚之醯胺低聚物、二羧酸及三羧酸與二胺及三胺經環狀縮聚之醯胺低聚物等。 The aforementioned cyclic amide oligomers include: dicarboxylic acid and diamine cyclic polycondensation amide oligomer, tricarboxylic acid and diamine cyclic polycondensation amide oligomer, dicarboxylic acid and Amine oligomers obtained by cyclic condensation polymerization of triamines, amide oligomers obtained by cyclic condensation polymerization of tricarboxylic acids and triamines, amide oligomers obtained by cyclic condensation polymerization of dicarboxylic acids and tricarboxylic acids and diamines , Dicarboxylic acid and tricarboxylic acid and triamine by cyclic polycondensation of amide oligomer, dicarboxylic acid and diamine and triamine by cyclic polycondensation of amide oligomer, tricarboxylic acid and diamine and triamine Amine oligomers obtained by cyclic polycondensation of amines, amide oligomers obtained by cyclic polycondensation of dicarboxylic acids and tricarboxylic acids with diamines and triamines, etc.

此外,前述非環狀醯胺低聚物可列舉出:單羧酸與二胺及/或三胺經非環狀縮聚之醯胺低聚物之情形,以及二羧酸及/或三羧酸與單胺經非環狀縮 聚之醯胺低聚物之情形等。如為含有單羧酸或單胺之醯胺低聚物時,單羧酸、單胺係發揮終端分子(terminal molecules)的功能,而成為降低分子量之非環狀醯胺低聚物。此外,在非環狀醯胺低聚物為二羧酸及/或三羧酸與二胺及/或三胺經非環狀縮聚之醯胺化合物之情形下,係成為非環狀高分子系醯胺聚合物。再者,非環狀醯胺低聚物亦包含單羧酸與單胺經非環狀縮聚之醯胺低聚物。 In addition, the aforementioned non-cyclic amide oligomers include: monocarboxylic acid and diamine and/or triamine through non-cyclic polycondensation of amide oligomer, and dicarboxylic acid and/or tricarboxylic acid Acyclic condensation with monoamine The case of polyamide oligomers, etc. In the case of an amide oligomer containing a monocarboxylic acid or a monoamine, the monocarboxylic acid and the monoamine function as a terminal molecule and become an acyclic amide oligomer with a lower molecular weight. In addition, when the acyclic amide oligomer is a dicarboxylic acid and/or tricarboxylic acid and diamine and/or triamine through acyclic polycondensation of the amide compound, it becomes a non-cyclic polymer system Amide polymer. Furthermore, the non-cyclic amide oligomer also includes a non-cyclic polycondensation of a monocarboxylic acid and a monoamine.

山梨醇系搖變減黏劑例如可列舉出:二苯亞甲基-D-山梨醇、雙(4-甲基苯亞甲基)-D-山梨醇、(D-)山梨醇、單苯亞甲基(-D-)山梨醇、單(4-甲基苯亞甲基)-(D-)山梨醇等。 Examples of sorbitol-based thixotropic viscosity-reducing agents include dibenzylidene-D-sorbitol, bis(4-methylbenzylidene)-D-sorbitol, (D-)sorbitol, and monobenzene Methylene (-D-)sorbitol, mono(4-methylbenzylidene)-(D-)sorbitol, etc.

金屬減活劑例如可列舉出:醯肼系氮化合物、醯胺系氮化合物、三唑系氮化合物、三聚氰胺系氮化合物等氮化合物;受阻酚系化合物等。 Examples of the metal deactivator include nitrogen compounds such as hydrazine-based nitrogen compounds, amide-based nitrogen compounds, triazole-based nitrogen compounds, and melamine-based nitrogen compounds; hindered phenol-based compounds.

在此所謂「金屬減活劑」,意指具有防止金屬因與某種化合物之接觸而劣化之性能的化合物。 The term "metal deactivator" here means a compound that has the ability to prevent metal from being degraded due to contact with a certain compound.

界面活性劑例如可列舉出非離子系界面活性劑、弱陽離子系界面活性劑等。 Examples of the surfactant include nonionic surfactants and weak cationic surfactants.

非離子系界面活性劑可列舉出:聚環氧烷乙炔二醇類、聚環氧烷甘油醚、聚環氧烷烷醚、聚環氧烷酯、聚環氧烷烷胺、聚環氧烷烷醯胺、脂肪族醇聚環氧乙烷加成物、芳香族醇聚環氧乙烷加成物、多元醇聚環氧乙烷加成物等。 Examples of nonionic surfactants include polyalkylene oxide acetylene glycols, polyalkylene oxide glycerol ether, polyalkylene oxide ether, polyalkylene oxide ester, polyalkylene oxide amine, and polyalkylene oxide. Alkylamine, aliphatic alcohol polyethylene oxide adduct, aromatic alcohol polyethylene oxide adduct, polyol polyethylene oxide adduct, etc.

弱陽離子系界面活性劑可列舉出:末端二胺聚乙二醇、末端二胺聚乙二醇-聚丙二醇共聚物、脂肪族胺聚環氧乙烷加成物、芳香族胺聚環氧乙烷加成物、多胺聚環氧乙烷加成物等。 Weak cationic surfactants include: terminal diamine polyethylene glycol, terminal diamine polyethylene glycol-polypropylene glycol copolymer, aliphatic amine polyethylene oxide adduct, aromatic amine polyethylene oxide Alkyl adducts, polyamine polyethylene oxide adducts, etc.

溶劑例如可列舉出:水、醇系溶劑、二醇醚系溶劑、有機酸酯系溶劑、萜品醇(terpineol)類、烴類等。 Examples of the solvent include water, alcohol-based solvents, glycol ether-based solvents, organic acid ester-based solvents, terpineols, and hydrocarbons.

醇系溶劑可列舉出:異丙醇、1,2-丁二醇、異莰基環己醇、2,4-二乙基-1,5-戊二醇、2,2-二甲基-1,3-丙二醇、2,5-二甲基-2,5-己二醇、2,5-二甲基-3-己炔-2,5-二醇、2,3-二甲基-2,3-丁二醇、1,1,1-三(羥基甲基)乙烷、2-乙基-2-羥基甲基-1,3-丙二醇、2,2'-氧基雙(亞甲基)雙(2-乙基-1,3-丙二醇)、2,2-雙(羥基甲基)-1,3-丙二醇、1,2,6-三羥基己烷、雙[2,2,2-三(羥基甲基)乙基]醚、1-乙炔基-1-環己醇、1,4-環己二醇、1,4-環己烷二甲醇、赤藻糖醇(erythritol)、蘇糖醇(threitol)、癒創木酚甘油醚(guaiacol glycerol ether)、3,6-二甲基-4-辛炔-3,6-二醇、2,4,7,9-四甲基-5-癸炔-4,7-二醇、1-十六醇、2-己基癸醇、異十六醇、1-十七醇、1-十八醇、異硬脂醇等。 Examples of alcohol solvents include isopropanol, 1,2-butanediol, isobornylcyclohexanol, 2,4-diethyl-1,5-pentanediol, and 2,2-dimethyl- 1,3-propanediol, 2,5-dimethyl-2,5-hexanediol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,3-dimethyl- 2,3-Butanediol, 1,1,1-tris(hydroxymethyl)ethane, 2-ethyl-2-hydroxymethyl-1,3-propanediol, 2,2'-oxybis(ethylene Methyl)bis(2-ethyl-1,3-propanediol), 2,2-bis(hydroxymethyl)-1,3-propanediol, 1,2,6-trihydroxyhexane, bis(2,2 ,2-Tris(hydroxymethyl)ethyl)ether, 1-ethynyl-1-cyclohexanol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, erythritol ), threitol, guaiacol glycerol ether, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetra Methyl-5-decyne-4,7-diol, 1-hexadecanol, 2-hexyldecanol, isocetyl alcohol, 1-heptadecanol, 1-octadecyl alcohol, isostearyl alcohol, etc.

二醇醚系溶劑可列舉出:二乙二醇單-2-乙基己醚、乙二醇單苯醚、2-甲基戊烷-2,4-二醇、二乙二醇單己醚、二乙二醇二丁醚、三乙二醇單丁醚等。 Examples of glycol ether solvents include: diethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, 2-methylpentane-2,4-diol, and diethylene glycol monohexyl ether , Diethylene glycol dibutyl ether, triethylene glycol monobutyl ether, etc.

有機酸酯系溶劑可列舉出:己二酸二甲酯、己二酸二異丙酯、順丁烯二酸二丁酯、癸二酸二甲酯、己二酸二異丁酯、癸二酸二乙酯、癸二酸二異丙酯、癸二酸二丁酯、癸二酸二辛酯等。 Organic acid ester solvents include: dimethyl adipate, diisopropyl adipate, dibutyl maleate, dimethyl sebacate, diisobutyl adipate, sebacate Diethyl sebacate, diisopropyl sebacate, dibutyl sebacate, dioctyl sebacate, etc.

烴類可列舉出甲苯、二甲苯、正己烷等。 Examples of hydrocarbons include toluene, xylene, and n-hexane.

於本實施型態之焊料膏所使用之助焊劑中,例如相對於助焊劑的全部質量,樹脂成分的含量較佳為20質量%以上70質量%以下,更佳為35質量%以上60質量%以下。 In the flux used in the solder paste of this embodiment, for example, relative to the total mass of the flux, the content of the resin component is preferably 20% by mass to 70% by mass, more preferably 35% by mass to 60% by mass the following.

例如相對於助焊劑的全部質量,有機酸的含量較佳為超過0質量%且為15質量%以下,更佳為0.2質量%以上10質量%以下。 For example, relative to the total mass of the flux, the content of the organic acid is preferably more than 0% by mass and 15% by mass or less, more preferably 0.2% by mass or more and 10% by mass or less.

例如相對於助焊劑的全部質量,胺的含量較佳為0質量%以上8質量%以下,更佳為1質量%以上6質量%以下。 For example, the content of the amine is preferably 0% by mass or more and 8% by mass or less, and more preferably 1% by mass or more and 6% by mass or less with respect to the total mass of the flux.

例如相對於助焊劑的全部質量,胺氫鹵酸鹽的含量較佳為0質量%以上8質量%以下,更佳為0.5質量%以上5質量%以下。 For example, relative to the total mass of the flux, the content of the amine hydrohalide is preferably 0% by mass or more and 8% by mass or less, and more preferably 0.5% by mass or more and 5% by mass or less.

例如相對於助焊劑的全部質量,有機鹵素化合物的含量較佳為0質量%以上8質量%以下,更佳為0.5質量%以上6質量%以下。 For example, relative to the total mass of the flux, the content of the organic halogen compound is preferably 0% by mass or more and 8% by mass or less, and more preferably 0.5% by mass or more and 6% by mass or less.

例如相對於助焊劑的全部質量,抗氧化劑的含量較佳為0質量%以上8質量%以下,更佳為1質量%以上6質量%以下。 For example, relative to the total mass of the flux, the content of the antioxidant is preferably from 0% by mass to 8% by mass, and more preferably from 1% by mass to 6% by mass.

助焊劑的含量: The content of flux:

相對於焊料膏的全部質量,焊料膏中之助焊劑的含量較佳為5至95質量%,更佳為5至15質量。 The content of the flux in the solder paste is preferably 5 to 95% by mass, and more preferably 5 to 15% by mass relative to the total mass of the solder paste.

焊料膏中之助焊劑的含量於此範圍時,可充分地發揮由焊料粉末所引起之增黏抑制效果。除此之外,容易達成調配於助焊劑之成分的效果,例如因應其使用條件或用途等,容易達成焊料之潤濕速度的提升、接合對象物之金屬表面(例如銅板)的腐蝕抑制、印刷性的提升、空隙抑制等各種特性。 When the content of the flux in the solder paste is within this range, the effect of suppressing the increase in viscosity caused by the solder powder can be fully exerted. In addition, it is easy to achieve the effect of the components of the flux. For example, depending on its use conditions or applications, it is easy to achieve the improvement of the wetting speed of the solder, the corrosion suppression of the metal surface of the bonding object (such as copper plate), and the printing Various features such as improved performance and gap suppression.

焊料膏的製造方法: Manufacturing method of solder paste:

本實施型態之焊料膏可藉由該技術領域中之一般的方法來製造。 The solder paste of this embodiment can be manufactured by a general method in the technical field.

首先,焊料粉末的製造可採用使熔融的焊料材料滴落而得到粒子之滴落法,或是進行離心噴霧之噴霧法,或是將塊體的焊料材料粉碎之方法等一般所知的方法。於滴落法或噴霧法中,為了形成為粒子狀,滴落或噴霧較佳是在惰性氣體環境或是溶劑中進行。然後加熱混合上述各成分而調製助焊劑,並將上述焊料粉末導入助焊劑中,並攪拌混合而製造。 First, the solder powder can be produced by the dropping method of dropping molten solder material to obtain particles, or the spraying method of centrifugal spraying, or the method of crushing the bulk solder material, and other commonly known methods. In the dripping method or spraying method, in order to form particles, the dripping or spraying is preferably performed in an inert gas environment or in a solvent. Then, the above-mentioned components are heated and mixed to prepare a flux, and the above-mentioned solder powder is introduced into the flux and stirred and mixed to produce.

〈本實施型態之焊料膏的作用效果例〉 <Example of the effect of the solder paste of this embodiment>

於本實施型態之焊料膏中,係採用含有焊料合金之焊料粉末,該焊料合金具有連同Sn以特定的比率併用特定的元素(As、Bi、Pb及Sb的至少一種)之合金組成。 In the solder paste of this embodiment, a solder powder containing a solder alloy is used, and the solder alloy has an alloy composition with Sn and a specific element (at least one of As, Bi, Pb, and Sb) in a specific ratio.

於組合該焊料粉末與助焊劑之焊料膏中,係顯示出不易發生黏度上升等之經時變化,潤濕性優異以及高的機械特性。 In the solder paste that combines the solder powder and flux, the solder paste is less prone to changes with time such as a rise in viscosity, has excellent wettability, and high mechanical properties.

再者,根據此焊料膏,藉由選擇調配於助焊劑之成分,可進一步提高焊料之潤濕速度的提升、接合對象物之金屬表面(例如銅板)的腐蝕抑制、印刷性的提升、空隙抑制等各種特性。 Furthermore, according to this solder paste, by selecting the components blended in the flux, the wetting speed of the solder can be further improved, the corrosion suppression of the metal surface (for example, copper plate) of the joining object, the improvement of the printability, and the suppression of voids can be further improved. And other characteristics.

如上述般,本實施型態之焊料膏係含有特定的焊料粉末與助焊劑。 As mentioned above, the solder paste of this embodiment contains specific solder powder and flux.

特定的焊料粉末可列舉出含有下列所示之焊料合金(S1)至焊料合金(S9)中的任一種之焊料粉末作為較佳實施型態。 The specific solder powder may include solder powder containing any one of the following solder alloys (S1) to solder alloys (S9) as a preferred embodiment.

焊料合金(S1): Solder alloy (S1):

係具有由As:10質量ppm以上且未達40質量ppm,以及Bi:0至10000質量ppm、Pb:0至5100質量ppm及Sb:0至3000質量ppm中的至少一種,以及剩餘部分為Sn所構成之合金組成,並且滿足下述(1)式及(2)式之焊料合金。 It has at least one of As: 10 mass ppm or more and less than 40 mass ppm, Bi: 0 to 10,000 mass ppm, Pb: 0 to 5100 mass ppm, and Sb: 0 to 3000 mass ppm, and the remainder is Sn The constituted alloy composition, and satisfies the following (1) formula and (2) formula solder alloy.

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition.

焊料合金(S2): Solder alloy (S2):

係具有由As:10質量ppm以上且未達40質量ppm,以及Bi:超過0質量ppm且為10000質量ppm以下、Pb:超過0質量ppm且為5100質量ppm以下及Sb:超過0質量ppm且為3000質量ppm以下中的至少一種,以及剩餘部分為Sn所構成之合金組成,並且滿足下述(1)式及(2)式之焊料合金。 The system has As: 10 mass ppm or more and less than 40 mass ppm, Bi: more than 0 mass ppm and less than 10000 mass ppm, Pb: more than 0 mass ppm and less than 5100 mass ppm, and Sb: more than 0 mass ppm and It is at least one of 3000 mass ppm or less, and the remainder is a solder alloy composed of Sn, and satisfies the following formulas (1) and (2).

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition.

焊料合金(S3): Solder alloy (S3):

係具有由As:10質量ppm以上且未達40質量ppm,以及Bi:50至10000質量ppm、Pb:超過0質量ppm且為5100質量ppm以下及Sb:超過0質量ppm且為3000質量ppm以下中的至少一種,以及剩餘部分為Sn所構成之合金組成,並且滿足下述(1)式及(2)式之焊料合金。 The system has As: 10 mass ppm or more and less than 40 mass ppm, Bi: 50 to 10,000 mass ppm, Pb: more than 0 mass ppm and less than 5100 mass ppm, and Sb: more than 0 mass ppm and less than 3000 mass ppm At least one of them and the remainder are alloy compositions composed of Sn, and satisfy the following formula (1) and (2) solder alloy.

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition.

焊料合金(S4): Solder alloy (S4):

係具有由As:10質量ppm以上且未達40質量ppm,以及Bi:超過0質量ppm且為10000質量ppm以下、Pb:50至5100質量ppm及Sb:超過0質量ppm且為3000質量ppm以下的至少一種,以及剩餘部分為Sn所構成之合金組成,並且滿足下述(1)式及(2)式之焊料合金。 The system consists of As: 10 mass ppm or more and less than 40 mass ppm, and Bi: more than 0 mass ppm and less than 10000 mass ppm, Pb: 50 to 5100 mass ppm, and Sb: more than 0 mass ppm and less than 3000 mass ppm At least one of, and the remainder is a solder alloy composed of Sn, and satisfies the following formulas (1) and (2).

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition.

焊料合金(S5): Solder alloy (S5):

係具有由As:10質量ppm以上且未達40質量ppm,以及Bi:超過0質量ppm且為10000質量ppm以下、Pb:超過0質量ppm且為5100質量ppm以下及Sb:50至3000質量ppm以下中的至少一種,以及剩餘部分為Sn所構成之合金組成,並且滿足下述(1)式及(2)式之焊料合金。 The system consists of As: 10 mass ppm or more and less than 40 mass ppm, and Bi: more than 0 mass ppm and less than 10000 mass ppm, Pb: more than 0 mass ppm and less than 5100 mass ppm, and Sb: 50 to 3000 mass ppm At least one of the following, and the remainder is a solder alloy composed of Sn and satisfying the following formulas (1) and (2).

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition.

焊料合金(S6): Solder alloy (S6):

係具有由As:10質量ppm以上且未達40質量ppm,以及Bi:50至10000質量ppm、Pb:50至5100質量ppm及Sb:超過0質量ppm且為3000質量ppm以下中的至少一種,以及剩餘部分為Sn所構成之合金組成,並且滿足下述(1)式及(2)式之焊料合金。 It has at least one of As: 10 mass ppm or more and less than 40 mass ppm, Bi: 50 to 10,000 mass ppm, Pb: 50 to 5100 mass ppm, and Sb: more than 0 mass ppm and less than 3000 mass ppm, And the remaining part is the alloy composition composed of Sn, and meets the following formula (1) and (2) of the solder alloy.

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition.

焊料合金(S7): Solder alloy (S7):

係具有由As:10質量ppm以上且未達40質量ppm,以及Bi:超過0質量ppm且為10000質量ppm以下、Pb:50至5100質量ppm及Sb:50至3000質量ppm中的至少一種,以及剩餘部分為Sn所構成之合金組成,並且滿足下述(1)式及(2)式之焊料合金。 It has at least one of As: 10 mass ppm or more and less than 40 mass ppm, Bi: more than 0 mass ppm and 10,000 mass ppm or less, Pb: 50 to 5100 mass ppm, and Sb: 50 to 3000 mass ppm, And the remaining part is the alloy composition composed of Sn, and meets the following formula (1) and (2) of the solder alloy.

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition.

焊料合金(S8): Solder alloy (S8):

係具有由As:10質量ppm以上且未達40質量ppm,以及Bi:50至10000質量ppm、Pb:超過0質量ppm且為5100質量ppm以下及Sb:50至3000質量ppm中的至少一種,以及剩餘部分為Sn所構成之合金組成,並且滿足下述(1)式及(2)式之焊料合金。 It has at least one of As: 10 mass ppm or more and less than 40 mass ppm, Bi: 50 to 10,000 mass ppm, Pb: more than 0 mass ppm and less than 5100 mass ppm, and Sb: 50 to 3000 mass ppm, And the remainder is the alloy composition composed of Sn, and the solder alloy that satisfies the following formulas (1) and (2).

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm) In the above formula (1) and (2), As, Sb, Bi and Pb each represent the content (mass ppm) in the aforementioned alloy composition

焊料合金(S9): Solder alloy (S9):

係具有由As:10質量ppm以上且未達40質量ppm,以及Bi:50至10000質量ppm、Pb:50至5100質量ppm及Sb:50至3000質量ppm中的至少一種,以及剩餘部分為Sn所構成之合金組成,並且滿足下述(1)式及(2)式之焊料合金。 It has at least one of As: 10 mass ppm or more and less than 40 mass ppm, Bi: 50 to 10,000 mass ppm, Pb: 50 to 5100 mass ppm, and Sb: 50 to 3000 mass ppm, and the remainder is Sn The constituted alloy composition, and satisfies the following (1) formula and (2) formula solder alloy.

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition.

本實施型態之焊料膏中的助焊劑並無特別限定,例如可使用含有樹脂成分與活性成分與溶劑者。 The flux in the solder paste of this embodiment is not particularly limited. For example, one containing a resin component, an active component, and a solvent can be used.

該助焊劑可列舉出下列所示之助焊劑(F1)至助焊劑(F12)的各組成物作為較佳實施型態。 The flux can include the following flux (F1) to flux (F12) as a preferred embodiment.

助焊劑(F1): Flux (F1):

助焊劑(F1)為含有酸改質松香之組成物,例如可列舉出含有酸改質松香與搖變減黏劑與溶劑者。 The flux (F1) is a composition containing acid-modified rosin, and examples include acid-modified rosin, a thixotropic viscosity reducer, and a solvent.

酸改質松香係在焊接所預想之溫度區域中具有耐熱性,於焊接時發揮活性劑的功能。 Acid-modified rosin has heat resistance in the temperature range expected for soldering and functions as an active agent during soldering.

助焊劑(F1)所含有之酸改質松香較佳為選自由丙烯酸改質松香、丙烯酸改質氫化松香、順丁烯二酸改質松香及順丁烯二酸改質氫化松香所組成群組中之至少一種。 The acid modified rosin contained in the flux (F1) is preferably selected from the group consisting of acrylic modified rosin, acrylic modified hydrogenated rosin, maleic acid modified rosin and maleic acid modified hydrogenated rosin At least one of them.

相對於助焊劑(F1)全體的總量,酸改質松香的含量較佳為3.0質量%以上60.0質量%以下,更佳為5.0質量%以上50.0質量%以下,又更佳為10.0質量%以上50.0質量%以下。 The content of acid-modified rosin relative to the total amount of flux (F1) is preferably 3.0% by mass or more and 60.0% by mass or less, more preferably 5.0% by mass or more and 50.0% by mass or less, and still more preferably 10.0% by mass or more 50.0% by mass or less.

助焊劑(F1)所使用之搖變減黏劑例如可列舉出醯胺系搖變減黏劑、山梨醇系搖變減黏劑、蠟系搖變減黏劑(酯化合物)等。 The thixotropic agent used in the flux (F1) includes, for example, an amide-based thixotropic agent, a sorbitol-based thixotropic agent, and a wax-based thixotropic agent (ester compound).

相對於助焊劑(F1)的全部質量,該搖變減黏劑的含量較佳為0.1至15.0質量%,更佳為0.2質量%以上10.0質量%以下。 Relative to the total mass of the flux (F1), the content of the thixotropic viscosity reducing agent is preferably 0.1 to 15.0% by mass, more preferably 0.2% by mass to 10.0% by mass.

助焊劑(F1)所使用之溶劑例如可列舉出:水、醇系溶劑、二醇醚系溶劑、萜品醇類等。 Examples of the solvent used for the flux (F1) include water, alcohol-based solvents, glycol ether-based solvents, and terpineols.

助焊劑(F1)可含有酸改質松香以外的松香(其他松香)。其他松香例如可列舉出:脂松香、木松香及妥爾油松香等原料松香,以及從該原料松香所得到之衍生物。該衍生物例如可列舉出:精製松香、氫化松香、歧化松香、聚合松香、酚改質松香、以及該聚合松香的精製物、氫化物及歧化物,可使用此等的1種或2種以上。 The flux (F1) may contain rosin (other rosin) other than acid-modified rosin. Examples of other rosins include raw rosins such as gum rosin, wood rosin, and tall oil rosin, and derivatives derived from the raw rosin. Examples of the derivative include: refined rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, phenol-modified rosin, and refined products, hydrogenated products, and disproportionated products of the polymerized rosin. One or more of these can be used. .

助焊劑(F1)較佳係含有超過0質量%且為60.0質量%以下的其他松香,更佳係含有超過0質量%且為45質量%以下的其他松香。 The flux (F1) preferably contains more than 0% by mass and 60.0% by mass or less of other rosin, and more preferably contains more than 0% by mass and 45% by mass or less of other rosin.

助焊劑(F1)較佳係含有合計為20質量%以上70質量%以下的酸改質松香與其他松香,更佳係含有合計為35質量%以上60質量%以下的酸改質松香與其他松香。 The flux (F1) preferably contains acid-modified rosin and other rosins in a total of 20% by mass to 70% by mass, and more preferably contains acid-modified rosin and other rosins in a total of 35% to 60% by mass. .

助焊劑(F1)可含有有機酸、胺、鹵素系活性劑、抗氧化劑。助焊劑(F1)可更含有界面活性劑。 The flux (F1) may contain organic acids, amines, halogen-based activators, and antioxidants. The flux (F1) may further contain a surfactant.

藉由將上述助焊劑(F1)與含有焊料合金(S1)至焊料合金(S9)中的任一種之焊料粉末組合,可提供一種焊料膏,其係不易發生黏度上升等之經時變化,潤濕性優異,具有高的機械特性且經提升焊料的潤濕速度者。 By combining the above-mentioned flux (F1) and solder powder containing any one of solder alloys (S1) to solder alloys (S9), a solder paste can be provided, which is less prone to changes in viscosity over time, such as increased viscosity. Excellent wettability, high mechanical properties and improved solder wetting speed.

此外,根據助焊劑(F1),可提供一種焊料膏用助焊劑,其係即使在熱負荷大之條件下亦可得到良好的潤濕速度者。 In addition, according to the flux (F1), it is possible to provide a flux for solder paste, which can obtain a good wetting speed even under conditions of a large heat load.

助焊劑(F2): Flux (F2):

助焊劑(F2)為含有丙烯酸系樹脂之組成物,例如可列舉出含有丙烯酸系樹脂與有機酸與溶劑者。 The flux (F2) is a composition containing an acrylic resin, and examples thereof include those containing an acrylic resin, an organic acid, and a solvent.

丙烯酸系樹脂係在焊接所預想之溫度區域中具有耐熱性,藉由殘存於加熱後硬化之助焊劑殘渣中,使助焊劑殘渣成為軟殘渣。藉此,即使溫度產生變化亦可抑制助焊劑殘渣破裂,而提升溫度循環可靠度。 Acrylic resin has heat resistance in the temperature range expected for soldering, and by remaining in the flux residue that hardens after heating, the flux residue becomes a soft residue. Thereby, even if the temperature changes, the cracking of the flux residue can be suppressed, and the reliability of the temperature cycle can be improved.

助焊劑(F2)所含有之丙烯酸系樹脂係可列舉出以丙烯酸、丙烯酸與醇的反應物之丙烯酸酯、甲基丙烯酸、甲基丙烯酸與醇的反應物之甲基丙烯酸酯作為單體之丙烯酸的聚合物、丙烯酸酯的聚合物、丙烯酸與丙烯酸酯的聚合物等。 The acrylic resin contained in the flux (F2) includes acrylic acid, acrylic acid ester of the reaction product of acrylic acid and alcohol, methacrylic acid, methacrylic acid ester of the reaction product of methacrylic acid and alcohol as the monomer. The polymer, acrylate polymer, acrylic acid and acrylate polymer, etc.

此外,可列舉出:甲基丙烯酸的聚合物、甲基丙烯酸酯的聚合物、甲基丙烯酸與甲基丙烯酸酯之聚合物等。 In addition, a polymer of methacrylic acid, a polymer of methacrylate, a polymer of methacrylic acid and methacrylate, and the like can be cited.

再者,可列舉出:丙烯酸與甲基丙烯酸之聚合物、丙烯酸與甲基丙烯酸酯之聚合物、甲基丙烯酸與丙烯酸酯之聚合物、丙烯酸酯與甲基丙烯酸酯之聚合物、丙烯酸與甲基丙烯酸與丙烯酸酯之聚合物、丙烯酸與甲基丙烯酸與甲基丙烯酸酯之聚合物、丙烯酸與甲基丙烯酸與丙烯酸酯與甲基丙烯酸酯之聚合物、丙烯酸與丙烯酸酯與甲基丙烯酸酯之聚合物、甲基丙烯酸與丙烯酸酯與甲基丙烯酸酯之聚合物等。 Furthermore, examples include: polymers of acrylic acid and methacrylic acid, polymers of acrylic acid and methacrylate, polymers of methacrylic acid and acrylate, polymers of acrylate and methacrylate, acrylic acid and methacrylate Acrylic acid and acrylic acid ester polymers, acrylic acid and methacrylic acid and methacrylic acid ester polymers, acrylic acid and methacrylic acid and acrylic acid ester and methacrylic acid ester polymers, acrylic acid and acrylic acid esters and methacrylic acid esters Polymers, polymers of methacrylic acid and acrylic acid esters and methacrylic acid esters, etc.

丙烯酸酯例如可列舉出丙烯酸丁酯,以丙烯酸丁酯作為單體之丙烯酸系樹脂可列舉出:丙烯酸丁酯的聚合物、丙烯酸丁酯以外的丙烯酸酯與丙烯酸丁酯之聚合物、丙烯酸與丙烯酸丁酯之聚合物、丙烯酸與丙烯酸丁酯以外的丙烯酸酯與丙烯酸丁酯之聚合物等。 Examples of acrylic esters include butyl acrylate, and acrylic resins that use butyl acrylate as a monomer include butyl acrylate polymers, acrylates other than butyl acrylate and butyl acrylate polymers, acrylic acid and acrylic acid. Polymers of butyl ester, polymers of acrylic acid and butyl acrylate other than acrylic acid and butyl acrylate, etc.

此外,甲基丙烯酸酯例如可列舉出甲基丙烯酸丁酯,以甲基丙烯酸丁酯作為單體之丙烯酸系樹脂可列舉出:甲基丙烯酸丁酯的聚合物、甲基丙烯酸丁酯以外的甲基丙烯酸酯與甲基丙烯酸丁酯之聚合物、甲基丙烯酸與甲基丙烯酸丁酯之聚合物、甲基丙烯酸與甲基丙烯酸丁酯以外的甲基丙烯酸酯與甲基丙烯酸丁酯之聚合物等。 In addition, examples of methacrylates include butyl methacrylate, and examples of acrylic resins using butyl methacrylate as a monomer include polymers of butyl methacrylate and methyl methacrylate other than butyl methacrylate. A polymer of methacrylic acid ester and butyl methacrylate, a polymer of methacrylic acid and butyl methacrylate, a polymer of methacrylic acid and butyl methacrylate other than methacrylic acid and butyl methacrylate Wait.

再者,可列舉出:丙烯酸與甲基丙烯酸丁酯之聚合物、丙烯酸與甲基丙烯酸丁酯以外的甲基丙烯酸酯與甲基丙烯酸丁酯之聚合物、甲基丙烯酸與丙烯酸丁酯之聚合物、甲基丙烯酸與丙烯酸丁酯以外的丙烯酸酯與丙烯酸丁酯之聚合物、丙烯酸丁酯與甲基丙烯酸丁酯之聚合物、丙烯酸丁酯以外的丙烯酸酯與甲基丙烯酸丁酯之聚合物、丙烯酸丁酯與甲基丙烯酸丁酯以外的甲基丙烯酸酯之聚合物等。 In addition, the polymer of acrylic acid and butyl methacrylate, the polymer of methacrylate and butyl methacrylate other than acrylic acid and butyl methacrylate, the polymerization of methacrylic acid and butyl acrylate Polymers, polymers of acrylate and butyl acrylate other than methacrylic acid and butyl acrylate, polymers of butyl acrylate and butyl methacrylate, polymers of acrylate and butyl methacrylate other than butyl acrylate , Butyl acrylate and methacrylate polymers other than butyl methacrylate, etc.

聚合反應可為無規共聚合和嵌段共聚合等。 The polymerization reaction can be random copolymerization, block copolymerization, and the like.

而且,上述醇係碳鏈為直鏈狀之碳數1至24的醇或是碳鏈為分枝狀之碳數3至24的醇,上述醇可列舉出:碳數1的甲醇、碳數2的乙醇、碳數3的1-丙醇、碳數3的2-丙醇、碳數3的乙二醇單甲醚、碳數4的1-丁醇、碳數4的2-丁醇、碳數4的異丁醇、碳數6的1-己醇、碳數6的二乙二醇單乙醚、碳數7的苯甲醇、碳數8的1-辛醇、碳數8的2-乙基己醇、碳數8的苯基甘醇(phenyl glycol)、碳數9的1-癸醇、碳數12的月桂醇、碳數16的鯨蠟醇、碳數18的硬脂醇、碳數18的油醇、碳數22的山萮醇等。 In addition, the above-mentioned alcohols have a linear carbon chain with a carbon number of 1 to 24 or a branched carbon chain with a carbon number of 3 to 24. Examples of the above-mentioned alcohol include: methanol with carbon number 1, carbon number 2 ethanol, carbon number 3 1-propanol, carbon number 3 2-propanol, carbon number 3 ethylene glycol monomethyl ether, carbon number 4 1-butanol, carbon number 4 2-butanol , Isobutanol with 4 carbons, 1-hexanol with 6 carbons, diethylene glycol monoethyl ether with 6 carbons, benzyl alcohol with 7 carbons, 1-octanol with 8 carbons, 2 with 8 carbons -Ethylhexanol, phenyl glycol with carbon number 8, 1-decanol with carbon number 9, lauryl alcohol with carbon number 12, cetyl alcohol with carbon number 16 and stearyl alcohol with carbon number 18 , C18 oleyl alcohol, C22 behenyl alcohol, etc.

關於丙烯酸系樹脂的分子量,其藉由凝膠滲透層析法(GPC:Gel Permeation Chromatography)所測定之經聚苯乙烯換算的重量平均分子量(Mw)較佳為5000至30000,重量平均分子量(Mw)更佳為6000至15000。 Regarding the molecular weight of the acrylic resin, the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC: Gel Permeation Chromatography) in terms of polystyrene is preferably 5000 to 30,000, and the weight average molecular weight (Mw ) Is more preferably 6000 to 15000.

該丙烯酸系樹脂可列舉出:聚丙烯酸2-乙基己酯(Mw=8300)、分子量相異之聚丙烯酸2-乙基己酯(Mw=11700)、聚甲基丙烯酸月桂酯(Mw=10080)等。 The acrylic resin may include: poly-2-ethylhexyl acrylate (Mw=8300), poly-2-ethylhexyl acrylate (Mw=11700) with different molecular weights, polylauryl methacrylate (Mw=10080) )Wait.

此外,丙烯酸系樹脂可為上述丙烯酸系樹脂與其他樹脂之聚合物,例如可為上述各丙烯酸系樹脂與聚乙烯之共聚物。該丙烯酸-聚乙烯共聚樹脂可列舉出聚丙烯酸2-乙基己酯-聚乙烯(Mw=12300)等。 In addition, the acrylic resin may be a polymer of the aforementioned acrylic resin and other resins, for example, a copolymer of the aforementioned acrylic resins and polyethylene. Examples of the acrylic-polyethylene copolymer resin include polyacrylic acid 2-ethylhexyl-polyethylene (Mw=12300) and the like.

相對於助焊劑(F2)的全部質量,丙烯酸系樹脂的含量較佳為5質量%以上50質量%以下,更佳為5質量%以上45質量%以下,又更佳為10質量%以上30質量%以下。 Relative to the total mass of the flux (F2), the content of the acrylic resin is preferably 5% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 45% by mass or less, and still more preferably 10% by mass or more and 30% by mass %the following.

相對於助焊劑(F2)的全部質量,助焊劑(F2)所使用之有機酸的含量較佳係超過0質量%且為15質量%以下,更佳為0.2質量%以上13質量%以下。 Relative to the total mass of the flux (F2), the content of the organic acid used in the flux (F2) is preferably more than 0% by mass and 15% by mass or less, more preferably 0.2% by mass or more and 13% by mass or less.

助焊劑(F2)所使用之溶劑例如可列舉出:水、醇系溶劑、二醇醚系溶劑、萜品醇類等。 Examples of the solvent used for the flux (F2) include water, alcohol-based solvents, glycol ether-based solvents, and terpineols.

助焊劑(F2)可含有超過0質量%且為45.0質量%以下的松香。在含有松香之情形下,1種松香或2種以上的松香與1種丙烯酸系樹脂或2種以上的丙烯酸系樹脂之合計含量,較佳為35.0質量%以上60.0質量%以下。 The flux (F2) may contain more than 0% by mass and 45.0% by mass or less of rosin. When rosin is contained, the total content of one type of rosin or two or more types of rosin and one type of acrylic resin or two or more types of acrylic resins is preferably 35.0% by mass or more and 60.0% by mass or less.

此外,在含有松香之情形下,1種松香或2種以上的松香之合計含量與1種丙烯酸系樹脂或2種以上的丙烯酸系樹脂之合計含量的比率(松香合計量/丙烯酸樹脂合計量),較佳為0.1以上9..0以下。 In addition, when rosin is contained, the ratio of the total content of one type of rosin or two or more types of rosin to the total content of one type of acrylic resin or two or more types of acrylic resin (total amount of rosin/total amount of acrylic resin) , Preferably 0.1 or more and 9..0 or less.

助焊劑(F2)可含有丙烯酸系樹脂與松香系樹脂以外的其他樹脂,且含有0質量%以上10.0質量%以下的其他樹脂。 The flux (F2) may contain resins other than acrylic resins and rosin-based resins, and may contain other resins in an amount of 0% by mass or more and 10.0% by mass or less.

助焊劑(F2)可更含有胺、鹵素。 The flux (F2) may further contain amines and halogens.

相對於助焊劑(F2)的全部質量,較佳係含有0質量%以上20.0質量%以下的胺,更佳係含有0質量%以上5.0質量%以下,此外,相對於助焊劑(F2)的全部質量,作為鹵素較佳係含有0質量%以上2.0質量%以下的胺氫鹵酸鹽,更佳係含有0質量%以上5.0質量%以下的胺氫鹵酸鹽。 Relative to the total mass of the flux (F2), it is preferable to contain 0% by mass or more and 20.0% by mass or less of amine, more preferably 0% by mass or more and 5.0% by mass or less. In addition, relative to the entire flux (F2) In terms of mass, the halogen preferably contains 0% by mass or more and 2.0% by mass or less of amine hydrohalide, and more preferably contains 0% by mass or more and 5.0% by mass or less of amine hydrohalide.

助焊劑(F2)可含有搖變減黏劑,相對於助焊劑(F2)的全部質量較佳係含有0質量%以上10.0質量%以下的搖變減黏劑。 The flux (F2) may contain a thixotropic viscosity reducing agent, and it is preferable to contain 0 mass% or more and 10.0 mass% or less of the thixotropic viscosity reducing agent relative to the total mass of the flux (F2).

可含有醯胺系搖變減黏劑作為搖變減黏劑,相對於助焊劑(F2)的全部質量較佳係含有0質量%以上10.0質量%以下的醯胺系搖變減黏劑,更佳係含有0質量%以上6.0質量%以下的醯胺系搖變減黏劑。 It may contain an amide-based thixotropic agent as a thixotropic agent. Relative to the total mass of the flux (F2), it is preferable to contain 0% by mass or more and 10.0% by mass or less of the amide-based thixotropic agent. The best system contains 0% by mass or more and 6.0% by mass or less of the amide-based thixotropic viscosity reducer.

此外,助焊劑(F2)可含有酯化合物作為搖變減黏劑,相對於助焊劑(F2)的全部質量,較佳係含有0質量%以上8.0質量%以下的酯化合物,更佳係含有0質量%以上4.0質量%以下的酯化合物。 In addition, the soldering flux (F2) may contain an ester compound as a thixotropic viscosity reducing agent. It is preferable to contain 0% by mass or more and 8.0% by mass or less of the ester compound relative to the total mass of the flux (F2), and more preferably 0 Ester compound with a mass% or more and 4.0 mass% or less.

