TWI746647B - Thermosetting flux composition and manufacturing method of electronic substrate - Google Patents

Thermosetting flux composition and manufacturing method of electronic substrate Download PDF

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TWI746647B
TWI746647B TW106132755A TW106132755A TWI746647B TW I746647 B TWI746647 B TW I746647B TW 106132755 A TW106132755 A TW 106132755A TW 106132755 A TW106132755 A TW 106132755A TW I746647 B TWI746647 B TW I746647B
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flux composition
thermosetting flux
component
mass
solder
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TW106132755A
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TW201835209A (en
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喜多村明
飯島紀成
谷口裕亮
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日商田村製作所股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3457—Solder materials or compositions; Methods of application thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
    • B23K35/3613—Polymers, e.g. resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/18—Oxetanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
    • H01L2224/81009—Pre-treatment of the bump connector or the bonding area
    • H01L2224/81024—Applying flux to the bonding area

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)

Abstract

本發明之熱固性助焊劑組合物之特徵在於：其係於藉由回流焊接使具有包含熔點為200℃以上且240℃以下之焊料合金的焊料凸塊之電子零件接合於電子基板之情形時所使用者，且含有(A)氧雜環丁烷化合物、與(B)活性劑，上述(A)成分含有(A1)於1分子中具有2個氧雜環丁烷環之二官能氧雜環丁烷化合物，上述(B)成分含有(B1)有機酸，且該熱固性助焊劑組合物於以5℃/min之升溫速度自溫度25℃升溫之情形時，溫度200℃下之黏度為5 Pa・s以下，且溫度250℃下之黏度為50 Pa・s以上。The thermosetting flux composition of the present invention is characterized in that it is used when reflow soldering is used to bond electronic parts having solder bumps containing solder alloys with a melting point of 200°C or more and 240°C or less to an electronic substrate. And contains (A) an oxetane compound and (B) an active agent, and the above-mentioned (A) component contains (A1) a bifunctional oxetane having two oxetane rings in one molecule Alkyl compound, the above-mentioned (B) component contains (B1) organic acid, and when the thermosetting flux composition is heated from a temperature of 25°C at a temperature rise rate of 5°C/min, the viscosity at a temperature of 200°C is 5 Pa· s or less, and the viscosity at a temperature of 250°C is 50 Pa·s or more.

Description

熱固性助焊劑組合物及電子基板之製造方法Thermosetting flux composition and manufacturing method of electronic substrate

本發明係關於一種熱固性助焊劑組合物及電子基板之製造方法。The present invention relates to a method for manufacturing a thermosetting flux composition and an electronic substrate.

伴隨著電子機器之小型化及薄型化，而使用具有焊料球之封裝零件(例如球柵陣列封裝：BGA封裝)。並且，關於此種BGA封裝，亦要求微間距者，但於將微間距之BGA封裝接合於安裝基板之情形時，若僅為焊料球，則有接合部分之強度較弱之問題。因此，通常藉由於BGA封裝與安裝基板之間填充底部填充材並使之硬化而補強接合部分。然而，為了填充底部填充材並使之硬化，需要耗費勞力與時間，因此於生產成本之方面上存在問題。 另一方面，揭示有於安裝基板上預先印刷含有助熔劑之接著劑，於印刷部分安裝封裝零件之方法(參照文獻1：日本專利特開平4-280443號公報)。 伴隨著近年來焊料之無鉛化，而開始使用高熔點(例如熔點為200℃以上)之焊料合金。然而，於藉由文獻1中所記載之使用接著劑之方法而進行包含高熔點之焊料合金的焊料凸塊之回流焊接(reflow soldering)之情形時，存在損害回焊(reflow)中之焊接性或自動校準性之問題。 又，於文獻1中所記載之使用接著劑之方法中，接著劑之硬化物會殘留於安裝基板。因此，對於該接著劑之硬化物，亦與安裝基板所用之材料(阻焊劑等)同樣地要求絕緣性。並且，即便欲藉由例如降低環氧樹脂之硬化率之類之方法來謀求自動校準性之提高，接著劑之硬化物之絕緣性亦成為問題。 如上所述，硬化物之絕緣性、與回焊中之焊接性及自動校準性為取捨之關係，而難以使該等一併提高。With the miniaturization and thinning of electronic equipment, package parts with solder balls (such as ball grid array package: BGA package) are used. In addition, for this type of BGA package, fine pitch is also required, but when the fine pitch BGA package is bonded to the mounting substrate, if only solder balls are used, there is a problem that the strength of the bonding portion is weak. Therefore, the joint part is usually reinforced by filling and hardening the underfill material between the BGA package and the mounting substrate. However, in order to fill and harden the underfill material, labor and time are required, and therefore there is a problem in terms of production cost. On the other hand, there is disclosed a method of pre-printing an adhesive containing a flux on the mounting substrate and mounting package parts on the printed part (refer to Document 1: Japanese Patent Laid-Open No. 4-280443). With the lead-free soldering in recent years, solder alloys with high melting points (for example, a melting point of 200°C or higher) have begun to be used. However, in the case of reflow soldering of solder bumps containing high melting point solder alloys by the method of using an adhesive described in Document 1, the solderability in reflow is impaired. Or the problem of automatic calibration. In addition, in the method of using an adhesive described in Document 1, the cured product of the adhesive remains on the mounting substrate. Therefore, the cured product of the adhesive requires insulation similarly to the material (solder resist, etc.) used for the mounting board. Furthermore, even if it is desired to improve the auto-calibration performance by reducing the curing rate of the epoxy resin, the insulation of the cured product of the adhesive becomes a problem. As described above, the insulation of the hardened material is a trade-off with the weldability and auto-calibration in reflow, and it is difficult to improve these at the same time.