再者,助焊劑(F2)可含有山梨醇系搖變減黏劑作為搖變減黏劑,相對於助焊劑(F2)的全部質量,較佳係含有0質量%以上10.0質量%以下的山梨醇系搖變減黏劑,更佳係含有0質量%以上6.0質量%以下的山梨醇系搖變減黏劑。 In addition, the flux (F2) may contain a sorbitol-based thixotropic reducer as a thixotropic reducer. Relative to the total mass of the flux (F2), it is preferable to contain 0% by mass to 10.0% by mass of sorbus The alcohol-based thixotropic agent, more preferably, contains a sorbitol-based thixotropic agent in an amount of 0% by mass or more and 6.0% by mass or less.

相對於助焊劑(F2)的全部質量,複數種搖變減黏劑的合計含量較佳為10.0質量%以下。 The total content of the plurality of thixotropic viscosity reducing agents is preferably 10.0% by mass or less with respect to the total mass of the flux (F2).

助焊劑(F2)可更含有抗氧化劑,相對於助焊劑(F2)的全部質量,較佳係含有0質量%以上5.0質量%以下的抗氧化劑。 The flux (F2) may further contain an antioxidant, and it is preferable to contain 0% by mass or more and 5.0% by mass or less of the antioxidant relative to the total mass of the flux (F2).

藉由將上述助焊劑(F2)與含有焊料合金(S1)至焊料合金(S9)中的任一種之焊料粉末組合,可提供一種焊料膏,其係不易發生黏度上升等之經時變化,潤濕性優異,具有高的機械特性並且助焊劑殘渣的溫度循環可靠度優異者。 By combining the above-mentioned flux (F2) and solder powder containing any one of solder alloys (S1) to solder alloys (S9), a solder paste can be provided, which is less prone to changes with time such as increased viscosity, Excellent wettability, high mechanical properties, and excellent temperature cycle reliability of flux residue.

此外,根據助焊劑(F2),可提供一種焊料膏用助焊劑,其係使殘渣具有柔軟性而可抑制殘渣的破裂,以得到溫度循環可靠度優異之效果者。 In addition, according to the flux (F2), it is possible to provide a flux for solder paste, which imparts flexibility to the residue and suppresses the cracking of the residue, thereby obtaining the effect of excellent temperature cycle reliability.

助焊劑(F3): Flux (F3):

助焊劑(F3)為含有選自由屬於單羧酸的反應物且為二聚物之二聚物酸、將氫添加於二聚物酸而得之氫化二聚物酸、屬於單羧酸的反應物且為三聚物之三聚物酸、以及將氫添加於三聚物酸而得之氫化三聚物酸所組成群組中之至少一種有機酸之組成物。 Flux (F3) is a reaction of dimer acid containing dimers selected from reactants belonging to monocarboxylic acids, hydrogenated dimer acid obtained by adding hydrogen to the dimer acid, and belonging to monocarboxylic acids It is a composition of at least one organic acid in the group consisting of a trimer acid of a trimer and a hydrogenated trimer acid obtained by adding hydrogen to the trimer acid.

助焊劑(F3)例如可列舉出:含有選自由前述二聚物酸、前述氫化二聚物酸、前述三聚物酸以及前述氫化三聚物酸所組成群組中之至少一種有機酸,與松香,與搖變減黏劑,與溶劑者。 The flux (F3) includes, for example, containing at least one organic acid selected from the group consisting of the aforementioned dimer acid, the aforementioned hydrogenated dimer acid, the aforementioned trimer acid, and the aforementioned hydrogenated trimer acid, and Rosin, and thixotropic viscosity reducer, and solvent.

二聚物酸及三聚物酸係在焊接所預想之溫度區域中具有耐熱性,於焊接時發揮活性劑的功能。 Dimer acid and trimer acid have heat resistance in the temperature range expected for soldering, and function as an active agent during soldering.

助焊劑(F3)所含有之二聚物酸、三聚物酸可列舉出:油酸與亞麻油酸的反應物之二聚物酸、油酸與亞麻油酸的反應物之三聚物酸、丙烯酸的反應物之二聚物酸、丙烯酸的反應物之三聚物酸、甲基丙烯酸的反應物之二聚物酸、甲基丙烯酸的反應物之三聚物酸、丙烯酸與甲基丙烯酸的反應物之二聚物酸、丙烯酸與甲基丙烯酸的反應物之三聚物酸、油酸的反應物之二聚物酸、油酸的反應物之三聚物酸、亞麻油酸的反應物之二聚物酸、亞麻油酸的反應物之三聚物酸、亞麻仁油酸的反應物之二聚物酸、亞麻仁油酸的反應物之三聚物酸、丙烯酸與油 酸的反應物之二聚物酸、丙烯酸與油酸的反應物之三聚物酸、丙烯酸與亞麻油酸的反應物之二聚物酸、丙烯酸與亞麻油酸的反應物之三聚物酸、丙烯酸與亞麻仁油酸的反應物之二聚物酸、丙烯酸與亞麻仁油酸的反應物之三聚物酸、甲基丙烯酸與油酸的反應物之二聚物酸、甲基丙烯酸與油酸的反應物之三聚物酸、甲基丙烯酸與亞麻油酸的反應物之二聚物酸、甲基丙烯酸與亞麻油酸的反應物之三聚物酸、甲基丙烯酸與亞麻仁油酸的反應物之二聚物酸、甲基丙烯酸與亞麻仁油酸的反應物之三聚物酸、油酸與亞麻仁油酸的反應物之二聚物酸、油酸與亞麻仁油酸的反應物之三聚物酸、亞麻油酸與亞麻仁油酸的反應物之二聚物酸、亞麻油酸與亞麻仁油酸的反應物之三聚物酸、上述各二聚物酸的氫化物之二聚物酸、上述各三聚物酸的氫化物之三聚物酸等。 The dimer acid and trimer acid contained in the flux (F3) include: dimer acid, which is a reactant of oleic acid and linoleic acid, and trimer acid, which is a reactant of oleic acid and linoleic acid. , Dimer acid of the reactant of acrylic acid, trimer acid of the reactant of acrylic acid, dimer acid of the reactant of methacrylic acid, trimer acid of the reactant of methacrylic acid, acrylic acid and methacrylic acid Reaction of the dimer acid of the reactant of the dimer acid, the reactant of acrylic acid and methacrylic acid, the dimer acid of the reactant of oleic acid, the reaction of the trimer acid of the reactant of oleic acid, and the reaction of linoleic acid Dimer acid, the reactant of linoleic acid, the terpolymer acid of the reactant of linoleic acid, the dimer acid of the reactant of linoleic acid, the terpolymer of the reactant of linoleic acid, acrylic acid and oil The dimer acid of the reactant of acid, the trimer acid of the reactant of acrylic acid and oleic acid, the dimer acid of the reactant of acrylic acid and linoleic acid, the trimer acid of the reactant of acrylic acid and linoleic acid , Dimer acid of the reactant of acrylic acid and linoleic acid, terpolymer of the reactant of acrylic acid and linoleic acid, dimer acid of the reactant of methacrylic acid and oleic acid, methacrylic acid and Trimer acid of the reactant of oleic acid, dimer acid of the reactant of methacrylic acid and linoleic acid, terpolymer of the reactant of methacrylic acid and linoleic acid, methacrylic acid and linseed oil Dimer acid of the reactant of acid, terpolymer of the reactant of methacrylic acid and linoleic acid, dimer acid of the reactant of oleic acid and linoleic acid, oleic acid and linoleic acid Trimer acid of the reactant, the dimer acid of the reactant of linoleic acid and linoleic acid, the trimer acid of the reactant of linoleic acid and linoleic acid, the above-mentioned dimer acid Dimer acid of hydride, trimer acid of hydride of each of the above-mentioned trimer acids, etc.

例如,油酸與亞麻油酸的反應物之二聚物酸為碳數36的二聚物。此外,油酸與亞麻油酸的反應物之三聚物酸為碳數54的三聚物。 For example, the dimer acid of the reactant of oleic acid and linoleic acid is a dimer with 36 carbon atoms. In addition, the terpolymer acid of the reactant of oleic acid and linoleic acid is a trimer with 54 carbon atoms.

助焊劑(F3)較佳係含有相對於助焊劑的全部質量為0.5質量%以上20質量%以下之選自由二聚物酸、氫化二聚物酸、三聚物酸以及氫化三聚物酸所組成群組中之至少一種,更佳係含有2質量%以上10質量%以下。 The flux (F3) preferably contains 0.5% by mass to 20% by mass relative to the total mass of the flux, selected from dimer acids, hydrogenated dimer acids, trimer acids, and hydrogenated trimer acids. It constitutes at least one of the groups, and more preferably contains 2% by mass to 10% by mass.

於選自由二聚物酸、氫化二聚物酸、三聚物酸以及氫化三聚物酸所組成群組中之至少一種的含量為0.5質量%以上時,更容易得到焊料的潤濕擴展性、焊料之潤濕不良(去濕(dewetting))的抑制效果。 When the content of at least one selected from the group consisting of dimer acid, hydrogenated dimer acid, trimer acid, and hydrogenated trimer acid is 0.5% by mass or more, it is easier to obtain the wettability of the solder , The inhibitory effect of solder's poor wetting (dewetting).

除了選自由二聚物酸、氫化二聚物酸、三聚物酸以及氫化三聚物酸所組成群組中之至少一種之外,助焊劑(F3)可更併用此等以外的有機酸。 In addition to at least one selected from the group consisting of dimer acid, hydrogenated dimer acid, trimer acid, and hydrogenated trimer acid, the flux (F3) may use organic acids other than these in combination.

此等以外的有機酸較佳為選自由琥珀酸、戊二酸及己二酸所組成群組中之至少一種。選自由琥珀酸、戊二酸及己二酸所組成群組中之至少一種的含量,相對於助焊劑的全部質量較佳為0.1質量%以上5質量%以下。 The organic acid other than these is preferably at least one selected from the group consisting of succinic acid, glutaric acid and adipic acid. The content of at least one selected from the group consisting of succinic acid, glutaric acid and adipic acid is preferably 0.1% by mass to 5% by mass relative to the total mass of the flux.

相對於助焊劑的全部質量,選自由二聚物酸、氫化二聚物酸、三聚物酸以及氫化三聚物酸所組成群組中之至少一種與此等以外的有機酸之總含量較佳為0.5質量%以上20質量%以下,更佳為3質量%以上15質量%以下,又更佳為5質量%以上10質量%以下。 Relative to the total mass of the flux, at least one selected from the group consisting of dimer acid, hydrogenated dimer acid, trimer acid, and hydrogenated trimer acid is compared with the total content of other organic acids Preferably it is 0.5 mass% or more and 20 mass% or less, more preferably 3 mass% or more and 15 mass% or less, and still more preferably 5 mass% or more and 10 mass% or less.

助焊劑(F3)所使用之松香例如可列舉出天然松香以及從該天然松香所得到之衍生物等。天然松香例如可列舉出:脂松香、木松香及妥爾油松香等。該衍生物例如可列舉出精製松香、改質松香等。改質松香可列舉出:氫化松香、聚合松香、歧化松香、酸改質松香、松香酯、酚改質松香及α,β不飽和羧酸改質物(丙烯酸化松香、順丁烯二酸化松香、反丁烯二酸化松香、丙烯酸改質氫化松香等),以及該聚合松香的精製物、氫化物及歧化物,以及該α,β不飽和羧酸改質物的精製物、氫化物及歧化物等,可使用此等的1種或2種以上。 The rosin used in the flux (F3) includes, for example, natural rosin and derivatives derived from the natural rosin. Examples of natural rosin include gum rosin, wood rosin, tall oil rosin, and the like. Examples of such derivatives include refined rosin and modified rosin. The modified rosin can include: hydrogenated rosin, polymerized rosin, disproportionated rosin, acid-modified rosin, rosin ester, phenol-modified rosin, and α, β-unsaturated carboxylic acid-modified products (acrylated rosin, maleated rosin, reverse Butenediolated rosin, acrylic modified hydrogenated rosin, etc.), as well as refined products, hydrides and disproportions of the polymerized rosin, and refined products, hydrides and disproportions of the modified α, β unsaturated carboxylic acids, etc. Use one or more of these.

助焊劑(F3)較佳係含有15質量%以上70質量%以下的松香,更佳係含有35質量%以上60質量%以下的松香。 The flux (F3) preferably contains 15% by mass or more and 70% by mass or less of rosin, and more preferably contains 35% by mass or more and 60% by mass or less of rosin.

助焊劑(F3)所使用之搖變減黏劑例如可列舉出醯胺系搖變減黏劑、山梨醇系搖變減黏劑、蠟系搖變減黏劑(酯化合物)等。相對於助焊劑(F3)的全部質量,該搖變減黏劑的含量較佳為0.1至15.0質量%,更佳為0.2質量%以上10.0質量%以下。 The thixotropic agent used in the flux (F3) includes, for example, an amide-based thixotropic agent, a sorbitol-based thixotropic agent, and a wax-based thixotropic agent (ester compound). Relative to the total mass of the flux (F3), the content of the thixotropic viscosity reducing agent is preferably from 0.1 to 15.0% by mass, more preferably from 0.2% by mass to 10.0% by mass.

助焊劑(F3)所使用之溶劑可列舉出:水、醇系溶劑、二醇醚系溶劑、萜品醇類等。 Examples of the solvent used for the flux (F3) include water, alcohol-based solvents, glycol ether-based solvents, and terpineols.

助焊劑(F3)可含有有機酸、松香、搖變減黏劑及溶劑以外的成分,例如可列舉出:胺、鹵素系活性劑、抗氧化劑、松香以外的樹脂成分、界面活性劑等。 The flux (F3) may contain components other than organic acids, rosin, thixotropic viscosity reducers, and solvents, and examples thereof include amines, halogen-based activators, antioxidants, resin components other than rosin, surfactants, and the like.

藉由將上述助焊劑(F3)與含有焊料合金(S1)至焊料合金(S9)中的任一種之焊料粉末組合,可提供一種焊料膏,其係不易發生黏度上升等之經時變化,潤濕性優異,具有高的機械特性,並且焊料的潤濕擴展性良好且已抑制去濕的產生者。 By combining the above-mentioned flux (F3) with a solder powder containing any one of solder alloys (S1) to solder alloys (S9), a solder paste can be provided, which is less prone to changes in viscosity over time, such as increase in viscosity. It has excellent wettability and high mechanical properties, and the solder has good wettability and spreadability and has suppressed the cause of dewetting.

此外,根據助焊劑(F3),可提供一種焊料膏用助焊劑,其係即使在熱負荷大之條件下亦可顯示良好的潤濕擴展性,並且可抑制去濕的產生者。 In addition, according to the flux (F3), it is possible to provide a flux for solder paste that exhibits good wettability and spreadability even under conditions of large heat load, and can suppress the occurrence of dehumidification.

助焊劑(F4): Flux (F4):

助焊劑(F4)為含有以下述通式(1)所表示之化合物之組成物。 The flux (F4) is a composition containing a compound represented by the following general formula (1).

助焊劑(F4)例如可列舉出含有以下述通式(1)所表示之化合物與松香與溶劑者。 Examples of the flux (F4) include those containing a compound represented by the following general formula (1), rosin, and a solvent.

Figure 109117353-A0202-12-0042-144
Figure 109117353-A0202-12-0042-144

該式(1)中,R1、R2、R3及R4各自獨立地表示氫原子或碳數1至4的烷基。 In the formula (1), R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

於前述通式(1)中,R1、R2、R3及R4各自獨立地表示氫原子或碳數1至4的烷基。碳數1至4的烷基可列舉出:甲基、乙基、丙基、環丙基、丁基、 環丁基。其中,R1、R2、R3及R4較佳為氫原子、甲基、乙基、環丙基,更佳為氫原子、甲基,特佳為氫原子。R1、R2、R3及R4可為相同或相異。 In the aforementioned general formula (1), R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, cyclopropyl, butyl, and cyclobutyl. Among them, R 1 , R 2 , R 3 and R 4 are preferably a hydrogen atom, a methyl group, an ethyl group, or a cyclopropyl group, more preferably a hydrogen atom and a methyl group, and particularly preferably a hydrogen atom. R 1 , R 2 , R 3 and R 4 may be the same or different.

以前述通式(1)所表示之化合物可列舉出:2-吡啶甲酸、6-甲基2-吡啶甲酸、6-乙基2-吡啶甲酸、3-環丙基2-吡啶甲酸、4-環丙基2-吡啶甲酸、6-環丙基2-吡啶甲酸、5-丁基2-吡啶甲酸、6-環丁基2-吡啶甲酸等。此等當中,特佳為2-吡啶甲酸。 The compounds represented by the aforementioned general formula (1) include: 2-picolinic acid, 6-methyl 2-picolinic acid, 6-ethyl 2-picolinic acid, 3-cyclopropyl 2-picolinic acid, 4- Cyclopropyl 2-picolinic acid, 6-cyclopropyl 2-picolinic acid, 5-butyl 2-picolinic acid, 6-cyclobutyl 2-picolinic acid, etc. Among these, 2-picolinic acid is particularly preferred.

以通式(1)所表示之化合物可單獨使用1種或混合2種以上而使用。 The compound represented by general formula (1) can be used individually by 1 type or in mixture of 2 or more types.

助焊劑(F4)較佳係含有相對於助焊劑(F4)的全部質量為0.5質量%以上7質量%以下之以通式(1)所表示之化合物,更佳係含有1.0質量%以上7.0質量%以下之以通式(1)所表示之化合物,又更佳係含有3.0質量%以上7.0質量%以下,特佳係含有3.0質量%以上5.0質量%以下。 The flux (F4) preferably contains the compound represented by the general formula (1) of 0.5% by mass to 7% by mass relative to the total mass of the flux (F4), and more preferably contains 1.0% by mass or more and 7.0% by mass % Or less of the compound represented by the general formula (1), more preferably contains 3.0% by mass or more and 7.0% by mass or less, and particularly preferably contains 3.0% by mass or more and 5.0% by mass or less.

助焊劑(F4)所使用之松香例如可列舉出:脂松香、木松香及妥爾油松香等原料松香,以及從該原料松香所得到之衍生物。該衍生物例如可列舉出:精製松香、氫化松香、歧化松香、聚合松香、酸改質松香、酚改質松香及α,β不飽和羧酸改質物(丙烯酸化松香、順丁烯二酸化松香、反丁烯二酸化松香等),以及該聚合松香的精製物、氫化物及歧化物,以及該α,β不飽和羧酸改質物的精製物、氫化物及歧化物等,可使用此等的1種或2種以上。 The rosin used in the flux (F4) includes, for example, raw rosin such as gum rosin, wood rosin, and tall oil rosin, and derivatives derived from the raw rosin. Examples of such derivatives include refined rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, acid-modified rosin, phenol-modified rosin, and α,β-unsaturated carboxylic acid-modified products (acrylated rosin, maleated rosin, Fumarated rosin, etc.), as well as refined products, hydrides and disproportions of the polymerized rosin, and refined products, hydrides and disproportions of the modified α,β unsaturated carboxylic acid, etc., can be used 1 One or more than two.

助焊劑(F4)較佳係含有相對於助焊劑(F4)的全部質量為30質量%以上60質量%以下的松香,更佳係含有相對於助焊劑(F4)的全部質量為35質量%以上60質量%以下的松香。 The flux (F4) preferably contains 30% by mass or more and 60% by mass or less of rosin relative to the total mass of the flux (F4), and more preferably contains 35% by mass or more relative to the total mass of the flux (F4) Rosin less than 60% by mass.

助焊劑(F4)所使用之溶劑可列舉出:水、醇系溶劑、二醇醚系溶劑、萜品醇類等。 Examples of the solvent used in the flux (F4) include water, alcohol-based solvents, glycol ether-based solvents, and terpineols.

助焊劑(F4)可進一步併用有機酸(排除以通式(1)所表示之化合物)。有機酸可無特別限制地使用上述所例示者,較佳者例如可列舉出選自由琥珀酸、戊二酸、己二酸及氫化二聚物酸所組成群組中之至少一種。 The flux (F4) can be further combined with an organic acid (excluding the compound represented by the general formula (1)). The organic acid can be used without any particular limitation. Preferably, for example, at least one selected from the group consisting of succinic acid, glutaric acid, adipic acid, and hydrogenated dimer acid can be used.

於助焊劑(F4)中,在未併用以通式(1)所表示之化合物與有機酸(排除以通式(1)所表示之化合物)之情形下,較佳係含有相對於助焊劑(F4)的全部質量為1質量%以上7質量%以下之以通式(1)所表示之化合物,更佳係含有2質量%以上7質量%以下之以通式(1)所表示之化合物,又更佳係含有3質量%以上7質量%以下之以通式(1)所表示之化合物,特佳係含有3質量%以上5質量%以下之以通式(1)所表示之化合物。 In the flux (F4), in the case where the compound represented by the general formula (1) and the organic acid are not used together (excluding the compound represented by the general formula (1)), it is preferable to contain relative to the flux ( F4) is a compound represented by general formula (1) whose total mass is 1% by mass to 7 mass%, and more preferably contains a compound represented by general formula (1) with 2 mass% to 7 mass%, More preferably, the compound represented by the general formula (1) is contained in an amount of 3% by mass or more and 7% by mass or less, and particularly preferably, the compound represented by the general formula (1) is contained in an amount of 3% by mass or more and 5% by mass or less.

在於助焊劑(F4)中併用以通式(1)所表示之化合物與有機酸(排除以通式(1)所表示之化合物)之情形下,相對於助焊劑(F4)的全部質量,較佳係含有0.5質量%以上7質量%以下之以通式(1)所表示之化合物,更佳係含有0.5質量%以上5質量%以下之以通式(1)所表示之化合物,又更佳係含有1質量%以上5質量%以下之以通式(1)所表示之化合物。 In the case where the compound represented by the general formula (1) and organic acid (excluding the compound represented by the general formula (1)) are used in the flux (F4), compared to the total mass of the flux (F4) Preferably, it contains 0.5% by mass or more and 7% by mass or less of the compound represented by the general formula (1), more preferably 0.5% by mass or more and 5% by mass or less of the compound represented by the general formula (1), and even more preferably It is a compound represented by general formula (1) containing 1% by mass to 5% by mass.

助焊劑(F4)較佳為相對於助焊劑(F4)的全部質量係含有0質量%以上10質量%以下的有機酸,更佳係含有0.2質量%以上10質量%以下,又更佳係含有0.5質量%以上8質量%以下,特佳係含有1質量%以上6質量%以下。 The flux (F4) preferably contains 0% by mass or more and 10% by mass or less of organic acid relative to the total mass of the flux (F4), more preferably contains 0.2% by mass or more and 10% by mass or less, and more preferably contains 0.5% by mass or more and 8% by mass or less, and the particularly preferred system contains 1% by mass or more and 6% by mass or less.

此外,相對於助焊劑(F4)的全部質量,較佳係含有合計為3質量%以上之以通式(1)所表示之化合物與前述有機酸(排除以通式(1)所表示之化合物),更佳係含有合計為5質量%以上,又更佳係含有合計為6質量%以上,特佳係含有合計為6.5質量%以上15質量%以下。 In addition, relative to the total mass of the flux (F4), it is preferable to contain the compound represented by the general formula (1) and the aforementioned organic acid (excluding the compound represented by the general formula (1) in a total amount of 3% by mass or more) ), more preferably the total content is 5% by mass or more, still more preferably the total content is 6% by mass or more, and particularly preferably the total content is 6.5% by mass or more and 15% by mass or less.

助焊劑(F4)可更含有胺、有機鹵素化合物、胺氫鹵酸鹽。 The flux (F4) may further contain amines, organic halogen compounds, and amine hydrohalides.

此外,助焊劑(F4)可更含有搖變減黏劑。助焊劑(F4)所使用之搖變減黏劑例如可列舉出:醯胺系搖變減黏劑、山梨醇系搖變減黏劑、蠟系搖變減黏劑(酯化合物)等。 In addition, the flux (F4) can contain a thixotropic reducer. The thixotropic agent used in the flux (F4) includes, for example, an amide-based thixotropic agent, a sorbitol-based thixotropic agent, and a wax-based thixotropic agent (ester compound).

相對於助焊劑(F4)的全部質量,該搖變減黏劑的含量較佳為0.1至15.0質量%,更佳為0.2質量%以上10.0質量%以下。 Relative to the total mass of the flux (F4), the content of the thixotropic viscosity reducing agent is preferably from 0.1 to 15.0% by mass, more preferably from 0.2% by mass to 10.0% by mass.

此外,助焊劑(F4)可更含有例如松香以外的樹脂成分、界面活性劑、抗氧化劑等。 In addition, the flux (F4) may further contain, for example, resin components other than rosin, surfactants, antioxidants, and the like.

藉由將上述助焊劑(F4)與含有焊料合金(S1)至焊料合金(S9)中的任一種之焊料粉末組合,可提供一種焊料膏,其係不易發生黏度上升等之經時變化,潤濕性優異,具有高的機械特性,且焊料的潤濕性經提高者。 By combining the above-mentioned flux (F4) and solder powder containing any one of solder alloys (S1) to solder alloys (S9), a solder paste can be provided, which is less prone to changes in viscosity over time, such as increased viscosity. Excellent wettability, high mechanical properties, and improved solder wettability.

此外,根據助焊劑(F4),可提供一種焊料膏用助焊劑,其係可以提高增黏抑制效果,並且可以提高接合對象物之金屬表面的焊料潤濕性者。 In addition, according to the flux (F4), it is possible to provide a flux for solder paste that can increase the effect of suppressing the increase in viscosity and can improve the solder wettability of the metal surface of the object to be joined.

助焊劑(F5): Flux (F5):

助焊劑(F5)為含有唑類之組成物。 The flux (F5) is a composition containing azoles.

助焊劑(F5)例如可列舉出含有唑類與有機酸與松香與溶劑者,根據此型態,可提高接合對象物之金屬表面(例如銅板)的腐蝕抑制性。 Examples of the flux (F5) include those containing azoles, organic acids, rosin, and solvents. According to this type, the corrosion inhibitory properties of the metal surface (for example, copper plate) of the joining object can be improved.

在此所謂「唑類」,意指具有包含1個以上的氮原子之五員雜環結構之化合物,亦包含該五員雜環結構與其他環結構之縮合環。 The term "azoles" here means a compound having a five-membered heterocyclic structure containing one or more nitrogen atoms, and also includes a condensed ring of the five-membered heterocyclic structure and other ring structures.

唑類例如可列舉出:2-甲基咪唑、2-十一基咪唑、2-十七基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苯甲基-2-甲基咪唑、1-苯甲基-2-苯基咪唑、1-氰基乙基-2-甲基咪唑、1-氰基乙基-2-十一基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑、1-氰基乙基-2-苯基咪唑、2-苯基咪唑異 三聚氰酸加成物、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑、2,3-二氫-1H-吡咯[1,2-a]苯并咪唑、環氧基咪唑加成物、2-甲基苯并咪唑、2-辛基苯并咪唑、2-戊基苯并咪唑、2-(1-乙基戊基)苯并咪唑、2-壬基苯并咪唑、2-(4-噻唑基)苯并咪唑、苯并咪唑、2-(2'-羥基-5'-甲基苯基)苯并三唑、2-(2'-羥基-3'-三級丁基-5'-甲基苯基)-5-氯苯并三唑、2-(2'-羥基-3',5'-二(三級戊基)苯基)苯并三唑、2-(2'-羥基-5'-三級辛基苯基)苯并三唑、2,2'-亞甲基雙[6-(2H-苯并三唑-2-基)-4-三級辛基酚]、1,2,3-苯并三唑、1-[N,N-雙(2-乙基己基)胺基甲基]苯并三唑、羧基苯并三唑、1-[N,N-雙(2-乙基己基)胺基甲基]甲基苯并三唑、2,2'-[[(甲基-1H-苯并三唑-1-基)甲基]亞胺基]雙乙醇、1-(1',2'-二羧基乙基)苯并三唑、1-(2,3-二羧基丙基)苯并三唑、1-[(2-乙基己基胺基)甲基]苯并三唑、2,6-雙[(1H-苯并三唑-1-基)甲基]-4-甲基酚、5-甲基苯并三唑、5-苯基四唑、1-氰基乙基-2-十一基咪唑鎓偏苯三酸酯、1-氰基乙基-2-苯基咪唑鎓偏苯三酸酯、2,4-二胺基-6-[2'-甲基咪唑基-(1')]-乙基-均三嗪、2,4-二胺基-6-[2'-十一基咪唑基-(1')]-乙基-均三嗪、2,4-二胺基-6-[2'-乙基-4'-甲基咪唑基-(1')]-乙基-均三嗪、2,4-二胺基-6-[2'-甲基咪唑基-(1')]-乙基-均三嗪異三聚氰酸加成物、氯化1-十二基-2-甲基-3-苯甲基咪唑鎓、2-甲基咪唑啉、2-苯基咪唑啉、6-(2-苯并三唑基)4-三級辛基-6'-三級丁基-4'-甲基-2,2'-亞甲基雙酚等。 Examples of the azoles include: 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-benzene 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole , 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl Imidazole Cyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrole [1,2-a] Benzimidazole, epoxy imidazole adduct, 2-methylbenzimidazole, 2-octylbenzimidazole, 2-pentylbenzimidazole, 2-(1-ethyl Pentyl)benzimidazole, 2-nonylbenzimidazole, 2-(4-thiazolyl)benzimidazole, benzimidazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole Azole, 2-(2'-hydroxy-3'-tertiary butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di (Tertiary pentyl) phenyl) benzotriazole, 2-(2'-hydroxy-5'-tertiary octyl phenyl) benzotriazole, 2,2'-methylenebis[6-( 2H-benzotriazol-2-yl)-4-tertiary octylphenol], 1,2,3-benzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl Base]benzotriazole, carboxybenzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]methylbenzotriazole, 2,2'-[[(methyl -1H-benzotriazol-1-yl)methyl)imino)diethanol, 1-(1',2'-dicarboxyethyl)benzotriazole, 1-(2,3-dicarboxyl) Propyl)benzotriazole, 1-[(2-ethylhexylamino)methyl]benzotriazole, 2,6-bis[(1H-benzotriazol-1-yl)methyl]- 4-methylphenol, 5-methylbenzotriazole, 5-phenyltetrazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2 -Phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino -6-[2'-Undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl -(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid Adduct, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, 6-(2-benzotriazolyl) 4-tertiary octyl-6'-tertiary butyl-4'-methyl-2,2'-methylene bisphenol, etc.

唑類可單獨使用1種或混合2種以上而使用。 The azoles can be used individually by 1 type or in mixture of 2 or more types.

唑類較佳係選自由2-苯基咪唑、2-苯基-4-甲基咪唑、2-十七基咪唑、苯并咪唑及2-辛基苯并咪唑所組成群組中之至少一種,更佳係含有2-苯基咪唑。 The azoles are preferably at least one selected from the group consisting of 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, benzimidazole and 2-octylbenzimidazole , More preferably contains 2-phenylimidazole.

助焊劑(F5)較佳係含有相對於助焊劑(F5)的全部質量為0.1質量%以上10質量%以下的唑類,更佳係含有相對於助焊劑(F5)的全部質量為0.5質量%以上5.0質量%以下。 The flux (F5) preferably contains 0.1% by mass to 10% by mass relative to the total mass of the flux (F5), and more preferably contains 0.5% by mass relative to the total mass of the flux (F5) Above 5.0% by mass or less.

相對於助焊劑(F5)的全部質量,助焊劑(F5)所使用之有機酸的含量較佳為0.5質量%以上20質量%以下,更佳為3質量%以上18質量%以下。 Relative to the total mass of the flux (F5), the content of the organic acid used in the flux (F5) is preferably 0.5% by mass to 20% by mass, and more preferably 3% by mass to 18% by mass.

於助焊劑(F5)中,作為有機酸的含量/唑類的含量所表示之質量比,有機酸的含量與唑類的含量之比率較佳為0.5以上10以下,更佳為1以上9以下。若此質量比位於前述的較佳範圍內,則更容易提高接合對象物之金屬表面(例如銅板)的腐蝕抑制性。 In the flux (F5), as the mass ratio represented by the content of organic acid/content of azoles, the ratio of the content of organic acids to the content of azoles is preferably 0.5 or more and 10 or less, more preferably 1 or more and 9 or less . If this mass ratio is within the aforementioned preferable range, it is easier to improve the corrosion inhibitory properties of the metal surface (for example, copper plate) of the joining object.

於助焊劑(F5)中,相對於助焊劑(F5)的全部質量,有機酸的含量與唑類的含量之合計量較佳為3質量%以上25質量%以下,更佳為5質量%以上20質量%以下,又更佳為5質量%以上18質量%以下,特佳為5質量%以上15質量%以下。 In the flux (F5), the total amount of the organic acid content and the azole content relative to the total mass of the flux (F5) is preferably 3% by mass or more and 25% by mass or less, more preferably 5% by mass or more 20% by mass or less, more preferably 5% by mass or more and 18% by mass or less, particularly preferably 5% by mass or more and 15% by mass or less.

助焊劑(F5)所使用之松香例如可列舉出:脂松香、木松香及妥爾油松香等原料松香,以及從該原料松香所得到之衍生物。該衍生物例如可列舉出:精製松香、氫化松香、歧化松香、聚合松香、酸改質松香、酚改質松香及α,β不飽和羧酸改質物(丙烯酸化松香、順丁烯二酸化松香、反丁烯二酸化松香等),以及該聚合松香的精製物、氫化物及歧化物,以及該α,β不飽和羧酸改質物的精製物、氫化物及歧化物等,可使用此等的1種或2種以上。 The rosin used in the flux (F5) includes, for example, raw rosin such as gum rosin, wood rosin, and tall oil rosin, and derivatives derived from the raw rosin. Examples of such derivatives include refined rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, acid-modified rosin, phenol-modified rosin, and α,β-unsaturated carboxylic acid-modified products (acrylated rosin, maleated rosin, Fumarated rosin, etc.), as well as refined products, hydrides and disproportions of the polymerized rosin, and refined products, hydrides and disproportions of the modified α,β unsaturated carboxylic acid, etc., can be used 1 One or more than two.

助焊劑(F5)較佳係含有相對於助焊劑(F5)的全部質量為30質量%以上60質量%以下的松香,更佳係含有相對於助焊劑(F5)的全部質量為35質量%以上60質量%以下的松香。 The flux (F5) preferably contains 30% by mass or more and 60% by mass or less of rosin relative to the total mass of the flux (F5), and more preferably contains 35% by mass or more relative to the total mass of the flux (F5) Rosin less than 60% by mass.

助焊劑(F5)所使用之溶劑可列舉出:水、醇系溶劑、二醇醚系溶劑、萜品醇類等。 Examples of the solvent used in the flux (F5) include water, alcohol-based solvents, glycol ether-based solvents, and terpineols.

助焊劑(F5)可更含有胺、有機鹵素化合物、胺氫鹵酸鹽。 The flux (F5) may further contain amines, organic halogen compounds, and amine hydrohalides.

此外,助焊劑(F5)可更含有搖變減黏劑。助焊劑(F5)所使用之搖變減黏劑例如可列舉出:醯胺系搖變減黏劑、山梨醇系搖變減黏劑、蠟系搖變減黏劑(酯化合物)等。 In addition, the flux (F5) can contain a thixotropic reducer. Examples of the thixotropic agent used in the flux (F5) include amide-based thixotropic agent, sorbitol-based thixotropic agent, wax-based thixotropic agent (ester compound), and the like.

相對於助焊劑(F5)的全部質量,該搖變減黏劑的含量較佳為0.1至15.0質量%,更佳為0.2質量%以上10.0質量%以下,又更佳為1.0質量%以上10.0質量%以下,特佳為2.0質量%以上8.3質量%以下。 Relative to the total mass of the flux (F5), the content of the thixotropic viscosity reducing agent is preferably 0.1 to 15.0 mass%, more preferably 0.2 mass% or more and 10.0 mass% or less, and still more preferably 1.0 mass% or more and 10.0 mass% % Or less, particularly preferably 2.0% by mass or more and 8.3% by mass or less.

此外,助焊劑(F5)可更含有例如松香以外的樹脂成分、界面活性劑、抗氧化劑等。 In addition, the flux (F5) may further contain, for example, resin components other than rosin, surfactants, antioxidants, and the like.

藉由將上述助焊劑(F5)與含有焊料合金(S1)至焊料合金(S9)中的任一種之焊料粉末組合,可提供一種焊料膏,其係不易發生黏度上升等之經時變化,潤濕性優異,具有高的機械特性,並且可提高接合對象物之金屬表面(例如銅板)的腐蝕抑制能力者。 By combining the above-mentioned flux (F5) with solder powder containing any one of solder alloys (S1) to solder alloys (S9), a solder paste can be provided, which is less prone to changes in viscosity over time, such as increase in viscosity. It has excellent wettability, high mechanical properties, and can improve the corrosion inhibition ability of the metal surface (for example, copper plate) of the object to be joined.

此外,根據助焊劑(F5),可提供一種焊料膏用助焊劑,其係能夠提高接合對象物之金屬表面(例如銅板)的腐蝕抑制性者。 In addition, according to the flux (F5), it is possible to provide a flux for solder paste that can improve the corrosion inhibition of the metal surface (for example, copper plate) of the object to be joined.

助焊劑(F6): Flux (F6):

助焊劑(F6)為含有芳香族胍化合物之組成物。 The flux (F6) is a composition containing an aromatic guanidine compound.

助焊劑(F6)例如可列舉出含有芳香族胍化合物與松香與有機酸與溶劑者。 The flux (F6) includes, for example, those containing an aromatic guanidine compound, rosin, an organic acid, and a solvent.

芳香族胍化合物例如可列舉出:二苯基胍(diphenyl guanidine)、二甲苯基胍(ditolyl guanidine)等。 Examples of the aromatic guanidine compound include diphenyl guanidine and ditolyl guanidine.

芳香族胍化合物可單獨使用1種或混合2種以上而使用。 An aromatic guanidine compound can be used individually by 1 type or in mixture of 2 or more types.

前述芳香族胍化合物較佳係選自由二苯基胍及二甲苯基胍所組成群組中之至少一種,更佳係含有二苯基胍。 The aforementioned aromatic guanidine compound is preferably at least one selected from the group consisting of diphenylguanidine and xylylguanidine, and more preferably contains diphenylguanidine.

相對於助焊劑(F6)的全部質量,助焊劑(F6)較佳係含有0.2質量%以上15質量%以下的芳香族胍化合物,更佳係含有0.5質量%以上7.0質量%以下的芳香族胍化合物。 Relative to the total mass of the flux (F6), the flux (F6) preferably contains 0.2% by mass or more and 15% by mass or less of aromatic guanidine compounds, more preferably 0.5% by mass or more and 7.0% by mass or less of aromatic guanidine compounds Compound.

助焊劑(F6)所使用之松香例如可列舉出天然松香以及從該天然松香所得到之衍生物等。天然松香例如可列舉出:脂松香、木松香及妥爾油松香等。該衍生物例如可列舉出精製松香、改質松香等。改質松香可列舉出:氫化松香、聚合松香、歧化松香、酸改質松香、松香酯、酚改質松香及α,β不飽和羧酸改質物(丙烯酸化松香、順丁烯二酸化松香、反丁烯二酸化松香、丙烯酸改質氫化松香等),以及該聚合松香的精製物、氫化物及歧化物,以及該α,β不飽和羧酸改質物的精製物、氫化物及歧化物等,可使用此等的1種或2種以上。 The rosin used in the flux (F6) includes, for example, natural rosin and derivatives derived from the natural rosin. Examples of natural rosin include gum rosin, wood rosin, tall oil rosin, and the like. Examples of such derivatives include refined rosin and modified rosin. The modified rosin can include: hydrogenated rosin, polymerized rosin, disproportionated rosin, acid-modified rosin, rosin ester, phenol-modified rosin, and α, β-unsaturated carboxylic acid-modified products (acrylated rosin, maleated rosin, reverse Butenediolated rosin, acrylic modified hydrogenated rosin, etc.), as well as refined products, hydrides and disproportions of the polymerized rosin, and refined products, hydrides and disproportions of the modified α, β unsaturated carboxylic acids, etc. Use one or more of these.

助焊劑(F6)較佳係含有相對於助焊劑(F6)的全部質量為15質量%以上70質量%以下的松香,更佳係含有相對於助焊劑(F6)的全部質量為35質量%以上60質量%以下的松香。 The flux (F6) preferably contains 15% by mass or more and 70% by mass or less of rosin relative to the total mass of the flux (F6), and more preferably contains 35% by mass or more relative to the total mass of the flux (F6) Rosin less than 60% by mass.

相對於助焊劑(F6)的全部質量,助焊劑(F6)所使用之有機酸的含量較佳為0.1質量%以上15質量%以下,更佳為0.2質量%以上10質量%以下。 The content of the organic acid used in the flux (F6) is preferably 0.1% by mass to 15% by mass, and more preferably 0.2% by mass to 10% by mass, relative to the total mass of the flux (F6).

於助焊劑(F6)中,相對於助焊劑(F6)的全部質量,較佳係含有合計為2質量%以上18質量%以下之有機酸與芳香族胍化合物,更佳係含有合計為3質量%以上18質量%以下之有機酸與芳香族胍化合物。 In the flux (F6), relative to the total mass of the flux (F6), it is preferable to contain an organic acid and an aromatic guanidine compound in a total amount of 2% by mass to 18% by mass, and more preferably a total of 3 mass% % To 18% by mass or less of organic acids and aromatic guanidine compounds.