因此，本發明之目的在於提供一種硬化物之絕緣性、以及回焊中之焊接性及自動校準性優異之熱固性助焊劑組合物、以及使用其之電子基板之製造方法。 為了解決上述問題，本發明提供如以下之熱固性助焊劑組合物及電子基板之製造方法。 即，本發明之熱固性助焊劑組合物之特徵在於：其係於藉由回流焊接使具有包含熔點為200℃以上且240℃以下之焊料合金的焊料凸塊之電子零件接合於電子基板之情形時所使用者，且含有(A)氧雜環丁烷化合物、與(B)活性劑，上述(A)成分含有(A1)於1分子中具有2個氧雜環丁烷環之二官能氧雜環丁烷化合物，上述(B)成分含有(B1)有機酸，且該熱固性助焊劑組合物於以5℃/min之升溫速度自溫度25℃升溫之情形時，於溫度200℃下之黏度為5 Pa・s以下，且於溫度250℃下之黏度為50 Pa・s以上。 關於本發明之熱固性助焊劑組合物，亦可進而含有(C)環氧樹脂。 關於本發明之熱固性助焊劑組合物，上述(A)成分亦可進而含有(A2)於1分子中具有1個氧雜環丁烷環之單官能氧雜環丁烷化合物。 關於本發明之熱固性助焊劑組合物，上述(B)成分較佳為選自由戊二酸、己二酸、庚二酸及辛二酸所組成之群中之至少1種。 關於本發明之熱固性助焊劑組合物，較佳為製作將包含錫96.5質量%、銀3.0質量%及銅0.5質量%之焊料合金且平均粒徑為30 μm之焊料粉末、與上述熱固性助焊劑組合物以質量比成為1：1之方式進行混合而成之焊料組合物，於將上述焊料組合物以5℃/min之升溫速度自溫度25℃升溫之情形時，溫度200℃下之黏度為5 Pa・s以下，且溫度250℃下之黏度為50 Pa・s以上。 本發明之電子基板之製造方法之特徵在於包括：塗佈步驟，其係於配線基板上塗佈上述熱固性助焊劑組合物；搭載步驟，其係將具有焊料凸塊之電子零件搭載於上述配線基板之接合用焊墊上；回焊步驟，其係藉由對搭載有上述電子零件之配線基板進行加熱，而使上述焊料凸塊熔融，從而將上述焊料凸塊接合於上述接合用焊墊；及熱硬化步驟，其係對上述熱固性助焊劑組合物進行加熱而使之硬化。 本發明之熱固性助焊劑組合物其硬化物之絕緣性、以及回焊中之焊接性及自動校準性優異之原因未必明確，但本發明人等推測如下。 即，本發明之熱固性助焊劑組合物係使用如於回焊步驟中熱固性助焊劑組合物之硬化不會那麼充分地進行之(A)氧雜環丁烷化合物。因此，熔融焊料之流動性不會受到熱固性助焊劑組合物之硬化物妨礙，故而能夠維持回焊中之焊接性或自動校準性。另一方面，本發明之熱固性助焊劑組合物由於能夠於回焊步驟後之熱硬化步驟中充分地硬化，故而可確保硬化物之絕緣性。本發明人等推測如此會達成上述本發明之效果。 根據本發明，可提供一種硬化物之絕緣性、以及回焊中之焊接性及自動校準性優異之熱固性助焊劑組合物、以及使用其之電子基板之製造方法。Therefore, the object of the present invention is to provide a thermosetting flux composition with excellent insulation properties of hardened materials, solderability and auto-calibration during reflow, and a method for manufacturing electronic substrates using the thermosetting flux composition. In order to solve the above-mentioned problems, the present invention provides the following thermosetting flux composition and a manufacturing method of an electronic substrate. That is, the thermosetting flux composition of the present invention is characterized in that it is used when an electronic component having solder bumps containing a solder alloy having a melting point of 200°C or more and 240°C or less is joined to an electronic substrate by reflow soldering The user, and contains (A) an oxetane compound, and (B) an active agent. The above component (A) contains (A1) a bifunctional oxetane with two oxetane rings in one molecule Cyclobutane compound, the above component (B) contains (B1) organic acid, and when the thermosetting flux composition is heated from a temperature of 25°C at a heating rate of 5°C/min, the viscosity at a temperature of 200°C is 5 Pa·s or less, and the viscosity at a temperature of 250°C is 50 Pa·s or more. The thermosetting flux composition of the present invention may further contain (C) epoxy resin. Regarding the thermosetting flux composition of the present invention, the above-mentioned (A) component may further contain (A2) a monofunctional oxetane compound having one oxetane ring in one molecule. Regarding the thermosetting flux composition of the present invention, the aforementioned component (B) is preferably at least one selected from the group consisting of glutaric acid, adipic acid, pimelic acid, and suberic acid. Regarding the thermosetting flux composition of the present invention, it is preferable to make a combination of solder powder containing 96.5 mass% tin, 3.0 mass% silver, and 0.5 mass% copper and an average particle diameter of 30 μm solder alloy with the above-mentioned thermosetting flux The solder composition is mixed in such a way that the mass ratio becomes 1:1. When the above solder composition is heated from a temperature of 25°C at a temperature increase rate of 5°C/min, the viscosity at a temperature of 200°C is 5 Pa·s or less, and the viscosity at a temperature of 250°C is 50 Pa·s or more. The method of manufacturing an electronic substrate of the present invention is characterized by including: a coating step of coating the above-mentioned thermosetting flux composition on a wiring substrate; and a mounting step of mounting electronic components with solder bumps on the wiring substrate On the bonding pad; the reflow step, which is by heating the wiring board on which the electronic components are mounted to melt the solder bumps, thereby bonding the solder bumps to the bonding pads; and heat The hardening step is to heat the above-mentioned thermosetting flux composition to harden it. The reason why the thermosetting flux composition of the present invention is excellent in the insulation of the hardened product, the weldability during reflow, and the auto-calibration is not necessarily clear, but the inventors of the present invention speculate as follows. That is, the thermosetting flux composition of the present invention uses (A) an oxetane compound in which the hardening of the thermosetting flux composition does not proceed sufficiently in the reflow step. Therefore, the fluidity of the molten solder will not be hindered by the hardened substance of the thermosetting flux composition, so the solderability or auto-calibration during reflow can be maintained. On the other hand, since the thermosetting flux composition of the present invention can be sufficiently hardened in the thermal hardening step after the reflow step, the insulation of the hardened product can be ensured. The inventors of the present invention speculate that the above-mentioned effects of the present invention can be achieved in this way. According to the present invention, it is possible to provide a thermosetting flux composition with excellent insulation properties of hardened materials, solderability and auto-calibration during reflow, and a method for manufacturing an electronic substrate using the same.

[熱固性助焊劑組合物] 首先，對本實施形態之熱固性助焊劑組合物進行說明。 本實施形態之熱固性助焊劑組合物係於藉由回流焊接使具有焊料凸塊之電子零件接合於電子基板之情形時所使用者，且具有以下所說明之(A)氧雜環丁烷化合物及(B)有機酸。 關於本實施形態之熱固性助焊劑組合物，必須於以5℃/min之升溫速度自溫度25℃升溫之情形時，於溫度200℃下之黏度為5 Pa・s以下，且於溫度250℃下之黏度為50 Pa・s以上。於溫度200℃下之黏度超過5 Pa・s之情形時，熱固性助焊劑組合物之硬化過度進行，而有礙熔融焊料之流動性，故而回焊中之焊接性或自動校準性降低。另一方面，於溫度250℃下之黏度未達50 Pa・s之情形時，熱固性助焊劑組合物之硬化性不充分，因此硬化物之絕緣性變得不充分。 此處，黏度可藉由流變計進行測定。具體而言，可使用流變計(HAAKE公司製造，商品名「MARS-III」)並藉由特定之條件測定黏度。 又，製作將包含錫96.5質量%、銀3.0質量%及銅0.5質量%之焊料合金且平均粒徑為30 μm之焊料粉末、與上述熱固性助焊劑組合物以質量比成為1：1之方式進行混合而成之焊料組合物，於將上述焊料組合物以5℃/min之升溫速度自溫度25℃升溫之情形時，較佳為溫度200℃下之黏度為5 Pa・s以下，且溫度250℃下之黏度為50 Pa・s以上。於滿足此種條件之情形時，可更確實地謀求硬化物之絕緣性、以及回焊中之焊接性及自動校準性之兼顧。 於使用熱固性助焊劑組合物進行回流焊接之情形時，熱固性助焊劑組合物係與焊料接觸。並且，焊料亦發揮作為熱固性助焊劑組合物之熱硬化觸媒之功能。因此，根據將熱固性助焊劑組合物與焊料粉末進行混合而成之焊料組合物之黏度變化，可更正確地界定進行回流焊接之情形時之熱固性助焊劑組合物之硬化溫度。 再者，作為將熱固性助焊劑組合物及焊料組合物於200℃及250℃下之黏度調整為上述範圍之方法，可列舉如以下之方法。 熱固性助焊劑組合物及焊料組合物於200℃及250℃下之黏度可藉由變更氧雜環丁烷化合物及有機酸等之種類，或併用氧雜環丁烷化合物與環氧樹脂，或使用硬化劑而進行調整。 [(A)成分] 作為本實施形態所使用之(A)氧雜環丁烷化合物，可適當使用公知之氧雜環丁烷化合物。又，該(A)成分必須含有(A1)於1分子中具有2個氧雜環丁烷環之二官能氧雜環丁烷化合物。 又，該(A)成分亦可含有(A2)於1分子中具有1個氧雜環丁烷環之單官能氧雜環丁烷化合物。藉由含有該(A2)成分，可提高熱固性助焊劑組合物之硬化溫度，而可調整熱固性助焊劑組合物之硬化溫度。 作為上述(A1)成分，可列舉：苯二甲基雙氧雜環丁烷(東亞合成公司製造之「OXT-121」)、3-乙基-3{[(3-乙基氧雜環丁烷-3-基)甲氧基]甲基}氧雜環丁烷(東亞合成公司製造之「OXT-221」)、及具有聯苯骨架之二官能氧雜環丁烷化合物(宇部興產公司製造之「ETERNACOLL OXBP」)等。 作為上述(A2)成分，可列舉：3-乙基-3-羥甲基氧雜環丁烷(東亞合成公司製造之「OXT-101」)、2-乙基己基氧雜環丁烷(東亞合成公司製造之「OXT-212」)、及3-乙基-3-(甲基丙烯醯氧基)甲基氧雜環丁烷(宇部興產公司製造之「ETERNACOLL OXMA」)等。 於併用上述(A1)成分及上述(A2)成分之情形時，上述(A1)成分相對於上述(A2)成分之質量比((A1)/(A2))較佳為1以上且50以下，更佳為3/2以上且30以下，尤佳為2以上且20以下。若質量比為上述範圍內，則可一面維持熱固性助焊劑組合物之硬化物之絕緣性，一面調整熱固性助焊劑組合物之硬化溫度。 上述(A)成分之調配量相對於熱固性助焊劑組合物之固形物成分總量，較佳為40質量%以上且95質量%以下，更佳為60質量%以上且92質量%以下，尤佳為70質量%以上且90質量%以下。若(A)成分之調配量為上述範圍內，則可確保充分之硬化性，而可充分地補強電子零件與電子基板之焊料接合。 [(B)成分] 關於本實施形態所使用之(B)活性劑，可列舉：有機酸、有機酸胺鹽、包含非解離性鹵化化合物之非解離型活性劑、及胺系活性劑等。該等活性劑可單獨使用1種，亦可混合2種以上使用。又，該(B)成分必須含有(B1)有機酸。於回焊步驟中，由於有機酸與氧雜環丁烷化合物之硬化反應不會那麼充分地進行，故而可將熱固性助焊劑組合物之硬化溫度調整至較佳之範圍。 作為上述(B1)成分，除單羧酸、二羧酸等以外，還可列舉其他有機酸。該等可單獨使用1種，亦可混合2種以上使用。 作為單羧酸，可列舉：甲酸、乙酸、丙酸、丁酸、戊酸、己酸、庚酸、癸酸、月桂酸、肉豆蔻酸、十五烷酸、棕櫚酸、珠光子酸、硬脂酸、結核菌硬脂酸(tuberculostearic acid)、花生酸、山萮酸、二十四碳酸、及乙醇酸等。 作為二羧酸，可列舉：草酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、富馬酸、馬來酸、酒石酸、及二甘醇酸等。該等中，就熱固性助焊劑組合物之硬化物之物性之觀點而言，較佳為戊二酸、己二酸、庚二酸、辛二酸。 作為其他有機酸，可列舉：二聚酸、乙醯丙酸、乳酸、丙烯酸、苯甲酸、水楊酸、大茴香酸、檸檬酸、及吡啶甲酸等。 作為上述(B1)成分之調配量，相對於熱固性助焊劑組合物之固形物成分總量，較佳為1質量%以上且15質量%以下，更佳為2質量%以上且12質量%以下，尤佳為3質量%以上且10質量%以下。若(B1)成分之調配量為上述下限以上，則可更確實地防止焊料接合之不良。又，若(B1)成分之調配量為上述上限以下，則可確保熱固性助焊劑組合物之絕緣性。 上述(B)成分亦可視需要含有上述(B1)成分以外之活性劑((B2)成分)。作為(B2)成分，可列舉有機酸胺鹽、包含非解離性鹵化化合物之非解離型活性劑、及胺系活性劑等。 上述有機酸胺鹽係上述(B1)成分之胺鹽。作為上述胺，可適當使用公知之胺。此種胺可為芳香族胺，亦可為脂肪族胺。該等可單獨使用1種，亦可混合2種以上使用。作為此種胺，就有機酸胺鹽之穩定性等觀點而言，較佳為使用碳數為3以上且13以下之胺，更佳為使用碳數為4以上且7以下之一級胺。 作為上述芳香族胺，可列舉：苄胺、苯胺、1,3-二苯胍等。該等中，尤佳為苄胺。 作為上述脂肪族胺，可列舉：丙基胺、丁基胺、戊基胺、己基胺、庚基胺、辛基胺、環己基胺、三乙醇胺等。 作為上述包含非解離性鹵化化合物之非解離型活性劑，可列舉藉由共價鍵結而鍵結有鹵素原子之非鹽系有機化合物。作為該鹵化化合物，可為如氯化物、溴化物、氟化物般藉由氯、溴、氟之各單獨元素之共價鍵之化合物，亦可為具有氯、溴及氟之任意2個或全部之各自之共價鍵的化合物。為了提高對於水性溶劑之溶解性，該等化合物例如較佳為如鹵化醇或鹵化羧酸般具有羥基或羧基等極性基。作為鹵化醇，例如可列舉：2,3-二溴丙醇、2,3-二溴丁二醇、反-2,3-二溴-2-丁烯-1,4-二醇、1,4-二溴-2-丁醇、及三溴新戊醇等溴化醇；1,3-二氯-2-丙醇、及1,4-二氯-2-丁醇等氯化醇；3-氟鄰苯二酚等氟化醇；以及類似該等之化合物。作為鹵化羧酸，可列舉：2-碘苯甲酸、3-碘苯甲酸、2-碘丙酸、5-碘水楊酸、及5-碘鄰胺苯甲酸等碘化羧酸；2-氯苯甲酸、及3-氯丙酸等氯化羧酸；2,3-二溴丙酸、2,3-二溴丁二酸、及2-溴苯甲酸等溴化羧酸；以及類似該等之化合物。 作為上述胺系活性劑，可列舉：胺類(乙二胺等聚胺等)、胺鹽類(乙基胺、二乙胺、三羥甲基胺、環己基胺、及二乙胺等胺或胺基醇等之有機酸鹽或無機酸鹽(鹽酸、硫酸、氫溴酸等))、胺基酸類(甘胺酸、丙胺酸、天冬胺酸、麩胺酸、及纈胺酸等)、及醯胺系化合物等。具體而言，可列舉：乙基胺氫溴酸鹽、二苯胍氫溴酸鹽、環己基胺氫溴酸鹽、二乙基胺鹽(鹽酸鹽、丁二酸鹽、己二酸鹽、及癸二酸鹽等)、三乙醇胺、單乙醇胺、及該等胺之氫溴酸鹽等。 作為上述(B)成分之調配量，相對於熱固性助焊劑組合物之固形物成分總量，較佳為1質量%以上且25質量%以下，更佳為2質量%以上且20質量%以下，尤佳為3質量%以上且15質量%以下。若(B)成分之調配量為上述下限以上，則可更確實地防止焊料接合之不良。又，若(B)成分之調配量為上述上限以下，則可確保熱固性助焊劑組合物之絕緣性。 本實施形態之熱固性助焊劑組合物亦可視需要，除上述(A)成分及上述(B)成分以外，進而含有選自由(C)環氧樹脂、(D)硬化劑及(E)觸變劑所組成之群中之至少1種。 [(C)成分] 作為本實施形態中所使用之(C)環氧樹脂，可適當使用公知之環氧樹脂。藉由該(C)成分，可提高硬化物之玻璃轉移點，或提高耐衝擊性。又，藉由該(C)成分，可調整熱固性助焊劑組合物之硬化溫度。 作為此種環氧樹脂，例如可列舉：雙酚A型、雙酚F型、聯苯型、萘型、甲酚酚醛清漆型、酚系酚醛清漆型等環氧樹脂。該等環氧樹脂可單獨使用1種，亦可混合2種以上使用。又，就硬化物之耐衝擊性之觀點而言，該等環氧樹脂較佳為經橡膠改性者。進而，該等環氧樹脂較佳為含有常溫下為液狀者，於使用常溫下為固體者之情形時，較佳為與常溫下為液狀者併用。 又，就提高硬化物之玻璃轉移點並提高耐衝擊性之觀點而言，上述(C)成分更佳為雙酚A型環氧樹脂、萘型環氧樹脂。 