助焊劑(F6)所使用之溶劑可列舉出:水、醇系溶劑、二醇醚系溶劑、萜品醇類等。 Examples of the solvent used in the flux (F6) include water, alcohol-based solvents, glycol ether-based solvents, and terpineols.

助焊劑(F6)可更含有搖變減黏劑。 Flux (F6) can further contain thixotropic viscosity reducer.

助焊劑(F6)所使用之搖變減黏劑例如可列舉出醯胺系搖變減黏劑、山梨醇系搖變減黏劑、蠟系搖變減黏劑(酯化合物)等。 The thixotropic agent used in the flux (F6) includes, for example, an amide-based thixotropic agent, a sorbitol-based thixotropic agent, and a wax-based thixotropic agent (ester compound).

相對於助焊劑(F6)的全部質量,該搖變減黏劑的含量較佳為0.1至15.0質量%,更佳為0.2質量%以上10.0質量%以下。 Relative to the total mass of the flux (F6), the content of the thixotropic viscosity reducing agent is preferably 0.1 to 15.0% by mass, more preferably 0.2% by mass to 10.0% by mass.

助焊劑(F6)可更含有胺、有機鹵素化合物、胺氫鹵酸鹽。 The flux (F6) may further contain amines, organic halogen compounds, and amine hydrohalides.

此外,助焊劑(F6)可更含有例如松香以外的樹脂成分、界面活性劑、抗氧化劑等。 In addition, the flux (F6) may further contain, for example, resin components other than rosin, surfactants, antioxidants, and the like.

藉由將上述助焊劑(F6)與含有焊料合金(S1)至焊料合金(S9)中的任一種之焊料粉末組合,可提供一種焊料膏,其係不易發生黏度上升等之經時變化,潤濕性優異,具有高的機械特性,且焊料對於接合對象物的金屬表面之潤濕速度經提高者。 By combining the above-mentioned flux (F6) and solder powder containing any one of solder alloys (S1) to solder alloys (S9), a solder paste can be provided, which is less prone to changes in viscosity over time, such as increase in viscosity. It has excellent wettability, high mechanical properties, and the wetting speed of the solder to the metal surface of the joining object has been improved.

此外,根據助焊劑(F6),可提供一種焊料膏用助焊劑,其係焊料對於接合對象物的金屬表面之潤濕速度高且焊料潤濕性良好者。 In addition, according to the flux (F6), it is possible to provide a flux for solder paste, which has a high wettability of the solder to the metal surface of the object to be joined and good solder wettability.

助焊劑(F7): Flux (F7):

助焊劑(F7)為含有屬於醯胺化合物之醯胺系搖變減黏劑之組成物。 The flux (F7) is a composition containing an amide-based thixotropic agent, which is a amide compound.

助焊劑(F7)例如可列舉出:含有前述屬於醯胺化合物之醯胺系搖變減黏劑、與有機酸、與選自由松香系樹脂及丙烯酸系樹脂所組成群組中的至少一種之樹脂成分、與溶劑者。 The flux (F7) includes, for example, a resin containing at least one of the aforementioned amide-based thixotropic agent, which is a amide compound, an organic acid, and at least one selected from the group consisting of rosin-based resins and acrylic resins. Ingredients and solvents.

醯胺系搖變減黏劑(醯胺化合物)例如可列舉出聚醯胺、雙醯胺、單醯胺。 Examples of the amide-based thixotropic viscosity-reducing agent (amide compound) include polyamide, bisamide, and monoamide.

該醯胺系搖變減黏劑(醯胺化合物)例如可列舉出:月桂醯胺、棕櫚醯胺、硬脂醯胺、山萮醯胺、羥基硬脂醯胺、飽和脂肪醯胺、油醯胺、芥子醯胺、不飽和脂肪醯胺、對甲苯醯胺、對甲苯甲烷醯胺、芳香族醯胺、六亞甲基羥基硬脂醯胺、取代醯胺、羥甲基硬脂醯胺、羥甲基醯胺、脂肪酸酯醯胺等單醯胺;亞甲基雙硬脂醯胺、乙烯雙月桂醯胺、乙烯雙羥基脂肪(脂肪酸的碳數C6至C24)醯胺、乙烯雙羥基硬脂醯胺、飽和脂肪雙醯胺、亞甲基雙油醯胺、不飽和脂肪雙醯胺、間二甲苯雙硬脂醯胺、芳香族雙醯胺等雙醯胺;飽和脂肪酸聚醯胺、不飽和脂肪酸聚醯胺、芳香族聚醯胺、1,2,3-丙烷三羧酸三(2-甲基環己基醯胺)、環狀醯胺低聚物、非環狀醯胺低聚物等聚醯胺。 The amide-based thixotropic viscosity reducing agent (amide compound) includes, for example, lauryl amide, palm amide, stearyl amide, behenyl amide, hydroxystearyl amide, saturated fatty amide, and oleamide. Amine, mustard amide, unsaturated fatty amide, p-toluamide, p-toluene methane amide, aromatic amide, hexamethylene hydroxystearyl amide, substituted amide, methylol stearyl amide, Monoamines such as hydroxymethyl amide and fatty acid ester amide; methylene bis-stearyl amide, ethylene bis-lauric amide, ethylene dihydroxy fat (fatty acid carbon number C6 to C24) amide, ethylene dihydroxy Stearyl amine, saturated fatty bisamide, methylene bis-oleamide, unsaturated fatty bis-amide, meta-xylene bis-stearyl amide, aromatic bis-amide, etc.; saturated fatty acid polyamide , Unsaturated fatty acid polyamide, aromatic polyamide, 1,2,3-propane tricarboxylic acid tris (2-methylcyclohexyl amide), cyclic amide oligomer, acyclic amide low Polymers and other polyamides.

前述環狀醯胺低聚物可列舉出:二羧酸與二胺經環狀縮聚之醯胺低聚物、三羧酸與二胺經環狀縮聚之醯胺低聚物、二羧酸與三胺經環狀縮聚之醯胺低聚物、三羧酸與三胺經環狀縮聚之醯胺低聚物、二羧酸及三羧酸與二胺經環狀縮聚之醯胺低聚物、二羧酸及三羧酸與三胺經環狀縮聚之醯胺低聚物、二羧酸與二胺及三胺經環狀縮聚之醯胺低聚物、三羧酸與二胺及三胺經環狀縮聚之醯胺低聚物、二羧酸及三羧酸與二胺及三胺經環狀縮聚之醯胺低聚物等。 The aforementioned cyclic amide oligomers include: dicarboxylic acid and diamine cyclic polycondensation amide oligomer, tricarboxylic acid and diamine cyclic polycondensation amide oligomer, dicarboxylic acid and Amine oligomers obtained by cyclic condensation polymerization of triamines, amide oligomers obtained by cyclic condensation polymerization of tricarboxylic acids and triamines, amide oligomers obtained by cyclic condensation polymerization of dicarboxylic acids and tricarboxylic acids and diamines , Dicarboxylic acid and tricarboxylic acid and triamine by cyclic polycondensation of amide oligomer, dicarboxylic acid and diamine and triamine by cyclic polycondensation of amide oligomer, tricarboxylic acid and diamine and triamine Amine oligomers obtained by cyclic polycondensation of amines, amide oligomers obtained by cyclic polycondensation of dicarboxylic acids and tricarboxylic acids with diamines and triamines, etc.

此外,前述非環狀醯胺低聚物可列舉出:單羧酸與二胺及/或三胺經非環狀縮聚之醯胺低聚物之情形,以及二羧酸及/或三羧酸與單胺經非環狀縮聚之醯胺低聚物之情形等。當為包含單羧酸或單胺之醯胺低聚物時,單羧酸、單胺係發揮終端分子(terminal molecules)的功能,而成為降低分子量之非環狀醯胺低聚物。此外,在非環狀醯胺低聚物為二羧酸及/或三羧酸與二胺及/或三胺經非環狀縮聚之醯胺化合物之情形下,係成為非環狀高分子系醯胺聚合物。再者,非環狀醯胺低聚物亦包含單羧酸與單胺經非環狀縮聚之醯胺低聚物。 In addition, the aforementioned non-cyclic amide oligomers include: monocarboxylic acid and diamine and/or triamine through non-cyclic polycondensation of amide oligomer, and dicarboxylic acid and/or tricarboxylic acid In the case of amide oligomers that are non-cyclic polycondensed with monoamines, etc. In the case of an amide oligomer containing a monocarboxylic acid or a monoamine, the monocarboxylic acid and monoamine function as a terminal molecule and become an acyclic amide oligomer with a lower molecular weight. In addition, when the acyclic amide oligomer is a dicarboxylic acid and/or tricarboxylic acid and diamine and/or triamine through acyclic polycondensation of the amide compound, it becomes a non-cyclic polymer system Amide polymer. Furthermore, the non-cyclic amide oligomer also includes a non-cyclic polycondensation of a monocarboxylic acid and a monoamine.

本實施型態之助焊劑(F7)所含有之醯胺系搖變減黏劑(醯胺化合物),較佳係使用含有選自由聚醯胺、雙醯胺及單醯胺所組成群組中的至少一種者。其中更佳係使用選自由對甲苯醯胺、乙烯雙羥基脂肪(C6至C24)醯胺、六亞甲基羥基硬脂醯胺、1,2,3-丙烷三羧酸三(2-甲基環己醯胺)、聚醯胺及環狀醯胺低聚物所組成群組中的至少一種。 The amide-based thixotropic agent (amide compound) contained in the flux (F7) of this embodiment is preferably selected from the group consisting of polyamide, bisamide and monoamide At least one of. Among them, it is more preferable to use selected from p-toluamide, ethylene dihydroxy fatty acid (C6 to C24) amide, hexamethylene hydroxystearyl amide, 1,2,3-propane tricarboxylic acid tris (2-methyl At least one of the group consisting of cyclohexamide), polyamide and cyclic amide oligomer.

本實施型態之助焊劑(F7)之醯胺系搖變減黏劑的含量,相對於前述助焊劑(F7)的全部質量較佳係超過0質量%且為15質量%以下,更佳為1.5質量%以上10.0質量%以下。 The content of the amide-based thixotropic viscosity reducer of the flux (F7) of this embodiment is preferably more than 0% by mass and 15% by mass or less relative to the total mass of the aforementioned flux (F7), more preferably 1.5% by mass or more and 10.0% by mass or less.

醯胺化合物以外的搖變減黏劑可列舉出蠟系搖變減黏劑。蠟系搖變減黏劑例如可列舉出酯化合物,具體可列舉出蓖麻硬化油。本實施型態之助焊劑較佳係含有相對於前述助焊劑(F7)的全部質量為0質量%以上15質量%以下的酯化合物,更佳係含有超過0質量%且為12.0質量%以下的酯化合物。 Examples of thixotropic agents other than amide compounds include wax-based thixotropic agents. Examples of the wax-based thixotropic agent include ester compounds, and specific examples include castor oil. The flux of this embodiment preferably contains an ester compound of 0% by mass to 15% by mass relative to the total mass of the aforementioned flux (F7), and more preferably contains more than 0% by mass and 12.0% by mass or less Ester compound.

本實施型態之助焊劑相對於前述助焊劑(F7)的全部質量,較佳係含有合計為3.0質量%以上15.0質量%以下之屬於搖變減黏劑之醯胺化合物與酯化合物,更佳係含有5.0質量%以上10.0質量%以下之屬於搖變減黏劑之醯胺化合物與酯化合物。 The flux of this embodiment preferably contains 3.0 mass% to 15.0 mass% of the total mass of the flux (F7), which is a thixotropic viscosity reducer, of an amide compound and an ester compound, more preferably Contains 5.0% by mass or more and 10.0% by mass or less of amide compounds and ester compounds which are thixotropic viscosity reducers.

相對於助焊劑(F7)的全部質量,助焊劑(F7)所使用之有機酸的含量較佳為0.1質量%以上15質量%以下,更佳為0.2質量%以上10質量%以下。 Relative to the total mass of the flux (F7), the content of the organic acid used in the flux (F7) is preferably 0.1% by mass to 15% by mass, and more preferably 0.2% by mass to 10% by mass.

相對於助焊劑(F7)的全部質量,助焊劑(F7)較佳係含有15質量%以上70質量%以下之選自由松香系樹脂及丙烯酸系樹脂所組成群組中的至少一種之樹脂成分,更佳係含有相對於助焊劑(F7)的全部質量為35質量%以上60質量%以下。 Relative to the total mass of the flux (F7), the flux (F7) preferably contains 15% by mass or more and 70% by mass or less of at least one resin component selected from the group consisting of rosin-based resins and acrylic resins, More preferably, the content is 35% by mass or more and 60% by mass or less with respect to the total mass of the flux (F7).

助焊劑(F7)所使用之溶劑可列舉出:水、醇系溶劑、二醇醚系溶劑、萜品醇類等。 Examples of the solvent used in the flux (F7) include water, alcohol-based solvents, glycol ether-based solvents, and terpineols.

助焊劑(F7)可更含有松香系樹脂及丙烯酸系樹脂以外的樹脂成分、胺、鹵素系活性劑、界面活性劑、抗氧化劑等。 The flux (F7) may further contain resin components other than rosin-based resins and acrylic resins, amines, halogen-based activators, surfactants, antioxidants, and the like.

藉由將上述助焊劑(F7)與含有焊料合金(S1)至焊料合金(S9)中的任一種之焊料粉末組合,可提供一種焊料膏,其係不易發生黏度上升等之經時變化,潤濕性優異,具有高的機械特性,並且不易產生印刷流掛及加熱流掛者。 By combining the above-mentioned flux (F7) and solder powder containing any one of solder alloys (S1) to solder alloys (S9), a solder paste can be provided, which is less prone to changes in viscosity over time, such as increased viscosity. Excellent wettability, high mechanical properties, and not easy to produce printing sagging and heating sagging.

此外,根據助焊劑(F7),可提供一種焊料膏用助焊劑,其係不易產生稱為印刷流掛之印刷後的焊料的流掛、和稱為加熱流掛之藉由加熱而熔融時之焊料的流掛者。 In addition, according to the flux (F7), a flux for solder paste can be provided, which is less likely to cause the sag of the solder after printing called printing sag, and the sag that is called heating sag when it is melted by heating. The sag of solder.

助焊劑(F8): Flux (F8):

助焊劑(F8)為含有屬於山梨醇化合物之山梨醇系搖變減黏劑之組成物。 The flux (F8) is a composition containing a sorbitol-based thixotropic agent which is a sorbitol compound.

助焊劑(F8)例如可列舉出:含有前述屬於山梨醇化合物之山梨醇系搖變減黏劑與松香系樹脂與溶劑者。 Examples of the flux (F8) include those containing the aforementioned sorbitol-based thixotropic agent which is a sorbitol compound, a rosin-based resin, and a solvent.

山梨醇系搖變減黏劑(山梨醇化合物)例如可列舉出二苯亞甲基山梨醇、雙(4-甲基苯亞甲基)-D-山梨醇等。 Examples of the sorbitol-based thixotropic viscosity reducer (sorbitol compound) include dibenzylidene sorbitol, bis(4-methylbenzylidene)-D-sorbitol, and the like.

相對於助焊劑(F8)的全部質量,此山梨醇系搖變減黏劑的含量較佳為0.2質量%以上,更佳為0.5質量%以上,又更佳為0.5質量%以上5.0質量%以下,特佳為0.5質量%以上3.5質量%以下。 The content of the sorbitol-based thixotropic viscosity reducer relative to the total mass of the flux (F8) is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and still more preferably 0.5% by mass or more and 5.0% by mass or less , Particularly preferably 0.5% by mass or more and 3.5% by mass or less.

本實施型態之助焊劑(F8)所使用之搖變減黏劑,亦可併用前述山梨醇系搖變減黏劑以外的搖變減黏劑。 The thixotropic viscosity reducer used in the flux (F8) of this embodiment can also be used in combination with a thixotropic viscosity reducer other than the aforementioned sorbitol-based thixotropic reducer.

山梨醇系搖變減黏劑以外的搖變減黏劑例如可列舉出山梨醇系添加劑、其他搖變減黏劑等。 Examples of the thixotropic agent other than the sorbitol-based thixotropic agent include sorbitol-based additives and other thixotropic agents.

山梨醇系添加劑可列舉出:(D-)山梨醇、單苯亞甲基(-D-)山梨醇、單(4-甲基苯亞甲基)-(D-)山梨醇等。 Examples of sorbitol-based additives include (D-)sorbitol, monobenzylidene (-D-)sorbitol, mono(4-methylbenzylidene)-(D-)sorbitol, and the like.

相對於助焊劑(F8)的全部質量,此山梨醇系添加劑的含量較佳係超過0質量%且為0.035質量%以下,更佳為0.00025質量%以上0.035質量%以下。 The content of this sorbitol-based additive relative to the total mass of the flux (F8) is preferably more than 0% by mass and 0.035% by mass or less, more preferably 0.00025% by mass or more and 0.035% by mass or less.

其他搖變減黏劑可列舉出選自由蠟系搖變減黏劑及醯胺系搖變減黏劑(醯胺化合物)所組成群組中的至少一種。 Other thixotropic agents can include at least one selected from the group consisting of wax-based thixotropic agents and amide-based thixotropic agents (amide compounds).

屬於其他搖變減黏劑之蠟系搖變減黏劑例如可列舉出酯化合物,具體上可列舉出蓖麻硬化油等。 Examples of wax-based thixotropic agents belonging to other thixotropic agents include ester compounds, specifically, castor oil and the like.

屬於其他搖變減黏劑之醯胺系搖變減黏劑(醯胺化合物)例如可列舉出前述聚醯胺、雙醯胺、單醯胺。 Examples of the amide-based thixotropic agent (amide compound) that are other thixotropic viscosity reducers include the aforementioned polyamides, bisamides, and monoamides.

相對於助焊劑(F8)的全部質量,該其他搖變減黏劑的含量較佳為0.5至15.0質量%,更佳為1質量%以上10質量%以下。 Relative to the total mass of the flux (F8), the content of the other thixotropic viscosity reducing agent is preferably 0.5 to 15.0% by mass, more preferably 1% by mass to 10% by mass.

相對於助焊劑(F8)的全部質量,本實施型態之助焊劑(F8)較佳係含有合計為2質量%以上15質量%以下之山梨醇系搖變減黏劑及其他搖變減黏劑;相對於助焊劑(F8)的全部質量,更佳係含有合計為2.5質量%以上11.5質量%以下之山梨醇系搖變減黏劑及其他搖變減黏劑。 Relative to the total mass of the flux (F8), the flux (F8) of this embodiment preferably contains a total of 2% by mass to 15% by mass of a sorbitol-based thixotropic viscosity reducing agent and other tremor reducing viscosity Agent; relative to the total mass of the flux (F8), it is more preferable to contain a total of 2.5% by mass to 11.5% by mass of sorbitol-based thixotropic agent and other thixotropic agents.

就本實施型態之助焊劑(F8)而言,相對於助焊劑(F8)的全部質量,搖變減黏劑的總量較佳係含有2質量%以上15質量%以下,更佳係含有2.5質量%以上11.5質量%以下。 Regarding the flux (F8) of this embodiment, relative to the total mass of the flux (F8), the total amount of the thixotropic viscosity reducer is preferably 2% by mass or more and 15% by mass or less, and more preferably contains 2.5% by mass or more and 11.5% by mass or less.

相對於本實施型態之助焊劑(F8)的全部質量之搖變減黏劑,較佳係組合使用:選自由二苯亞甲基山梨醇及雙(4-甲基苯亞甲基)山梨醇所組成群組中的至少一種之山梨醇系搖變減黏劑,與除此之外的搖變減黏劑。藉此,除了賦予搖變減黏性之外,亦變得容易抑制助焊劑及使用該助焊劑之焊料膏中之結晶的析出、結塊的產生。 Relative to the total mass of the flux (F8) of this embodiment, the thixotropic viscosity reducing agent is preferably used in combination: selected from benzhydryl sorbitol and bis(4-methylbenzylidene) sorbitol At least one sorbitol-based thixotropic agent in the group consisting of alcohols, and other thixotropic agents. Thereby, in addition to imparting thixotropic viscosity reduction, it becomes easy to suppress the precipitation of crystals in the flux and the solder paste using the flux and the occurrence of agglomeration.

本實施型態之助焊劑(F8)的搖變減黏劑較佳係併用前述山梨醇系搖變減黏劑與前述山梨醇系添加劑。 The thixotropy reducing agent of the flux (F8) of this embodiment is preferably a combination of the aforementioned sorbitol-based thixotropic reducing agent and the aforementioned sorbitol-based additive.

更佳的搖變減黏劑係含有前述山梨醇系搖變減黏劑與山梨醇系添加劑,該山梨醇系添加劑係選自由(D-)山梨醇、單苯亞甲基(-D-)山梨醇及單(4-甲基苯亞甲基)-(D-)山梨醇所組成群組中的至少一種。 A more preferable thixotropic viscosity reducer system contains the aforementioned sorbitol-based thixotropic viscosity reducer and a sorbitol-based additive, and the sorbitol-based additive is selected from (D-)sorbitol and monobenzylidene (-D-) At least one of sorbitol and mono(4-methylbenzylidene)-(D-)sorbitol.

前述山梨醇系添加劑相對於前述山梨醇系搖變減黏劑之比率(質量比)較佳為0.03至1.50,更佳為0.05至1.00。 The ratio (mass ratio) of the aforementioned sorbitol-based additive to the aforementioned sorbitol-based thixotropic agent is preferably 0.03 to 1.50, more preferably 0.05 to 1.00.

此外,本實施型態之助焊劑(F8)的搖變減黏劑較佳係併用:前述山梨醇系搖變減黏劑、與前述山梨醇系添加劑、與前述其他搖變減黏劑。 In addition, the thixotropy reducing agent of the flux (F8) of this embodiment is preferably used in combination: the aforementioned sorbitol-based thixotropy reducing agent, the aforementioned sorbitol-based additive, and the aforementioned other thixotropic reducing agent.

助焊劑(F8)較佳係含有相對於助焊劑(F8)的全部質量為15質量%以上70質量%以下的松香系樹脂,更佳係含有相對於助焊劑(F8)的全部質量為35質量%以上60質量%以下的松香系樹脂。 Flux (F8) preferably contains 15% to 70% by mass of rosin resin relative to the total mass of flux (F8), and more preferably contains 35% by mass relative to the total mass of flux (F8) Rosin-based resin containing 60% or more and 60% by mass or less.

助焊劑(F8)所使用之溶劑可列舉出:水、醇系溶劑、二醇醚系溶劑、萜品醇類等。 Examples of the solvent used for the flux (F8) include water, alcohol-based solvents, glycol ether-based solvents, and terpineols.

助焊劑(F8)可更含有搖變減黏劑、松香系樹脂及溶劑以外的樹脂成分,例如可列舉出:有機酸、胺、鹵素系活性劑、界面活性劑、抗氧化劑等。 The flux (F8) may further contain resin components other than a thixotropic agent, a rosin-based resin, and a solvent, and examples thereof include organic acids, amines, halogen-based activators, surfactants, and antioxidants.

藉由將上述助焊劑(F8)與含有焊料合金(S1)至焊料合金(S9)中的任一種之焊料粉末組合,可提供一種焊料膏,其係不易發生黏度上升等之經時變化,潤濕性優異,具有高的機械特性,並且流動性及保形性良好者。 By combining the above-mentioned flux (F8) and solder powder containing any one of solder alloys (S1) to solder alloys (S9), a solder paste can be provided, which is less prone to changes in viscosity over time, such as increase in viscosity. Excellent wettability, high mechanical properties, and good fluidity and shape retention.

此外,根據助焊劑(F8),可提供一種焊料膏用助焊劑,其係能夠賦予充分的搖變減黏性,較佳係抑制結晶的析出且不易產生結塊者。 In addition, according to the flux (F8), it is possible to provide a flux for solder paste, which can impart sufficient thixotropic viscosity reduction, and preferably suppresses the precipitation of crystals and is less likely to cause agglomeration.

又,焊料膏往印刷電路板的電極上之供給,通常是藉由分注吐出或網版印刷來進行。因此,對於焊料膏係要求吐出性、脫版等之印刷性,再者,於供給後亦須保持其形狀。於焊料膏中,兼具於吐出/印刷時的流動性(低黏性)與供給後的保形性(高黏性)之流動特性(搖變減黏性),於近年來持續往高密度化發展之基板表面組裝中的細微間距印刷時,乃成為重要的因素。 In addition, the supply of solder paste to the electrodes of the printed circuit board is usually performed by dispensing discharge or screen printing. Therefore, the solder paste is required to have printing properties such as ejection and release, and moreover, it must maintain its shape after being supplied. In the solder paste, it has both fluidity (low viscosity) during discharge/printing and flow characteristics (thixotropic viscosity reduction) after supplying shape retention (high viscosity). In recent years, it has continued to increase in density. The fine pitch printing in the surface assembly of substrates has become an important factor.

助焊劑(F9): Flux (F9):

助焊劑(F9)為一併具有二醇系溶劑與有機酸酯之組成物。 The flux (F9) is a composition having both a glycol solvent and an organic acid ester.

助焊劑(F9)例如可列舉出含有樹脂成分與溶劑與各種活性成分者。較佳的助焊劑(F9)可列舉出含有松香系樹脂與有機酸與作為溶劑之二醇系溶劑及有機酸酯者。 Examples of the flux (F9) include those containing a resin component, a solvent, and various active ingredients. Preferable flux (F9) includes those containing rosin-based resin, organic acid, and glycol-based solvents and organic acid esters as solvents.

可使用在助焊劑(F9)之松香系樹脂例如可列舉出:脂松香、木松香等天然松香或是其衍生物(聚合松香、氫化松香、歧化松香、酸改質松香、松香酯等)。 Rosin-based resins that can be used in the flux (F9) include, for example, natural rosins such as gum rosin and wood rosin or their derivatives (polymerized rosin, hydrogenated rosin, disproportionated rosin, acid-modified rosin, rosin ester, etc.).

助焊劑(F9)中之松香系樹脂的含量並無特別限定,例如相對於助焊劑(F9)的全部質量,較佳為10至80質量%的範圍內,更佳為20至70質量%的範圍內,又更佳為30至60質量%的範圍內。 The content of the rosin resin in the flux (F9) is not particularly limited. For example, relative to the total mass of the flux (F9), it is preferably in the range of 10 to 80% by mass, more preferably 20 to 70% by mass. Within the range, it is more preferably within the range of 30 to 60% by mass.

助焊劑(F9)中之有機酸的含量並無特別限定,例如相對於助焊劑(F9)的全部質量,較佳為1至15質量%的範圍內,更佳為3至10質量%的範圍內。 The content of the organic acid in the flux (F9) is not particularly limited. For example, relative to the total mass of the flux (F9), it is preferably in the range of 1 to 15% by mass, more preferably in the range of 3 to 10% by mass Inside.

於本實施型態之助焊劑(F9)中,溶劑係至少一併具有二醇系溶劑與有機酸酯。如此有機酸酯的沸點位於適當的範圍,於一般的焊接所採用之接合溫度下,在接合初期係殘存於助焊劑中以保持助焊劑的熔融黏度為低者,而容易釋放分解氣體等,並且於接合後期亦有一定程度的揮發。 In the flux (F9) of this embodiment, the solvent has at least a diol solvent and an organic acid ester. The boiling point of the organic acid ester is in the proper range. At the bonding temperature used in general soldering, it remains in the flux in the initial stage of bonding to keep the melt viscosity of the flux low, and it is easy to release decomposition gas, etc., and There is also a certain degree of volatilization in the later stage of joining.

在此所謂「二醇系溶劑」,意指由二醇(具有於脂肪族或脂環式烴的2個相異碳原子各鍵結1個羥基之結構之化合物)或其衍生物所構成之溶劑。 The term "diol-based solvent" here means a diol (a compound having a structure in which two different carbon atoms of an aliphatic or alicyclic hydrocarbon are each bonded to a hydroxyl group) or its derivatives. Solvent.

於本實施型態之助焊劑(F9)中,二醇系溶劑的種類並無特別限定,例如可使用一般使用在焊接用助焊劑者。就二醇系溶劑的具體例而言,除了二乙二醇、二丙二醇、三乙二醇、己二醇、苯基甘醇、己基二甘醇、2-乙基己基二甘醇之外,可列舉出:二乙二醇單丁醚(丁基卡必醇)、二乙二醇單甲醚(甲基卡必醇)、二乙二醇單己醚(己基卡必醇)、丙二醇單苯醚等二醇醚類。 In the flux (F9) of this embodiment, the type of glycol solvent is not particularly limited. For example, fluxes generally used for soldering can be used. With regard to specific examples of glycol-based solvents, in addition to diethylene glycol, dipropylene glycol, triethylene glycol, hexanediol, phenyl glycol, hexyl diethylene glycol, and 2-ethylhexyl diethylene glycol, Examples include: diethylene glycol monobutyl ether (butyl carbitol), diethylene glycol monomethyl ether (methyl carbitol), diethylene glycol monohexyl ether (hexyl carbitol), propylene glycol mono Glycol ethers such as phenyl ether.

此等當中,較佳為碳數2至24之醇的二醇醚(具體而言為單二醇醚(碳數:4至26)、二甘醇醚(碳數:6至28)、低聚二醇醚(碳數:2+2×n至24+2×n),更佳為碳數4至16的醇之二醇醚,特佳為碳數6至8的醇之二醇醚。 Among these, glycol ethers of alcohols having 2 to 24 carbon atoms (specifically, monoglycol ether (carbon number: 4 to 26), diethylene glycol ether (carbon number: 6 to 28), low Polyglycol ether (carbon number: 2+2×n to 24+2×n), more preferably glycol ether of alcohol with carbon number 4 to 16, particularly preferably glycol ether of alcohol with carbon number 6 to 8 .

二醇系溶劑可單獨使用一種或併用兩種以上。 The diol-based solvent may be used alone or in combination of two or more.

助焊劑(F9)中之二醇系溶劑的含量(在使用複數種二醇系溶劑之情形時為其總含量)並無特別限定,例如相對於助焊劑(F9)的全部質量,較佳為在10至60質量%的範圍內,更佳為在15至50質量%的範圍內,又更佳為在20至45質量%的範圍內。 The content of the diol-based solvent in the flux (F9) (the total content in the case of using multiple diol-based solvents) is not particularly limited. For example, relative to the total mass of the flux (F9), it is preferably It is in the range of 10 to 60% by mass, more preferably in the range of 15 to 50% by mass, and still more preferably in the range of 20 to 45% by mass.

於本實施型態中,除了上述二醇系溶劑之外,亦可併用有機酸酯作為溶劑。藉此,於焊接時可實現熔融黏度低的助焊劑。 In this embodiment, in addition to the above-mentioned glycol-based solvents, organic acid esters may also be used as a solvent in combination. Thereby, a flux with low melt viscosity can be realized during soldering.

含有有機酸酯之助焊劑由於在焊料膏的保管中可抑制焊料合金粉末與活性劑之反應,故即使不調整活性劑的活性度和調配量,其活性力亦會殘存,而可確保焊接時的良好潤濕性,並抑制空隙的產生。 The flux containing organic acid ester can inhibit the reaction of the solder alloy powder and the activator during the storage of the solder paste. Therefore, even if the activation degree and the blending amount of the activator are not adjusted, the activity will remain, and the soldering time can be ensured. The good wettability, and inhibit the generation of voids.

有機酸酯例如可列舉出:己二酸二甲酯、己二酸二異丙酯、順丁烯二酸二丁酯、癸二酸二甲酯、己二酸二異丁酯、癸二酸二乙酯、癸二酸二異丙酯、癸二酸二丁酯、癸二酸二辛酯等。此等可單獨使用1種或混合複數種而使用。 Examples of organic acid esters include: dimethyl adipate, diisopropyl adipate, dibutyl maleate, dimethyl sebacate, diisobutyl adipate, sebacic acid Diethyl, diisopropyl sebacate, dibutyl sebacate, dioctyl sebacate, etc. These can be used individually by 1 type or in mixture of multiple types.

助焊劑(F9)中之有機酸酯的含量(在使用複數種有機酸酯之情形時為其總含量)並無特別限定,相對於助焊劑(F9)的全部質量,較佳為0.5質量%以上,更佳為1質量%以上,又更佳為5質量%以上。另一方面,從消除助焊劑或焊料膏的乾燥不良以抑制沾黏之點來看,含量係以少者為佳,較佳例如為30質量%以下,更佳為25質量%以下,又更佳為20質量%以下,特佳為15質量%以下。 The content of the organic acid ester in the flux (F9) (the total content in the case of using multiple organic acid esters) is not particularly limited, and is preferably 0.5% by mass relative to the total mass of the flux (F9) Above, it is more preferably 1% by mass or more, and still more preferably 5% by mass or more. On the other hand, from the viewpoint of eliminating poor drying of the flux or solder paste and suppressing sticking, the content is preferably less, preferably, for example, 30% by mass or less, more preferably 25% by mass or less, and more It is preferably 20% by mass or less, and particularly preferably 15% by mass or less.

此外,有機酸酯的含量(質量%)(在使用複數種之情形時為其總量)相對於二醇系溶劑的含量(質量%)之質量比(有機酸酯的含量/二醇系溶劑的含量)並無特別限定,惟從防止空隙產生之點來看,較佳為0.01至1.25,更佳為0.10至1.0,又更佳為0.15至0.75,特佳為0.15至0.50。 In addition, the mass ratio of the content (mass %) of the organic acid ester (the total amount when using multiple types) to the content (mass %) of the glycol solvent (content of organic acid ester/diol solvent The content) is not particularly limited, but from the viewpoint of preventing the generation of voids, it is preferably 0.01 to 1.25, more preferably 0.10 to 1.0, still more preferably 0.15 to 0.75, and particularly preferably 0.15 to 0.50.

於本實施型態之助焊劑(F9)中,除了二醇系溶劑及有機酸酯之外,亦可更併用其他一般所知的溶劑。 In the flux (F9) of this embodiment, in addition to glycol-based solvents and organic acid esters, other commonly known solvents can also be used in combination.

如此溶劑例如可列舉出:苯甲醇、乙醇、異丙醇、丁醇、1,5-戊二醇、辛二醇、萜品醇、乙基賽璐蘇、丁基賽璐蘇等醇類;甲苯、二甲苯、正己烷等烴類,可使用此等的一種或兩種以上。 Examples of such solvents include alcohols such as benzyl alcohol, ethanol, isopropanol, butanol, 1,5-pentanediol, octanediol, terpineol, ethyl cellulose, and butyl cellulose; For hydrocarbons such as toluene, xylene, and n-hexane, one or two or more of these can be used.

本實施型態之助焊劑(F9)中之溶劑的含量相對於助焊劑(F9)的全部質量較佳為20至70質量%的範圍內,更佳為25至60質量%的範圍內,又更佳為30至60質量%的範圍內。 The content of the solvent in the flux (F9) of this embodiment is preferably in the range of 20 to 70% by mass, more preferably in the range of 25 to 60% by mass relative to the total mass of the flux (F9), and More preferably, it is in the range of 30 to 60% by mass.

本實施型態之助焊劑(F9)可含有松香系樹脂以外的樹脂成分、搖變減黏劑、胺、鹵素系活性劑、界面活性劑、抗氧化劑。 The flux (F9) of this embodiment can contain resin components other than rosin-based resins, thixotropic viscosity reducers, amines, halogen-based activators, surfactants, and antioxidants.

藉由將上述助焊劑(F9)與含有焊料合金(S1)至焊料合金(S9)中的任一種之焊料粉末組合,可提供一種焊料膏,其係不易發生黏度上升等之經時變化,潤濕性優異,具有高的機械特性,並且可在不損及製造效率和保存穩定性下實現空隙的產生少之焊接者。 By combining the above-mentioned flux (F9) and solder powder containing any one of solder alloys (S1) to solder alloys (S9), a solder paste can be provided, which is less prone to changes in viscosity over time, such as increased viscosity. Excellent wettability, high mechanical properties, and can be welded with less voids without compromising manufacturing efficiency and storage stability.

此外,根據助焊劑(F9),可提供一種焊料膏用助焊劑,其係在不損及製造效率和保存穩定性下可實現空隙的產生少之焊接者。 In addition, according to the flux (F9), it is possible to provide a flux for solder paste, which can achieve soldering with less voids without compromising manufacturing efficiency and storage stability.

助焊劑(F10): Flux (F10):

助焊劑(F10)為一併具有二醇系溶劑與碳數16至18的一元醇之組成物。 The flux (F10) is a composition containing a glycol solvent and a monohydric alcohol with 16 to 18 carbon atoms.

助焊劑(F10)可列舉出含有樹脂成分與溶劑與各種活性成分者。較佳的助焊劑(F10)可列舉出含有松香系樹脂與有機酸與作為溶劑之二醇系溶劑及碳數16至18的一元醇者。 The flux (F10) includes resin components, solvents, and various active ingredients. Preferable flux (F10) includes rosin-based resins, organic acids, glycol-based solvents as solvents, and monohydric alcohols with 16 to 18 carbons.

可使用在助焊劑(F10)之松香系樹脂例如可列舉出:脂松香、木松香等天然松香或是其衍生物(聚合松香、氫化松香、歧化松香、酸改質松香、松香酯等)。 Rosin-based resins that can be used in the flux (F10) include, for example, natural rosins such as gum rosin and wood rosin or their derivatives (polymerized rosin, hydrogenated rosin, disproportionated rosin, acid-modified rosin, rosin ester, etc.).

助焊劑(F10)中之松香系樹脂的含量並無特別限定,例如相對於助焊劑(F10)的全部質量較佳為10至80質量%的範圍內,更佳為20至70質量%的範圍內,又更佳為30至60質量%的範圍內。 The content of the rosin-based resin in the flux (F10) is not particularly limited. For example, relative to the total mass of the flux (F10), it is preferably in the range of 10 to 80% by mass, more preferably in the range of 20 to 70% by mass. Within, more preferably within the range of 30 to 60% by mass.

助焊劑(F10)中之有機酸的含量並無特別限定,例如相對於助焊劑(F10)的全部質量,較佳為1至15質量%的範圍內,更佳為3至10質量%的範圍內。 The content of the organic acid in the flux (F10) is not particularly limited. For example, relative to the total mass of the flux (F10), it is preferably in the range of 1 to 15% by mass, more preferably in the range of 3 to 10% by mass Inside.

於本實施型態之助焊劑(F10)中,係至少一併具有二醇系溶劑與碳數16至18的一元醇來作為溶劑。如此之碳數的一元醇的沸點係位於適當的範圍,於一般的焊接所採用之接合溫度中,係於接合初期殘存於助焊劑中以保持助焊劑的熔融黏度為低者而容易釋放分解氣體等,並且於接合後期亦有一定程度的揮發。 In the flux (F10) of this embodiment, at least a diol-based solvent and a monohydric alcohol with 16 to 18 carbon atoms are used as the solvent. The boiling point of the monoalcohol with such a carbon number is in an appropriate range. In the bonding temperature used in general soldering, it remains in the flux in the initial stage of bonding to keep the flux's melt viscosity low and easily release decomposition gas. And so on, and there is a certain degree of volatilization in the later stage of joining.

在此所謂二醇系溶劑,意指由二醇(具有於脂肪族或脂環式烴的2個相異碳原子各鍵結1個羥基之結構之化合物)或其衍生物所構成之溶劑。 The diol-based solvent here means a solvent composed of a diol (a compound having a structure in which two different carbon atoms of an aliphatic or alicyclic hydrocarbon are each bonded to a hydroxyl group) or a derivative thereof.

於本實施型態之助焊劑(F10)中,二醇系溶劑的種類並無特別限定,例如可使用一般使用在焊接用助焊劑者。二醇系溶劑的具體例除了二乙二醇、二丙二醇、三乙二醇、己二醇、苯基甘醇、己基二甘醇、2-乙基己基二甘醇之外,可列舉出:二乙二醇單丁醚(丁基卡必醇)、二乙二醇單甲醚(甲基卡必醇)、二乙二醇單己醚(己基卡必醇)、丙二醇單苯醚等二醇醚類。 In the flux (F10) of this embodiment, the type of glycol-based solvent is not particularly limited. For example, fluxes generally used for soldering can be used. Specific examples of glycol-based solvents include diethylene glycol, dipropylene glycol, triethylene glycol, hexanediol, phenyl glycol, hexyl diethylene glycol, and 2-ethylhexyl diethylene glycol: Diethylene glycol monobutyl ether (butyl carbitol), diethylene glycol monomethyl ether (methyl carbitol), diethylene glycol monohexyl ether (hexyl carbitol), propylene glycol monophenyl ether, etc. Alcohol ethers.

此等當中,較佳為碳數2至24的醇之二醇醚[具體而言為單二醇醚(碳數:4至26)、二甘醇醚(碳數:6至28)、低聚二醇醚(碳數:2+2×n至24+2×n)],更佳為碳數4至16的醇之二醇醚,特佳為碳數6至8的醇之二醇醚。 Among these, glycol ethers of alcohols having 2 to 24 carbon atoms [specifically, monoglycol ether (carbon number: 4 to 26), diethylene glycol ether (carbon number: 6 to 28), low Polyglycol ether (carbon number: 2+2×n to 24+2×n)], more preferably a glycol ether of an alcohol with a carbon number of 4 to 16, particularly preferably a glycol with a carbon number of 6 to 8 ether.