於使用上述(C)成分之情形時，其調配量相對於熱固性助焊劑組合物之固形物成分總量，較佳為1質量%以上且30質量%以下，更佳為2質量%以上且25質量%以下，尤佳為3質量%以上且20質量%以下。若(C)成分之調配量為上述範圍內，則不會使熱固性助焊劑組合物之硬化溫度變得過低而可提高熱固性助焊劑組合物之硬化物之強度。 又，就相同之觀點而言，上述(C)成分相對於上述(A)成分之質量比((C)/(A))較佳為1/20以上且1/2以下，更佳為1/15以上且1/3以下，尤佳為1/10以上且1/3以下。 [(D)成分] 作為本實施形態中所使用之(D)硬化劑，可適當使用公知之硬化劑。藉由該(D)成分，可調整熱固性助焊劑組合物之硬化溫度。作為該(D)成分，可列舉：咪唑系硬化劑、三聚氰胺類及雙氰胺類等。該等可單獨使用1種，亦可混合2種以上使用。 作為上述咪唑系硬化劑，可列舉：2-苯基-4-甲基-5-羥甲基咪唑、2-苯基-4,5-二羥甲基咪唑、2,4-二胺基-6-[2'-乙基-4'-甲基咪唑基-(1')]-乙基-對稱三𠯤、2,4-二胺基-6-[2'-甲基咪唑基-(1')]-乙基-對稱三𠯤、2,4-二胺基-6-[2'-甲基咪唑基-(1')]-乙基-對稱三𠯤異三聚氰酸加成物、1-氰乙基-2-苯基咪唑、1-氰乙基-2-苯基咪唑鎓三酸酯、1-氰乙基-2-十一烷基咪唑、及2,4-二胺基-6-[2'-十一烷基咪唑基-(1')]-乙基-對稱三𠯤。其中，較佳為使用2-苯基-4-甲基-5-羥甲基咪唑、2,4-二胺基-6-[2'-甲基咪唑基-(1')]-乙基-對稱三𠯤異三聚氰酸加成物、及1-氰乙基-2-苯基咪唑鎓偏苯三酸酯等。該等可單獨使用1種，亦可混合2種以上使用。 作為上述咪唑系硬化劑之市售品，可列舉：2P4MHZ、2PHZ-PW、2E4MZ-A、2MZ-A、2MA-OK、2PZ-CN、2PZCNS-PW、C11Z-CN、及C11Z-A(四國化成工業公司製造等，商品名)。 作為上述三聚氰胺類，可列舉：三聚氰胺、乙胍𠯤、及苯并胍胺等。 作為上述雙氰胺類，可列舉：雙氰胺、及N苯基雙氰胺等。 於使用上述(D)成分之情形時，其調配量相對於熱固性助焊劑組合物之固形物成分總量，較佳為0.1質量%以上且10質量%以下。更佳為0.2質量%以上且5質量%以下，尤佳為0.5質量%以上且3質量%以下。若(D)成分之調配量為上述下限以上，則可提高熱固性助焊劑組合物之硬化性。另一方面，若(D)成分之調配量為上述上限以下，則可確保熱固性助焊劑組合物之保存穩定性。 [(E)成分] 作為本實施形態中所使用之(E)觸變劑，可列舉：氫化蓖麻油、醯胺類、高嶺土、膠體氧化矽、有機膨潤土、及玻璃料等。該等觸變劑可單獨使用1種，亦可混合2種以上使用。 於使用上述(E)成分之情形時，其調配量相對於熱固性助焊劑組合物之固形物成分總量，較佳為0.1質量%以上且5質量%以下，更佳為0.5質量%以上且2質量%以下。若(E)成分之調配量為上述範圍內，則可將熱固性助焊劑組合物之觸變性調整至較佳之範圍。 [其他成分] 本實施形態之熱固性助焊劑組合物亦可視需要，除上述(A)成分～上述(E)成分以外，還含有界面活性劑、偶合劑、消泡劑、粉末表面處理劑、反應抑制劑、防沈澱劑、及填料等添加劑。作為該等添加劑之調配量，相對於熱固性助焊劑組合物之固形物成分總量，較佳為0.01質量%以上且10質量%以下，更佳為0.05質量%以上且5質量%以下。又，就塗佈性之調整等觀點而言，本實施形態之熱固性助焊劑組合物亦可含有溶劑。於使用溶劑之情形時，其調配量並無特別限制。 [熱固性助焊劑組合物之製造方法] 本實施形態之熱固性助焊劑組合物可藉由將上述(A)成分及上述(B)成分等以上述特定之比率進行調配並進行攪拌混合而製造。 [電子基板之製造方法] 其次，對本實施形態之電子基板之製造方法進行說明。再者，本實施形態之熱固性助焊劑組合物之使用方法並不限於本實施形態之電子基板之製造方法。 本實施形態之電子基板之製造方法係使用上述本實施形態之熱固性助焊劑組合物的方法，該方法包括以下所說明之塗佈步驟、搭載步驟、回焊步驟及熱硬化步驟。 於塗佈步驟中，於配線基板上塗佈上述熱固性助焊劑組合物。 作為配線基板，可列舉：印刷配線基板、設置有配線之矽基板等。 作為塗佈裝置，可列舉：旋轉塗佈機、噴霧塗佈機、棒式塗佈機、敷料器、分注器、及網版印刷機等。再者，於使用旋轉塗佈機、噴霧塗佈機等作為塗佈裝置之情形時，較佳為利用溶劑稀釋熱固性助焊劑組合物後使用。 作為溶劑，可列舉：酮類(甲基乙基酮及環己酮等)、芳香族烴類(甲苯及二甲苯等)、醇類(甲醇、異丙醇及環己醇等)、脂環烴類(環己烷及甲基環己烷等)、石油系溶劑類(石油醚及石腦油等)、溶纖劑類(溶纖劑及丁基溶纖劑等)、卡必醇類(卡必醇及丁基卡必醇等)、以及酯類(例如乙酸乙酯、乙酸丁酯、乙酸溶纖劑、丁基溶纖劑乙酸酯、卡必醇乙酸酯、丁基卡必醇乙酸酯、二乙二醇乙醚乙酸酯、二乙二醇單甲醚乙酸酯、及二乙二醇單乙醚乙酸酯等)等。該等可單獨使用1種，亦可混合2種以上使用。 塗佈膜之厚度(塗佈膜厚)可適當設定。 於搭載步驟中，將具有焊料凸塊之電子零件搭載於上述配線基板之接合用焊墊上。 作為具有焊料凸塊之電子零件，例如可列舉：BGA封裝、及晶方尺寸封裝等。 焊料凸塊包含熔點為200℃以上且240℃以下之焊料合金。再者，焊料凸塊亦可為其表面經焊料合金鍍覆者。作為熔點為200℃以上且240℃以下之焊料合金，可列舉Sn-Ag-Cu系、及Sn-Ag系等焊料合金。 作為搭載步驟中所用之裝置，可適當使用公知之晶片安裝裝置。 又，作為接合用焊墊之材質，可適當使用公知之導電性材料(銅、銀等)。 於回焊步驟中，藉由對搭載有上述電子零件之配線基板進行加熱，而使上述焊料凸塊熔融，從而將上述焊料凸塊接合於上述接合用焊墊。 作為此處所使用之裝置，可適當使用公知之回焊爐。 回焊條件只要視焊料之熔點適當設定即可。例如於使用Sn-Ag-Cu系焊料合金之情形時，只要於溫度150～180℃下進行60～120秒鐘預熱，並將峰值溫度設為220～260℃即可。 於熱硬化步驟中，對上述熱固性助焊劑組合物進行加熱而使之硬化。 作為加熱條件，加熱溫度較佳為150℃以上且220℃以下，更佳為180℃以上且200℃以下。若加熱溫度為上述範圍內，則可使熱固性助焊劑組合物充分地硬化，且對搭載於電子基板之電子零件之不良影響亦較少。 加熱時間較佳為10分鐘以上且3小時以下，更佳為30分鐘以上且90分鐘以下。若加熱時間為上述範圍內，則可使熱固性助焊劑組合物充分地硬化，且對搭載於電子基板之電子零件之不良影響亦較少。 根據如以上之電子基板之製造方法，可藉由熱固性助焊劑組合物之硬化物而補強利用焊料凸塊之接合部。 再者，本實施形態之電子基板之製造方法並不限定於上述實施形態，於本發明中包括於可達成本發明之目的之範圍內之變化、改良等。實施例 繼而，藉由實施例及比較例對本發明進一步詳細地進行說明，但本發明並不受該等例任何限定，再者，將實施例及比較例中所使用之材料示於以下。 ((A1)成分) 二官能氧雜環丁烷化合物A：商品名「ETERNACOLL OXBP」，宇部興產公司製造 二官能氧雜環丁烷化合物B：商品名「ARON OXETANE OXT-121」，東亞合成公司製造 二官能氧雜環丁烷化合物C：商品名「ARON OXETANE OXT-221」，東亞合成公司製造 ((A2)成分) 單官能氧雜環丁烷化合物A：商品名「ETERNACOLL OXMA」，宇部興產公司製造 單官能氧雜環丁烷化合物B：商品名「ARON OXETANE OXT-212」，東亞合成公司製造 ((B1)成分) 活性劑A：己二酸 ((B2)成分) 活性劑B：苄胺己二酸鹽 ((C)成分) 環氧樹脂A：雙酚A型環氧樹脂，商品名「EPICLON EXA-850CRP」，DIC公司製造 環氧樹脂B：萘型環氧樹脂，商品名「EPICLON HP-4032D」，DIC公司製造 ((D)成分) 硬化劑A：2-苯基-4-甲基-5-羥甲基咪唑，商品名「2P4MHZ」，四國化成工業公司製造 硬化劑B：乙胍𠯤 硬化劑C：N苯基雙氰胺 ((E)成分) 觸變劑：商品名「GEL ALL D」，新日本理化公司製造 [實施例1] 將二官能氧雜環丁烷化合物A 80質量份、環氧樹脂A 10質量份、活性劑A 5質量份及活性劑B 5質量份投入容器中，利用粉碎混合機進行粉碎混合而使該等分散，從而獲得熱固性助焊劑組合物。 又，相對於所獲得之熱固性助焊劑組合物100質量份，加入溶劑(丙二醇單甲醚乙酸酯)10質量份，而製備旋轉塗佈機用塗佈液。 其次，準備能夠搭載晶片零件之基板，藉由網版印刷法將焊膏(Tamura製作所公司製造，SAC系焊膏)塗佈於該基板之電極上，進行回焊處理，而形成焊料凸塊，其後進行清洗。 然後，使用旋轉塗佈機將旋轉塗佈機用塗佈液塗佈至所獲得之基板上。塗佈膜之塗佈膜厚為30 μm。其次，將晶片零件(1005晶片，焊料合金：Sn-Ag3.0-Cu0.5，焊料之熔點：217℃～220℃)搭載於塗膜形成後之基板之接合用焊墊上，通過回焊爐(Tamura製作所公司製造)以加熱。此處之回焊條件係預熱溫度為150～180℃(60秒鐘)，溫度220℃以上之時間為50秒鐘，峰值溫度為230℃。其後，將回焊後之基板投入加熱爐中，於溫度200℃下實施1小時之加熱處理，而製作冷熱循環試驗用基板。 [實施例2～5及比較例1～3] 依據表1所示之組成調配各材料，除此以外，以與實施例1相同之方式獲得熱固性助焊劑組合物及旋轉塗佈機用塗佈液。 再者，關於實施例5，依據表1所示之組成調配各材料，除此以外，以與實施例1相同之方式製作冷熱循環試驗用基板。 ＜熱固性助焊劑組合物之評價＞ 藉由如以下之方法進行熱固性助焊劑組合物之評價(熱固性助焊劑組合物於200℃及250℃下之黏度、焊料組合物於200℃及250℃下之黏度、焊料熔融性、絕緣性、冷熱循環試驗)。將所獲得之結果示於表1。 (1)熱固性助焊劑組合物之黏度 使用流變計(HAAKE公司製造，商品名「MARS-III」)，一面以5℃/min之升溫速度自溫度25℃升溫至焊料之熔點，一面測定熱固性助焊劑組合物之黏度。自所獲得之結果求出(i)溫度200℃下之黏度、及(ii)溫度250℃下之黏度。然後，對於黏度，依據下述基準進行劃分。 A：黏度為5 Pa・s以下。 B：黏度超過5 Pa・s且未達50 Pa・s。 C：黏度為50 Pa・s以上。 (2)焊料組合物之黏度 將熱固性助焊劑組合物50質量%、與焊料粉末(焊料合金：Sn-Ag3.0-Cu0.5，平均粒徑：20 μm，粒徑分佈：10～40 μm)50質量%進行混合，而獲得焊料組合物。藉由與上述(1)熱固性助焊劑組合物之黏度相同之方法對所獲得之焊料組合物於200℃及250℃下之黏度進行測定。然後，對於黏度，依據下述基準進行劃分。 A：黏度為5 Pa・s以下。 B：黏度超過5 Pa・s且未達50 Pa・s。 C：黏度為50 Pa・s以上。 (3)焊料熔融性 將熱固性助焊劑組合物50質量%、與焊料粉末(焊料合金：Sn-Ag3.0-Cu0.5，平均粒徑：20 μm，粒徑分佈：10～40 μm)50質量%進行混合，而獲得焊料組合物。藉由網版印刷法將所獲得之焊料組合物於基板(表面之材質：銅)上形成為直徑1 cm、厚度50 μm之塗膜，於設定為溫度250℃之加熱板上加熱30秒鐘。然後，利用目視觀察焊料之熔融狀態，依據下述基準評價焊料熔融性。 A：焊料已熔融。 B：焊料未熔融。 (4)絕緣性 將熱固性助焊劑組合物50質量%、與焊料粉末(焊料合金：Sn-Ag3.0-Cu0.5，平均粒徑：20 μm，粒徑分佈：10～40 μm)50質量%進行混合，而獲得焊料組合物。 對於所獲得之焊料組合物，依據JIS Z3284-1及JIS Z3197之8.5.3中所記載之絕緣電阻試驗測定絕緣電阻值。即，於梳狀電極基板(導體寬度：0.318 mm，導體間隔：0.318 mm，大小：30 mm×30 mm)上使用金屬遮罩(與梳狀電極圖案匹配並加工成狹縫狀者，厚度：100 μm)印刷焊料組合物。其後，於將預熱150℃設為60秒鐘，將溫度250℃下之熔融時間設為30秒鐘之條件下進行回焊，而製作試驗基板。將該試驗基板投入設定為溫度85℃、相對濕度95%之高溫高濕試驗機中，測定500小時後之絕緣電阻值。然後，依據下述基準評價絕緣性。 A：絕緣電阻值為1.0×109 以上。 B：絕緣電阻值未達1.0×109 。 (5)冷熱循環試驗 將冷熱循環試驗用基板投入冷熱循環試驗機中，進行如下冷熱循環試驗(依據車輛用焊膏之冷熱循環試驗)，即以於在溫度-40℃下放置10分鐘後在溫度125℃下放置10分鐘作為1個循環，將其反覆進行2000個循環。利用顯微鏡觀察冷熱循環試驗後之基板，確認晶片零件中有無焊料龜裂，依據下述基準評價對冷熱循環試驗之耐受性。 A：產生焊料龜裂之部位未達50%。 B：產生焊料龜裂之部位為50%以上且未達90%。 C：產生焊料龜裂之部位為90%以上。 [表1]

Figure 106132755-A0304-0001
自表1所示之結果可明確地確認到如下情況：於使用本發明之熱固性助焊劑組合物之情形時(實施例1～5)，焊料熔融性及絕緣性良好。又，確認到由於焊料熔融性良好，故而回焊中之焊接性及自動校準性優異。 相對於此，可知於使用不含有(A1)成分或(B1)成分之熱固性助焊劑組合物之情形時(比較例1～3)，焊料熔融性及絕緣性之至少一者不充分。[Thermosetting flux composition] First, the thermosetting flux composition of this embodiment will be described. The thermosetting flux composition of this embodiment is used when electronic parts with solder bumps are joined to an electronic substrate by reflow soldering, and has the (A) oxetane compound described below and (B) Organic acids. Regarding the thermosetting flux composition of this embodiment, when the temperature rises from 25°C at a temperature rise rate of 5°C/min, the viscosity at 200°C is 5 Pa·s or less and the temperature is 250°C. The viscosity is above 50 Pa·s. When the viscosity at a temperature of 200°C exceeds 5 Pa·s, the hardening of the thermosetting flux composition proceeds excessively, which hinders the fluidity of the molten solder, and therefore the solderability or auto-calibration during reflow is reduced. On the other hand, when the viscosity at a temperature of 250°C is less than 50 Pa·s, the curability of the thermosetting flux composition is insufficient, and therefore the insulation of the cured product becomes insufficient. Here, the viscosity can be measured with a rheometer. Specifically, a rheometer (manufactured by HAAKE, trade name "MARS-III") can be used to measure the viscosity under specific conditions. In addition, a solder alloy containing 96.5 mass% of tin, 3.0 mass% of silver, and 0.5 mass% of copper, and solder powder with an average particle diameter of 30 μm, and the thermosetting flux composition described above were produced so that the mass ratio becomes 1:1 When the solder composition is heated from a temperature of 25°C at a temperature increase rate of 5°C/min, the mixed solder composition preferably has a viscosity of 5 Pa·s or less at a temperature of 200°C and a temperature of 250 The viscosity at ℃ is above 50 Pa·s. When these conditions are met, it is possible to more reliably achieve the insulation of the hardened material, as well as the weldability and auto-calibration during reflow. When the thermosetting flux composition is used for reflow soldering, the thermosetting flux composition is in