二醇系溶劑可單獨使用一種或併用兩種以上。 The diol-based solvent may be used alone or in combination of two or more.

助焊劑(F10)中之二醇系溶劑的含量(在使用複數種二醇系溶劑之情形時為其總含量)並無特別限定,例如相對於助焊劑(F10)的全部質量,較佳為在10至60質量%的範圍內,更佳為在15至50質量%的範圍內,又更佳為在20至45質量%的範圍內。 The content of the diol-based solvent in the flux (F10) (the total content in the case of using multiple diol-based solvents) is not particularly limited. For example, relative to the total mass of the flux (F10), it is preferably It is in the range of 10 to 60% by mass, more preferably in the range of 15 to 50% by mass, and still more preferably in the range of 20 to 45% by mass.

於本實施型態之助焊劑(F10)中,作為溶劑係除了上述二醇系溶劑之外,亦可併用碳數16至18的一元醇。藉此,於焊接時可實現熔融黏度低的助焊劑。 In the flux (F10) of this embodiment, in addition to the above-mentioned glycol-based solvents, monohydric alcohols having 16 to 18 carbon atoms may also be used in combination as the solvent system. Thereby, a flux with low melt viscosity can be realized during soldering.

碳數16至18的一元醇可列舉出:1-十六醇(碳數16)、2-十六醇(碳數16)、異十六醇(碳數16)、1-十七醇(碳數17)、1-十八醇(碳數18)、異硬脂醇(碳數18)等。可僅使用一種或併用兩種以上。 Monohydric alcohols with carbon numbers 16 to 18 include: 1-hexadecanol (carbon number 16), 2-hexadecanol (carbon number 16), isocetyl alcohol (carbon number 16), 1-heptadecanol ( Carbon number 17), 1-octadecyl alcohol (carbon number 18), isostearyl alcohol (carbon number 18), etc. Only one type or two or more types may be used in combination.

其中,較佳為碳數16者,尤其2-十六醇(CAS編號:2425-77-6)因沾黏少而佳。就2-十六醇而言,例如可使用Fineoxocol 1600(日產化學工業股份有限公司製,註冊商標)等。 Among them, those with 16 carbon atoms are preferred, and 2-hexadecanol (CAS number: 2425-77-6) is particularly preferred because of less stickiness. For 2-hexadecanol, for example, Fineoxocol 1600 (manufactured by Nissan Chemical Industry Co., Ltd., registered trademark) or the like can be used.

助焊劑(F10)中之碳數16至18的一元醇的含量並無特別限定,只要於助焊劑(F10)中含有碳數16至18的一元醇即可。 The content of the monohydric alcohol with 16 to 18 carbons in the flux (F10) is not particularly limited, as long as the monohydric alcohol with 16 to 18 carbons is contained in the flux (F10).

從降低助焊劑或焊料膏於焊接時的熔融黏度之點來看,助焊劑(F10)中之碳數16至18的一元醇的含量係以多者為佳,例如較佳為0.5質量%以上,更佳為1質量%以上,又更佳為5質量%以上。 From the point of view of reducing the melt viscosity of the flux or solder paste during soldering, the content of the monoalcohol with 16 to 18 carbons in the flux (F10) is preferably more, for example, 0.5% by mass or more , More preferably 1% by mass or more, and still more preferably 5% by mass or more.

另一方面,從消除助焊劑和焊料膏的乾燥不良、抑制沾黏之點來看,助焊劑(F10)中之碳數16至18的一元醇的含量係以少者愈佳,例如較佳為30質量%以下,更佳為20質量%以下,又更佳為10質量%以下。 On the other hand, from the point of view of eliminating poor drying of flux and solder paste and suppressing sticking, the content of monoalcohols with carbon numbers of 16 to 18 in the flux (F10) is the less the better, for example, the better It is 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less.

此外,碳數16至18的一元醇的含量(質量%)(在使用複數種之情形時為其總量)相對於二醇系溶劑的含量(質量%)之質量比(碳數16至18的一元醇的含量/二醇系溶劑的含量)並無特別限定,惟從空隙產生的防止與乾燥之均衡之點來看,較佳為0.01至1.25,更佳為0.15至1.25,又更佳為0.15至0.72。 In addition, the mass ratio of the content (mass%) of monohydric alcohols having 16 to 18 carbon atoms (the total amount in the case of using more than one type) to the content (mass%) of the glycol-based solvent (carbon numbers 16 to 18 The content of the monohydric alcohol/the content of the glycol-based solvent) is not particularly limited, but from the viewpoint of the prevention of void generation and the balance of drying, it is preferably 0.01 to 1.25, more preferably 0.15 to 1.25, and still more preferably It is 0.15 to 0.72.

於本實施型態之助焊劑(F10)中,除了二醇系溶劑及碳數16至18的一元醇之外,亦可更併用其他一般所知的溶劑。 In the flux (F10) of this embodiment, in addition to glycol solvents and monohydric alcohols with 16 to 18 carbons, other commonly known solvents can also be used in combination.

如此溶劑例如可列舉出:苯甲醇、乙醇、異丙醇、丁醇、1,5-戊二醇、辛二醇、萜品醇、乙基賽璐蘇、丁基賽璐蘇等醇類;甲苯、二甲苯、正己烷等烴類;乙酸異丙酯、苯甲酸丁酯等酯類,可使用此等的一種或兩種以上。 Examples of such solvents include alcohols such as benzyl alcohol, ethanol, isopropanol, butanol, 1,5-pentanediol, octanediol, terpineol, ethyl cellulose, and butyl cellulose; Hydrocarbons such as toluene, xylene, and n-hexane; esters such as isopropyl acetate and butyl benzoate. One or two or more of these can be used.

相對於助焊劑(F10)的全部質量,本實施型態之助焊劑(F10)中之溶劑的合計含量較佳為在20至70質量%的範圍內,更佳為在25至60質量%的範圍內,又更佳為在30至55質量%的範圍內。 Relative to the total mass of the flux (F10), the total content of the solvent in the flux (F10) of this embodiment is preferably in the range of 20 to 70% by mass, and more preferably in the range of 25 to 60% by mass Within the range, it is more preferably within the range of 30 to 55% by mass.

本實施型態之助焊劑(F10)可含有松香系樹脂以外的樹脂成分、搖變減黏劑、胺、鹵素系活性劑、界面活性劑、抗氧化劑。 The flux (F10) of this embodiment can contain resin components other than rosin-based resins, thixotropic viscosity reducers, amines, halogen-based activators, surfactants, and antioxidants.

藉由將上述助焊劑(F10)與含有焊料合金(S1)至焊料合金(S9)中的任一種之焊料粉末組合,可提供一種焊料膏,其係不易發生黏度上升等之經時變化,潤濕性優異,具有高的機械特性,並且可在不損及製造效率和保存穩定性下實現空隙的產生少之焊接者。 By combining the above-mentioned flux (F10) and solder powder containing any one of solder alloys (S1) to solder alloys (S9), a solder paste can be provided, which is less prone to changes in viscosity over time, such as increase in viscosity. Excellent wettability, high mechanical properties, and can be welded with less voids without compromising manufacturing efficiency and storage stability.

此外,根據助焊劑(F10),可提供一種焊料膏用助焊劑,其係可在不損及製造效率和保存穩定性下實現空隙的產生少之焊接者。 In addition, according to the flux (F10), it is possible to provide a flux for solder paste, which can realize soldering with less void generation without compromising the manufacturing efficiency and storage stability.

助焊劑(F11): Flux (F11):

助焊劑(F11)為含有受阻酚系化合物之組成物。 The flux (F11) is a composition containing hindered phenolic compounds.

助焊劑(F11)例如可列舉出:含有受阻酚系化合物、與有機酸、與選自由松香系樹脂及丙烯酸系樹脂所組成群組中的至少一種之樹脂成分、與溶劑者。 The flux (F11) includes, for example, those containing hindered phenol-based compounds, organic acids, and at least one resin component selected from the group consisting of rosin-based resins and acrylic resins, and solvents.

助焊劑(F11)係含有作為金屬減活劑之受阻酚系化合物。藉由使助焊劑含有受阻酚系化合物,於焊料膏中可達到增黏抑制效果。 The flux (F11) contains hindered phenolic compounds as metal deactivators. By making the flux contain hindered phenolic compounds, the effect of suppressing the increase in viscosity can be achieved in the solder paste.

所謂受阻酚系化合物,意指酚之鄰位的至少一者具有龐大的取代基(例如三級丁基等分枝狀或環狀烷基)之酚系化合物。 The term "hindered phenol-based compound" means a phenol-based compound in which at least one of the ortho positions of the phenol has a bulky substituent (for example, branched or cyclic alkyl groups such as tertiary butyl).

受阻酚系化合物並無特別限定,例如可列舉出:雙[3-(3-三級丁基-4-羥基-5-甲基苯基)丙酸][伸乙基雙(氧基伸乙基)]、N,N'-六亞甲基雙[3-(3,5-二(三級丁基)-4-羥基苯基)丙烷醯胺]、1,6-己二醇雙[3-(3,5-二(三級丁基)-4-羥基苯基)丙酸酯]、2,2'-亞甲基雙[6-(1-甲基環己基)-對甲酚]、2,2'-亞甲基雙(6-三級丁基對甲酚)、2,2'-亞甲基雙(6-三級丁基-4-乙基酚)、三乙二醇-雙[3-(3-三級丁基-5-甲基-4-羥基苯基)丙酸酯]、1,6-己二醇雙[3-(3,5-二(三級丁基)-4-羥基苯基)丙酸酯]、2,4-雙(正辛基硫基)-6-(4-羥基-3,5-二(三級丁基)苯胺基)-1,3,5-三嗪、新戊四醇-四[3-(3,5-二(三級丁基)-4-羥基苯基)丙酸酯]、2,2-硫基-二伸乙基雙[3-(3,5-二(三級丁基)-4-羥基苯基)丙酸酯]、十八基-3-(3,5-二(三級丁基)-4-羥基苯基)丙酸酯、N,N'-六亞甲基雙(3,5-二(三級丁基)-4-羥基-氫桂皮醯胺)、3,5-二(三級丁基)-4-羥基苯甲基膦酸酯-二乙酯、1,3,5-三甲基-2,4,6-三(3,5-二(三級丁基)-4-羥基苯甲基)苯、N,N'-雙[2-[2-(3,5-二(三級丁基)-4-羥基苯基)乙基羰氧基]乙基]草醯胺、以下述式(2)所表示之化合物等。 The hindered phenol compound is not particularly limited. For example, bis[3-(3-tertiarybutyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene )], N,N'-hexamethylenebis[3-(3,5-bis(tertiary butyl)-4-hydroxyphenyl)propaneamide], 1,6-hexanediol bis[3 -(3,5-bis(tertiarybutyl)-4-hydroxyphenyl)propionate], 2,2'-methylenebis[6-(1-methylcyclohexyl)-p-cresol] , 2,2'-methylene bis (6-tertiary butyl p-cresol), 2,2'-methylene bis (6-tertiary butyl-4-ethyl phenol), triethylene glycol -Bis[3-(3-tertiary butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis[3-(3,5-bis(tertiary butane) Yl)-4-hydroxyphenyl)propionate), 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-bis(tertiary butyl)anilino)-1 ,3,5-triazine, neopentylerythritol-tetrakis[3-(3,5-di(tertiary butyl)-4-hydroxyphenyl)propionate], 2,2-sulfanyl-diethylene Ethyl bis[3-(3,5-bis(tertiary butyl)-4-hydroxyphenyl) propionate], octadecyl-3-(3,5-bis(tertiary butyl)-4 -Hydroxyphenyl)propionate, N,N'-hexamethylenebis(3,5-bis(tertiary butyl)-4-hydroxy-hydrocinnamamide), 3,5-bis(tertiary Butyl)-4-hydroxybenzylphosphonate-diethyl, 1,3,5-trimethyl-2,4,6-tris(3,5-bis(tertiary butyl)-4- Hydroxybenzyl)benzene, N,N'-bis[2-[2-(3,5-bis(tertiary butyl)-4-hydroxyphenyl)ethylcarbonyloxy]ethyl) glufamide , A compound represented by the following formula (2), etc.

Figure 109117353-A0202-12-0064-145
Figure 109117353-A0202-12-0064-145

式中,Z為可經取代之伸烷基;R5及R6各自獨立為可經取代之烷基、芳烷基、芳基、雜芳基、環烷基或雜環烷基;R7及R8各自獨立為可經取代之烷基。 In the formula, Z is an alkylene which may be substituted; R 5 and R 6 are each independently an alkyl, aralkyl, aryl, heteroaryl, cycloalkyl or heterocycloalkyl which may be substituted; R 7 And R 8 are each independently an alkyl group which may be substituted.

上述受阻酚系化合物可單獨使用1種或組合2種以上而使用。 The above-mentioned hindered phenol-based compounds can be used singly or in combination of two or more kinds.

相對於助焊劑(F11)的全部質量,受阻酚系化合物的含量較佳為0.5至10質量%。藉由使含量成為0.5質量%以上,焊料膏可進一步提升增黏抑制效果。藉由使含量成為10質量%以下,焊料膏可進一步提升焊料潤濕性。從同樣的觀點來看,相對於助焊劑(F11)的全部質量,受阻酚系化合物的含量更佳為1.0至5.0質量%,相對於助焊劑(F11)的全部質量更佳為2.0至4.0質量%。 The content of the hindered phenol-based compound is preferably 0.5 to 10% by mass relative to the total mass of the flux (F11). By making the content 0.5% by mass or more, the solder paste can further enhance the effect of suppressing the increase in viscosity. By making the content 10% by mass or less, the solder paste can further improve solder wettability. From the same point of view, the content of the hindered phenolic compound is more preferably 1.0 to 5.0% by mass relative to the total mass of the flux (F11), and more preferably 2.0 to 4.0 mass% relative to the total mass of the flux (F11) %.

助焊劑(F11)所使用之有機酸的含量,較佳係相對於助焊劑(F11)的全部質量為0.1質量%以上15質量%以下,更佳係相對於助焊劑(F11)的全部質量為0.2質量%以上10質量%以下。 The content of the organic acid used in the flux (F11) is preferably 0.1% by mass to 15% by mass relative to the total mass of the flux (F11), and more preferably relative to the total mass of the flux (F11) 0.2% by mass or more and 10% by mass or less.

相對於助焊劑(F11)的全部質量,助焊劑(F11)較佳係含有15質量%以上70質量%以下之選自由松香系樹脂及丙烯酸系樹脂所組成群組中的至少一種之樹脂成分,更佳係相對於助焊劑(F11)的全部質量為含有20質量%以上60質量%以下者。 Relative to the total mass of the flux (F11), the flux (F11) preferably contains 15% by mass or more and 70% by mass or less of at least one resin component selected from the group consisting of rosin resins and acrylic resins, More preferably, it contains 20 mass% or more and 60 mass% or less with respect to the total mass of the flux (F11).

助焊劑(F11)所使用之溶劑可列舉出:水、醇系溶劑、二醇醚系溶劑、萜品醇類等。 Examples of the solvent used for the flux (F11) include water, alcohol-based solvents, glycol ether-based solvents, and terpineols.

助焊劑(F11)可更含有松香系樹脂及丙烯酸系樹脂以外的樹脂成分、搖變減黏劑、胺、鹵素系活性劑、界面活性劑、抗氧化劑。 The flux (F11) may further contain resin components other than rosin resin and acrylic resin, thixotropic viscosity reducer, amine, halogen-based activator, surfactant, and antioxidant.

藉由將上述助焊劑(F11)與含有焊料合金(S1)至焊料合金(S9)中的任一種之焊料粉末組合,可提供一種焊料膏,其係不易發生黏度上升等之經時變化,潤濕性優異,具有高的機械特性,並且提高可靠度者。 By combining the above-mentioned flux (F11) and solder powder containing any one of solder alloys (S1) to solder alloys (S9), a solder paste can be provided, which is less prone to changes with time such as increase in viscosity, and moisturizes Excellent wettability, high mechanical properties, and improved reliability.

此外,根據助焊劑(F11),可提供一種焊料膏用助焊劑,其係能夠均衡性佳地兼顧焊料膏的增黏抑制效果、可靠度及潤濕性者。 In addition, according to the flux (F11), a flux for solder paste can be provided, which can balance the viscosity suppression effect, reliability, and wettability of the solder paste in a well-balanced manner.

助焊劑(F12): Flux (F12):

助焊劑(F12)為含有屬於氮化合物之金屬減活劑之組成物。 Flux (F12) is a composition containing a metal deactivator which is a nitrogen compound.

助焊劑(F12)例如可列舉出:含有屬於氮化合物之金屬減活劑、與選自由松香系樹脂及丙烯酸系樹脂所組成群組中的至少一種之樹脂成分、與溶劑者。 The flux (F12) includes, for example, those containing a metal deactivator belonging to a nitrogen compound, at least one resin component selected from the group consisting of a rosin-based resin and an acrylic resin, and a solvent.

助焊劑(F12)係含有作為金屬減活劑之氮化合物。藉由使助焊劑含有屬於氮化合物之金屬減活劑,於焊料膏中可達到增黏抑制效果。 Flux (F12) contains nitrogen compounds as metal deactivators. By making the flux contain a metal deactivator belonging to a nitrogen compound, the effect of suppressing the increase in viscosity can be achieved in the solder paste.

該氮化合物若為具有氮原子且能夠使用作為金屬減活劑之化合物,即無特別限定。從增黏抑制效果優異之觀點來看,在此之氮化合物較佳為選自由醯肼(hydrazide)系氮化合物、醯胺系氮化合物、三唑(triazole)系氮化合物及三聚氰胺系氮化合物所組成群組中之至少一種氮化合物,更佳為選自由醯肼系氮化合物及三唑系氮化合物所組成群組中之至少一種。 The nitrogen compound is not particularly limited as long as it has a nitrogen atom and can be used as a metal deactivator. From the viewpoint of excellent viscosity increasing inhibitory effect, the nitrogen compound here is preferably selected from the group consisting of hydrazide-based nitrogen compounds, amide-based nitrogen compounds, triazole-based nitrogen compounds, and melamine-based nitrogen compounds. At least one nitrogen compound in the group is more preferably at least one selected from the group consisting of hydrazine-based nitrogen compounds and triazole-based nitrogen compounds.

醯肼系氮化合物若為是具有醯肼骨架之氮化合物即可,可列舉出:十二烷二酸雙[N2-(2羥基苯甲醯基)醯肼]、N,N'-雙[3-(3,5-二(三級丁基)-4-羥基苯基)丙醯基]肼、癸二羧酸二柳醯基醯肼、N-亞柳基-N'-柳基醯肼、間硝基苯甲醯肼、3-胺基鄰苯二甲醯肼、鄰苯二甲二醯肼、己二醯肼、草醯基雙(2-羥基- 5-辛基苯亞甲基醯肼)、N'-苯甲醯基吡咯啶酮羧醯肼、N,N'-雙(3-(3,5-二(三級丁基)-4-羥基苯基)丙醯基)肼等。 If the hydrazine-based nitrogen compound is a nitrogen compound having a hydrazine skeleton, examples include: dodecanedioic acid bis[N2-(2-hydroxybenzyl)hydrazine], N,N'-bis[ 3-(3,5-bis(tertiary butyl)-4-hydroxyphenyl)propanyl)hydrazine, sebacic acid disalicylic hydrazine, N-salicylic acid-N'-salicylic hydrazine, M-Nitrobenzyl hydrazine, 3-amino phthalic hydrazine, phthalic dimethyl hydrazine, hexamethylene dihydrazide, oxalinyl bis(2-hydroxy- 5-octylbenzylidene hydrazine), N'-benzylpyrrolidone carboxyhydrazine, N,N'-bis(3-(3,5-bis(tertiary butyl)-4- Hydroxyphenyl)propionyl)hydrazine and the like.

醯胺系氮化合物若為具有醯胺骨架之氮化合物即可,可列舉出:N,N'-雙{2-[3-(3,5-二(三級丁基)-4-羥基苯基)丙醯基氧基]乙基}草醯胺等。 If the amide-based nitrogen compound is a nitrogen compound having an amide skeleton, it can include: N,N'-bis{2-[3-(3,5-di(tertiarybutyl)-4-hydroxybenzene Yl)propanyloxy]ethyl}glazamide and the like.

三唑系氮化合物若為具有三唑骨架之氮化合物即可,可列舉出:N-(2H-1,2,4-三唑-5-基)柳醯胺、3-胺基-1,2,4-三唑、3-(N-柳醯基)胺基-1,2,4-三唑等。 The triazole-based nitrogen compound may be a nitrogen compound having a triazole skeleton, and examples thereof include: N-(2H-1,2,4-triazol-5-yl)salanamide, 3-amino-1, 2,4-triazole, 3-(N-salicylic)amino-1,2,4-triazole, etc.

三聚氰胺系氮化合物若為具有三聚氰胺骨架之氮化合物即可,可列舉出三聚氰胺、三聚氰胺衍生物等。 As long as the melamine-based nitrogen compound is a nitrogen compound having a melamine skeleton, melamine, melamine derivatives, and the like can be mentioned.

更具體而言,例如可列舉出:三胺基三嗪、烷基化三胺基三嗪、烷氧基烷基化三胺基三嗪、三聚氰胺、烷基化三聚氰胺、烷氧基烷基化三聚氰胺、N2-丁基三聚氰胺、N2,N2-二乙基三聚氰胺、N,N,N',N',N",N"-六(甲氧基甲基)三聚氰胺等。 More specifically, for example, triaminotriazine, alkylated triaminotriazine, alkoxyalkylated triaminotriazine, melamine, alkylated melamine, alkoxyalkylated Melamine, N2-butyl melamine, N2,N2-diethyl melamine, N,N,N',N',N",N"-hexa(methoxymethyl)melamine, etc.

此外,三聚氰胺系氮化合物可使用市售品,例如可列舉出ADEKA公司製ADK STAB ZS-27、ZS-90等,更佳為ADK STAB ZS-27。從增黏抑制效果更顯著之觀點來看,係以此等具體的市售品為佳。 In addition, commercially available products can be used for the melamine-based nitrogen compound, and examples include ADK STAB ZS-27 and ZS-90 manufactured by ADEKA Corporation, and ADK STAB ZS-27 is more preferable. From the standpoint of a more significant viscosity-increasing suppression effect, such specific commercially available products are preferable.

上述氮化合物可單獨使用1種或組合2種以上而使用。 The said nitrogen compound can be used individually by 1 type or in combination of 2 or more types.

相對於助焊劑(F12)的全部質量,氮化合物的含量較佳係超過0質量%且為10質量%以下,更佳為0.05至5.0質量%,又更佳為0.10至2.0質量%,特佳為0.10至1.0質量%。藉由使含量超過0質量%,焊料膏的增黏抑制效果變得優異。 Relative to the total mass of the flux (F12), the content of the nitrogen compound is preferably more than 0% by mass and 10% by mass or less, more preferably 0.05 to 5.0% by mass, and still more preferably 0.10 to 2.0% by mass, particularly preferred It is 0.10 to 1.0% by mass. By making the content more than 0% by mass, the effect of suppressing thickening of the solder paste becomes excellent.

於助焊劑(F12)中,就金屬減活劑而言,除了使用上述氮化合物之外,可更併用受阻酚系化合物。 In the flux (F12), as for the metal deactivator, in addition to the above-mentioned nitrogen compound, a hindered phenol compound may be used in combination.

藉由進一步使用受阻酚系化合物作為金屬減活劑,焊料膏的增黏抑制效果會更為優異。 By further using hindered phenolic compounds as the metal deactivator, the thickening suppression effect of the solder paste will be more excellent.

受阻酚系化合物並無特別限定,例如可列舉出與上述助焊劑(F11)的說明中所例示之受阻酚系化合物為相同者。 The hindered phenol-based compound is not particularly limited. For example, the same hindered phenol-based compound as exemplified in the description of the flux (F11) can be mentioned.

相對於助焊劑(F12)的全部質量,受阻酚系化合物的含量較佳例如為0至10質量%,更佳為1至10質量%,又更佳為2至10質量%。 The content of the hindered phenolic compound is preferably, for example, 0 to 10% by mass, more preferably 1 to 10% by mass, and still more preferably 2 to 10% by mass relative to the total mass of the flux (F12).

相對於助焊劑(F12)的全部質量,助焊劑(F12)較佳係含有15質量%以上70質量%以下之選自由松香系樹脂及丙烯酸系樹脂所組成群組中的至少一種之樹脂成分,更佳係相對於助焊劑(F12)的全部質量為含有35質量%以上60質量%以下者。 Relative to the total mass of the flux (F12), the flux (F12) preferably contains 15% by mass or more and 70% by mass or less of at least one resin component selected from the group consisting of rosin resins and acrylic resins, More preferably, it contains 35 mass% or more and 60 mass% or less with respect to the total mass of the flux (F12).

助焊劑(F12)所使用之溶劑可列舉出:水、醇系溶劑、二醇醚系溶劑、萜品醇類等。 Examples of the solvent used for the flux (F12) include water, alcohol-based solvents, glycol ether-based solvents, and terpineols.

助焊劑(F12)可更含有有機酸。 The flux (F12) may further contain organic acids.

相對於助焊劑(F12)的全部質量,助焊劑(F12)所使用之有機酸的含量較佳為0.1質量%以上15質量%以下,更佳係相對於助焊劑(F12)的全部質量為0.2質量%以上10質量%以下,又更佳為1質量%以上8質量%以下。 Relative to the total mass of the flux (F12), the content of the organic acid used in the flux (F12) is preferably 0.1% by mass to 15% by mass, and more preferably 0.2 relative to the total mass of the flux (F12) Mass% or more and 10 mass% or less, more preferably 1 mass% or more and 8 mass% or less.

助焊劑(F12)可更含有松香系樹脂及丙烯酸系樹脂以外的樹脂成分、搖變減黏劑、胺、鹵素系活性劑、界面活性劑、抗氧化劑。 The flux (F12) may further contain resin components other than rosin-based resin and acrylic resin, thixotropic viscosity reducer, amine, halogen-based activator, surfactant, and antioxidant.

藉由將上述助焊劑(F12)與含有焊料合金(S1)至焊料合金(S9)中的任一種之焊料粉末組合,可提供一種焊料膏,其係不易發生黏度上升等之經時變化,潤濕性優異,具有高的機械特性,並且能夠提高可靠度者。 By combining the above-mentioned flux (F12) with solder powder containing any one of solder alloys (S1) to solder alloys (S9), a solder paste can be provided, which is less prone to changes in viscosity over time, such as increase in viscosity. Those who have excellent wettability, high mechanical properties, and can improve reliability.

此外,根據助焊劑(F12),可提供一種焊料膏用助焊劑,其係能夠均衡性佳的兼顧焊料膏的增黏抑制效果、可靠度及潤濕性者。 In addition, according to the flux (F12), a flux for solder paste can be provided, which can balance the viscosity suppression effect, reliability, and wettability of the solder paste with a good balance.

以上所說明之本發明之焊料膏係適合於使用在半導體封裝中之IC晶片與其基板(中介層(interposer))之接合,或是半導體封裝與印刷電路板之接合。 The solder paste of the present invention described above is suitable for bonding an IC chip and its substrate (interposer) used in a semiconductor package, or bonding a semiconductor package and a printed circuit board.

使用本發明之焊料膏之接合方法例如可使用回焊法並依循常用方法來進行。進行流焊(flow soldering)的情形下之焊料合金的熔融溫度大致可為高於液相線溫度20℃左右之溫度。此外,在使用本實施型態之焊料合金進行接合之情形下,從組織的細微化之觀點來看,較佳係考量到凝固時的冷卻速度。例如,以2至3℃/s以上的冷卻速度來冷卻焊料接頭。其他的接合條件可因應焊料合金的合金組成來適當地調整。 The joining method using the solder paste of the present invention can be carried out by using a reflow method and following a common method, for example. In the case of flow soldering, the melting temperature of the solder alloy may be approximately 20°C higher than the liquidus temperature. In addition, in the case of joining using the solder alloy of this embodiment, it is preferable to consider the cooling rate during solidification from the viewpoint of microstructure. For example, the solder joint is cooled at a cooling rate of 2 to 3°C/s or more. Other joining conditions can be adjusted appropriately according to the alloy composition of the solder alloy.

本實施型態之焊料合金可藉由使用低α射線量材質作為其原材料而製造出低α射線量合金。如此之低α射線量合金使用在記憶體周邊之焊料凸塊的形成時,可抑制軟性誤差。 The solder alloy of this embodiment can be used to produce a low-α-radiation alloy by using a low-α-radiation material as its raw material. Such a low alpha dose alloy can suppress softness errors when used in the formation of solder bumps around the memory.

本實施型態之焊料膏較佳係更含有氧化鋯粉末。藉由含有氧化鋯,可抑制焊料膏之經時變化所導致之黏度上升。此可推測係因為藉由含有氧化鋯,焊料粉末表面的氧化膜厚會維持在投入至助焊劑中之前的狀態之故。其詳細機制雖不明瞭,惟可推測如下。通常,助焊劑的活性成分即使在常溫下亦具有些許活性,所以焊料粉末的表面氧化膜會因還原而變薄,而成為粉末彼此凝聚之原因。因此推測,藉由將氧化鋯粉末添加於焊料膏,助焊劑的活性成分會優先與氧化鋯粉末進行反應,而使焊料粉末表面的氧化膜能夠維持在不凝聚之程度。 The solder paste of this embodiment preferably further contains zirconia powder. By containing zirconia, the increase in viscosity caused by changes in solder paste over time can be suppressed. This is presumably because by containing zirconia, the oxide film thickness on the surface of the solder powder is maintained in the state before being put into the flux. Although the detailed mechanism is not clear, it can be inferred as follows. Generally, the active components of the flux have a little activity even at room temperature, so the surface oxide film of the solder powder becomes thin due to reduction, which causes the powders to agglomerate with each other. Therefore, it is speculated that by adding zirconia powder to the solder paste, the active components of the flux will preferentially react with the zirconia powder, so that the oxide film on the surface of the solder powder can be maintained to a degree that does not aggregate.

為了充分地發揮如此作用效果,相對於焊料膏的全部質量,焊料膏中之氧化鋯粉末的含量較佳為0.05至20.0質量%。如為0.05質量%以上時,可發揮上述作用效果,如為20.0質量%以下時,可確保金屬粉末的含量,並可發揮增黏抑制效果。氧化鋯粉末的含量更佳為0.05至10.0質量%,又更佳的含量為0.1至3質量%。 In order to fully exert such effects, the content of the zirconia powder in the solder paste is preferably 0.05 to 20.0% by mass relative to the total mass of the solder paste. If it is 0.05% by mass or more, the above-mentioned effect can be exerted, and if it is 20.0% by mass or less, the content of the metal powder can be ensured and the effect of suppressing the increase in viscosity can be exerted. The content of the zirconia powder is more preferably 0.05 to 10.0% by mass, and still more preferably 0.1 to 3% by mass.

焊料膏中之氧化鋯粉末的粒徑較佳為5μm以下。粒徑為5μm以下時,可維持膏的印刷性。粒徑的下限並無特別限定,惟宜為0.5μm以上。 The particle size of the zirconia powder in the solder paste is preferably 5 μm or less. When the particle size is 5 μm or less, the printability of the paste can be maintained. The lower limit of the particle size is not particularly limited, but it is preferably 0.5 μm or more.

上述氧化鋯粉末的粒徑係拍攝氧化鋯粉末的SEM照片,並藉由對0.1μm以上的各粉末進行圖像解析而求取投影圓等效直徑,並將其設為平均值。 The particle size of the above-mentioned zirconia powder is obtained by taking a SEM photograph of the zirconia powder, and by performing image analysis of each powder of 0.1 μm or more to obtain the projected circle equivalent diameter, and set it as an average value.

氧化鋯粉末的形狀並無特別限定,惟若為特異形狀者,則與助焊劑之接觸面積增大而具有增黏抑制效果。為球形時,可得到良好的流動性,故可得到作為膏之優異的印刷性。可因應期望的特性而選擇適當的形狀。 The shape of the zirconium oxide powder is not particularly limited, but if it is a special shape, the contact area with the flux increases and it has an effect of suppressing viscosity increase. When it is spherical, good fluidity can be obtained, so excellent printability as a paste can be obtained. The appropriate shape can be selected according to the desired characteristics.

〈焊料膏用助焊劑〉 〈Flux for solder paste〉

本實施型態之焊料膏用助焊劑係使用在採用了上述特定的焊料粉末之焊料膏。該助焊劑較佳係含有樹脂成分與活性成分與溶劑。 The flux for solder paste of this embodiment is used for solder paste using the above-mentioned specific solder powder. The flux preferably contains a resin component, an active component, and a solvent.

本實施型態之焊料膏用助焊劑係採用了特定的焊料粉末,亦即包含焊料合金之焊料粉末,為適合用於焊料膏的助焊劑;該焊料合金具有由As:10質量ppm以上且未達40質量ppm,以及Bi:0至10000質量ppm、Pb:0至5100質量ppm及Sb:0至3000質量ppm中的至少一種,以及剩餘部分為Sn所構成之合金組成,並且滿足下述(1)式及(2)式; The flux for solder paste of this embodiment uses specific solder powder, that is, solder powder containing solder alloy, which is suitable for solder paste; the solder alloy has an As: 10 mass ppm or more and no Up to 40 mass ppm, and at least one of Bi: 0 to 10000 mass ppm, Pb: 0 to 5100 mass ppm, and Sb: 0 to 3000 mass ppm, and the remainder is an alloy composition composed of Sn, and satisfies the following ( 1) formula and (2) formula;

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition.

此外,本實施型態之焊料膏用助焊劑係採用了特定的焊料粉末,亦即包含焊料合金之焊料粉末,為適合用於焊料膏的助焊劑;該焊料合金具有:由As:10質量ppm以上且未達40質量ppm,以及Bi:超過0質量ppm且為10000質量ppm以下、Pb:超過0質量ppm且為5100質量ppm以下及Sb:超過0質量ppm且為3000質量ppm以下中的至少一種,以及剩餘部分為Sn所構成之合金組成,並且滿足下述(1)式及(2)式; In addition, the solder paste flux of this embodiment uses a specific solder powder, that is, solder powder containing a solder alloy, which is suitable for solder paste; the solder alloy has: As: 10 mass ppm Above and less than 40 mass ppm, and Bi: more than 0 mass ppm and less than 10000 mass ppm, Pb: more than 0 mass ppm and less than 5100 mass ppm, and Sb: more than 0 mass ppm and at least 3000 mass ppm or less One type, and the remainder is an alloy composed of Sn, and satisfies the following (1) and (2) formulas;

300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1)

0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2)

上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition.

於組合有本實施型態之焊料膏用助焊劑與上述特定的焊料粉末之焊料膏中,係不易發生黏度上升等之經時變化,潤濕性優異,並顯示出高的機械特性。再者,根據組合有此焊料膏用助焊劑與前述特定的焊料粉末之焊料膏,藉由選擇調配於該助焊劑之成分,可將焊料之潤濕速度的提升、接合對象物之金屬表面(例如銅板)的腐蝕抑制、印刷性的提升、空隙抑制等各種特性予以進一步提高。 In the solder paste that combines the solder paste flux of this embodiment and the above-mentioned specific solder powder, the viscosity rises and other changes over time are not prone to occur, the wettability is excellent, and it exhibits high mechanical properties. Furthermore, according to the solder paste combining this solder paste flux and the aforementioned specific solder powder, by selecting the components blended in the flux, the wetting speed of the solder can be increased, and the metal surface of the joining object can be increased ( For example, the corrosion inhibition of copper plates, the improvement of printability, and the suppression of voids are further improved.

[實施例] [Example]

以下係藉由實施例來更詳細地說明本發明,惟本發明並不限定於此等例子。 The following examples illustrate the present invention in more detail, but the present invention is not limited to these examples.

焊料粉末的製作: Production of solder powder:

首先,製作出具有表1至表24所示之合金組成,並且於JIS Z 3284-1:2014中之粉末大小的分類(表2)中符合記號4之大小(粒度分布)的焊料粉末(試驗例1至498、試驗例501至578)。 First, produce solder powders with the alloy composition shown in Table 1 to Table 24 and the size (particle size distribution) of the symbol 4 in the JIS Z 3284-1:2014 powder size classification (Table 2) (test Examples 1 to 498, Test Examples 501 to 578).

助焊劑(F0)的調製: Preparation of flux (F0):

使用松香作為樹脂成分。 Rosin is used as the resin component.

使用作為活性成分之搖變減黏劑、有機酸、胺及鹵素系活性劑。 Use as active ingredients, thixotropic viscosity reducers, organic acids, amines and halogen-based active agents.

使用二醇系溶劑作為溶劑。 A glycol-based solvent is used as the solvent.

混合松香42質量份、二醇系溶劑35質量份、搖變減黏劑8質量份、有機酸10質量份、胺2質量份、鹵素系活性劑3質量份而調製助焊劑(F0)。 42 parts by mass of rosin, 35 parts by mass of glycol solvent, 8 parts by mass of thixotropic agent, 10 parts by mass of organic acid, 2 parts by mass of amine, and 3 parts by mass of halogen-based activator were mixed to prepare flux (F0).

混合前述所調製之助焊劑(F0)與具有表1至表24所示之各例的合金組成之焊料粉末,而調製出焊料膏。助焊劑(F0)與焊料粉末之質量比係設為助焊劑(F0):焊料粉末=11:89。 The flux (F0) prepared above and the solder powder having the alloy composition of each example shown in Table 1 to Table 24 were mixed to prepare a solder paste. The mass ratio of flux (F0) to solder powder is set as flux (F0): solder powder=11:89.

對於使用各例的焊料粉末之情形,係測定焊料膏中之黏度之經時變化。此外,測定焊料粉末的液相線溫度及固相線溫度。再者,使用剛製作的焊料膏來進行潤濕性的評估。詳細內容如以下所述。 In the case of using the solder powder of each example, the change in viscosity in the solder paste was measured with time. In addition, the liquidus temperature and solidus temperature of the solder powder were measured. Furthermore, the wettability evaluation was performed using the solder paste just produced. The details are as follows.

〈焊料膏中之黏度之經時變化之評估〉 <Evaluation of the change of viscosity in solder paste over time>

(1)驗證方法 (1) Verification method

對剛製作的各焊料膏使用Malcom股份有限公司製:PCU-205,於轉速:10rpm、25℃、大氣下測定12小時黏度。 For each solder paste just produced, PCU-205 manufactured by Malcom Co., Ltd. was used, and the viscosity was measured for 12 hours at a rotation speed of 10 rpm, 25° C., and the atmosphere.

(2)判定基準 (2) Judgment criteria

A:12小時後的黏度與製作焊料膏後經過30分鐘時的黏度相比為1.2倍以下。 A: The viscosity after 12 hours is 1.2 times or less compared to the viscosity after 30 minutes after the solder paste is produced.

B:12小時後的黏度與製作焊料膏後經過30分鐘時的黏度相比為超過1.2倍。 B: The viscosity after 12 hours is more than 1.2 times the viscosity after 30 minutes after the solder paste is produced.

〈△T的評估〉 <Assessment of △T>

(1)驗證方法 (1) Verification method

對與助焊劑(F0)混合前之焊料粉末使用SII Nano Technology股份有限公司製、型號:EXSTAR DSC7020,在樣本量:約30mg、升溫速度:15℃/min下進行DSC測定,而得到液相線溫度及固相線溫度。從所得到之液相線溫度減去固相線溫度以求取△T。 For the solder powder before mixing with the flux (F0), use the SII Nano Technology Co., Ltd. product, model: EXSTAR DSC7020, and perform the DSC measurement at a sample size: about 30 mg and a heating rate: 15°C/min to obtain the liquidus Temperature and solidus temperature. Subtract the solidus temperature from the obtained liquidus temperature to obtain ΔT.

(2)判定基準 (2) Judgment criteria

A:△T為10℃以下。 A: ΔT is 10°C or less.

B:△T超過10℃。 B: ΔT exceeds 10°C.

〈潤濕性的評估〉 <Assessment of wettability>

(1)驗證方法 (1) Verification method

將剛製作的各焊料膏印刷於Cu板上,用回焊爐在N2氣體環境中以1℃/s的升溫速度從25℃加熱至260℃為止之後,冷卻至室溫。以光學顯微鏡來觀察冷卻後之焊料凸塊的外觀以評估潤濕性。 Each solder paste just produced was printed on a Cu board, heated from 25°C to 260°C at a temperature increase rate of 1°C/s in a N 2 gas atmosphere in a reflow furnace, and then cooled to room temperature. Observe the appearance of the solder bumps after cooling with an optical microscope to evaluate the wettability.

(2)判定基準 (2) Judgment criteria

A:並未觀察到未完全熔融的焊料粉末之情形。 A: The solder powder that was not completely melted was not observed.

B:觀察到未完全熔融的焊料粉末之情形。 B: Incompletely molten solder powder is observed.