contact with the solder. In addition, the solder also functions as a thermosetting catalyst for the thermosetting flux composition. Therefore, according to the viscosity change of the solder composition obtained by mixing the thermosetting flux composition and the solder powder, the hardening temperature of the thermosetting flux composition in the case of reflow soldering can be defined more accurately. Furthermore, as a method of adjusting the viscosity of the thermosetting flux composition and the solder composition at 200°C and 250°C to the above-mentioned range, the following methods can be cited. The viscosity of thermosetting flux composition and solder composition at 200°C and 250°C can be changed by changing the types of oxetane compounds and organic acids, or using oxetane compounds and epoxy resin in combination, or using The hardener is adjusted. [(A) Component] As the (A) oxetane compound used in this embodiment, a known oxetane compound can be suitably used. Moreover, this (A) component must contain (A1) the bifunctional oxetane compound which has 2 oxetane rings in 1 molecule. Moreover, this (A) component may contain (A2) the monofunctional oxetane compound which has 1 oxetane ring in 1 molecule. By containing the component (A2), the curing temperature of the thermosetting flux composition can be increased, and the curing temperature of the thermosetting flux composition can be adjusted. Examples of the above (A1) component include: xylylene dioxetane ("OXT-121" manufactured by Toagosei Co., Ltd.), 3-ethyl-3{[(3-ethyloxetane Alk-3-yl)methoxy)methyl)oxetane ("OXT-221" manufactured by Toagosei Co., Ltd.), and a bifunctional oxetane compound with a biphenyl skeleton (Ube Kosan Co., Ltd.) Manufactured "ETERNACOLL OXBP") etc. Examples of the above-mentioned (A2) component include: 3-ethyl-3-hydroxymethyloxetane ("OXT-101" manufactured by Toagosei Co., Ltd.), 2-ethylhexyloxetane (toa "OXT-212" manufactured by Synthetic Co., Ltd.), and 3-ethyl-3-(methacryloxy) methyloxetane ("ETERNACOLL OXMA" manufactured by Ube Industries Co., Ltd.), etc. When the above-mentioned (A1) component and the above-mentioned (A2) component are used in combination, the mass ratio of the above-mentioned (A1) component to the above-mentioned (A2) component ((A1)/(A2)) is preferably 1 or more and 50 or less, It is more preferably 3/2 or more and 30 or less, and particularly preferably 2 or more and 20 or less. If the mass ratio is within the above range, the curing temperature of the thermosetting flux composition can be adjusted while maintaining the insulation of the cured product of the thermosetting flux composition. The blending amount of the above-mentioned (A) component relative to the total solid content of the thermosetting flux composition is preferably 40% by mass or more and 95% by mass or less, more preferably 60% by mass or more and 92% by mass or less, especially It is 70% by mass or more and 90% by mass or less. If the blending amount of the component (A) is within the above range, sufficient hardenability can be ensured, and the solder joint between the electronic component and the electronic substrate can be sufficiently strengthened. [(B) Component] The (B) activating agent used in this embodiment includes organic acids, organic acid amine salts, non-dissociating activating agents containing non-dissociating halogenated compounds, and amine activating agents. These active agents may be used individually by 1 type, and may mix and use 2 or more types. Moreover, this (B) component must contain (B1) organic acid. In the reflow step, since the hardening reaction of the organic acid and the oxetane compound does not proceed so fully, the hardening temperature of the thermosetting flux composition can be adjusted to a preferable range. As said (B1) component, other organic acids may be mentioned besides a monocarboxylic acid, a dicarboxylic acid, etc.. These may be used individually by 1 type, and may mix and use 2 or more types. Examples of monocarboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, pearlic acid, hard Fatty acid, tuberculostearic acid, arachidic acid, behenic acid, tetracosic acid, glycolic acid, etc. Examples of dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, Tartaric acid, and diglycolic acid, etc. Among them, from the viewpoint of the physical properties of the cured product of the thermosetting flux composition, glutaric acid, adipic acid, pimelic acid, and suberic acid are preferred. Examples of other organic acids include dimer acid, acetyl propionic acid, lactic acid, acrylic acid, benzoic acid, salicylic acid, anisic acid, citric acid, picolinic acid, and the like. The blending amount of the above-mentioned (B1) component is preferably 1% by mass or more and 15% by mass or less, more preferably 2% by mass and 12% by mass relative to the total solid content of the thermosetting flux composition, Particularly preferably, it is 3% by mass or more and 10% by mass or less. If the blending amount of the component (B1) is more than the above lower limit, it is possible to more reliably prevent solder joint defects. In addition, if the blending amount of the component (B1) is equal to or less than the above upper limit, the insulation of the thermosetting flux composition can be ensured. The above-mentioned (B) component may optionally contain an active agent ((B2) component) other than the above-mentioned (B1) component. (B2) Components include organic acid amine salts, non-dissociative activating agents containing non-dissociable halogenated compounds, and amine activating agents. The said organic acid amine salt is the amine salt of the said (B1) component. As the above-mentioned amine, a well-known amine can be suitably used. Such amines may be aromatic amines or aliphatic amines. These may be used individually by 1 type, and may mix and use 2 or more types. As such an amine, it is preferable to use an amine having a carbon number of 3 or more and 13 or less from the viewpoint of the stability of the amine salt of an organic acid, and more preferably an amine having a carbon number of 4 or more and 7 or less. As said aromatic amine, benzylamine, aniline, 1, 3- diphenylguanidine, etc. are mentioned. Among them, benzylamine is particularly preferred. As said aliphatic amine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, cyclohexylamine, triethanolamine, etc. are mentioned. Examples of the non-dissociable active agent containing the non-dissociable halogenated compound include non-salt-based organic compounds to which a halogen atom is bonded by covalent bonding. As the halogenated compound, it may be a compound that is covalently bonded to each individual element of chlorine, bromine, and fluorine, such as chloride, bromide, and fluoride, or may have any two or all of chlorine, bromine, and fluorine. The respective covalent bond compounds. In order to improve the solubility in aqueous solvents, these compounds preferably have polar groups such as hydroxyl or carboxyl groups like halogenated alcohols or halogenated carboxylic acids, for example. Examples of halogenated alcohols include 2,3-dibromopropanol, 2,3-dibromobutanediol, trans-2,3-dibromo-2-butene-1,4-diol, 1, Brominated alcohols such as 4-dibromo-2-butanol and tribromonepentanol; 1,3-dichloro-2-propanol, and chlorinated alcohols such as 1,4-dichloro-2-butanol; Fluorinated alcohols such as 3-fluorocatechol; and similar compounds. Examples of halogenated carboxylic acids include iodinated carboxylic acids such as 2-iodobenzoic acid, 3-iodobenzoic acid, 2-iodopropionic acid, 5-iodosalicylic acid, and 5-iodoanthranilic acid; 2-chloro Chlorinated carboxylic acids such as benzoic acid and 3-chloropropionic