〈綜合評估〉 <Comprehensive Evaluation>

A:於表1至表24中,經時變化、△T、潤濕性之各項的評估皆為A。 A: In Tables 1 to 24, the evaluations of changes over time, ΔT, and wettability are all A.

B:於表1至表24中,經時變化、△T、潤濕性之各項的評估中之至少一項為B。 B: In Tables 1 to 24, at least one of the evaluations of changes over time, ΔT, and wettability is B.

評估結果係如表1至表24所示。於表21至表24中,底線表示超出本發明的範圍。 The evaluation results are shown in Table 1 to Table 24. In Table 21 to Table 24, the bottom line indicates that it is beyond the scope of the present invention.

[表1]

Figure 109117353-A0202-12-0073-146
[Table 1]
Figure 109117353-A0202-12-0073-146

[表2]

Figure 109117353-A0202-12-0074-147
[Table 2]
Figure 109117353-A0202-12-0074-147

[表3]

Figure 109117353-A0202-12-0075-148
[table 3]
Figure 109117353-A0202-12-0075-148

[表4]

Figure 109117353-A0202-12-0076-149
[Table 4]
Figure 109117353-A0202-12-0076-149

[表5]

Figure 109117353-A0202-12-0077-150
[table 5]
Figure 109117353-A0202-12-0077-150

[表6]

Figure 109117353-A0202-12-0078-151
[Table 6]
Figure 109117353-A0202-12-0078-151

[表7]

Figure 109117353-A0202-12-0079-152
[Table 7]
Figure 109117353-A0202-12-0079-152

[表8]

Figure 109117353-A0202-12-0080-153
[Table 8]
Figure 109117353-A0202-12-0080-153

[表9]

Figure 109117353-A0202-12-0081-154
[Table 9]
Figure 109117353-A0202-12-0081-154

[表10]

Figure 109117353-A0202-12-0082-155
[Table 10]
Figure 109117353-A0202-12-0082-155

[表11]

Figure 109117353-A0202-12-0083-156
[Table 11]
Figure 109117353-A0202-12-0083-156

[表12]

Figure 109117353-A0202-12-0084-157
[Table 12]
Figure 109117353-A0202-12-0084-157

[表13]

Figure 109117353-A0202-12-0085-158
[Table 13]
Figure 109117353-A0202-12-0085-158

[表14]

Figure 109117353-A0202-12-0086-159
[Table 14]
Figure 109117353-A0202-12-0086-159

[表15]

Figure 109117353-A0202-12-0087-160
[Table 15]
Figure 109117353-A0202-12-0087-160

[表16]

Figure 109117353-A0202-12-0088-161
[Table 16]
Figure 109117353-A0202-12-0088-161

[表17]

Figure 109117353-A0202-12-0089-162
[Table 17]
Figure 109117353-A0202-12-0089-162

[表18]

Figure 109117353-A0202-12-0090-163
[Table 18]
Figure 109117353-A0202-12-0090-163

[表19]

Figure 109117353-A0202-12-0091-164
[Table 19]
Figure 109117353-A0202-12-0091-164

[表20]

Figure 109117353-A0202-12-0092-165
[Table 20]
Figure 109117353-A0202-12-0092-165

[表21]

Figure 109117353-A0202-12-0093-166
[Table 21]
Figure 109117353-A0202-12-0093-166

[表22]

Figure 109117353-A0202-12-0094-167
[Table 22]
Figure 109117353-A0202-12-0094-167

[表23]

Figure 109117353-A0202-12-0095-168
[Table 23]
Figure 109117353-A0202-12-0095-168

[表24]

Figure 109117353-A0202-12-0096-169
[Table 24]
Figure 109117353-A0202-12-0096-169

如表1至表24所示,就含有具有試驗例1至498的合金組成之焊料粉末、與助焊劑(F0)之焊料膏而言,任一者之合金組成皆滿足本發明之要件,故確認到係顯示出優異的增黏抑制效果、△T的窄化及優異的潤濕性。 As shown in Tables 1 to 24, for the solder paste containing the solder powder having the alloy composition of Test Examples 1 to 498 and the flux (F0), the alloy composition of any one of them satisfies the requirements of the present invention, so It was confirmed that the system exhibits an excellent viscosity-increasing suppression effect, narrowing of ΔT, and excellent wettability.

此等含有具有試驗例1至498的合金組成之焊料粉末與助焊劑(F0)之焊料膏,係應用本發明之實施例的焊料膏。 These solder pastes containing solder powder and flux (F0) having the alloy composition of Test Examples 1 to 498 are the solder pastes of the embodiments of the present invention.

另一方面,就含有具有試驗例501至578的合金組成之焊料粉末與助焊劑(F0)之焊料膏而言,任一者之合金組成皆為未滿足本發明之至少一項要件,故顯示出於增黏抑制效果、△T的窄化及優異的潤濕性中之至少一項為較差的結果。 On the other hand, for the solder paste containing the solder powder and the flux (F0) having the alloy composition of Test Examples 501 to 578, the alloy composition of any one of them does not satisfy at least one of the requirements of the present invention, so it is shown At least one of the effect of suppressing the viscosity increase, the narrowing of ΔT, and the excellent wettability is a poor result.

[含有助焊劑(F1)之焊料膏的評估] [Evaluation of solder paste containing flux (F1)]

接著,就對於具有試驗例1所示之合金組成之焊料粉末使用表25至表33所示之調配例(F1-1)至(F1-55)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經時變化之評估〉。此外,測定焊料粉末的液相線溫度及固相線溫度來進行上述〈△T的評估〉。再者,使用剛製作的焊料膏來進行上述〈潤濕性的評估〉。 Next, for the solder powder having the alloy composition shown in Test Example 1 using the fluxes of the blending examples (F1-1) to (F1-55) shown in Table 25 to Table 33, the above-mentioned <Solder Paste "Evaluation of the change of viscosity over time in the medium." In addition, the liquidus temperature and solidus temperature of the solder powder were measured to perform the above-mentioned <Evaluation of ΔT>. In addition, the above-mentioned "Evaluation of wettability" was performed using the solder paste just produced.

從此等之結果中,可確認到對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F1-1)至(F1-55)的各助焊劑之情形下的焊料膏,皆顯示出增黏抑制效果、△T的窄化及優異的潤濕性。 From these results, it can be confirmed that the solder pastes in the case of using the fluxes of the blending examples (F1-1) to (F1-55) for the solder powder having the alloy composition shown in Test Example 1 all show Thickness suppression effect, narrowing of △T and excellent wettability.

接著,就對於具有試驗例1所示之合金組成之焊料粉末使用表25至表33所示之調配例(F1-1)至(F1-55)的各助焊劑之情形,進行焊料之潤濕速度(焊料潤濕性)的評估。 Next, for the solder powder having the alloy composition shown in Test Example 1 using the fluxes of the blending examples (F1-1) to (F1-55) shown in Table 25 to Table 33, the solder is wetted Evaluation of speed (solder wettability).

〈焊料之潤濕速度(焊料潤濕性)的評估〉 <Assessment of solder wetting speed (solder wettability)>

(1)驗證方法 (1) Verification method

焊料之潤濕速度(焊料潤濕性)的評估試驗係以如下之方式來進行。 The evaluation test of the solder wetting speed (solder wettability) was performed as follows.

依據弧面狀沾焊料試驗(meniscograph test)的方法,對寬5mm×長25mm×厚0.5mm的銅板用150℃進行1小時的氧化處理而得到試驗板的氧化銅板,使用Solder Checker SAT-5200(RHESCA公司製)作為試驗裝置,並使用具有試驗例1所示之合金組成之焊料粉末作為焊料,以下列方式進行評估。 According to the method of the arc-shaped solder dip test (meniscograph test), a copper plate with a width of 5 mm × a length of 25 mm × a thickness of 0.5 mm was oxidized at 150°C for 1 hour to obtain the copper oxide plate of the test board. Solder Checker SAT-5200 ( RHESCA Corporation) was used as the test device, and the solder powder having the alloy composition shown in Test Example 1 was used as the solder, and the evaluation was performed in the following manner.

首先,對於量取至燒杯之調配例(F1-1)至(F1-55)的各助焊劑浸漬試驗板3mm,以將助焊劑塗佈於試驗板。接著,在塗佈助焊劑後,迅速地將塗佈有助焊劑之試驗板浸漬在試驗例1所示之合金組成的焊料槽,而得到零交叉(zero crossing)時間(sec)。 First, 3 mm of each flux-immersed test board of the formulation examples (F1-1) to (F1-55) measured into a beaker was applied to the test board with flux. Next, after the flux was applied, the test board coated with the flux was quickly immersed in the solder tank of the alloy composition shown in Test Example 1, and the zero crossing time (sec) was obtained.

接著,對各調配例的助焊劑進行5次的測定,並算出所得到之5個零交叉時間(sec)的平均值。試驗條件係設定如下。 Next, the flux of each blending example was measured 5 times, and the average value of the obtained 5 zero-crossing times (sec) was calculated. The test conditions are set as follows.

於焊料槽之浸漬速度:5mm/sec(JIS Z 3198-4:2003) Dipping speed in solder tank: 5mm/sec (JIS Z 3198-4: 2003)

於焊料槽之浸漬深度:2mm(JIS Z 3198-4:2003) Dipping depth in solder tank: 2mm (JIS Z 3198-4: 2003)

於焊料槽之浸漬時間:10sec(JIS Z 3198-4:2003) Dipping time in solder tank: 10sec (JIS Z 3198-4: 2003)

焊料槽溫度:245℃(JIS C 60068-2-69:2019附錄B)零交叉時間(sec)的平均值愈短,係意指潤濕速度變得愈高,而焊料潤濕性愈佳。 Solder tank temperature: 245°C (JIS C 60068-2-69: 2019 Appendix B) The shorter the average value of the zero crossing time (sec), the higher the wetting speed, and the better the solder wettability.

(2)判定基準 (2) Judgment criteria

A:零交叉時間(sec)的平均值為2.5秒以下。 A: The average value of the zero-crossing time (sec) is 2.5 seconds or less.

B:零交叉時間(sec)的平均值超過2.5秒。 B: The average value of the zero crossing time (sec) exceeds 2.5 seconds.

評估結果係如表25至表33所示。 The evaluation results are shown in Table 25 to Table 33.

表中,係使用脂肪族聚醯胺作為聚醯胺,使用六亞甲基雙羥基硬脂醯胺作為雙醯胺,使用對甲苯醯胺作為單醯胺。 In the table, aliphatic polyamide is used as polyamide, hexamethylene bishydroxystearylamine is used as bisamide, and p-toluamide is used as monoamide.

[表25]

Figure 109117353-A0202-12-0099-170
[Table 25]
Figure 109117353-A0202-12-0099-170

[表26]

Figure 109117353-A0202-12-0100-171
[Table 26]
Figure 109117353-A0202-12-0100-171

[表27]

Figure 109117353-A0202-12-0101-172
[Table 27]
Figure 109117353-A0202-12-0101-172

[表28]

Figure 109117353-A0202-12-0102-173
[Table 28]
Figure 109117353-A0202-12-0102-173

[表29]

Figure 109117353-A0202-12-0103-174
[Table 29]
Figure 109117353-A0202-12-0103-174

[表30]

Figure 109117353-A0202-12-0104-175
[Table 30]
Figure 109117353-A0202-12-0104-175

[表31]

Figure 109117353-A0202-12-0105-176
[Table 31]
Figure 109117353-A0202-12-0105-176

[表32]

Figure 109117353-A0202-12-0106-177
[Table 32]
Figure 109117353-A0202-12-0106-177

[表33]

Figure 109117353-A0202-12-0107-178
[Table 33]
Figure 109117353-A0202-12-0107-178

在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F1-1)至(F1-54)的各助焊劑之情形下,可確認到任一者與使用調配例(F1-55)的助焊劑之情形相比,皆為焊料的潤濕速度變得較高,焊料潤濕性更良好。其中,含有具有試驗例1的合金組成之焊料粉末與調配例(F1-1)至(F1-54)的各助焊劑之焊料膏,為含有助焊劑(F1)之實施型態之焊料膏。 In the case of using the fluxes of the blending examples (F1-1) to (F1-54) for the solder powder with the alloy composition shown in Test Example 1, it is possible to confirm that any one of them and the use blending example (F1-55) Compared with the case of the flux of ), the wetting speed of the solder becomes higher, and the solder wettability is better. Among them, the solder paste containing the solder powder having the alloy composition of Test Example 1 and the fluxes of the blending examples (F1-1) to (F1-54) is an implementation type solder paste containing the flux (F1).

接著,就對於具有試驗例2至498、試驗例501至578所示之各合金組成之焊料粉末分別使用調配例(F1-1)至(F1-55)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經時變化之評估〉、〈△T的評估〉及〈潤濕性的評估〉,以及〈潤濕速度的評估〉。 Next, for the solder powders having the alloy compositions shown in Test Examples 2 to 498 and Test Examples 501 to 578, the fluxes of the formulation examples (F1-1) to (F1-55) were used, and the above-mentioned < Evaluation of the change of viscosity in solder paste with time", "Evaluation of △T", "Evaluation of wettability", and "Evaluation of wetting speed".

從該評估的結果中,可確認到於含有具有試驗例2至498的合金組成之焊料粉末之焊料膏的情形下,係顯示出增黏抑制效果、△T的窄化及優異的潤濕性。此等當中,含有具有試驗例2至498的合金組成之各焊料粉末與調配例(F1-1)至(F1-54)的各助焊劑之焊料膏,為含有助焊劑(F1)之實施型態之焊料膏。 From the results of this evaluation, it can be confirmed that in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498, it exhibits the effect of suppressing viscosity increase, narrowing of ΔT, and excellent wettability. . Among them, the solder paste containing each solder powder with the alloy composition of Test Examples 2 to 498 and the fluxes of Blending Examples (F1-1) to (F1-54) is an implementation type containing flux (F1) State of the solder paste.

另一方面,於含有具有試驗例501至578的合金組成之焊料粉末之焊料膏的情形下,係顯示出於增黏抑制效果、△T的窄化及優異的潤濕性中之至少一項為較差的結果。 On the other hand, in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, it exhibits at least one of the effect of suppressing thickening, narrowing of ΔT, and excellent wettability Is a poor result.

此外,在對於試驗例2至498之焊料粉末分別使用調配例(F1-1)至(F1-54)的各助焊劑之情形下,可確認到任一者與使用調配例(F1-55)的助焊劑之情形相比,皆為焊料的潤濕速度變得較高,焊料潤濕性更良好。 In addition, in the case of using the fluxes of the blending examples (F1-1) to (F1-54) for the solder powders of test examples 2 to 498, it is possible to confirm any one and the use blending example (F1-55) Compared with the case of the flux, the wetting speed of the solder becomes higher, and the solder wettability is better.

[含有助焊劑(F2)之焊料膏的評估] [Evaluation of solder paste containing flux (F2)]

接著,就對於具有試驗例1所示之合金組成之焊料粉末使用表34至表46所示之調配例(F2-1)至(F2-62)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經時變化之評估〉。此外,測定焊料粉末的液相線溫度及固相線溫度來進行上述〈△T的評估〉。再者,使用剛製作的焊料膏來進行上述〈潤濕性的評估〉。 Next, for the solder powder having the alloy composition shown in Test Example 1 using the fluxes of the blending examples (F2-1) to (F2-62) shown in Table 34 to Table 46, the above-mentioned <Solder Paste "Evaluation of the change of viscosity over time in the medium." In addition, the liquidus temperature and solidus temperature of the solder powder were measured to perform the above-mentioned <Evaluation of ΔT>. In addition, the above-mentioned "Evaluation of wettability" was performed using the solder paste just produced.

從此等之結果中,可確認到在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F2-1)至(F2-62)的各助焊劑之情形下的焊料膏,皆顯示出增黏抑制效果、△T的窄化及優異的潤濕性。 From these results, it can be confirmed that the solder pastes in the case of using the fluxes of the blending examples (F2-1) to (F2-62) for the solder powder having the alloy composition shown in Test Example 1 all show It has the effect of suppressing viscosity increase, narrowing of △T and excellent wettability.

接著,就對於具有試驗例1所示之合金組成之焊料粉末使用表34至表46所示之調配例(F2-1)至(F2-62)的各助焊劑之情形,進行助焊劑之溫度循環可靠度的評估。 Next, for the solder powder having the alloy composition shown in Test Example 1 using the fluxes of the blending examples (F2-1) to (F2-62) shown in Table 34 to Table 46, the temperature of the flux was performed Evaluation of cyclic reliability.

<溫度循環可靠度的評估> <Evaluation of temperature cycle reliability>

(1)驗證方法 (1) Verification method

溫度循環可靠度的評估係將調配例(F2-1)至(F2-62)的各助焊劑塗佈於Cu板上,而於Cu板上形成殘渣。重複進行將形成於此Cu板上之殘渣分別於-30℃與+110℃保持30分鐘之處理的試驗,並將此試驗進行500次循環,然後以目視來評估經進行500次循環時之殘渣有無破裂。 The evaluation of the reliability of the temperature cycle is to apply the fluxes of the deployment examples (F2-1) to (F2-62) on the Cu board, and a residue is formed on the Cu board. Repeat the test of holding the residue formed on the Cu plate at -30°C and +110°C for 30 minutes, and perform the test for 500 cycles, and then visually evaluate the residue after 500 cycles Whether it is broken.

(2)判定基準 (2) Judgment criteria

A:於殘渣中未觀察到龜裂的產生,溫度循環可靠度優異。 A: The generation of cracks is not observed in the residue, and the temperature cycle reliability is excellent.

B:於殘渣中觀察到龜裂的產生,溫度循環可靠度差。 B: The generation of cracks is observed in the residue, and the reliability of the temperature cycle is poor.

評估結果係如表34至表46所示。 The evaluation results are shown in Table 34 to Table 46.

又,表34至表46中的組成率係將助焊劑的全部量設為100之情形下的wt(質量)%。 In addition, the composition ratios in Tables 34 to 46 are wt (mass)% when the total amount of flux is set to 100.

於各表中,丙烯酸樹脂A為聚丙烯酸2-乙基己酯(Mw=8300)。丙烯酸樹脂B為分子量相異之聚丙烯酸2-乙基己酯(Mw=11700)。丙烯酸樹脂C為聚甲基丙烯酸月桂酯(Mw=10080)。丙烯酸樹脂D為聚丙烯酸2-乙基己酯-聚乙烯(Mw=12300)。 In each table, acrylic resin A is poly-2-ethylhexyl acrylate (Mw=8300). Acrylic resin B is poly(2-ethylhexyl acrylate) with different molecular weights (Mw=11700). Acrylic resin C is polylauryl methacrylate (Mw=10080). Acrylic resin D is polyacrylate 2-ethylhexyl-polyethylene (Mw=12300).

於各表中,係使用脂肪族聚醯胺作為聚醯胺,使用六亞甲基雙羥基硬脂醯胺作為雙醯胺,使用對甲苯醯胺作為單醯胺。 In each table, aliphatic polyamide is used as polyamide, hexamethylene bishydroxystearyl amide is used as bisamide, and p-toluamide is used as monoamide.

[表34]

Figure 109117353-A0202-12-0110-179
[Table 34]
Figure 109117353-A0202-12-0110-179

[表35]

Figure 109117353-A0202-12-0111-180
[Table 35]
Figure 109117353-A0202-12-0111-180

[表36]

Figure 109117353-A0202-12-0112-181
[Table 36]
Figure 109117353-A0202-12-0112-181

[表37]

Figure 109117353-A0202-12-0113-182
[Table 37]
Figure 109117353-A0202-12-0113-182

[表38]

Figure 109117353-A0202-12-0114-183
[Table 38]
Figure 109117353-A0202-12-0114-183

[表39]

Figure 109117353-A0202-12-0115-184
[Table 39]
Figure 109117353-A0202-12-0115-184

[表40]

Figure 109117353-A0202-12-0116-185
[Table 40]
Figure 109117353-A0202-12-0116-185

[表41]

Figure 109117353-A0202-12-0117-186
[Table 41]
Figure 109117353-A0202-12-0117-186

[表42]

Figure 109117353-A0202-12-0118-187
[Table 42]
Figure 109117353-A0202-12-0118-187

[表43]

Figure 109117353-A0202-12-0119-188
[Table 43]
Figure 109117353-A0202-12-0119-188

[表44]

Figure 109117353-A0202-12-0120-189
[Table 44]
Figure 109117353-A0202-12-0120-189

[表45]

Figure 109117353-A0202-12-0121-190
[Table 45]
Figure 109117353-A0202-12-0121-190

[表46]

Figure 109117353-A0202-12-0122-191
[Table 46]
Figure 109117353-A0202-12-0122-191

在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F2-1)至(F2-60)的各助焊劑之情形下,可確認到任一者與使用調配例(F2-61)至(F2-62)的各助焊劑之情形相比,皆係抑制殘渣之龜裂的產生,而能夠提高溫度循環可靠度。其中,含有具有試驗例1的合金組成之焊料粉末與調配例(F2-1)至(F2-60)的各助焊劑之焊料膏,為含有助焊劑(F2)之實施型態之焊料膏。 In the case of using the fluxes of the blending examples (F2-1) to (F2-60) for the solder powder having the alloy composition shown in Test Example 1, it is possible to confirm that any one of them and the use blending example (F2-61 Compared with the fluxes of (F2-62), all of them suppress the generation of residue cracking, and can improve the reliability of temperature cycle. Among them, the solder paste containing the solder powder having the alloy composition of Test Example 1 and the fluxes of the blending examples (F2-1) to (F2-60) is the solder paste of the implementation form containing the flux (F2).

接著,就對於具有試驗例2至498、試驗例501至578所示之各合金組成之焊料粉末分別使用調配例(F2-1)至(F2-62)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經時變化之評估〉、〈△T的評估〉及〈潤濕性的評估〉,以及〈溫度循環可靠度的評估〉。 Next, for the solder powders having the respective alloy compositions shown in Test Examples 2 to 498 and Test Examples 501 to 578, the fluxes of the blending examples (F2-1) to (F2-62) were used, and the above-mentioned < Evaluation of the change of viscosity in solder paste with time", "Evaluation of △T" and "Evaluation of wettability", and "Evaluation of reliability of temperature cycling".

從該評估的結果中,可確認到於含有具有試驗例2至498的合金組成之焊料粉末之焊料膏的情形下,係顯示出增黏抑制效果、△T的窄化及優異的潤濕性。此等當中,含有具有試驗例2至498的合金組成之各焊料粉末與調配例(F2-1)至(F2-60)的各助焊劑之焊料膏,為含有助焊劑(F2)之實施型態之焊料膏。 From the results of this evaluation, it can be confirmed that in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498, it exhibits the effect of suppressing viscosity increase, narrowing of ΔT, and excellent wettability. . Among them, the solder paste containing each solder powder with the alloy composition of Test Examples 2 to 498 and the fluxes of Blending Examples (F2-1) to (F2-60) is an implementation type containing flux (F2) State of the solder paste.

另一方面,於含有具有試驗例501至578的合金組成之焊料粉末之焊料膏的情形下,係顯示出於增黏抑制效果、△T的窄化及優異的潤濕性中之至少一項為較差的結果。 On the other hand, in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, it exhibits at least one of the effect of suppressing thickening, narrowing of ΔT, and excellent wettability Is a poor result.

此外,在對於試驗例2至498之焊料粉末分別使用調配例(F2-1)至(F2-60)的各助焊劑之情形下,可確認到任一者與使用調配例(F2-61)至(F2-62)的助焊劑之情形相比,皆係抑制殘渣中之龜裂的產生,溫度循環可靠度提高。 In addition, in the case of using the fluxes of the blending examples (F2-1) to (F2-60) for the solder powders of test examples 2 to 498, it is possible to confirm any one and the use blending example (F2-61) Compared with the flux of (F2-62), it suppresses the generation of cracks in the residue and improves the reliability of temperature cycle.

[含有助焊劑(F3)之焊料膏的評估] [Evaluation of solder paste containing flux (F3)]

接著,就對於具有試驗例1所示之合金組成之焊料粉末使用表47至表54所示之調配例(F3-1)至(F3-51)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經 時變化之評估〉。此外,測定焊料粉末的液相線溫度及固相線溫度來進行上述〈△T的評估〉。再者,使用剛製作的焊料膏來進行上述〈潤濕性的評估〉。 Next, for the solder powder having the alloy composition shown in Test Example 1 using the fluxes of the blending examples (F3-1) to (F3-51) shown in Table 47 to Table 54, the above-mentioned <Solder Paste The longitude of viscosity "Assessment of Changes in Time." In addition, the liquidus temperature and solidus temperature of the solder powder were measured to perform the above-mentioned <Evaluation of ΔT>. In addition, the above-mentioned "Evaluation of wettability" was performed using the solder paste just produced.

從此等之結果中,可確認到在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F3-1)至(F3-51)的各助焊劑之情形下的焊料膏,皆顯示出增黏抑制效果、△T的窄化及優異的潤濕性。 From these results, it can be confirmed that the solder pastes in the case of using the fluxes of the blending examples (F3-1) to (F3-51) for the solder powder having the alloy composition shown in Test Example 1 all show It has the effect of suppressing viscosity increase, narrowing of △T and excellent wettability.

接著,對於具有試驗例1所示之合金組成之焊料粉末使用表47至表54所示之調配例(F3-1)至(F3-51)的各助焊劑之情形下的焊料膏(助焊劑:焊料粉末=11:89的質量比),分別進行焊料之潤濕擴展性、焊料之去濕抑制能力的評估。 Next, for the solder powder having the alloy composition shown in Test Example 1, the solder paste (flux flux) in the case of using the fluxes of the blending examples (F3-1) to (F3-51) shown in Table 47 to Table 54 : Solder powder = mass ratio of 11:89), respectively evaluate the wettability of the solder and the dewetting suppression ability of the solder.

〈焊料之潤濕擴展性的評估〉 〈Assessment of solder wettability and spreadability〉

(1)驗證方法 (1) Verification method

焊料之潤濕擴展性的評估試驗係以如下方式來進行。 The evaluation test of the wettability and spreadability of the solder was carried out in the following manner.

藉由JIS Z 3284-3:2014所記載之既定的圖案,使用形成有焊料膏的印刷部之不鏽鋼製的遮罩將各焊料膏印刷於縱50mm×橫50mm×厚0.5mm的Bare-Cu板。 According to the predetermined pattern described in JIS Z 3284-3:2014, each solder paste is printed on a Bare-Cu board of 50 mm in length × 50 mm in width × 0.5 mm in thickness using a stainless steel mask formed with the printing part of the solder paste .

形成於遮罩之印刷部為四角形的開口,大小為3.0mm×1.5mm。印刷部係使相同大小的複數個開口以相異間隔來排列,開口的間隔為0.2-0.3-0.4-0.5-0.6-0.7-0.8-0.9-1.0-1.1-1.2mm。 The printed part formed on the mask is a quadrangular opening with a size of 3.0mm×1.5mm. In the printing part, a plurality of openings of the same size are arranged at different intervals, and the interval of the openings is 0.2-0.3-0.4-0.5-0.6-0.7-0.8-0.9-1.0-1.1-1.2mm.

於印刷焊料膏後將遮罩移除,於回焊前,在並列之印刷部的最小間隔之0.2mm處確認焊料膏為未接觸,並進行回焊。回焊的條件係在大氣環境下於190℃進行120秒的預熱後,將升溫速度設為1℃/秒並從190℃升溫至260℃來進行主要加熱。 Remove the mask after printing the solder paste. Before reflowing, confirm that the solder paste is not in contact with the minimum distance between the printed parts of the side by 0.2mm, and perform reflowing. The conditions of the reflow were preheated at 190°C for 120 seconds in an atmospheric environment, and then the heating rate was set to 1°C/sec, and the temperature was increased from 190°C to 260°C to perform main heating.

(2)判定基準 (2) Judgment criteria

確認上述以既定間隔印刷出之焊料膏於回焊後係潤濕擴展並接觸而熔合之處的間隔(N=4)。 Confirm that the above-mentioned solder paste printed at a predetermined interval is wetted and expanded after reflowing, contacting and fusing the interval (N=4).

A:間隔L為0.8mm以下之處全部熔合。 A: All the places where the interval L is 0.8 mm or less are fused.

B:間隔L為0.8mm以下之處即使是1處亦有未熔合者。 B: Even if the interval L is 0.8 mm or less, there are some unfused parts even in one place.

〈焊料之去濕抑制能力的評估〉 <Assessment of Dehumidification Suppression Ability of Solder>

(1)驗證方法 (1) Verification method

焊料之去濕抑制能力的評估試驗係以如下方式來進行。 The evaluation test of the dehumidification suppression ability of the solder was carried out in the following manner.

將各焊料膏印刷於縱0.8mm×橫0.8mm的Cu-OSP焊墊(CU-OSP Land)上並實施回焊。焊料膏的印刷厚度係設為0.12mm。回焊的條件係在大氣環境下於190℃進行120秒的預熱後,將升溫速度設為1℃/秒,並從190℃升溫至260℃來進行主要加熱。 Each solder paste was printed on a Cu-OSP pad (CU-OSP Land) of 0.8 mm in length x 0.8 mm in width, and reflow was performed. The printing thickness of the solder paste is set to 0.12 mm. The conditions of the reflow were preheated at 190°C for 120 seconds in an atmospheric environment, and the heating rate was set to 1°C/sec, and the temperature was increased from 190°C to 260°C to perform the main heating.

(2)判定基準 (2) Judgment criteria

使用光學顯微鏡來觀察於回焊後有無產生潤濕不良(去濕)(N=12)。 Use an optical microscope to observe whether poor wetting (dewetting) occurs after reflow (N=12).

A:塗佈有焊料膏之部分皆為經焊料潤濕之狀態。 A: The parts coated with solder paste are all wetted with solder.

B:雖然塗佈有焊料膏之部分的過半為經焊料潤濕之狀態(亦包含去濕),惟亦產生潤濕不良。或者,並非成為經焊料潤濕之模樣,而是熔融的焊料成為一個或複數個焊料球之狀態(不潤濕(nonwetting))。 B: Although more than half of the part coated with solder paste is in the state of being wetted by the solder (including dewetting), poor wetting is also caused. Or, instead of being wetted by the solder, the molten solder becomes one or more solder balls (nonwetting).

〈綜合評估〉 <Comprehensive Evaluation>

A:於表47至表54中,焊料之潤濕擴展性、去濕抑制能力係各項的評估皆為A。 A: In Table 47 to Table 54, the evaluation of the wetting spreadability and dehumidification inhibition ability of the solder is A.

B:於表47至表54中,焊料之潤濕擴展性、去濕抑制能力係各項的評估中之至少一項為B。 B: In Table 47 to Table 54, at least one of the evaluations of the wetting spreadability and dewetting suppression ability of the solder is B.

評估結果係如表47至表54所示。 The evaluation results are shown in Table 47 to Table 54.

表中,係使用脂肪族聚醯胺作為聚醯胺,使用六亞甲基雙羥基硬脂醯胺作為雙醯胺,使用對甲苯醯胺作為單醯胺。 In the table, aliphatic polyamide is used as polyamide, hexamethylene bishydroxystearylamine is used as bisamide, and p-toluamide is used as monoamide.

[表47]

Figure 109117353-A0202-12-0127-55
[Table 47]
Figure 109117353-A0202-12-0127-55

[表48]

Figure 109117353-A0202-12-0128-56
[Table 48]
Figure 109117353-A0202-12-0128-56

[表49]

Figure 109117353-A0202-12-0129-57
[Table 49]
Figure 109117353-A0202-12-0129-57

[表50]

Figure 109117353-A0202-12-0130-58
[Table 50]
Figure 109117353-A0202-12-0130-58

[表51]

Figure 109117353-A0202-12-0131-59
[Table 51]
Figure 109117353-A0202-12-0131-59

[表52]

Figure 109117353-A0202-12-0132-60
[Table 52]
Figure 109117353-A0202-12-0132-60

[表53]

Figure 109117353-A0202-12-0133-61
[Table 53]
Figure 109117353-A0202-12-0133-61

[表54]

Figure 109117353-A0202-12-0134-62
[Table 54]
Figure 109117353-A0202-12-0134-62

在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F3-1)至(F3-50)的各助焊劑之情形下,可確認到任一者與使用調配例(F3-51)的助焊劑之情形相比,皆係潤濕擴展性較為良好,去濕抑制能力變高。其中,含有具有試驗例1的合金組成之焊料粉末與調配例(F3-1)至(F3-50)的各助焊劑之焊料膏,為含有助焊劑(F3)之實施型態之焊料膏。 In the case of using the fluxes of the blending examples (F3-1) to (F3-50) for the solder powder with the alloy composition shown in Test Example 1, it can be confirmed that any one of them and the use blending example (F3-51) Compared with the case of the flux of ), the wetting and spreading properties are better, and the dewetting suppression ability is higher. Among them, the solder paste containing the solder powder having the alloy composition of Test Example 1 and the fluxes of the blending examples (F3-1) to (F3-50) is an implementation type solder paste containing the flux (F3).

接著,就對於具有試驗例2至498、試驗例501至578所示之各合金組成之焊料粉末分別使用調配例(F3-1)至(F3-51)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經時變化之評估〉、〈△T的評估〉及〈潤濕性的評估〉,以及〈焊料之潤濕擴展性的評估〉及〈焊料之去濕抑制能力的評估〉。 Next, for the solder powders having the respective alloy compositions shown in Test Examples 2 to 498 and Test Examples 501 to 578, each of the fluxes of Blending Examples (F3-1) to (F3-51) was used, and the above-mentioned < Evaluation of the change of viscosity in solder paste with time", "Evaluation of △T" and "Evaluation of wettability", and "Evaluation of solder wettability extension" and "Evaluation of solder dewetting inhibition ability" .

從該評估的結果中,可確認到於含有具有試驗例2至498的合金組成之焊料粉末之焊料膏的情形下,係顯示出增黏抑制效果、△T的窄化及優異的潤濕性。此等當中,含有具有試驗例2至498的合金組成之各焊料粉末與調配例(F3-1)至(F3-50)的各助焊劑之焊料膏,為含有助焊劑(F3)之實施型態之焊料膏。 From the results of this evaluation, it can be confirmed that in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498, it exhibits the effect of suppressing viscosity increase, narrowing of ΔT, and excellent wettability. . Among them, the solder paste containing each solder powder with the alloy composition of Test Examples 2 to 498 and the fluxes of Blending Examples (F3-1) to (F3-50) is an implementation type containing flux (F3) State of the solder paste.

另一方面,於含有具有試驗例501至578的合金組成之焊料粉末之焊料膏的情形下,係顯示出於增黏抑制效果、△T的窄化及優異的潤濕性中之至少一項為較差的結果。 On the other hand, in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, it exhibits at least one of the effect of suppressing thickening, narrowing of ΔT, and excellent wettability Is a poor result.

此外,在對於試驗例2至498之焊料粉末分別使用調配例(F3-1)至(F3-50)的各助焊劑之情形下,可確認到任一者與使用調配例(F3-51)的助焊劑之情形相比,皆係潤濕擴展性更為良好,去濕抑制能力變高。 In addition, in the case of using the fluxes of the blending examples (F3-1) to (F3-50) for the solder powders of test examples 2 to 498, it is possible to confirm any one and the use blending example (F3-51) Compared with the case of the fluxes, all systems have better wetting and spreading properties and higher dewetting suppression capabilities.

[含有助焊劑(F4)之焊料膏的評估] [Evaluation of solder paste containing flux (F4)]

接著,就對於具有試驗例1所示之合金組成之焊料粉末使用表55至表66所示之調配例(F4-1)至(F4-58)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經時變化之評估〉。此外,測定焊料粉末的液相線溫度及固相線溫度來進行上述〈△T的評估〉。再者,使用剛製作的焊料膏來進行上述〈潤濕性的評估〉。 Next, for the solder powder having the alloy composition shown in Test Example 1 using the fluxes of the blending examples (F4-1) to (F4-58) shown in Table 55 to Table 66, the above-mentioned <Solder Paste "Evaluation of the change of viscosity over time in the medium." In addition, the liquidus temperature and solidus temperature of the solder powder were measured to perform the above-mentioned <Evaluation of ΔT>. In addition, the above-mentioned "Evaluation of wettability" was performed using the solder paste just produced.

從此等之結果中,可確認到在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F4-1)至(F4-58)的各助焊劑之情形下的焊料膏,皆顯示出增黏抑制效果、△T的窄化及優異的潤濕性。 From these results, it can be confirmed that the solder pastes in the case of using the fluxes of the blending examples (F4-1) to (F4-58) for the solder powder having the alloy composition shown in Test Example 1 all show It has the effect of suppressing viscosity increase, narrowing of △T and excellent wettability.

接著,就對於具有試驗例1所示之合金組成之焊料粉末使用表55至表66所示之調配例(F4-1)至(F4-58)的各助焊劑之情形,進行焊料之潤濕速度(焊料潤濕性)的評估。 Next, for the solder powder having the alloy composition shown in Test Example 1 using the fluxes of the blending examples (F4-1) to (F4-58) shown in Table 55 to Table 66, the solder is wetted Evaluation of speed (solder wettability).

〈焊料潤濕性(潤濕速度)的評估〉 <Evaluation of solder wettability (wetting rate)>

(1)驗證方法 (1) Verification method

助焊劑的潤濕速度係依據弧面狀沾焊料試驗的方法,對寬5mm×長25mm×厚0.5mm的銅板用150℃進行1小時的氧化處理,而得到試驗板的氧化銅板,使用Solder Checker SAT-5200(RHESCA公司製)作為試驗裝置,並使用具有試驗例1所示之合金組成之焊料粉末作為焊料,以下列方式進行評估。 The flux wetting speed is based on the arc surface solder test method. A copper plate with a width of 5 mm × a length of 25 mm × a thickness of 0.5 mm is oxidized at 150°C for 1 hour to obtain the copper oxide plate of the test board, using Solder Checker SAT-5200 (manufactured by RHESCA) was used as a test device, and solder powder having the alloy composition shown in Test Example 1 was used as the solder, and the evaluation was performed in the following manner.

首先,對於量取至燒杯之調配例(F4-1)至(F4-58)的各助焊劑浸漬試驗板5mm,以將各助焊劑塗佈於試驗板。接著,在塗佈助焊劑後,迅速地將塗佈有助焊劑之試驗板浸漬在焊料槽,而得到零交叉時間(sec)。接著,對調配例(F4-1)至(F4-58)的各助焊劑進行5次的測定,並算出所得到之5個零交叉時間(sec)的平均值。試驗條件係設定如下。 First, 5 mm of each flux immersion test board of the preparation examples (F4-1) to (F4-58) measured into a beaker was applied to the test board. Next, after the flux is applied, the test board coated with the flux is quickly immersed in the solder tank to obtain the zero crossing time (sec). Next, the fluxes of the formulation examples (F4-1) to (F4-58) were measured 5 times, and the average value of the obtained 5 zero-crossing times (sec) was calculated. The test conditions are set as follows.

於焊料槽之浸漬速度:5mm/sec(JIS Z 3198-4:2003) Dipping speed in solder tank: 5mm/sec (JIS Z 3198-4: 2003)

於焊料槽之浸漬深度:2mm(JIS Z 3198-4:2003) Dipping depth in solder tank: 2mm (JIS Z 3198-4: 2003)

於焊料槽之浸漬時間:10sec(JIS Z 3198-4:2003) Dipping time in solder tank: 10sec (JIS Z 3198-4: 2003)

焊料槽溫度:245℃(JIS C 60068-2-69:2019附錄B)零交叉時間(sec)的平均值愈短,係意指潤濕速度變得愈高,而焊料潤濕性愈佳。 Solder tank temperature: 245°C (JIS C 60068-2-69: 2019 Appendix B) The shorter the average value of the zero crossing time (sec), the higher the wetting speed, and the better the solder wettability.

(2)判定基準 (2) Judgment criteria

A:零交叉時間(sec)的平均值為6秒以下。 A: The average value of the zero-crossing time (sec) is 6 seconds or less.

B:零交叉時間(sec)的平均值超過6秒。 B: The average value of the zero crossing time (sec) exceeds 6 seconds.

評估結果係如表55至表66所示。 The evaluation results are shown in Table 55 to Table 66.

表中,係使用脂肪族聚醯胺作為聚醯胺,使用六亞甲基雙羥基硬脂醯胺作為雙醯胺,使用對甲苯醯胺作為單醯胺。 In the table, aliphatic polyamide is used as polyamide, hexamethylene bishydroxystearylamine is used as bisamide, and p-toluamide is used as monoamide.

[表55]

Figure 109117353-A0202-12-0138-63
[Table 55]
Figure 109117353-A0202-12-0138-63

[表56]

Figure 109117353-A0202-12-0139-64
[Table 56]
Figure 109117353-A0202-12-0139-64

[表57]

Figure 109117353-A0202-12-0140-65
[Table 57]
Figure 109117353-A0202-12-0140-65

[表58]

Figure 109117353-A0202-12-0141-66
[Table 58]
Figure 109117353-A0202-12-0141-66

[表59]

Figure 109117353-A0202-12-0142-68
[Table 59]
Figure 109117353-A0202-12-0142-68

[表60]

Figure 109117353-A0202-12-0143-69
[Table 60]
Figure 109117353-A0202-12-0143-69

[表61]

Figure 109117353-A0202-12-0144-70
[Table 61]
Figure 109117353-A0202-12-0144-70

[表62]

Figure 109117353-A0202-12-0145-71
[Table 62]
Figure 109117353-A0202-12-0145-71

[表63]

Figure 109117353-A0202-12-0146-72
[Table 63]
Figure 109117353-A0202-12-0146-72

[表64]

Figure 109117353-A0202-12-0147-73
[Table 64]
Figure 109117353-A0202-12-0147-73

[表65]

Figure 109117353-A0202-12-0148-74
[Table 65]
Figure 109117353-A0202-12-0148-74

[表66]

Figure 109117353-A0202-12-0149-75
[Table 66]
Figure 109117353-A0202-12-0149-75

在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F4-1)至(F4-57)的各助焊劑之情形下,可確認到任一者與使用調配例(F4-58)的助焊劑之情形相比,皆為焊料的潤濕速度變高,而焊料潤濕性提高。其中,含有具有試驗例1的合金組成之焊料粉末與調配例(F4-1)至(F4-57)的各助焊劑之焊料膏,為含有助焊劑(F4)之實施型態之焊料膏。 In the case of using the fluxes of the blending examples (F4-1) to (F4-57) for the solder powder having the alloy composition shown in Test Example 1, it can be confirmed that any one of them and the use blending example (F4-58) Compared with the case of the flux of ), the wetting speed of the solder is higher, and the solder wettability is improved. Among them, the solder paste containing the solder powder having the alloy composition of Test Example 1 and the fluxes of the blending examples (F4-1) to (F4-57) is an implementation type solder paste containing the flux (F4).

接著,就對於具有試驗例2至498、試驗例501至578所示之各合金組成之焊料粉末分別使用調配例(F4-1)至(F4-58)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經時變化之評估〉、〈△T的評估〉及〈潤濕性的評估〉,以及〈焊料潤濕性(潤濕速度)的評估〉。 Next, for the solder powders having the respective alloy compositions shown in Test Examples 2 to 498 and Test Examples 501 to 578, each of the fluxes of Blending Examples (F4-1) to (F4-58) was used, and the above-mentioned < Evaluation of the change of viscosity in solder paste with time", "Evaluation of △T" and "Evaluation of wettability", and "Evaluation of solder wettability (wetting speed)".

從該評估的結果中,可確認到於含有具有試驗例2至498的合金組成之焊料粉末之焊料膏的情形下,係顯示出增黏抑制效果、△T的窄化及優異的潤濕性。此等當中,含有具有試驗例2至498的合金組成之各焊料粉末與調配例(F4-1)至(F4-57)的各助焊劑之焊料膏,為含有助焊劑(F4)之實施型態之焊料膏。 From the results of this evaluation, it can be confirmed that in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498, it exhibits the effect of suppressing viscosity increase, narrowing of ΔT, and excellent wettability. . Among them, the solder paste containing each solder powder with the alloy composition of Test Examples 2 to 498 and the fluxes of Blending Examples (F4-1) to (F4-57) is an implementation type containing flux (F4) State of the solder paste.

另一方面,於含有具有試驗例501至578的合金組成之焊料粉末之焊料膏的情形下,係顯示出於增黏抑制效果、△T的窄化及優異的潤濕性中之至少一項為較差的結果。 On the other hand, in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, it exhibits at least one of the effect of suppressing thickening, narrowing of ΔT, and excellent wettability Is a poor result.

此外,在對於試驗例2至498之焊料粉末分別使用調配例(F4-1)至(F4-57)的各助焊劑之情形下,可確認到任一者與使用調配例(F4-58)的助焊劑之情形相比,皆為焊料的潤濕速度變高,而焊料潤濕性提高。 In addition, in the case of using the fluxes of the blending examples (F4-1) to (F4-57) for the solder powders of test examples 2 to 498, it is possible to confirm any one and the use blending example (F4-58) Compared with the case of the flux, the wetting speed of the solder becomes higher, and the solder wettability is improved.

[含有助焊劑(F5)之焊料膏的評估] [Evaluation of solder paste containing flux (F5)]

接著,就對於具有試驗例1所示之合金組成之焊料粉末使用表67至表79所示之調配例(F5-1)至(F5-62)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經時變化之評估〉。此外,測定焊料粉末的液相線溫度及固相線溫度來進行上述〈△T的評估〉。再者,使用剛製作的焊料膏來進行上述〈潤濕性的評估〉。 Next, for the solder powder having the alloy composition shown in Test Example 1 using the fluxes of the blending examples (F5-1) to (F5-62) shown in Table 67 to Table 79, the above-mentioned <Solder Paste "Evaluation of the change of viscosity over time in the medium." In addition, the liquidus temperature and solidus temperature of the solder powder were measured to perform the above-mentioned <Evaluation of ΔT>. In addition, the above-mentioned "Evaluation of wettability" was performed using the solder paste just produced.

從此等之結果中,可確認到在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F5-1)至(F5-62)的各助焊劑之情形下的焊料膏,皆顯示出增黏抑制效果、△T的窄化及優異的潤濕性。 From these results, it can be confirmed that the solder pastes in the case of using the fluxes of the blending examples (F5-1) to (F5-62) for the solder powder having the alloy composition shown in Test Example 1 all show It has the effect of suppressing viscosity increase, narrowing of △T and excellent wettability.

接著,就對於具有試驗例1所示之合金組成之焊料粉末使用表67至表79所示之調配例(F5-1)至(F5-62)的各助焊劑之情形,進行銅板腐蝕抑制能力的評估。 Next, for the solder powder having the alloy composition shown in Test Example 1 using the fluxes of the blending examples (F5-1) to (F5-62) shown in Table 67 to Table 79, the copper plate corrosion inhibition ability was performed evaluation of.

〈銅板腐蝕抑制能力的評估〉 〈Evaluation of corrosion inhibition ability of copper plate〉

(1)驗證方法 (1) Verification method

銅板腐蝕抑制能力的評估係依據JIS Z 3197:2012 8.4.1,而藉由下述銅板腐蝕試驗來進行。 The evaluation of copper plate corrosion inhibition ability is based on JIS Z 3197:2012 8.4.1, and is carried out by the following copper plate corrosion test.

試驗銅板的製作:於尺寸50mm×50mm×0.5mm之磷脫氧銅板的中央,藉由直徑20mm的鋼球作出深度3mm的凹陷而作為試驗片。試驗片在藉由丙酮進行脫脂後,浸漬於65℃的硫酸1分鐘以去除表面的氧化覆膜等。接著,浸漬在20℃的過硫酸銨溶液1分鐘後,以精製水洗淨並乾燥,而作為試驗銅板。 Fabrication of the test copper plate: In the center of a phosphorous deoxidized copper plate with a size of 50mm×50mm×0.5mm, a steel ball with a diameter of 20mm is used to make a 3mm deep depression as a test piece. After the test piece was degreased with acetone, it was immersed in sulfuric acid at 65°C for 1 minute to remove the oxide film on the surface. Next, after immersing in an ammonium persulfate solution at 20°C for 1 minute, it was washed with purified water and dried to obtain a test copper plate.

使用JIS Z 3197:2012 8.1.3所規定之方法來測定各例之助焊劑的固形份含量,將含有以固形份計為0.035至0.040g之適量的助焊劑加至前述試驗銅板中央的凹陷處。 Use the method specified in JIS Z 3197:2012 8.1.3 to determine the solid content of the flux of each example, add an appropriate amount of flux containing 0.035 to 0.040g based on the solid content to the depression in the center of the test copper plate .

接著,將試驗銅板投入至設定在溫度40℃、相對濕度90%的加濕條件之恆溫恆濕槽中,於槽內放置72小時。對於各例的每個助焊劑,係將試驗銅板設為2個,並加入1個空白試驗銅板(blank)。 Next, the test copper plate was put into a constant temperature and humidity tank set at a humidification condition of a temperature of 40° C. and a relative humidity of 90%, and it was left in the tank for 72 hours. For each flux of each example, two test copper plates were set, and one blank test copper plate was added.

於槽內放置96小時後,從恆溫恆濕槽取出,並藉由30倍的顯微鏡就腐蝕的痕跡與空白試驗銅板進行比較。根據以下所示之判定基準來評估銅板腐蝕抑制能力。 After being placed in the tank for 96 hours, it was taken out of the constant temperature and humidity tank, and the corrosion traces were compared with the blank test copper plate by a 30-fold microscope. Evaluate the corrosion inhibition ability of copper plates based on the criteria shown below.

(2)判定基準 (2) Judgment criteria

A:無變色 A: No discoloration

B:有變色 B: Discoloration

評估結果係如表67至表78所示。 The evaluation results are shown in Table 67 to Table 78.

表中,係使用脂肪族聚醯胺作為聚醯胺,使用六亞甲基雙羥基硬脂醯胺作為雙醯胺,使用對甲苯醯胺作為單醯胺。 In the table, aliphatic polyamide is used as polyamide, hexamethylene bishydroxystearylamine is used as bisamide, and p-toluamide is used as monoamide.

[表67]

Figure 109117353-A0202-12-0153-76
[Table 67]
Figure 109117353-A0202-12-0153-76

[表68]

Figure 109117353-A0202-12-0154-77
[Table 68]
Figure 109117353-A0202-12-0154-77

[表69]

Figure 109117353-A0202-12-0155-78
[Table 69]
Figure 109117353-A0202-12-0155-78

[表70]

Figure 109117353-A0202-12-0156-79
[Table 70]
Figure 109117353-A0202-12-0156-79

[表71]

Figure 109117353-A0202-12-0157-80
[Table 71]
Figure 109117353-A0202-12-0157-80

[表72]

Figure 109117353-A0202-12-0158-81
[Table 72]
Figure 109117353-A0202-12-0158-81

[表73]

Figure 109117353-A0202-12-0159-82
[Table 73]
Figure 109117353-A0202-12-0159-82

[表74]

Figure 109117353-A0202-12-0160-83
[Table 74]
Figure 109117353-A0202-12-0160-83

[表75]

Figure 109117353-A0202-12-0161-84
[Table 75]
Figure 109117353-A0202-12-0161-84

[表76]

Figure 109117353-A0202-12-0162-85
[Table 76]
Figure 109117353-A0202-12-0162-85

[表77]

Figure 109117353-A0202-12-0163-86
[Table 77]
Figure 109117353-A0202-12-0163-86

[表78]

Figure 109117353-A0202-12-0164-87
[Table 78]
Figure 109117353-A0202-12-0164-87

在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F5-1)至(F5-61)的各助焊劑之情形下,可確認到任一者與使用調配例(F5-62)的助焊劑之情形相比,銅板腐蝕抑制性皆為提高。其中,含有具有試驗例1的合金組成之焊料粉末與調配例(F5-1)至(F5-61)的各助焊劑之焊料膏,為含有助焊劑(F5)之實施型態之焊料膏。 In the case of using the fluxes of the blending examples (F5-1) to (F5-61) for the solder powder with the alloy composition shown in Test Example 1, it can be confirmed that any one of them and the use blending example (F5-62) Compared with the case of flux of ), the corrosion inhibition of copper plates is improved. Among them, the solder paste containing the solder powder having the alloy composition of Test Example 1 and the fluxes of the blending examples (F5-1) to (F5-61) is an implementation type solder paste containing the flux (F5).

接著,就對於具有試驗例2至498、試驗例501至578所示之各合金組成之焊料粉末分別使用調配例(F5-1)至(F5-62)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經時變化之評估〉、〈△T的評估〉及〈潤濕性的評估〉,以及〈銅板腐蝕抑制能力的評估〉。 Next, for the solder powders having the respective alloy compositions shown in Test Examples 2 to 498 and Test Examples 501 to 578, the fluxes of the blending examples (F5-1) to (F5-62) were used, and the above-mentioned < Evaluation of the change of viscosity in solder paste with time", "Evaluation of △T" and "Evaluation of wettability", and "Evaluation of corrosion inhibition ability of copper plate".

從該評估的結果中,可確認到於含有具有試驗例2至498的合金組成之焊料粉末之焊料膏的情形下,係顯示出增黏抑制效果、△T的窄化及優異的潤濕性。此等當中,含有具有試驗例2至498的合金組成之各焊料粉末與調配例(F5-1)至(F5-61)的各助焊劑之焊料膏,為含有助焊劑(F5)之實施型態之焊料膏。 From the results of this evaluation, it can be confirmed that in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498, it exhibits the effect of suppressing viscosity increase, narrowing of ΔT, and excellent wettability. . Among them, the solder paste containing each solder powder with the alloy composition of Test Examples 2 to 498 and the fluxes of Blending Examples (F5-1) to (F5-61) is an implementation type containing flux (F5) State of the solder paste.

另一方面,於含有具有試驗例501至578的合金組成之焊料粉末之焊料膏的情形下,係顯示出於增黏抑制效果、△T的窄化及優異的潤濕性中之至少一項為較差的結果。 On the other hand, in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, it exhibits at least one of the effect of suppressing thickening, narrowing of ΔT, and excellent wettability Is a poor result.

此外,在對於試驗例2至498之焊料粉末分別使用調配例(F5-1)至(F5-61)的各助焊劑之情形下,可確認到任一者與使用調配例(F5-62)的助焊劑之情形相比,銅板腐蝕抑制性皆為提高。 In addition, in the case of using the fluxes of the blending examples (F5-1) to (F5-61) for the solder powders of test examples 2 to 498, it is possible to confirm any one and the use blending example (F5-62) Compared with the case of the flux, the corrosion inhibition of the copper plate is improved.

[含有助焊劑(F6)之焊料膏的評估] [Evaluation of solder paste containing flux (F6)]

接著,就對於具有試驗例1所示之合金組成之焊料粉末使用表79至表87所示之調配例(F6-1)至(F6-60)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經時變化之評估〉。此外,測定焊料粉末的液相線溫度及固相線溫度來進行上述〈△T的評估〉。再者,使用剛製作的焊料膏來進行上述〈潤濕性的評估〉。 Next, for the solder powder having the alloy composition shown in Test Example 1 using the fluxes of the blending examples (F6-1) to (F6-60) shown in Table 79 to Table 87, the above-mentioned <Solder Paste "Evaluation of the change of viscosity over time in the medium." In addition, the liquidus temperature and solidus temperature of the solder powder were measured to perform the above-mentioned <Evaluation of ΔT>. In addition, the above-mentioned "Evaluation of wettability" was performed using the solder paste just produced.

從此等之結果中,可確認到在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F6-1)至(F6-60)的各助焊劑之情形下的焊料膏,任一者皆顯示出增黏抑制效果、△T的窄化及優異的潤濕性。 From these results, it can be confirmed that the solder paste in the case of using the fluxes of the blending examples (F6-1) to (F6-60) for the solder powder having the alloy composition shown in Test Example 1, either All of them showed the effect of suppressing viscosity increase, narrowing of △T and excellent wettability.

接著,就對於具有試驗例1所示之合金組成之焊料粉末使用表79至表87所示之調配例(F6-1)至(F6-60)的各助焊劑之情形,進行焊料之潤濕速度(焊料潤濕性)的評估。 Next, for the solder powder with the alloy composition shown in Test Example 1 using the fluxes of the blending examples (F6-1) to (F6-60) shown in Table 79 to Table 87, the solder is wetted Evaluation of speed (solder wettability).

〈焊料之潤濕速度(焊料潤濕性)的評估〉 <Assessment of solder wetting speed (solder wettability)>

(1)驗證方法 (1) Verification method

焊料之潤濕速度(焊料潤濕性)的評估試驗係以如下方式來進行。 The evaluation test of the solder wetting speed (solder wettability) was performed as follows.

依據弧面狀沾焊料試驗的方法,對寬5mm×長25mm×厚0.5mm的銅板用150℃進行1小時的氧化處理而得到試驗板的氧化銅板,使用Solder Checker SAT-5200(RHESCA公司製)作為試驗裝置,並使用由試驗例1所示之合金組成所構成之焊料粉末作為焊料,以下列方式進行評估。 According to the arc surface solder test method, a copper plate with a width of 5 mm × a length of 25 mm × a thickness of 0.5 mm was oxidized at 150°C for 1 hour to obtain the copper oxide plate of the test board. Solder Checker SAT-5200 (manufactured by RHESCA) was used. As a test device, a solder powder composed of the alloy composition shown in Test Example 1 was used as the solder, and the evaluation was performed in the following manner.

首先,對於量取至燒杯之各例的助焊劑浸漬試驗板5mm,以將助焊劑塗佈於試驗板。接著,在塗佈助焊劑後,迅速地將塗佈有助焊劑之試驗板浸漬在試驗例1所示之合金組成的焊料槽,而得到零交叉時間(sec)。 First, 5 mm of the flux-impregnated test board of each example measured into the beaker was applied to the test board with the flux. Next, after the flux was applied, the test board coated with the flux was quickly immersed in the solder tank of the alloy composition shown in Test Example 1, and the zero crossing time (sec) was obtained.

接著,對各例的助焊劑進行5次的測定,並算出所得到之5個零交叉時間(sec)的平均值。試驗條件係設定如下。 Next, the flux of each example was measured 5 times, and the average value of the obtained 5 zero-crossing times (sec) was calculated. The test conditions are set as follows.

於焊料槽之浸漬速度:5mm/sec(JIS Z 3198-4:2003) Dipping speed in solder tank: 5mm/sec (JIS Z 3198-4: 2003)

於焊料槽之浸漬深度:2mm(JIS Z 3198-4:2003) Dipping depth in solder tank: 2mm (JIS Z 3198-4: 2003)

於焊料槽之浸漬時間:10sec(JIS Z 3198-4:2003) Dipping time in solder tank: 10sec (JIS Z 3198-4: 2003)

焊料槽溫度:245℃(JIS C 60068-2-69:2019附錄B)零交叉時間(sec)的平均值愈短,係意指潤濕速度變得愈高,而焊料潤濕性愈佳。 Solder tank temperature: 245°C (JIS C 60068-2-69: 2019 Appendix B) The shorter the average value of the zero crossing time (sec), the higher the wetting speed, and the better the solder wettability.

(2)判定基準 (2) Judgment criteria

A:零交叉時間(sec)的平均值為6秒以下。 A: The average value of the zero-crossing time (sec) is 6 seconds or less.

B:零交叉時間(sec)的平均值超過6秒。 B: The average value of the zero crossing time (sec) exceeds 6 seconds.

評估結果係如表79至表87所示。 The evaluation results are shown in Table 79 to Table 87.

表中,係使用脂肪族聚醯胺作為聚醯胺,使用六亞甲基雙羥基硬脂醯胺作為雙醯胺,使用對甲苯醯胺作為單醯胺。 In the table, aliphatic polyamide is used as polyamide, hexamethylene bishydroxystearylamine is used as bisamide, and p-toluamide is used as monoamide.

[表79]

Figure 109117353-A0202-12-0168-88
[Table 79]
Figure 109117353-A0202-12-0168-88

[表80]

Figure 109117353-A0202-12-0169-90
[Table 80]
Figure 109117353-A0202-12-0169-90

[表81]

Figure 109117353-A0202-12-0170-91
[Table 81]
Figure 109117353-A0202-12-0170-91

[表82]

Figure 109117353-A0202-12-0171-92
[Table 82]
Figure 109117353-A0202-12-0171-92

[表83]

Figure 109117353-A0202-12-0172-93
[Table 83]
Figure 109117353-A0202-12-0172-93

[表84]

Figure 109117353-A0202-12-0173-94
[Table 84]
Figure 109117353-A0202-12-0173-94

[表85]

Figure 109117353-A0202-12-0174-95
[Table 85]
Figure 109117353-A0202-12-0174-95

[表86]

Figure 109117353-A0202-12-0175-96
[Table 86]
Figure 109117353-A0202-12-0175-96

[表87]

Figure 109117353-A0202-12-0176-97
[Table 87]
Figure 109117353-A0202-12-0176-97

在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F6-1)至(F6-59)的各助焊劑之情形下,可確認到任一者與使用調配例(F6-60)的助焊劑之情形相比,皆為焊料的潤濕速度變得較高,焊料潤濕性更良好。其中,含有具有試驗例1的合金組成之焊料粉末與調配例(F6-1)至(F6-59)的各助焊劑之焊料膏,為含有助焊劑(F6)之實施型態之焊料膏。 In the case of using the fluxes of the blending examples (F6-1) to (F6-59) for the solder powder with the alloy composition shown in Test Example 1, it is possible to confirm that any one of them and the use blending example (F6-60) Compared with the case of the flux of ), the wetting speed of the solder becomes higher, and the solder wettability is better. Among them, the solder paste containing the solder powder having the alloy composition of Test Example 1 and the fluxes of the blending examples (F6-1) to (F6-59) is an implementation type solder paste containing the flux (F6).

接著,就對於具有試驗例2至498、試驗例501至578所示之各合金組成之焊料粉末分別使用調配例(F6-1)至(F6-60)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經時變化之評估〉、〈△T的評估〉及〈潤濕性的評估〉,以及〈焊料之潤濕速度(焊料潤濕性)的評估〉。 Next, for the solder powders having the respective alloy compositions shown in Test Examples 2 to 498 and Test Examples 501 to 578, each of the fluxes of Blending Examples (F6-1) to (F6-60) was used, and the above-mentioned < Evaluation of the change of viscosity in solder paste with time", "Evaluation of △T" and "Evaluation of wettability", and "Evaluation of solder wetting speed (solder wettability)".

從該評估的結果中,可確認到於含有具有試驗例2至498的合金組成之焊料粉末之焊料膏的情形下,係顯示出增黏抑制效果、△T的窄化及優異的潤濕性。此等當中,含有具有試驗例2至498的合金組成之各焊料粉末與調配例(F6-1)至(F6-59)的各助焊劑之焊料膏,為含有助焊劑(F6)之實施型態之焊料膏。 From the results of this evaluation, it can be confirmed that in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498, it exhibits the effect of suppressing viscosity increase, narrowing of ΔT, and excellent wettability. . Among them, the solder paste containing each solder powder with the alloy composition of Test Examples 2 to 498 and the fluxes of Blending Examples (F6-1) to (F6-59) is an implementation type containing flux (F6) State of the solder paste.

另一方面,於含有具有試驗例501至578的合金組成之焊料粉末之焊料膏的情形下,係顯示出於增黏抑制效果、△T的窄化及優異的潤濕性中之至少一項為較差的結果。 On the other hand, in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, it exhibits at least one of the effect of suppressing thickening, narrowing of ΔT, and excellent wettability Is a poor result.

此外,在對於試驗例2至498之焊料粉末分別使用調配例(F6-1)至(F6-59)的各助焊劑之情形下,可確認到任一者與使用調配例(F6-60)的助焊劑之情形相比,皆為焊料的潤濕速度變得較高,焊料潤濕性更良好。 In addition, in the case of using the fluxes of the blending examples (F6-1) to (F6-59) for the solder powders of test examples 2 to 498, it is possible to confirm any one and the use blending example (F6-60) Compared with the case of the flux, the wetting speed of the solder becomes higher, and the solder wettability is better.

[含有助焊劑(F7)之焊料膏的評估] [Evaluation of solder paste containing flux (F7)]

接著,就對於具有試驗例1所示之合金組成之焊料粉末使用表88至表95所示之調配例(F7-1)至(F7-54)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經 時變化之評估〉。此外,測定焊料粉末的液相線溫度及固相線溫度來進行上述〈△T的評估〉。再者,使用剛製作的焊料膏來進行上述〈潤濕性的評估〉。 Next, for the solder powder having the alloy composition shown in Test Example 1 using the fluxes of the blending examples (F7-1) to (F7-54) shown in Table 88 to Table 95, the above-mentioned <Solder Paste The longitude of viscosity "Assessment of Changes in Time." In addition, the liquidus temperature and solidus temperature of the solder powder were measured to perform the above-mentioned <Evaluation of ΔT>. In addition, the above-mentioned "Evaluation of wettability" was performed using the solder paste just produced.

從此等之結果中,可確認到在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F7-1)至(F7-54)的各助焊劑之情形下的焊料膏,任一者皆顯示出增黏抑制效果、△T的窄化及優異的潤濕性。 From these results, it can be confirmed that the solder paste in the case of using the fluxes of the blending examples (F7-1) to (F7-54) for the solder powder having the alloy composition shown in Test Example 1, either All of them showed the effect of suppressing viscosity increase, narrowing of △T and excellent wettability.

接著,就對於具有試驗例1所示之合金組成之焊料粉末使用表88至表95所示之調配例(F7-1)至(F7-54)的各助焊劑之情形,進行助焊劑之搖變減黏性、焊料膏之印刷流掛抑制能力、焊料膏之加熱流掛抑制能力的評估。 Next, for the solder powder with the alloy composition shown in Test Example 1, the fluxes of the blending examples (F7-1) to (F7-54) shown in Table 88 to Table 95 were used, and the flux was shaken. Evaluation of viscosity reduction, printing sag suppression ability of solder paste, and heating sag suppression ability of solder paste.

〈助焊劑之搖變減黏性的評估〉 <Assessment of Flux Shake Viscosity Reduction>

(1)驗證方法 (1) Verification method

搖變減黏性的評估係依據JIS Z3284-3:2014 4.2並使用螺旋式黏度計來進行。將黏度計的旋轉速度設定為3rpm與30rpm,讀取旋轉既定時間後的黏度並算出搖變減黏比。 The evaluation of thixotropic viscosity reduction is carried out in accordance with JIS Z3284-3:2014 4.2 and using a spiral viscometer. Set the rotation speed of the viscometer to 3rpm and 30rpm, read the viscosity after a predetermined time of rotation, and calculate the sway viscosity reduction ratio.

(2)判定基準 (2) Judgment criteria

A:搖變減黏比為0.30以上 A: Shake viscosity reduction ratio is 0.30 or more

B:搖變減黏比為未達0.30 B: Shake viscosity reduction ratio is less than 0.30

〈焊料膏之印刷流掛抑制能力的評估〉 〈Evaluation of printing sagging suppression ability of solder paste〉

(1)驗證方法 (1) Verification method

焊料膏(助焊劑:焊料粉末=11:89的質量比)之印刷流掛抑制能力的評估係依據JIS Z3284-3:2014 4.3,使用以既定的圖案形成有焊料膏印刷部之不鏽鋼製金屬遮罩將焊料膏印刷於銅板,在移除金屬遮罩後,於室溫25±5℃、相對濕度50±10%下保管10至20分鐘,藉由目視來確認於所印刷之各圖案中,所印刷之 焊料膏未全部成為一體之最小間隔。金屬遮罩的厚度為0.2mm,焊料膏印刷部為四角形的開口且大小為3.0×1.5mm。焊料膏印刷部係使相同大小的複數個開口以相異間隔來排列,開口的間隔L為0.2-0.3-0.4-0.5-0.6-0.7-0.8-0.9-1.0-1.1-1.2mm。 The evaluation of the printing sagging suppression ability of solder paste (flux: solder powder = 11:89 mass ratio) is based on JIS Z3284-3:2014 4.3, using a stainless steel metal mask with a solder paste printing part formed in a predetermined pattern The mask is printed on the copper plate. After removing the metal mask, store it at room temperature 25±5°C and relative humidity 50±10% for 10 to 20 minutes. Visually confirm that it is in each printed pattern. Printed The minimum interval where solder paste is not all integrated. The thickness of the metal mask is 0.2mm, and the solder paste printing part is a quadrangular opening and the size is 3.0×1.5mm. In the solder paste printing part, a plurality of openings of the same size are arranged at different intervals, and the interval L of the openings is 0.2-0.3-0.4-0.5-0.6-0.7-0.8-0.9-1.0-1.1-1.2mm.

(2)判定基準 (2) Judgment criteria

A:於印刷後未成為一體之最小間隔為0.2mm以下 A: After printing, the minimum distance that is not integrated is 0.2mm or less

B:於印刷後未成為一體之最小間隔為超過0.2mm B: After printing, the minimum distance that is not integrated is more than 0.2mm

〈焊料膏之加熱流掛抑制能力的評估〉 <Evaluation of the ability to suppress heat sag of solder paste>

(1)驗證方法 (1) Verification method

焊料膏(助焊劑:焊料粉末=11:89的質量比)之加熱流掛抑制能力的評估係依據JIS Z3284-3:2014 4.4,使用以既定的圖案形成有焊料膏印刷部之不鏽鋼製金屬遮罩將焊料膏印刷於銅板,在移除金屬遮罩後,以150±10℃加熱10分鐘,藉由目視來確認於所印刷之各圖案中,所印刷之焊料膏未全部成為一體之最小間隔。金屬遮罩的厚度為0.2mm,焊料膏印刷部為四角形的開口且大小為3.0×1.5mm。焊料膏印刷部係使相同大小的複數個開口以相異間隔來排列,開口的間隔L為0.2-0.3-0.4-0.5-0.6-0.7-0.8-0.9-1.0-1.1-1.2mm。 The evaluation of the heating sag suppression ability of the solder paste (flux: solder powder = 11:89 mass ratio) is based on JIS Z3284-3: 2014 4.4, using a stainless steel metal mask with a solder paste printed part formed in a predetermined pattern The mask prints the solder paste on the copper plate. After removing the metal mask, heat it at 150±10°C for 10 minutes, and visually confirm that the printed solder paste is not all integrated in the printed patterns. The minimum interval . The thickness of the metal mask is 0.2mm, and the solder paste printing part is a quadrangular opening and the size is 3.0×1.5mm. In the solder paste printing part, a plurality of openings of the same size are arranged at different intervals, and the interval L of the openings is 0.2-0.3-0.4-0.5-0.6-0.7-0.8-0.9-1.0-1.1-1.2mm.

(2)判定基準 (2) Judgment criteria

A:未成為一體之最小間隔為1.0mm以下 A: The minimum distance of not being integrated is 1.0mm or less

B:未成為一體之最小間隔為超過1.0mm B: The minimum distance that is not integrated is more than 1.0mm

〈綜合評估〉 <Comprehensive Evaluation>

A:於表88至表95中,助焊劑之搖變減黏性、焊料膏之印刷流掛抑制能力、焊料膏之加熱流掛抑制能力係各項的評估皆為A。 A: In Table 88 to Table 95, all the evaluations of the flux sag reduction ability, the printing sag suppression ability of the solder paste, and the heating sag suppression ability of the solder paste are all evaluated as A in Tables 88 to 95.

B:於表88至表95中,助焊劑之搖變減黏性、焊料膏之印刷流掛抑制能力、焊料膏之加熱流掛抑制能力係各項的評估中之至少一項為B。 B: In Table 88 to Table 95, at least one of the evaluation of the sag reduction ability of the flux, the printing sag suppression ability of the solder paste, and the heating sag suppression ability of the solder paste is B.

評估結果係如表88至表95所示。 The evaluation results are shown in Table 88 to Table 95.

表中,係使用脂肪族聚醯胺作為聚醯胺。 In the table, an aliphatic polyamide is used as the polyamide.

表中,係使用以下述化學式(3)所表示之化合物的混合物(分子量300至1500)作為環狀醯胺低聚物。此化學式(3)中m1、m2、m3、m4為亞甲基(CH2)的重複數。p表示單元的重複數。 In the table, a mixture (molecular weight 300 to 1500) of compounds represented by the following chemical formula (3) is used as the cyclic amide oligomer. In this chemical formula (3), m1, m2, m3, and m4 are the repeating number of methylene (CH 2 ). p represents the repeating number of the unit.

Figure 109117353-A0202-12-0180-98
Figure 109117353-A0202-12-0180-98

[表88]

Figure 109117353-A0202-12-0181-99
[Table 88]
Figure 109117353-A0202-12-0181-99

[表89]

Figure 109117353-A0202-12-0182-100
[Table 89]
Figure 109117353-A0202-12-0182-100

[表90]

Figure 109117353-A0202-12-0183-101
[Table 90]
Figure 109117353-A0202-12-0183-101

[表91]

Figure 109117353-A0202-12-0184-102
[Table 91]
Figure 109117353-A0202-12-0184-102

[表92]

Figure 109117353-A0202-12-0185-103
[Table 92]
Figure 109117353-A0202-12-0185-103

[表93]

Figure 109117353-A0202-12-0186-104
[Table 93]
Figure 109117353-A0202-12-0186-104

[表94]

Figure 109117353-A0202-12-0187-105
[Table 94]
Figure 109117353-A0202-12-0187-105

[表95]

Figure 109117353-A0202-12-0188-106
[Table 95]
Figure 109117353-A0202-12-0188-106

在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F7-1)至(F7-52)的各助焊劑之情形下,可確認到任一者與使用調配例(F7-53)的助焊劑之情形相比,助焊劑的搖變減黏性皆提升,而抑制印刷後的焊料膏流動之印刷流掛,並且抑制因焊接時的加熱所致之焊料膏的加熱流掛。 In the case of using the fluxes of the blending examples (F7-1) to (F7-52) for the solder powder with the alloy composition shown in Test Example 1, it can be confirmed that any one of them and the use blending example (F7-53) Compared with the case of the flux of ), the thixotropic viscosity reduction of the flux is improved, and the printing sagging of the solder paste after printing is suppressed, and the heating sagging of the solder paste caused by the heating during soldering is suppressed.

此外,在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F7-1)至(F7-52)的各助焊劑之情形下,可確認到任一者與使用調配例(F7-54)的助焊劑之情形相比,皆係抑制因焊接時的加熱所致之焊料膏的加熱流掛。 In addition, in the case of using the fluxes of the blending examples (F7-1) to (F7-52) for the solder powder having the alloy composition shown in Test Example 1, it can be confirmed that any one of them is consistent with the use of the blending example (F7). Compared with the case of the flux of -54), it suppresses the heating and sagging of the solder paste caused by heating during soldering.

此等當中,含有具有試驗例1的合金組成之焊料粉末與調配例(F7-1)至(F7-52)的各助焊劑之焊料膏,為含有助焊劑(F7)之實施型態之焊料膏。 Among them, the solder paste containing the solder powder with the alloy composition of Test Example 1 and the fluxes of the blending examples (F7-1) to (F7-52) is the solder paste of the implementation type containing the flux (F7) paste.

接著,就對於具有試驗例2至498、試驗例501至578所示之各合金組成之焊料粉末分別使用調配例(F7-1)至(F7-54)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經時變化之評估〉、〈△T的評估〉及〈潤濕性的評估〉,以及〈助焊劑之搖變減黏性的評估〉、〈焊料膏之印刷流掛抑制能力的評估〉及〈焊料膏之加熱流掛抑制能力的評估〉。 Next, for the solder powders having the respective alloy compositions shown in Test Examples 2 to 498 and Test Examples 501 to 578, each of the fluxes of Blending Examples (F7-1) to (F7-54) was used, and the above-mentioned < Evaluation of the change of viscosity in solder paste with time", "Evaluation of △T" and "Evaluation of wettability", and "Evaluation of flux reduction viscosity", "Sag suppression of solder paste printing Evaluation of Ability> and <Evaluation of Heat Sag Inhibition Capability of Solder Paste>.

從該評估的結果中,可確認到於含有具有試驗例2至498的合金組成之焊料粉末之焊料膏的情形下,係顯示出增黏抑制效果、△T的窄化及優異的潤濕性。此等當中,含有具有試驗例2至498的合金組成之各焊料粉末與調配例(F7-1)至(F7-52)的各助焊劑之焊料膏,為含有助焊劑(F7)之實施型態之焊料膏。 From the results of this evaluation, it can be confirmed that in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498, it exhibits the effect of suppressing viscosity increase, narrowing of ΔT, and excellent wettability. . Among them, the solder paste containing each solder powder with the alloy composition of Test Examples 2 to 498 and the fluxes of Blending Examples (F7-1) to (F7-52) is an implementation type containing flux (F7) State of the solder paste.

另一方面,於含有具有試驗例501至578的合金組成之焊料粉末之焊料膏的情形下,係顯示出於增黏抑制效果、△T的窄化及優異的潤濕性中之至少一項為較差的結果。 On the other hand, in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, it exhibits at least one of the effect of suppressing thickening, narrowing of ΔT, and excellent wettability Is a poor result.

此外,在對於試驗例2至498之焊料粉末分別使用調配例(F7-1)至(F7-52)的各助焊劑之情形下,可確認到任一者與使用調配例(F7-53)的助焊劑之情形相比,助焊劑的搖變減黏性皆提升,抑制印刷後的焊料膏流動之印刷流掛,並且抑制因焊接時的加熱所致之焊料膏的加熱流掛。 In addition, in the case of using the fluxes of the blending examples (F7-1) to (F7-52) for the solder powders of test examples 2 to 498, it is possible to confirm any one and the use blending example (F7-53) Compared with the case of the soldering flux, the thixotropic viscosity reduction of the soldering flux is improved, which suppresses the printing sag of the solder paste after printing, and suppresses the heating sag of the solder paste caused by the heating during soldering.

此外,在對於試驗例2至498之焊料粉末分別使用調配例(F7-1)至(F7-52)的各助焊劑之情形下,可確認到任一者與使用調配例(F7-54)的助焊劑之情形相比,皆係抑制因焊接時的加熱所致之焊料膏的加熱流掛。 In addition, in the case of using the fluxes of the blending examples (F7-1) to (F7-52) for the solder powders of test examples 2 to 498, it is possible to confirm any one and the use blending example (F7-54) Compared with the case of the flux, all of them are to suppress the heating and sagging of the solder paste caused by heating during soldering.

[含有助焊劑(F8)之焊料膏的評估] [Evaluation of solder paste containing flux (F8)]

接著,就對於具有試驗例1所示之合金組成之焊料粉末使用表96至表104所示之調配例(F8-1)至(F8-54)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經時變化之評估〉。此外,測定焊料粉末的液相線溫度及固相線溫度來進行上述〈△T的評估〉。再者,使用剛製作的焊料膏來進行上述〈潤濕性的評估〉。 Next, for the solder powder having the alloy composition shown in Test Example 1 using the fluxes of the blending examples (F8-1) to (F8-54) shown in Table 96 to Table 104, the above-mentioned <Solder Paste "Evaluation of the change of viscosity over time in the medium." In addition, the liquidus temperature and solidus temperature of the solder powder were measured to perform the above-mentioned <Evaluation of ΔT>. In addition, the above-mentioned "Evaluation of wettability" was performed using the solder paste just produced.

從此等之結果中,可確認到在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F8-1)至(F8-54)的各助焊劑之情形下的焊料膏,皆顯示出增黏抑制效果、△T的窄化及優異的潤濕性。 From these results, it can be confirmed that the solder pastes in the case of using the fluxes of the blending examples (F8-1) to (F8-54) for the solder powder having the alloy composition shown in Test Example 1 all show It has the effect of suppressing viscosity increase, narrowing of △T and excellent wettability.

接著,就對於具有試驗例1所示之合金組成之焊料粉末使用表96至表104所示之調配例(F8-1)任一者至(F8-54)的各助焊劑之情形,進行搖變減黏性的評估。 Next, for the solder powder having the alloy composition shown in Test Example 1 using any one of the fluxes of the blending examples (F8-1) to (F8-54) shown in Table 96 to Table 104, shake Evaluation of viscosity reduction.

此外,就對於由試驗例1所示之合金組成所構成之焊料粉末使用表97至表104所示之調配例(F8-8)至(F8-54)的各助焊劑之情形,此外,進行助焊劑及焊料膏中之結晶的析出和結塊的產生之評估。 In addition, for the solder powder composed of the alloy composition shown in Test Example 1, the fluxes of the blending examples (F8-8) to (F8-54) shown in Table 97 to Table 104 were used. In addition, perform Evaluation of precipitation and agglomeration of crystals in flux and solder paste.

〈搖變減黏性的評估〉 <Assessment of Shake Viscosity Reduction>

(1)驗證方法 (1) Verification method

搖變減黏性的評估係使用雙重圓筒管型旋轉黏度計Malcom Viscometer PCU-205(Malcom公司製)來進行。 The evaluation of the shake viscosity reduction was performed using a double cylindrical tube type rotary viscometer Malcom Viscometer PCU-205 (manufactured by Malcom).

使用前述雙重圓筒管型旋轉黏度計,於25℃的條件下以下列所示之轉速(rpm)及測量時間(min)依序對各焊料膏測定黏度。 Using the aforementioned double cylindrical tube type rotary viscometer, the viscosity of each solder paste was sequentially measured at the following rotation speed (rpm) and measurement time (min) at 25°C.

依序將黏度計的旋轉速度改變為:於10rpm下3分鐘、於3rpm下6分鐘、於4rpm下3分鐘、於5rpm下3分鐘、於10rpm下3分鐘、於20rpm下2分鐘、於30rpm下2分鐘、於10rpm下1分鐘。 Change the rotation speed of the viscometer in sequence to: 3 minutes at 10rpm, 6 minutes at 3rpm, 3 minutes at 4rpm, 3 minutes at 5rpm, 3 minutes at 10rpm, 2 minutes at 20rpm, and at 30rpm 2 minutes, 1 minute at 10 rpm.

然後,根據下列式而由3轉(3rpm)時與30轉(30rpm)時的黏度求出搖變減黏比。 Then, the shake viscosity reduction ratio was obtained from the viscosity at 3 revolutions (3 rpm) and 30 revolutions (30 rpm) according to the following formula.

搖變減黏比=Log(3轉時的黏度/30轉時的黏度) Shake viscosity reduction ratio = Log (viscosity at 3 revolutions / viscosity at 30 revolutions)

然後,依循以下判定基準來進行評估。 Then, evaluate according to the following criteria.

(2)判定基準 (2) Judgment criteria

A:搖變減黏比為0.40以上 A: Shake viscosity reduction ratio is 0.40 or more

B:搖變減黏比為未達0.40 B: Shake viscosity reduction ratio is less than 0.40

〈結晶的析出與結塊的產生〉 <Precipitation of crystals and formation of agglomeration>

(1)驗證方法 (1) Verification method

藉由下列所示之方法對表97至表104所示之各例的助焊劑以及使用此等之焊料膏(助焊劑:焊料粉末=11:89的質量比)的各個進行結晶的析出和結塊的產生之評估。然後依循下列判定基準來進行評估。 The following methods are used to precipitate and crystallize the fluxes of the examples shown in Table 97 to Table 104 and the solder pastes (flux: solder powder = 11:89 mass ratio). Evaluation of block generation. Then follow the following criteria for evaluation.

對於表96所示之各例的助焊劑以及使用此等之焊料膏並未進行結晶的析出和結塊的產生之評估。 For the fluxes of the examples shown in Table 96 and the solder pastes using these, no evaluation of the precipitation of crystals and the occurrence of agglomeration has been carried out.

對助焊劑之評估: Evaluation of flux:

取各助焊劑100mL並裝入至容量200mL的玻璃燒杯,以藥勺攪拌10次而製作目視觀察用的試樣。進行同樣的操作,而就各助焊劑準備出3個目視觀察用的試樣。 100 mL of each flux was taken and put into a glass beaker with a capacity of 200 mL, and stirred with a spatula 10 times to prepare a sample for visual observation. The same operation was performed, and three samples for visual observation were prepared for each flux.

以目視來觀察各試樣之攪拌10次後的外觀,並評估結晶的析出和結塊的產生之狀態。 The appearance of each sample after stirring 10 times was visually observed, and the state of the precipitation of crystals and the occurrence of agglomeration was evaluated.

對焊料膏之評估: Evaluation of solder paste:

使用細度計(grind meter)GS-2256M(太佑機材股份有限公司製、測定範圍:0至100μm)對各焊料膏測定3次。然後,算出3次測定值的平均值,並將此平均值設為焊料膏所含有之凝聚物的大小(粒度)。 Each solder paste was measured 3 times using a grind meter GS-2256M (manufactured by Taiyou Machinery Co., Ltd., measurement range: 0 to 100 μm). Then, the average value of the three measurements is calculated, and this average value is used as the size (particle size) of the aggregate contained in the solder paste.

又,於細度計的表面係設置有溝槽,該溝槽係深度為從一端的0以一定值增加至另一端的最大值為止。當藉由刮板將焊料膏的試樣從最大深度側開始刮平時,會於因應凝聚物大小的深度之處殘留有線狀痕跡或粒狀痕跡。藉由有著線狀痕跡或粒狀痕跡之位置的深度,可評估焊料膏的試樣中之結晶的析出和結塊的產生。 In addition, a groove is provided on the surface of the fineness meter, and the depth of the groove increases from 0 at one end to a maximum value at the other end. When the solder paste sample is scraped flat from the maximum depth side with a squeegee, linear or granular traces will remain at the depth corresponding to the size of the aggregate. Based on the depth of the position where there are linear traces or granular traces, the precipitation of crystals and the occurrence of agglomeration in the solder paste sample can be evaluated.

(2)判定基準 (2) Judgment criteria

A:於助焊劑中以目視未確認到結晶及結塊,而且於焊料膏中以目視未確認到結晶及結塊。 A: No crystallization or agglomeration was visually confirmed in the flux, and no crystallization or agglomeration was visually confirmed in the solder paste.

B:於助焊劑中以目視未確認到結晶及結塊,而且,雖然於焊料膏中未有50μm以上的結晶或結塊,但有未達50μm的結晶或結塊。 B: Crystals and agglomerations were not visually confirmed in the flux, and although there were no crystals or agglomerations of 50 μm or more in the solder paste, there were crystals or agglomerations of less than 50 μm.

C:於助焊劑之3個試樣中的任1者以目視確認到結晶及結塊,或是於焊料膏中有50μm以上的結晶或結塊。 C: Crystals and agglomerations are visually confirmed in any of the three samples of the flux, or there are crystals or agglomerations of 50 μm or more in the solder paste.

〈綜合評估〉 <Comprehensive Evaluation>

A:於表97至表104中,搖變減黏性的評估為A,且結晶的析出和結塊的產生之評估為A。 A: In Table 97 to Table 104, the evaluation of the thixotropic viscosity reduction is A, and the evaluation of the precipitation of crystals and the generation of agglomeration is A.

B:於表97至表104中,搖變減黏性的評估為A,且結晶的析出和結塊的產生之評估為B。 B: In Table 97 to Table 104, the evaluation of the thixotropic viscosity reduction is A, and the evaluation of the precipitation of crystals and the generation of agglomeration is B.

C:於表97至表104中,搖變減黏性的評估至少為B。 C: In Table 97 to Table 104, the evaluation of thixotropic viscosity reduction is at least B.

評估結果係如表96至表104所示。 The evaluation results are shown in Table 96 to Table 104.

[表96]

Figure 109117353-A0202-12-0194-107
[Table 96]
Figure 109117353-A0202-12-0194-107

[表97]

Figure 109117353-A0202-12-0195-108
[Table 97]
Figure 109117353-A0202-12-0195-108

[表98]

Figure 109117353-A0202-12-0196-109
[Table 98]
Figure 109117353-A0202-12-0196-109

[表99]

Figure 109117353-A0202-12-0197-110
[Table 99]
Figure 109117353-A0202-12-0197-110

[表100]

Figure 109117353-A0202-12-0198-111
[Table 100]
Figure 109117353-A0202-12-0198-111

[表101]

Figure 109117353-A0202-12-0199-112
[Table 101]
Figure 109117353-A0202-12-0199-112

[表102]

Figure 109117353-A0202-12-0200-113
[Table 102]
Figure 109117353-A0202-12-0200-113

[表103]

Figure 109117353-A0202-12-0201-114
[Table 103]
Figure 109117353-A0202-12-0201-114

[表104]

Figure 109117353-A0202-12-0202-115
[Table 104]
Figure 109117353-A0202-12-0202-115

在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F8-1)至(F8-52)的各助焊劑之情形下,可確認到任一者與使用調配例(F8-53)、調配例(F8-54)的助焊劑之情形相比,焊料膏的搖變減黏性皆為提高,亦即,該焊料膏係流動性及保形性良好者。 In the case of using the fluxes of the blending examples (F8-1) to (F8-52) for the solder powder with the alloy composition shown in Test Example 1, it can be confirmed that any one of them is consistent with the use of blending examples (F8-53). Compared with the case of the flux of the blending example (F8-54), the thixotropic viscosity reduction of the solder paste is improved, that is, the solder paste has good fluidity and shape retention.

此外,在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F8-8)至(F8-54)的各助焊劑之情形下,可確認到任一者皆係抑制助焊劑及焊料膏中之結晶的析出和結塊的產生。 In addition, in the case of using the fluxes of the blending examples (F8-8) to (F8-54) for the solder powder having the alloy composition shown in Test Example 1, it can be confirmed that any one of them is a flux suppressor and Precipitation and agglomeration of crystals in solder paste.

此等當中,含有具有試驗例1的合金組成之焊料粉末與調配例(F8-1)至(F8-52)、(F8-54)的各助焊劑之焊料膏,為含有助焊劑(F8)之實施型態之焊料膏。 Among them, the solder paste containing the solder powder with the alloy composition of Test Example 1 and the fluxes of the blending examples (F8-1) to (F8-52) and (F8-54) contains the flux (F8) The implementation type of solder paste.

接著,就對於具有試驗例2至498、試驗例501至578所示之各合金組成之焊料粉末分別使用調配例(F8-1)至(F8-54)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經時變化之評估〉、〈△T的評估〉及〈潤濕性的評估〉,以及〈搖變減黏性的評估〉及〈結晶的析出與結塊的產生〉。 Next, for the solder powders having the alloy compositions shown in Test Examples 2 to 498 and Test Examples 501 to 578, the fluxes of the formulation examples (F8-1) to (F8-54) were used, and the above-mentioned < Evaluation of the change of viscosity in solder paste with time", "Evaluation of △T" and "Evaluation of wettability", as well as "Evaluation of thixotropic viscosity reduction" and "Precipitation of crystals and generation of agglomeration".

從該評估的結果中,可確認到於含有具有試驗例2至498的合金組成之焊料粉末之焊料膏的情形下,係顯示出增黏抑制效果、△T的窄化及優異的潤濕性。此等當中,含有具有試驗例2至498的合金組成之各焊料粉末與調配例(F8-1)至(F8-52)、(F8-54)的各助焊劑之焊料膏,為含有助焊劑(F8)之實施型態之焊料膏。 From the results of this evaluation, it can be confirmed that in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498, it exhibits the effect of suppressing viscosity increase, narrowing of ΔT, and excellent wettability. . Among them, the solder paste containing each solder powder with the alloy composition of Test Examples 2 to 498 and the fluxes of Blending Examples (F8-1) to (F8-52) and (F8-54) is a solder paste containing flux (F8) The implementation type of solder paste.

另一方面,於含有具有試驗例501至578的合金組成之焊料粉末之焊料膏的情形下,係顯示出於增黏抑制效果、△T的窄化及優異的潤濕性中之至少一項為較差的結果。 On the other hand, in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, it exhibits at least one of the effect of suppressing thickening, narrowing of ΔT, and excellent wettability Is a poor result.

此外,在對於試驗例2至498之焊料粉末分別使用調配例(F8-1)至(F8-52)的各助焊劑之情形下,可確認到任一者與使用調配例(F8-53)、調配例(F8-54)的助焊劑之情形相比,焊料膏的搖變減黏性皆為提高,亦即,該焊料膏係流動性及保形性良好者。 In addition, in the case of using the fluxes of the blending examples (F8-1) to (F8-52) for the solder powders of test examples 2 to 498, it is possible to confirm any one and the use blending example (F8-53) , Compared with the case of the flux of the blending example (F8-54), the thixotropic viscosity reduction of the solder paste is improved, that is, the solder paste has good fluidity and shape retention.

此外,在對於具有試驗例1所示之合金組成之焊料粉末分別使用調配例(F8-8)至(F8-54)的各助焊劑之情形下,可確認到皆係抑制助焊劑及焊料膏中之結晶的析出與結塊的產生。 In addition, in the case of using the fluxes of the blending examples (F8-8) to (F8-54) for the solder powder having the alloy composition shown in Test Example 1, it can be confirmed that the flux and the solder paste are suppressed. The precipitation and agglomeration of crystals.

[含有助焊劑(F9)之焊料膏的評估] [Evaluation of solder paste containing flux (F9)]

接著,就對於具有試驗例1所示之合金組成之焊料粉末使用表105至表119所示之調配例(F9-1)至(F9-76)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經時變化之評估〉。此外,測定焊料粉末的液相線溫度及固相線溫度來進行上述〈△T的評估〉。再者,使用剛製作的焊料膏來進行上述〈潤濕性的評估〉。 Next, for the solder powder having the alloy composition shown in Test Example 1 using the fluxes of the blending examples (F9-1) to (F9-76) shown in Table 105 to Table 119, the above-mentioned <Solder Paste "Evaluation of the change of viscosity over time in the medium." In addition, the liquidus temperature and solidus temperature of the solder powder were measured to perform the above-mentioned <Evaluation of ΔT>. In addition, the above-mentioned "Evaluation of wettability" was performed using the solder paste just produced.

從此等之結果中,可確認到在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F9-1)至(F9-76)的各助焊劑之情形下的焊料膏,任一者皆顯示出增黏抑制效果、△T的窄化及優異的潤濕性。 From these results, it can be confirmed that the solder paste in the case of using the fluxes of the blending examples (F9-1) to (F9-76) for the solder powder having the alloy composition shown in Test Example 1, either All of them showed the effect of suppressing viscosity increase, narrowing of △T and excellent wettability.

接著,就對於具有試驗例1所示之合金組成之焊料粉末使用表105至表119所示之調配例(F9-1)至(F9-76)的各助焊劑之情形下的焊料膏(助焊劑:焊料粉末=11:89的質量比),進行空隙產生及焊料之潤濕速度(焊料潤濕性)的評估。 Next, for the solder powder having the alloy composition shown in Test Example 1, the solder paste (assisted) in the case of using the fluxes of the blending examples (F9-1) to (F9-76) shown in Table 105 to Table 119 Flux: Solder powder = 11:89 mass ratio), the void generation and solder wetting speed (solder wettability) are evaluated.

〈空隙產生的評估〉 <Assessment of void generation>

(1)空隙產生率 (1) Void generation rate

使用金屬遮罩,於8mm×8mm的Cu-OSP電極(N=15)上將焊料膏印刷成高度120μm。然後,在大氣環境下進行回焊。回焊溫度曲線(reflow profile)係設為在190℃保持2分鐘,然後以1.5℃/秒升溫至260℃。 Using a metal mask, the solder paste was printed on an 8mm×8mm Cu-OSP electrode (N=15) to a height of 120μm. Then, reflow is performed in an atmospheric environment. The reflow profile is set to hold at 190°C for 2 minutes, and then heat up to 260°C at 1.5°C/sec.

使用UNi-HiTESYSTEM公司製的Microfocus X-ray System XVR-160來觀察回焊後之焊接部(焊料凸塊)的穿透圖像,並求取空隙產生率。 Microfocus X-ray System XVR-160 manufactured by UNi-HiTESYSTEM was used to observe the penetration image of the soldered part (solder bump) after reflow, and determine the void generation rate.

具體而言,對焊料凸塊從上部朝向下部進行穿透觀察,並得到圓形的焊料凸塊穿透圖像,根據其色調的對比來辨識金屬填充部與空隙部而藉由自動解析來算出空隙面積率,並將此設為空隙產生率。使用如此求得之空隙產生率,並以以下基準來評估空隙的產生難易度。 Specifically, through observation of the solder bump from the top to the bottom, a circular solder bump penetration image is obtained, and the metal filling part and the void part are distinguished based on the contrast of their tones, and the calculation is calculated by automatic analysis The void area ratio, and let this be the void generation rate. Using the void generation rate thus obtained, the difficulty of void generation was evaluated based on the following criteria.

A:於15個焊接部的全部係空隙產生率為15%以下之情形 A: When all the 15 welded parts have a void generation rate of 15% or less

B:於15個焊接部中雖包含有空隙產生率超過15%者,惟皆在20%以下之情形 B: Although there are 15 welded parts with a void generation rate exceeding 15%, all of them are below 20%

C:於15個焊接部中,包含有空隙產生率超過20%者之情形 C: Among the 15 welded parts, there are cases where the void generation rate exceeds 20%

〈焊料之潤濕速度(焊料潤濕性)的評估〉 <Assessment of solder wetting speed (solder wettability)>

依據JIS Z 3198-4:2003來評估助焊劑的焊料潤濕性。 According to JIS Z 3198-4:2003, the solder wettability of the flux is evaluated.

具體而言,係在經150℃煅燒1小時之寬5mm×長25mm×厚0.5mm的銅板表面之長度方向的下端至3mm為止的部分上,以針尖塗佈各調配例的助焊劑,以下述條件浸漬在焊料槽,並測定零交叉時間。 Specifically, a copper plate with a width of 5 mm × a length of 25 mm × a thickness of 0.5 mm was calcined at 150°C for 1 hour from the lower end to 3 mm in the longitudinal direction of the surface of the copper plate. Conditions are immersed in the solder bath, and the zero crossing time is measured.

〈浸漬條件〉 <Dipping conditions>

於焊料槽之浸漬速度:5mm/sec(JIS Z 3198-4:2003) Dipping speed in solder tank: 5mm/sec (JIS Z 3198-4: 2003)

於焊料槽之浸漬深度:2mm(JIS Z 3198-4:2003) Dipping depth in solder tank: 2mm (JIS Z 3198-4: 2003)

於焊料槽之浸漬時間:10sec(JIS Z 3198-4:2003) Dipping time in solder tank: 10sec (JIS Z 3198-4: 2003)

焊料槽溫度:250℃(JIS C 60068-2-69:2019附錄B) Solder tank temperature: 250°C (JIS C 60068-2-69: 2019 Appendix B)

焊料潤濕性係藉由以下基準來評估。 The solder wettability is evaluated based on the following criteria.

A:零交叉時間為5.5秒以下 A: The zero-crossing time is 5.5 seconds or less

B:零交叉時間為超過5.5秒 B: The zero-crossing time is more than 5.5 seconds

〈綜合評估〉 <Comprehensive Evaluation>

A:空隙產生的評估為A或B,以及焊料之潤濕速度(焊料潤濕性)的評估為A之情形 A: The evaluation of void generation is A or B, and the evaluation of solder wetting speed (solder wettability) is A

B:空隙產生的評估為C、或是焊料之潤濕速度(焊料潤濕性)的評估為B當中之至少一者之情形 B: The evaluation of void generation is C, or the evaluation of solder wetting speed (solder wettability) is at least one of B

評估結果係如表105至表119所示。 The evaluation results are shown in Table 105 to Table 119.

表中,係使用脂肪族聚醯胺作為聚醯胺,使用六亞甲基雙羥基硬脂醯胺作為雙醯胺,使用對甲苯醯胺作為單醯胺。 In the table, aliphatic polyamide is used as polyamide, hexamethylene bishydroxystearylamine is used as bisamide, and p-toluamide is used as monoamide.

[表105]

Figure 109117353-A0202-12-0207-116
[Table 105]
Figure 109117353-A0202-12-0207-116

[表106]

Figure 109117353-A0202-12-0208-117
[Table 106]
Figure 109117353-A0202-12-0208-117

[表107]

Figure 109117353-A0202-12-0209-118
[Table 107]
Figure 109117353-A0202-12-0209-118

[表108]

Figure 109117353-A0202-12-0210-119
[Table 108]
Figure 109117353-A0202-12-0210-119

[表109]

Figure 109117353-A0202-12-0211-120
[Table 109]
Figure 109117353-A0202-12-0211-120

[表110]

Figure 109117353-A0202-12-0212-121
[Table 110]
Figure 109117353-A0202-12-0212-121

[表111]

Figure 109117353-A0202-12-0213-122
[Table 111]
Figure 109117353-A0202-12-0213-122

[表112]

Figure 109117353-A0202-12-0214-123
[Table 112]
Figure 109117353-A0202-12-0214-123

[表113]

Figure 109117353-A0202-12-0215-124
[Table 113]
Figure 109117353-A0202-12-0215-124

[表114]

Figure 109117353-A0202-12-0216-125
[Table 114]
Figure 109117353-A0202-12-0216-125

[表115]

Figure 109117353-A0202-12-0217-126
[Table 115]
Figure 109117353-A0202-12-0217-126

[表116]

Figure 109117353-A0202-12-0218-127
[Table 116]
Figure 109117353-A0202-12-0218-127

[表117]

Figure 109117353-A0202-12-0219-128
[Table 117]
Figure 109117353-A0202-12-0219-128

[表118]

Figure 109117353-A0202-12-0220-129
[Table 118]
Figure 109117353-A0202-12-0220-129

[表119]

Figure 109117353-A0202-12-0221-130
[Table 119]
Figure 109117353-A0202-12-0221-130

在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F9-1)至(F9-74)的各助焊劑之情形下,可確認到任一者與使用調配例(F9-75)的助焊劑之情形相比,焊料潤濕性皆更良好。 In the case of using the fluxes of the blending examples (F9-1) to (F9-74) for the solder powder with the alloy composition shown in Test Example 1, it can be confirmed that any one of them and the using blending example (F9-75) Compared with the flux of ), the solder wettability is better.

此外,在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F9-1)至(F9-74)的各助焊劑之情形下,可確認到任一者與使用調配例(F9-76)的助焊劑之情形相比,皆係抑制空隙的產生。 In addition, in the case of using the fluxes of the blending examples (F9-1) to (F9-74) for the solder powder having the alloy composition shown in Test Example 1, it is possible to confirm that any one of them and the use blending example (F9 Compared with the case of the flux of -76), the generation of voids is suppressed.

此等當中,含有具有試驗例1的合金組成之焊料粉末與調配例(F9-1)至(F9-74)的各助焊劑之焊料膏,為含有助焊劑(F9)之實施型態之焊料膏。 Among them, the solder paste containing the solder powder with the alloy composition of Test Example 1 and the fluxes of the blending examples (F9-1) to (F9-74) is the solder paste of the implementation type containing the flux (F9) paste.

接著,就對於具有試驗例2至498、試驗例501至578所示之各合金組成之焊料粉末分別使用調配例(F9-1)至(F9-76)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經時變化之評估〉、〈△T的評估〉及〈潤濕性的評估〉,以及〈空隙產生的評估〉及〈焊料之潤濕速度(焊料潤濕性)的評估〉。 Next, for the solder powders having the respective alloy compositions shown in Test Examples 2 to 498 and Test Examples 501 to 578, the fluxes of the blending examples (F9-1) to (F9-76) were used, and the above-mentioned < Evaluation of the change of viscosity in solder paste with time", "Evaluation of △T" and "Evaluation of wettability", and "Evaluation of void generation" and "Evaluation of solder wetting speed (solder wettability) 〉.

從該評估的結果中,可確認到於含有具有試驗例2至498的合金組成之焊料粉末之焊料膏的情形下,係顯示出增黏抑制效果、△T的窄化及優異的潤濕性。此等當中,含有具有試驗例2至498的合金組成之各焊料粉末與調配例(F9-1)至(F9-74)的各助焊劑之焊料膏,為含有助焊劑(F9)之實施型態之焊料膏。 From the results of this evaluation, it can be confirmed that in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498, it exhibits the effect of suppressing viscosity increase, narrowing of ΔT, and excellent wettability. . Among them, the solder paste containing each solder powder with the alloy composition of Test Examples 2 to 498 and the fluxes of Blending Examples (F9-1) to (F9-74) is an implementation type containing flux (F9) State of the solder paste.

另一方面,於含有具有試驗例501至578的合金組成之焊料粉末之焊料膏的情形下,係顯示出於增黏抑制效果、△T的窄化及優異的潤濕性中之至少一項為較差的結果。 On the other hand, in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, it exhibits at least one of the effect of suppressing thickening, narrowing of ΔT, and excellent wettability Is a poor result.

此外,在對於試驗例2至498之焊料粉末分別使用調配例(F9-1)至(F9-74)的各助焊劑之情形下,可確認到任一者與使用調配例(F9-75)的助焊劑之情形相比,焊料潤濕性皆更良好。 In addition, in the case of using the fluxes of the blending examples (F9-1) to (F9-74) for the solder powders of test examples 2 to 498, it is possible to confirm any one and the use blending example (F9-75) Compared with the case of the flux, the solder wettability is better.

此外,在對於試驗例2至498之焊料粉末分別使用調配例(F9-1)至(F9-74)的各助焊劑之情形下,可確認到任一者與使用調配例(F9-76)的助焊劑之情形相比,皆係抑制空隙的產生。 In addition, in the case of using the fluxes of the blending examples (F9-1) to (F9-74) for the solder powders of test examples 2 to 498, it is possible to confirm any one and the use blending example (F9-76) Compared with the case of the flux, they all suppress the generation of voids.

[含有助焊劑(F10)之焊料膏的評估] [Evaluation of solder paste containing flux (F10)]

接著,就對於具有試驗例1所示之合金組成之焊料粉末使用表120至表125所示之調配例(F10-1)至(F10-30)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經時變化之評估〉。此外,測定焊料粉末的液相線溫度及固相線溫度來進行上述〈△T的評估〉。再者,使用剛製作的焊料膏來進行上述〈潤濕性的評估〉。 Next, for the solder powder having the alloy composition shown in Test Example 1 using the fluxes of the blending examples (F10-1) to (F10-30) shown in Table 120 to Table 125, the above-mentioned <Solder Paste "Evaluation of the change of viscosity over time in the medium." In addition, the liquidus temperature and solidus temperature of the solder powder were measured to perform the above-mentioned <Evaluation of ΔT>. In addition, the above-mentioned "Evaluation of wettability" was performed using the solder paste just produced.

從此等之結果中,可確認到在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F10-1)至(F10-30)的各助焊劑之情形下的焊料膏,皆顯示出增黏抑制效果、△T的窄化及優異的潤濕性。 From these results, it can be confirmed that the solder pastes in the case of using the fluxes of the blending examples (F10-1) to (F10-30) for the solder powder with the alloy composition shown in Test Example 1 all show It has the effect of suppressing viscosity increase, narrowing of △T and excellent wettability.

接著,就對於具有試驗例1所示之合金組成之焊料粉末使用表120至表125所示之調配例(F10-1)至(F10-30)的各助焊劑之情形下的焊料膏(助焊劑:焊料粉末=11:89的質量比),進行乾燥度、空隙產生及焊料之潤濕速度(焊料潤濕性)的評估。 Next, for the solder powder having the alloy composition shown in Test Example 1, the solder paste (assisted) in the case of using the fluxes of the blending examples (F10-1) to (F10-30) shown in Table 120 to Table 125 Flux: Solder powder = 11:89 mass ratio), the dryness, void generation, and solder wetting speed (solder wettability) are evaluated.

〈乾燥度的評估〉 <Assessment of dryness>

依據JIS Z 3197:2012,8.5.1乾燥度試驗來評估助焊劑的乾燥度。 According to JIS Z 3197: 2012, 8.5.1 dryness test to evaluate the dryness of the flux.

具體而言,係製作出以助焊劑:焊料粉末=11:89的質量比來混合調配例(F10-1)至(F10-30)的各助焊劑與具有試驗例1所示之合金組成之焊料粉末(平均粒徑

Figure 109117353-A0202-12-0223-142
:21μm)之焊料膏。 Specifically, a mixture of each flux of the formulation examples (F10-1) to (F10-30) and the alloy composition shown in Test Example 1 was produced at a mass ratio of flux: solder powder = 11:89. Solder powder (average particle size
Figure 109117353-A0202-12-0223-142
: 21μm) solder paste.

接著,依循上述JIS試驗方法來製作試驗片並進行試驗,並藉由撒佈至試驗片上的助焊劑殘渣表面之粉末滑石的附著程度來評估助焊劑的乾燥度(助焊劑的乾燥容易度,具體而言為助焊劑殘渣的黏著性)。 Next, follow the above-mentioned JIS test method to make a test piece and test it, and evaluate the dryness of the flux by the adhesion degree of the powder talc on the surface of the flux residue sprinkled on the test piece (the ease of drying of the flux, specifically In terms of the adhesiveness of flux residue).

評估是以粉末滑石可藉由刷清(brushing)來去除之情形為A,無法去除之情形為B。 The evaluation is based on the case where powder talc can be removed by brushing as A, and the case where it cannot be removed as B.

〈空隙產生的評估〉 <Assessment of void generation>

使用金屬遮罩,於8mm×8mm的Cu-OSP電極(N=15)上將與乾燥度試驗同樣地製作出之焊料膏印刷成高度120μm。然後,在大氣環境下進行回焊。回焊溫度曲線係設為在190℃保持2分鐘,然後以1.5℃/秒升溫至260℃。 Using a metal mask, the solder paste produced in the same way as in the dryness test was printed on an 8mm×8mm Cu-OSP electrode (N=15) to a height of 120μm. Then, reflow is performed in an atmospheric environment. The reflow temperature profile is set to hold at 190°C for 2 minutes, and then heat up to 260°C at 1.5°C/sec.

使用UNi-HiTESYSTEM公司製的Microfocus X-ray System XVR-160來觀察回焊後之焊接部(焊料凸塊)的穿透圖像,並求取空隙產生率。 Microfocus X-ray System XVR-160 manufactured by UNi-HiTESYSTEM was used to observe the penetration image of the soldered part (solder bump) after reflow, and determine the void generation rate.

具體而言,對焊料凸塊從上部朝向下部進行穿透觀察,並得到圓形的焊料凸塊穿透圖像,根據其色調的對比來辨識金屬填充部與空隙部,藉由自動解析來得到空隙面積率,並將此設為空隙產生率。使用如此求得之空隙產生率,並以以下基準來評估空隙的產生難易度。 Specifically, the solder bumps are observed through penetration from the top to the bottom, and a circular solder bump penetration image is obtained. The metal filling part and the void part are distinguished based on the contrast of their tones, and the result is obtained by automatic analysis The void area ratio, and let this be the void generation rate. Using the void generation rate thus obtained, the difficulty of void generation was evaluated based on the following criteria.

A:於15個焊接部的全部係空隙產生率為15%以下之情形 A: When all the 15 welded parts have a void generation rate of 15% or less

B:於15個焊接部中雖包含有空隙產生率超過15%者,惟皆於20%以下之情形 B: Although there are 15 welded parts with a void generation rate exceeding 15%, all of them are below 20%

C:於15個焊接部中,包含有空隙產生率超過20%者之情形 C: Among the 15 welded parts, there are cases where the void generation rate exceeds 20%

〈焊料之潤濕速度(焊料潤濕性)的評估〉 <Assessment of solder wetting speed (solder wettability)>

依據JIS Z 3198-4:2003來評估助焊劑的焊料潤濕性。 According to JIS Z 3198-4:2003, the solder wettability of the flux is evaluated.

具體而言,在經150℃煅燒1小時之寬5mm×長25mm×厚0.5mm的銅板表面之長度方向的下端至3mm為止的部分上,以針尖塗佈各調配例的助焊劑,以下述條件浸漬在焊料槽,並測定零交叉時間。 Specifically, the soldering flux of each blending example was applied to the part of the copper plate surface of width 5mm×length 25mm×thickness 0.5mm that was calcined at 150°C for 1 hour from the lower end to 3mm in the longitudinal direction. Dip in the solder bath and measure the zero crossing time.

〈浸漬條件〉 <Dipping conditions>

於焊料槽之浸漬速度:5mm/sec(JIS Z 3198-4:2003) Dipping speed in solder tank: 5mm/sec (JIS Z 3198-4: 2003)

於焊料槽之浸漬深度:2mm(JIS Z 3198-4:2003) Dipping depth in solder tank: 2mm (JIS Z 3198-4: 2003)

於焊料槽之浸漬時間:10sec(JIS Z 3198-4:2003) Dipping time in solder tank: 10sec (JIS Z 3198-4: 2003)

焊料槽溫度:250℃(JIS C 60068-2-69:2019附錄B) Solder tank temperature: 250°C (JIS C 60068-2-69: 2019 Appendix B)

焊料潤濕性係藉由以下基準來評估。 The solder wettability is evaluated based on the following criteria.

A:零交叉時間為5.5秒以下 A: The zero-crossing time is 5.5 seconds or less

B:零交叉時間為超過5.5秒 B: The zero-crossing time is more than 5.5 seconds

〈綜合評估〉 <Comprehensive Evaluation>

A:空隙產生的評估為A或B,並且乾燥度及焊料之潤濕速度(焊料潤濕性)的評估為A之情形 A: The evaluation of void generation is A or B, and the evaluation of dryness and solder wetting speed (solder wettability) is A

B:空隙產生的評估為C、或是乾燥度或焊料之潤濕速度(焊料潤濕性)的評估為 B: The evaluation of void generation is C, or the evaluation of dryness or solder wetting speed (solder wettability) is

B當中之至少一者之情形 At least one of B

評估結果係如表120至表125所示。 The evaluation results are shown in Table 120 to Table 125.

表中,係使用六亞甲基雙羥基硬脂醯胺作為雙醯胺。 In the table, hexamethylene bishydroxystearylamine is used as bisamide.

[表120]

Figure 109117353-A0202-12-0226-131
[Table 120]
Figure 109117353-A0202-12-0226-131

[表121]

Figure 109117353-A0202-12-0227-132
[Table 121]
Figure 109117353-A0202-12-0227-132

[表122]

Figure 109117353-A0202-12-0228-133
[Table 122]
Figure 109117353-A0202-12-0228-133

[表123]

Figure 109117353-A0202-12-0229-134
[Table 123]
Figure 109117353-A0202-12-0229-134

[表124]

Figure 109117353-A0202-12-0230-135
[Table 124]
Figure 109117353-A0202-12-0230-135

[表125]

Figure 109117353-A0202-12-0231-136
[Table 125]
Figure 109117353-A0202-12-0231-136

在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F10-1)至(F10-28)的各助焊劑之情形下,可確認到任一者與使用調配例(F10-29)的助焊劑之情形相比,皆具有良好的乾燥性,焊料潤濕性更良好。 In the case of using the fluxes of the blending examples (F10-1) to (F10-28) for the solder powder with the alloy composition shown in Test Example 1, it can be confirmed that any one of them and the use blending example (F10-29) Compared with the case of the flux of ), they all have better drying properties and better solder wettability.

此外,在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F10-1)至(F10-28)的各助焊劑之情形下,可確認到任一者與使用調配例(F10-30)的助焊劑之情形相比,皆更抑制空隙的產生。此等當中,含有具有試驗例1的合金組成 之焊料粉末與調配例(F10-1)至(F10-28)的各助焊劑之焊料膏,為含有助焊劑(F10)之實施型態之焊料膏。 In addition, in the case of using the fluxes of the blending examples (F10-1) to (F10-28) for the solder powder having the alloy composition shown in Test Example 1, it can be confirmed that any one of them and the used blending example (F10 Compared with the case of flux of -30), the generation of voids is more suppressed. Among these, the alloy composition of Test Example 1 is included The solder powder and the solder paste of each flux in the preparation examples (F10-1) to (F10-28) are the solder paste of the implementation type containing the flux (F10).

接著,就對於具有試驗例2至498、試驗例501至578所示之各合金組成之焊料粉末分別使用調配例(F10-1)至(F10-30)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經時變化之評估〉、〈△T的評估〉及〈潤濕性的評估〉,以及〈乾燥度的評估〉、〈空隙產生的評估〉及〈焊料之潤濕速度(焊料潤濕性)的評估〉。 Next, for the solder powders having the alloy compositions shown in Test Examples 2 to 498 and Test Examples 501 to 578, the fluxes of the blending examples (F10-1) to (F10-30) were used, and the above-mentioned < Evaluation of the change of viscosity in solder paste with time>, <Evaluation of △T> and <Evaluation of wettability>, as well as <Evaluation of dryness>, <Evaluation of void generation> and <Solder wetting rate ( Evaluation of solder wettability)>.

從該評估的結果中,可確認到於含有具有試驗例2至498的合金組成之焊料粉末之焊料膏的情形下,係顯示出增黏抑制效果、△T的窄化及優異的潤濕性。此等當中,含有具有試驗例2至498的合金組成之各焊料粉末與調配例(F10-1)至(F10-28)的各助焊劑之焊料膏,為含有助焊劑(F10)之實施型態之焊料膏。 From the results of this evaluation, it can be confirmed that in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498, it exhibits the effect of suppressing viscosity increase, narrowing of ΔT, and excellent wettability. . Among them, the solder paste containing each solder powder with the alloy composition of Test Examples 2 to 498 and the fluxes of Blending Examples (F10-1) to (F10-28) is an implementation type containing flux (F10) State of the solder paste.

另一方面,於含有具有試驗例501至578的合金組成之焊料粉末之焊料膏的情形下,係顯示出於增黏抑制效果、△T的窄化及優異的潤濕性中之至少一項為較差的結果。 On the other hand, in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, it exhibits at least one of the effect of suppressing thickening, narrowing of ΔT, and excellent wettability Is a poor result.

此外,在對於試驗例2至498之焊料粉末分別使用調配例(F10-1)至(F10-28)的各助焊劑之情形下,可確認到任一者與使用調配例(F10-29)的助焊劑之情形相比,皆具有良好的乾燥性,焊料潤濕性更良好。 In addition, in the case of using the fluxes of the blending examples (F10-1) to (F10-28) for the solder powders of test examples 2 to 498, it is possible to confirm any one and the use blending example (F10-29) Compared with the case of the flux, they all have good drying properties and better solder wettability.

此外,在對於試驗例2至498之焊料粉末分別使用調配例(F10-1)至(F10-28)的各助焊劑之情形下,可確認到任一者與使用調配例(F10-30)的助焊劑之情形相比,皆更抑制空隙的產生。 In addition, in the case of using the fluxes of the blending examples (F10-1) to (F10-28) for the solder powders of test examples 2 to 498, it is possible to confirm any one and the use blending example (F10-30) Compared with the case of the flux, both suppress the generation of voids.

[含有助焊劑(F11)之焊料膏的評估] [Evaluation of solder paste containing flux (F11)]

接著,就對於具有試驗例1所示之合金組成之焊料粉末使用表126至表128所示之調配例(F11-1)至(F11-18)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經時變化之評估〉。此外,測定焊料粉末的液相線溫度及固相線溫度來進行上述〈△T的評估〉。再者,使用剛製作的焊料膏來進行上述〈潤濕性的評估〉。 Next, for the solder powder with the alloy composition shown in Test Example 1 using the fluxes of the blending examples (F11-1) to (F11-18) shown in Table 126 to Table 128, the above-mentioned <Solder Paste "Evaluation of the change of viscosity over time in the medium." In addition, the liquidus temperature and solidus temperature of the solder powder were measured to perform the above-mentioned <Evaluation of ΔT>. In addition, the above-mentioned "Evaluation of wettability" was performed using the solder paste just produced.

從此等之結果中,可確認到在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F11-1)至(F11-18)的各助焊劑之情形下的焊料膏,皆顯示出增黏抑制效果、△T的窄化及優異的潤濕性。 From these results, it can be confirmed that the solder pastes in the case of using the fluxes of the blending examples (F11-1) to (F11-18) for the solder powder having the alloy composition shown in Test Example 1 all show It has the effect of suppressing viscosity increase, narrowing of △T and excellent wettability.

接著,對於具有試驗例1所示之合金組成之焊料粉末使用表126至表128所示之調配例(F11-1)至(F11-18)的各助焊劑之情形下的焊料膏(助焊劑:焊料粉末=11:89的質量比),分別進行增黏抑制評估及潤濕性的評估。 Next, for the solder powder having the alloy composition shown in Test Example 1, the solder paste (flux flux) in the case of using the fluxes of the blending examples (F11-1) to (F11-18) shown in Table 126 to Table 128 : Solder powder = mass ratio of 11:89), and evaluate the inhibition of viscosity increase and the evaluation of wettability respectively.

〈增黏抑制評估〉 <Evaluation of Thickening Suppression>

依循JIS Z 3284-3:2014的「4.2黏度特性試驗」所記載之方法,使用旋轉黏度計(PCU-205、Malcom股份有限公司製),於轉速:10rpm、測定溫度:25℃下對所得到之焊料膏持續測定12小時的黏度。然後,比較初期黏度(攪拌30分鐘後的黏度)與13小時後的黏度,並根據以下基準來進行增黏抑制效果的評估。 According to the method described in "4.2 Viscosity Characteristic Test" of JIS Z 3284-3:2014, using a rotary viscometer (PCU-205, manufactured by Malcom Co., Ltd.), the result was measured at a rotation speed of 10 rpm and a measurement temperature of 25°C. The viscosity of the solder paste was continuously measured for 12 hours. Then, the initial viscosity (viscosity after 30 minutes of stirring) and the viscosity after 13 hours were compared, and the viscosity increase suppression effect was evaluated based on the following criteria.

13小時後的黏度≦初期黏度×1.2:經時黏度上升小,為良好(A) Viscosity after 13 hours≦Initial viscosity×1.2: Viscosity rises little over time, which is good (A)

13小時後的黏度>初期黏度×1.2:經時黏度上升大,為不良(B) Viscosity after 13 hours>Initial viscosity×1.2: The viscosity increases over time, which is bad (B)

〈潤濕性的評估〉 <Assessment of wettability>

與上述〈增黏抑制評估〉以相同方式,使用開口徑6.5mm、開口數4個、遮罩厚度0.2mm的金屬遮罩,將調配例(F11-1)至(F11-18)的各助焊劑印刷於Cu板上,於回焊爐中在N2氣體環境中以1℃/sec的升溫速度從25℃加熱至260℃為 止後,空冷至室溫(25℃)而形成4個焊料凸塊。使用光學顯微鏡(倍率:100倍)來觀察所得到之凸塊的外觀,並根據以下基準來進行評估。 In the same manner as in the above "Evaluation of Tackification Inhibition", a metal mask with an opening diameter of 6.5 mm, 4 openings, and a mask thickness of 0.2 mm was used. The flux is printed on the Cu board, heated from 25°C to 260°C at a temperature increase rate of 1°C/sec in a N 2 gas atmosphere in a reflow furnace, and then air-cooled to room temperature (25°C) to form 4 solder bumps Piece. An optical microscope (magnification: 100 times) was used to observe the appearance of the obtained bumps, and evaluated based on the following criteria.

於4個焊料凸塊中,全部都未觀察到未完全熔融的焊料粒子:焊料潤濕性良好(A)。 Among the four solder bumps, none of the solder particles that were not completely melted were observed: the solder wettability was good (A).

於4個焊料凸塊中,觀察到1個以上未完全熔融的焊料粒子:焊料潤濕性不良(B)。 Among the four solder bumps, one or more solder particles that were not completely melted were observed: poor solder wettability (B).

評估結果係如表126至表128所示。 The evaluation results are shown in Table 126 to Table 128.

各表中,係使用下列所示之金屬減活劑A至H作為受阻酚系金屬減活劑。 In each table, the metal deactivators A to H shown below are used as hindered phenol-based metal deactivators.

‧「金屬減活劑A」 ‧「Metal Deactivator A」

試藥名稱:雙[3-(3-三級丁基-4-羥基-5-甲基苯基)丙酸][伸乙基雙(氧基伸乙基)];CAS No.36443-68-2。 Reagent name: Bis[3-(3-tertiarybutyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]; CAS No.36443-68- 2.

‧「金屬減活劑B」 ‧「Metal Deactivator B」

試藥名稱:N,N'-六亞甲基雙[3-(3,5-二(三級丁基)-4-羥基苯基)丙烷醯胺];CAS No.23128-74-7。 Reagent name: N,N'-hexamethylenebis[3-(3,5-di(tertiarybutyl)-4-hydroxyphenyl)propaneamide]; CAS No.23128-74-7.

‧「金屬減活劑C」 ‧「Metal Deactivator C」

試藥名稱:1,6-己二醇雙[3-(3,5-二(三級丁基)-4-羥基苯基)丙酸酯];CAS No.35074-77-2。 Reagent name: 1,6-hexanediol bis[3-(3,5-di(tertiarybutyl)-4-hydroxyphenyl)propionate]; CAS No. 35074-77-2.

‧「金屬減活劑D」 ‧「Metal Deactivator D」

試藥名稱:2,2'-亞甲基雙[6-(1-甲基環己基)-對甲酚];CAS No.77-62-3。 Reagent name: 2,2'-methylenebis[6-(1-methylcyclohexyl)-p-cresol]; CAS No. 77-62-3.

‧「金屬減活劑E」 ‧「Metal Deactivator E」

試藥名稱:2,2'-亞甲基雙(6-三級丁基對甲酚);CAS No.119-47-1。 Reagent name: 2,2'-methylene bis(6-tertiary butyl-p-cresol); CAS No. 119-47-1.

‧「金屬減活劑F」 ‧「Metal Deactivator F」

試藥名稱:2,2'-亞甲基雙(6-三級丁基-4-乙基酚);CAS No.88-24-4。 Reagent name: 2,2'-methylenebis(6-tertiarybutyl-4-ethylphenol); CAS No. 88-24-4.

‧「金屬減活劑G」 ‧「Metal Deactivator G」

試藥名稱:N-(2H-1,2,4-三唑-5-基)柳醯胺;CAS No.36411-52-6。 Reagent name: N-(2H-1,2,4-triazol-5-yl)salanamide; CAS No. 36411-52-6.

‧「金屬減活劑H」 ‧「Metal Deactivator H」

試藥名稱:N,N'-雙[2-[2-(3,5-二(三級丁基)-4-羥基苯基)乙基羰氧基]乙基]草醯胺;CAS No.70331-94-1。 Reagent name: N,N'-bis[2-[2-(3,5-di(tertiary butyl)-4-hydroxyphenyl)ethylcarbonyloxy]ethyl] glufamide; CAS No .70331-94-1.

[表126]

Figure 109117353-A0202-12-0236-137
[Table 126]
Figure 109117353-A0202-12-0236-137

[表127]

Figure 109117353-A0202-12-0237-138
[Table 127]
Figure 109117353-A0202-12-0237-138

[表128]

Figure 109117353-A0202-12-0238-139
[Table 128]
Figure 109117353-A0202-12-0238-139

在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F11-1)至(F11-17)的各助焊劑之情形下,可確認到任一者與使用調配例(F11-18)的助焊劑之情形相比,增黏抑制的效果皆為提高。 In the case of using the fluxes of the blending examples (F11-1) to (F11-17) for the solder powder with the alloy composition shown in Test Example 1, it is possible to confirm that any one of them and the use blending example (F11-18) Compared with the case of the flux of ), the effect of suppressing the viscosity increase is improved.

此等當中,含有具有試驗例1的合金組成之焊料粉末與調配例(F11-1)至(F11-17)的各助焊劑之焊料膏,為含有助焊劑(F11)之實施型態之焊料膏。 Among them, the solder paste containing the solder powder with the alloy composition of Test Example 1 and the fluxes of the blending examples (F11-1) to (F11-17) is an implementation type solder containing flux (F11) paste.

接著,就對於具有試驗例2至498、試驗例501至578所示之各合金組成之焊料粉末分別使用調配例(F11-1)至(F11-18)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經時變化之評估〉、〈△T的評估〉及〈潤濕性的評估〉,以及〈增黏抑制評估〉及〈潤濕性的評估〉。 Next, for the solder powders having the alloy compositions shown in Test Examples 2 to 498 and Test Examples 501 to 578, the fluxes of the blending examples (F11-1) to (F11-18) were used, and the above-mentioned < Evaluation of the change of viscosity in solder paste with time", "Evaluation of △T" and "Evaluation of wettability", as well as "Evaluation of inhibition of viscosity increase" and "Evaluation of wettability".

從該評估的結果中,可確認到於含有具有試驗例2至498的合金組成之焊料粉末之焊料膏的情形下,係顯示出增黏抑制效果、△T的窄化及優異的潤濕性。此等當中,含有具有試驗例2至498的合金組成之各焊料粉末與調配例(F11-1)至(F11-17)的各助焊劑之焊料膏,為含有助焊劑(F11)之實施型態之焊料膏。 From the results of this evaluation, it can be confirmed that in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498, it exhibits the effect of suppressing viscosity increase, narrowing of ΔT, and excellent wettability. . Among them, the solder paste containing each solder powder with the alloy composition of Test Examples 2 to 498 and the fluxes of Blending Examples (F11-1) to (F11-17) is an implementation type containing flux (F11) State of solder paste.

另一方面,於含有具有試驗例501至578的合金組成之焊料粉末之焊料膏的情形下,係顯示出於增黏抑制效果、△T的窄化及優異的潤濕性中之至少一項為較差的結果。 On the other hand, in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, it exhibits at least one of the effect of suppressing thickening, narrowing of ΔT, and excellent wettability Is a poor result.

此外,在對於試驗例2至498之焊料粉末分別使用調配例(F11-1)至(F11-17)的各助焊劑之情形下,可確認到任一者與使用調配例(F11-18)的助焊劑之情形相比,增黏抑制的效果皆為提高。 In addition, in the case of using the fluxes of the blending examples (F11-1) to (F11-17) for the solder powders of test examples 2 to 498, it is possible to confirm any one and the use blending example (F11-18) Compared with the case of the flux, the effect of viscosity increase suppression is improved.

[含有助焊劑(F12)之焊料膏的評估] [Evaluation of solder paste containing flux (F12)]

接著,就對於具有試驗例1所示之合金組成之焊料粉末使用表129所示之調配例(F12-1)至(F12-8)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經時變化之評估〉。此外,測定焊料粉末的液相線溫度及固相線溫度來進行上述〈△T的評估〉。再者,使用剛製作的焊料膏來進行上述〈潤濕性的評估〉。 Next, for the solder powder having the alloy composition shown in Test Example 1 using the fluxes of the blending examples (F12-1) to (F12-8) shown in Table 129, the above-mentioned "Viscosity in Solder Paste" "Assessment of Changes over Time." In addition, the liquidus temperature and solidus temperature of the solder powder were measured to perform the above-mentioned <Evaluation of ΔT>. In addition, the above-mentioned "Evaluation of wettability" was performed using the solder paste just produced.

從此等之結果中,可確認到在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F12-1)至(F12-8)的各助焊劑之情形下的焊料膏,皆顯示出增黏抑制效果、△T的窄化及優異的潤濕性。 From these results, it can be confirmed that the solder pastes in the case of using the fluxes of the blending examples (F12-1) to (F12-8) for the solder powder having the alloy composition shown in Test Example 1 all show It has the effect of suppressing viscosity increase, narrowing of △T and excellent wettability.

接著,對於具有試驗例1所示之合金組成之焊料粉末使用表129所示之調配例(F12-1)至(F12-8)的各助焊劑之情形下的焊料膏(助焊劑:焊料粉末=11:89的質量比),分別進行增黏抑制評估及潤濕性的評估。 Next, for the solder powder having the alloy composition shown in Test Example 1, the solder paste (flux: solder powder) in the case of using the fluxes of the blending examples (F12-1) to (F12-8) shown in Table 129 =11:89 mass ratio), the viscosity increase inhibition evaluation and wettability evaluation were carried out respectively.

〈增黏抑制評估〉 <Evaluation of Thickening Suppression>

依循JIS Z 3284-3:2014的「4.2黏度特性試驗」所記載之方法,使用旋轉黏度計(PCU-205、Malcom股份有限公司製),於轉速:10rpm、測定溫度:25℃下對所得到之焊料膏持續測定12小時的黏度。然後,比較初期黏度(攪拌30分鐘後的黏度)與13小時後的黏度,並根據以下基準來進行增黏抑制效果的評估。 According to the method described in "4.2 Viscosity Characteristic Test" of JIS Z 3284-3:2014, using a rotary viscometer (PCU-205, manufactured by Malcom Co., Ltd.), the result was measured at a rotation speed of 10 rpm and a measurement temperature of 25°C. The viscosity of the solder paste was continuously measured for 12 hours. Then, the initial viscosity (viscosity after 30 minutes of stirring) and the viscosity after 13 hours were compared, and the viscosity increase suppression effect was evaluated based on the following criteria.

13小時後的黏度≦初期黏度×1.2:經時黏度上升小,為良好(A) Viscosity after 13 hours≦Initial viscosity×1.2: Viscosity rises little over time, which is good (A)

13小時後的黏度>初期黏度×1.2:經時黏度上升大,為不良(B) Viscosity after 13 hours>Initial viscosity×1.2: The viscosity increases over time, which is bad (B)

〈潤濕性的評估〉 <Assessment of wettability>

與上述〈增黏抑制評估〉以相同方式,使用開口徑6.5mm、開口數4個、遮罩厚度0.2mm的金屬遮罩,將調配例(F12-1)至(F12-8)的各助焊劑印刷於Cu板上,於回焊爐中在N2氣體環境中以1℃/sec的升溫速度從25℃加熱至260℃為 止後,空冷至室溫(25℃)而形成4個焊料凸塊。使用光學顯微鏡(倍率:100倍)來觀察所得到之凸塊的外觀,並根據以下基準來進行評估。 In the same manner as in the above "Tackification suppression evaluation", a metal mask with an opening diameter of 6.5 mm, 4 openings, and a mask thickness of 0.2 mm was used. The flux is printed on the Cu board, heated from 25°C to 260°C at a temperature increase rate of 1°C/sec in a N 2 gas atmosphere in a reflow furnace, and then air-cooled to room temperature (25°C) to form 4 solder bumps Piece. An optical microscope (magnification: 100 times) was used to observe the appearance of the obtained bumps, and evaluated based on the following criteria.

於4個焊料凸塊中,全部都未觀察到未完全熔融的焊料粒子:焊料潤濕性良好(A)。 Among the four solder bumps, none of the solder particles that were not completely melted were observed: the solder wettability was good (A).

於4個焊料凸塊中,觀察到1個以上之未完全熔融的焊料粒子:焊料潤濕性不良(B)。 Among the four solder bumps, one or more solder particles that were not completely melted were observed: poor solder wettability (B).

評估結果係如表129所示。 The evaluation results are shown in Table 129.

各表中,係使用下列所示之金屬減活劑A至E作為含氮化合物系金屬減活劑。 In each table, the following metal deactivators A to E are used as nitrogen-containing compound metal deactivators.

‧「金屬減活劑A」 ‧「Metal Deactivator A」

試藥名稱:N-(2H-1,2,4-三唑-5-基)柳醯胺;CAS No.36411-52-6 Reagent name: N-(2H-1,2,4-triazol-5-yl)salanamide; CAS No.36411-52-6

‧「金屬減活劑B」 ‧「Metal Deactivator B」

試藥名稱:十二烷二酸雙[N2-(2羥基苯甲醯基)醯肼];CAS No.63245-38-5 Reagent name: Dodecanedioic acid bis[N2-(2-hydroxybenzyl)hydrazine]; CAS No.63245-38-5

‧「金屬減活劑C」 ‧「Metal Deactivator C」

試藥名稱:三聚氰胺 Reagent name: Melamine

‧「金屬減活劑D」 ‧「Metal Deactivator D」

試藥名稱:ADEKA公司製商品名稱「ADK STAB ZS-27」 Reagent name: Product name "ADK STAB ZS-27" manufactured by ADEKA

‧「金屬減活劑E」 ‧「Metal Deactivator E」

試藥名稱:ADEKA公司製商品名稱「ADK STAB ZS-90」 Reagent name: Product name "ADK STAB ZS-90" manufactured by ADEKA

各表中,係使用下列所示之金屬減活劑F作為受阻酚系金屬減活劑。 In each table, the metal deactivator F shown below is used as the hindered phenol-based metal deactivator.

‧「金屬減活劑F」 ‧「Metal Deactivator F」

試藥名稱:雙[3-(3-三級丁基-4-羥基-5-甲基苯基)丙酸][伸乙基雙(氧基伸乙基)];CAS No.36443-68-2 Reagent name: Bis[3-(3-tertiarybutyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]; CAS No.36443-68- 2

[表129]

Figure 109117353-A0202-12-0243-140
[Table 129]
Figure 109117353-A0202-12-0243-140

在對於具有試驗例1所示之合金組成之焊料粉末使用調配例(F12-1)至(F12-7)的各助焊劑之情形下,可確認到任一者與使用調配例(F12-8)的助焊劑之情形相比,增黏抑制的效果皆為提高。 In the case of using the fluxes of the blending examples (F12-1) to (F12-7) for the solder powder having the alloy composition shown in Test Example 1, it can be confirmed that any one of them and the use blending example (F12-8) Compared with the case of the flux of ), the effect of suppressing the viscosity increase is improved.

其中,含有具有試驗例1的合金組成之焊料粉末與調配例(F12-1)至(F12-7)的各助焊劑之焊料膏,為含有助焊劑(F12)之實施型態之焊料膏。 Among them, the solder paste containing the solder powder having the alloy composition of Test Example 1 and the fluxes of the blending examples (F12-1) to (F12-7) is an implementation type solder paste containing the flux (F12).

接著,就對於具有試驗例2至498、試驗例501至578所示之各合金組成之焊料粉末分別使用調配例(F12-1)至(F12-8)的各助焊劑之情形,進行上述〈焊料膏中之黏度之經時變化之評估〉、〈△T的評估〉及〈潤濕性的評估〉,以及〈增黏抑制評估〉及〈潤濕性的評估〉。 Next, for the solder powders having the respective alloy compositions shown in Test Examples 2 to 498 and Test Examples 501 to 578, each of the fluxes of Blending Examples (F12-1) to (F12-8) was used, and the above-mentioned < Evaluation of the change of viscosity in solder paste with time", "Evaluation of △T" and "Evaluation of wettability", as well as "Evaluation of inhibition of viscosity increase" and "Evaluation of wettability".

從該評估的結果中,可確認到於含有具有試驗例2至498的合金組成之焊料粉末之焊料膏的情形下,係顯示出增黏抑制效果、△T的窄化及優異的潤濕性。此等當中,含有具有試驗例2至498的合金組成之各焊料粉末與調配例(F12-1)至(F12-7)的各助焊劑之焊料膏,為含有助焊劑(F12)之實施型態之焊料膏。 From the results of this evaluation, it can be confirmed that in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 2 to 498, it exhibits the effect of suppressing viscosity increase, narrowing of ΔT, and excellent wettability. . Among them, the solder paste containing each solder powder with the alloy composition of Test Examples 2 to 498 and the fluxes of Blending Examples (F12-1) to (F12-7) is an implementation type containing flux (F12) State of solder paste.

另一方面,於含有具有試驗例501至578的合金組成之焊料粉末之焊料膏的情形下,係顯示出於增黏抑制效果、△T的窄化及優異的潤濕性中之至少一項為較差的結果。 On the other hand, in the case of the solder paste containing the solder powder having the alloy composition of Test Examples 501 to 578, it exhibits at least one of the effect of suppressing thickening, narrowing of ΔT, and excellent wettability Is a poor result.

此外,在對於試驗例2至498之焊料粉末分別使用調配例(F12-1)至(F12-7)的各助焊劑之情形下,可確認到任一者與使用調配例(F12-8)的助焊劑之情形相比,增黏抑制的效果皆為提高。 In addition, in the case of using the fluxes of the blending examples (F12-1) to (F12-7) for the solder powders of test examples 2 to 498, it is possible to confirm any one and the use blending example (F12-8) Compared with the case of the flux, the effect of viscosity increase suppression is improved.

在對於試驗例2至498之焊料粉末分別使用調配例(F12-1)至(F12-7)的各助焊劑之焊料膏中,更含有相對於焊料膏的全部質量為0.1質量%之粒徑1μm的氧化鋯粉末時,可確認到增黏抑制效果的提升。 For the solder powders of test examples 2 to 498, the solder pastes using the fluxes of the formulation examples (F12-1) to (F12-7) further contained a particle size of 0.1% by mass relative to the total mass of the solder paste In the case of 1μm zirconia powder, an improvement in the effect of suppressing thickening can be confirmed.

[產業上之可利用性] [Industrial availability]

根據本發明,可提供一種焊料膏,其係不易發生黏度上升等之經時變化,潤濕性優異,具有高的機械特性,除此之外可進一步提高各種特性者。 According to the present invention, it is possible to provide a solder paste which is less prone to changes with time such as increase in viscosity, is excellent in wettability, has high mechanical properties, and can further improve various properties.

此外,根據本發明,藉由與特定的焊料粉末組合並且選擇所調配之成分,可提供一種焊料膏用助焊劑,其係進一步達成焊料之潤濕速度的提升、接合對象物之金屬表面(例如銅板)的腐蝕抑制、印刷性的提升、空隙抑制等各種特性者。 In addition, according to the present invention, by combining with specific solder powder and selecting the blended ingredients, it is possible to provide a flux for solder paste, which can further improve the wetting speed of the solder and the metal surface of the joining object (such as Corrosion suppression, printability improvement, void suppression and other characteristics of copper plate).

Claims (52)

一種焊料膏,其係含有焊料粉末與助焊劑, A solder paste containing solder powder and flux, 前述焊料粉末係含有焊料合金,該焊料合金具有由As:10質量ppm以上且未達40質量ppm,以及Bi:0至10000質量ppm、Pb:0至5100質量ppm及Sb:0至3000質量ppm中的至少一種,以及剩餘部分為Sn所構成之合金組成,並且滿足下述(1)式及(2)式, The aforementioned solder powder system contains a solder alloy, which has As: 10 mass ppm or more and less than 40 mass ppm, and Bi: 0 to 10,000 mass ppm, Pb: 0 to 5100 mass ppm, and Sb: 0 to 3000 mass ppm At least one of them, and the remainder is an alloy composition composed of Sn, and satisfies the following formulas (1) and (2), 300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition. 一種焊料膏,其係含有焊料粉末與助焊劑, A solder paste containing solder powder and flux, 前述焊料粉末係含有焊料合金,該焊料合金具有由As:10質量ppm以上且未達40質量ppm,以及Bi:超過0質量ppm且為10000質量ppm以下、Pb:超過0質量ppm且為5100質量ppm以下及Sb:超過0質量ppm且為3000質量ppm以下中的至少一種,以及剩餘部分為Sn所構成之合金組成,並且滿足下述(1)式及(2)式, The aforementioned solder powder system contains a solder alloy having a composition of As: 10 mass ppm or more and less than 40 mass ppm, Bi: more than 0 mass ppm and 10,000 mass ppm or less, and Pb: more than 0 mass ppm and 5100 mass ppm ppm or less and Sb: at least one of more than 0 mass ppm and 3000 mass ppm or less, and the remainder is an alloy composition composed of Sn, and satisfies the following equations (1) and (2), 300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition. 一種焊料膏,其係含有焊料粉末與助焊劑, A solder paste containing solder powder and flux, 前述焊料粉末係含有焊料合金,該焊料合金具有由As:10質量ppm以上且未達40質量ppm,以及Bi:50至10000質量ppm、Pb:超過0質量ppm且為5100質量ppm以下及Sb:超過0質量ppm且為3000質量ppm以下中的至少一種,以及剩餘部分為Sn所構成之合金組成,並且滿足下述(1)式及(2)式, The aforementioned solder powder system contains a solder alloy, the solder alloy having As: 10 mass ppm or more and less than 40 mass ppm, Bi: 50 to 10,000 mass ppm, Pb: more than 0 mass ppm and less than 5100 mass ppm, and Sb: More than 0 mass ppm and at least one of 3000 mass ppm or less, and the remainder is an alloy composition composed of Sn, and satisfies the following formulas (1) and (2), 300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition. 一種焊料膏,其係含有焊料粉末與助焊劑, A solder paste containing solder powder and flux, 前述焊料粉末係含有焊料合金,該焊料合金具有由As:10質量ppm以上且未達40質量ppm,以及Bi:超過0質量ppm且為10000質量ppm以下、Pb:50至5100質量ppm及Sb:超過0質量ppm且為3000質量ppm以下中的至少一種,以及剩餘部分為Sn所構成之合金組成,並且滿足下述(1)式及(2)式, The aforementioned solder powder system contains a solder alloy, which has As: 10 mass ppm or more and less than 40 mass ppm, Bi: more than 0 mass ppm and 10,000 mass ppm or less, Pb: 50 to 5100 mass ppm, and Sb: More than 0 mass ppm and at least one of 3000 mass ppm or less, and the remainder is an alloy composition composed of Sn, and satisfies the following formulas (1) and (2), 300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition. 一種焊料膏,其係含有焊料粉末與助焊劑, A solder paste containing solder powder and flux, 前述焊料粉末係含有焊料合金,該焊料合金具有由As:10質量ppm以上且未達40質量ppm,以及Bi:超過0質量ppm且為10000質量ppm以下、Pb:超過0質量ppm且為5100質量ppm以下及Sb:50至3000質量ppm中的至少一種,以及剩餘部分為Sn所構成之合金組成,並且滿足下述(1)式及(2)式, The aforementioned solder powder system contains a solder alloy having a composition of As: 10 mass ppm or more and less than 40 mass ppm, Bi: more than 0 mass ppm and 10,000 mass ppm or less, and Pb: more than 0 mass ppm and 5100 mass ppm ppm or less and Sb: at least one of 50 to 3000 mass ppm, and the remainder is an alloy composition composed of Sn, and satisfies the following equations (1) and (2), 300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition. 一種焊料膏,其係含有焊料粉末與助焊劑, A solder paste containing solder powder and flux, 前述焊料粉末係含有焊料合金,該焊料合金係具有由As:10質量ppm以上且未達40質量ppm,以及Bi:50至10000質量ppm、Pb:50至5100質量ppm及Sb:超過0質量ppm且為3000質量ppm以下中的至少一種,以及剩餘部分為Sn所構成之合金組成,並滿足下述(1)式及(2)式, The aforementioned solder powder system contains a solder alloy having a composition of As: 10 mass ppm or more and less than 40 mass ppm, Bi: 50 to 10,000 mass ppm, Pb: 50 to 5100 mass ppm, and Sb: more than 0 mass ppm And is at least one of 3000 mass ppm or less, and the remainder is an alloy composition composed of Sn, and satisfies the following equations (1) and (2), 300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition. 一種焊料膏,其係含有焊料粉末與助焊劑, A solder paste containing solder powder and flux, 前述焊料粉末係含有焊料合金,該焊料合金係具有由As:10質量ppm以上且未達40質量ppm,以及Bi:超過0質量ppm且為10000質量ppm以下、Pb:50至5100質量ppm及Sb:50至3000質量ppm中的至少一種,以及剩餘部分為Sn所構成之合金組成,並滿足下述(1)式及(2)式, The aforementioned solder powder system contains a solder alloy, and the solder alloy system is composed of As: 10 mass ppm or more and less than 40 mass ppm, Bi: more than 0 mass ppm and 10,000 mass ppm or less, Pb: 50 to 5100 mass ppm and Sb : At least one of 50 to 3000 mass ppm, and the remainder is an alloy composition composed of Sn, and satisfies the following (1) and (2) formulas, 300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition. 一種焊料膏,其係含有焊料粉末與助焊劑, A solder paste containing solder powder and flux, 前述焊料粉末係含有焊料合金,該焊料合金係具有由As:10質量ppm以上且未達40質量ppm,以及Bi:50至10000質量ppm、Pb:超過0質量ppm且為5100質量ppm以下及Sb:50至3000質量ppm中的至少一種,以及剩餘部分為Sn所構成之合金組成,並滿足下述(1)式及(2)式, The aforementioned solder powder system contains a solder alloy, the solder alloy system is composed of As: 10 mass ppm or more and less than 40 mass ppm, Bi: 50 to 10,000 mass ppm, Pb: more than 0 mass ppm and less than 5100 mass ppm, and Sb : At least one of 50 to 3000 mass ppm, and the remainder is an alloy composition composed of Sn, and satisfies the following (1) and (2) formulas, 300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition. 一種焊料膏,其係含有焊料粉末與助焊劑, A solder paste containing solder powder and flux, 前述焊料粉末係含有焊料合金,該焊料合金係具有由As:10質量ppm以上且未達40質量ppm,以及Bi:50至10000質量ppm,Pb:50至5100質量ppm,及Sb:50至3000質量ppm中的至少一種,以及剩餘部分為Sn所構成之合金組成,並滿足下述(1)式及(2)式, The aforementioned solder powder system contains a solder alloy having a composition of As: 10 mass ppm or more and less than 40 mass ppm, and Bi: 50 to 10,000 mass ppm, Pb: 50 to 5100 mass ppm, and Sb: 50 to 3000 At least one of the mass ppm, and the remainder is an alloy composition composed of Sn, and satisfies the following formulas (1) and (2), 300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition. 如請求項1至9中任一項所述之焊料膏,其中,前述合金組成更含有Ni:0至600質量ppm。 The solder paste according to any one of claims 1 to 9, wherein the alloy composition further contains Ni: 0 to 600 ppm by mass. 如請求項1至9中任一項所述之焊料膏,其中,前述合金組成更含有Fe:0至100質量ppm。 The solder paste according to any one of claims 1 to 9, wherein the aforementioned alloy composition further contains Fe: 0 to 100 ppm by mass. 如請求項1至9中任一項所述之焊料膏,其中,前述合金組成更含有In:0至1200質量ppm。 The solder paste according to any one of claims 1 to 9, wherein the alloy composition further contains In: 0 to 1200 ppm by mass. 如請求項1至9中任一項所述之焊料膏,其中,前述合金組成更含有Ni:0至600質量ppm、Fe:0至100質量ppm及In:0至1200質量ppm中的至少兩種。 The solder paste according to any one of claims 1 to 9, wherein the alloy composition further contains at least two of Ni: 0 to 600 mass ppm, Fe: 0 to 100 mass ppm, and In: 0 to 1200 mass ppm Kind. 如請求項1至9中任一項所述之焊料膏,其中,前述合金組成更含有Ni:0至600質量ppm及Fe:0至100質量ppm,並且滿足下述(3)式, The solder paste according to any one of claims 1 to 9, wherein the alloy composition further contains Ni: 0 to 600 ppm by mass and Fe: 0 to 100 ppm by mass, and satisfies the following formula (3), 0≦Ni/Fe≦50 (3) 0≦Ni/Fe≦50 (3) 上述(3)式中,Ni及Fe各自表示前述合金組成中的含量(質量ppm)。 In the above formula (3), Ni and Fe each represent the content (mass ppm) in the aforementioned alloy composition. 如請求項1至14中任一項所述之焊料膏,其中,前述合金組成更滿足下述(1a)式, The solder paste according to any one of claims 1 to 14, wherein the aforementioned alloy composition further satisfies the following formula (1a), 300≦3As+Sb+Bi+Pb≦18214 (1a) 300≦3As+Sb+Bi+Pb≦18214 (1a) 上述(1a)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formula (1a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition. 如請求項1至15中任一項所述之焊料膏,其中,前述合金組成更滿足下述(2a)式, The solder paste according to any one of claims 1 to 15, wherein the alloy composition further satisfies the following formula (2a), 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦158.5 (2a) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦158.5 (2a) 上述(2a)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formula (2a), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition. 如請求項1至16中任一項所述之焊料膏,其中,前述合金組成更含有Ag:0至4質量%及Cu:0至0.9質量%中的至少一種。 The solder paste according to any one of claims 1 to 16, wherein the alloy composition further contains at least one of Ag: 0 to 4% by mass and Cu: 0 to 0.9% by mass. 如請求項1至17中任一項所述之焊料膏,其中,前述合金組成中的As為10質量ppm以上且未達25質量ppm。 The solder paste according to any one of claims 1 to 17, wherein As in the alloy composition is 10 mass ppm or more and less than 25 mass ppm. 如請求項1至18中任一項所述之焊料膏,其中,前述助焊劑係含有樹脂成分、活性成分及溶劑。 The solder paste according to any one of claims 1 to 18, wherein the flux system contains a resin component, an active component, and a solvent. 如請求項19所述之焊料膏,其中,前述助焊劑含有受阻酚系化合物。 The solder paste according to claim 19, wherein the soldering flux contains a hindered phenolic compound. 如請求項20所述之焊料膏,其中,相對於前述助焊劑的全部質量,前述受阻酚系化合物的含量為0.5質量%以上10質量%以下。 The solder paste according to claim 20, wherein the content of the hindered phenol-based compound is 0.5% by mass or more and 10% by mass or less with respect to the total mass of the flux. 如請求項19所述之焊料膏,其中,前述助焊劑含有屬於氮化合物之金屬減活劑。 The solder paste according to claim 19, wherein the aforementioned flux contains a metal deactivator which is a nitrogen compound. 如請求項22所述之焊料膏,其中,前述金屬減活劑為選自由醯肼(hydrazide)系氮化合物、醯胺系氮化合物、三唑(triazole)系氮化合物及三聚氰胺系氮化合物所組成群組中之至少一種氮化合物。 The solder paste according to claim 22, wherein the metal deactivator is selected from the group consisting of hydrazide-based nitrogen compounds, amide-based nitrogen compounds, triazole-based nitrogen compounds, and melamine-based nitrogen compounds At least one nitrogen compound in the group. 如請求項22或23所述之焊料膏,其中,相對於前述助焊劑的全部質量,前述金屬減活劑的含量係超過0質量%且為10質量%以下。 The solder paste according to claim 22 or 23, wherein the content of the metal deactivator is more than 0% by mass and 10% by mass or less with respect to the total mass of the flux. 如請求項19所述之焊料膏,其中,前述助焊劑係含有酸改質松香。 The solder paste according to claim 19, wherein the flux system contains acid-modified rosin. 如請求項25所述之焊料膏,其中,前述酸改質松香為選自由丙烯酸改質松香、丙烯酸改質氫化松香、順丁烯二酸改質松香及順丁烯二酸改質松香氫化松香所組成群組中之至少一種。 The solder paste according to claim 25, wherein the acid-modified rosin is selected from acrylic acid-modified rosin, acrylic acid-modified hydrogenated rosin, maleic acid-modified rosin, and maleic acid-modified rosin hydrogenated rosin At least one of the formed groups. 如請求項25或26所述之焊料膏,其中,相對於前述助焊劑的全部質量,前述酸改質松香的含量為3質量%以上60質量%以下。 The solder paste according to claim 25 or 26, wherein the content of the acid-modified rosin relative to the total mass of the flux is 3% by mass or more and 60% by mass or less. 如請求項19所述之焊料膏,其中,前述助焊劑含有丙烯酸系樹脂。 The solder paste according to claim 19, wherein the flux contains an acrylic resin. 如請求項28所述之焊料膏,其中,相對於前述助焊劑的全部質量,前述丙烯酸系樹脂的含量為5質量%以上50質量%以下。 The solder paste according to claim 28, wherein the content of the acrylic resin is 5% by mass or more and 50% by mass or less with respect to the total mass of the flux. 如請求項19所述之焊料膏,其中,前述助焊劑係含有:選自由屬於單羧酸的反應物且為二聚物之二聚物酸、將氫添加於二聚物酸而得之氫化二聚物酸、屬於單羧酸的反應物且為三聚物之三聚物酸、以及將氫添加於三聚物酸而得之氫化三聚物酸所組成群組中之至少一種有機酸。 The solder paste according to claim 19, wherein the soldering flux contains: a dimer acid selected from the group consisting of reactants of monocarboxylic acid and a dimer, and hydrogenated by adding hydrogen to the dimer acid At least one organic acid in the group consisting of a dimer acid, a trimer acid that is a reactant of a monocarboxylic acid and is a trimer, and a hydrogenated trimer acid obtained by adding hydrogen to the trimer acid . 如請求項30所述之焊料膏,其中,相對於前述助焊劑的全部質量,選自由前述二聚物酸、前述氫化二聚物酸、前述三聚物酸以及前述氫化三聚物酸所組成群組中之至少一種有機酸的含量為0.5質量%以上20質量%以下。 The solder paste according to claim 30, wherein the solder paste is selected from the group consisting of the dimer acid, the hydrogenated dimer acid, the trimer acid, and the hydrogenated trimer acid relative to the total mass of the flux The content of at least one organic acid in the group is 0.5% by mass or more and 20% by mass or less. 如請求項19所述之焊料膏,其中,前述助焊劑含有以下述通式(1)所表示之化合物, The solder paste according to claim 19, wherein the flux contains a compound represented by the following general formula (1),
Figure 109117353-A0202-13-0007-141
Figure 109117353-A0202-13-0007-141
式(1)中,R1、R2、R3及R4各自獨立地表示氫原子或碳數1至4的烷基。 In formula (1), R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
如請求項32所述之焊料膏,其中,以前述通式(1)所表示之化合物為2-吡啶甲酸(picolinic acid)。 The solder paste according to claim 32, wherein the compound represented by the aforementioned general formula (1) is 2-picolinic acid. 如請求項32或33所述之焊料膏,其中,相對於前述助焊劑的全部質量,以前述通式(1)所表示之化合物的含量為0.5質量%以上7質量%以下。 The solder paste according to claim 32 or 33, wherein the content of the compound represented by the general formula (1) is 0.5% by mass to 7% by mass relative to the total mass of the flux. 如請求項19所述之焊料膏,其中,前述助焊劑含有唑(azole)類。 The solder paste according to claim 19, wherein the soldering flux contains azoles. 如請求項35所述之焊料膏,其中,前述唑類為選自由2-苯基咪唑、2-苯基-4-甲基咪唑、2-十七基咪唑、苯并咪唑及2-辛基苯并咪唑所組成群組中之至少一種。 The solder paste according to claim 35, wherein the aforementioned azoles are selected from the group consisting of 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, benzimidazole and 2-octyl At least one of the group consisting of benzimidazole. 如請求項35或36所述之焊料膏,其中,相對於前述助焊劑的全部質量,前述唑類的含量為0.1質量%以上10質量%以下。 The solder paste according to claim 35 or 36, wherein the content of the azole is 0.1% by mass to 10% by mass relative to the total mass of the flux. 如請求項19所述之焊料膏,其中,前述助焊劑含有芳香族胍化合物。 The solder paste according to claim 19, wherein the flux contains an aromatic guanidine compound. 如請求項38所述之焊料膏,其中,前述芳香族胍化合物為選自由二苯基胍(diphenyl guanidine)及二甲苯基胍(ditolyl guanidine)所組成群組中之至少一種。 The solder paste according to claim 38, wherein the aromatic guanidine compound is at least one selected from the group consisting of diphenyl guanidine and ditolyl guanidine. 如請求項38或39所述之焊料膏,其中,相對於前述助焊劑的全部質量,前述芳香族胍化合物的含量為0.2質量%以上15質量%以下。 The solder paste according to claim 38 or 39, wherein the content of the aromatic guanidine compound relative to the total mass of the flux is 0.2% by mass or more and 15% by mass or less. 如請求項19所述之焊料膏,其中,前述助焊劑含有屬於醯胺化合物之醯胺系搖變減黏劑。 The solder paste according to claim 19, wherein the aforementioned flux contains an amide-based thixotropic agent which is an amide compound. 如請求項41所述之焊料膏,其中,前述醯胺系搖變減黏劑為選自由聚醯胺、雙醯胺及單醯胺所組成群組中之至少一種。 The solder paste according to claim 41, wherein the aforementioned amide-based thixotropic viscosity reducing agent is at least one selected from the group consisting of polyamide, bisamide, and monoamide. 如請求項41或42所述之焊料膏,其中,相對於前述助焊劑的全部質量,前述醯胺系搖變減黏劑的含量係超過0質量%且為15質量%以下。 The solder paste according to claim 41 or 42, wherein the content of the amide-based thixotropic viscosity reducer is more than 0% by mass and 15% by mass or less with respect to the total mass of the flux. 如請求項19所述之焊料膏,其中,前述助焊劑含有屬於山梨醇(sorbitol)化合物之山梨醇系搖變減黏劑。 The solder paste according to claim 19, wherein the aforementioned flux contains a sorbitol-based thixotropic agent which is a sorbitol compound. 如請求項44所述之焊料膏,其中,前述山梨醇系搖變減黏劑為選自由二苯亞甲基山梨醇及雙(4-甲基苯亞甲基)山梨醇所組成群組中之至少一種。 The solder paste according to claim 44, wherein the sorbitol-based thixotropic agent is selected from the group consisting of dibenzylidene sorbitol and bis(4-methylbenzylidene)sorbitol At least one of them. 如請求項44或45所述之焊料膏,其中,相對於前述助焊劑的全部質量,前述山梨醇系搖變減黏劑的含量為0.2質量%以上5質量%以下。 The solder paste according to claim 44 or 45, wherein the content of the sorbitol-based thixotropic viscosity reducer is 0.2% by mass to 5% by mass relative to the total mass of the flux. 如請求項19所述之焊料膏,其中,前述助焊劑一併具有二醇系溶劑與有機酸酯。 The solder paste according to claim 19, wherein the soldering flux includes a glycol solvent and an organic acid ester. 如請求項19所述之焊料膏,其中,前述助焊劑一併具有二醇系溶劑與碳數16至18的一元醇。 The solder paste according to claim 19, wherein the flux includes a glycol solvent and a monohydric alcohol having 16 to 18 carbon atoms. 如請求項1至48中任一項所述之焊料膏,其更含有氧化鋯粉末。 The solder paste according to any one of claims 1 to 48, which further contains zirconia powder. 如請求項49所述之焊料膏,其中,相對於前述焊料膏的全部質量,前述氧化鋯粉末的含量為0.05至20.0質量%。 The solder paste according to claim 49, wherein the content of the zirconia powder is 0.05 to 20.0% by mass relative to the total mass of the solder paste. 一種焊料膏用助焊劑,其為使用在焊料膏之助焊劑, A flux for solder paste, which is a flux used in solder paste, 前述焊料膏係含有包含焊料合金之焊料粉末,該焊料合金具有由As:10質量ppm以上且未達40質量ppm,以及Bi:0至10000質量ppm、Pb:0至5100質量ppm及Sb:0至3000質量ppm中的至少一種,以及剩餘部分為Sn所構成之合金組成,並且滿足下述(1)式及(2)式, The aforementioned solder paste contains a solder powder containing a solder alloy, the solder alloy having As: 10 mass ppm or more and less than 40 mass ppm, and Bi: 0 to 10,000 mass ppm, Pb: 0 to 5100 mass ppm, and Sb: 0 At least one of to 3000 mass ppm, and the remainder is an alloy composition composed of Sn, and satisfies the following formulas (1) and (2), 300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition. 一種焊料膏用助焊劑,其為使用在焊料膏之助焊劑, A flux for solder paste, which is a flux used in solder paste, 前述焊料膏係含有包含焊料合金之焊料粉末,該焊料合金具有由As:10質量ppm以上且未達40質量ppm,以及Bi:超過0質量ppm且為10000質量ppm以下、Pb:超過0質量ppm且為5100質量ppm以下及Sb:超過0質量ppm且為3000質量ppm以下中的至少一種,以及剩餘部分為Sn所構成之合金組成,並且滿足下述(1)式及(2)式, The aforementioned solder paste contains a solder powder containing a solder alloy. The solder alloy has As: more than 10 mass ppm and less than 40 mass ppm, and Bi: more than 0 mass ppm and less than 10,000 mass ppm, and Pb: more than 0 mass ppm And it is 5100 ppm by mass or less and Sb: at least one of more than 0 ppm by mass and 3,000 ppm by mass or less, and the remainder is an alloy composition composed of Sn, and satisfies the following equations (1) and (2), 300≦3As+Sb+Bi+Pb (1) 300≦3As+Sb+Bi+Pb (1) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 0.1≦{(3As+Sb)/(Bi+Pb)}×100≦200 (2) 上述(1)式及(2)式中,As、Sb、Bi及Pb各自表示前述合金組成中的含量(質量ppm)。 In the above formulas (1) and (2), As, Sb, Bi, and Pb each represent the content (mass ppm) in the aforementioned alloy composition.
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