acid; brominated carboxylic acids such as 2,3-dibromopropionic acid, 2,3-dibromosuccinic acid, and 2-bromobenzoic acid; and similar The compound. Examples of the above-mentioned amine-based active agents include amines (polyamines such as ethylenediamine, etc.), amine salts (ethylamine, diethylamine, trimethylolamine, cyclohexylamine, and amines such as diethylamine) Or organic or inorganic acid salts of amino alcohols (hydrochloric acid, sulfuric acid, hydrobromic acid, etc.), amino acids (glycine, alanine, aspartic acid, glutamine, and valine, etc.) ), and amide-based compounds. Specifically, examples include: ethylamine hydrobromide, diphenylguanidine hydrobromide, cyclohexylamine hydrobromide, diethylamine salt (hydrochloride, succinate, adipate , And sebacate, etc.), triethanolamine, monoethanolamine, and the hydrobromide of these amines, etc. The blending amount of the above-mentioned (B) component is preferably 1% by mass or more and 25% by mass or less, more preferably 2% by mass or more and 20% by mass, relative to the total solid content of the thermosetting flux composition, Particularly preferably, it is 3% by mass or more and 15% by mass or less. If the blending amount of the component (B) is more than the above lower limit, it is possible to more reliably prevent solder joint defects. Moreover, if the compounding amount of (B) component is below the said upper limit, the insulation of a thermosetting flux composition can be ensured. The thermosetting flux composition of this embodiment can also optionally contain (C) epoxy resin, (D) hardener and (E) thixotropic agent in addition to the above (A) component and the above (B) component, if necessary At least one of the group consisting of. [(C) Component] As the (C) epoxy resin used in this embodiment, a known epoxy resin can be suitably used. The (C) component can increase the glass transition point of the cured product or improve the impact resistance. In addition, by the component (C), the curing temperature of the thermosetting flux composition can be adjusted. Examples of such epoxy resins include epoxy resins such as bisphenol A type, bisphenol F type, biphenyl type, naphthalene type, cresol novolak type, and phenol novolak type. These epoxy resins may be used individually by 1 type, and may mix and use 2 or more types. In addition, from the viewpoint of the impact resistance of the hardened material, the epoxy resins are preferably rubber-modified. Furthermore, these epoxy resins preferably contain those that are liquid at room temperature, and when using those that are solid at room temperature, they are preferably used in combination with those that are liquid at room temperature. In addition, from the viewpoint of increasing the glass transition point of the cured product and improving the impact resistance, the component (C) is more preferably a bisphenol A epoxy resin or a naphthalene epoxy resin. In the case of using the above-mentioned (C) component, the blending amount relative to the total solid content of the thermosetting flux composition is preferably 1% by mass or more and 30% by mass or less, more preferably 2% by mass or more and 25% % By mass or less, more preferably 3% by mass or more and 20% by mass or less. If the blending amount of the component (C) is within the above range, the curing temperature of the thermosetting flux composition will not be too low, and the strength of the cured product of the thermosetting flux composition can be improved. In addition, from the same viewpoint, the mass ratio ((C)/(A)) of the component (C) to the component (A) is preferably 1/20 or more and 1/2 or less, more preferably 1 /15 or more and 1/3 or less, more preferably 1/10 or more and 1/3 or less. [(D) Component] As the (D) curing agent used in this embodiment, a known curing agent can be suitably used. With the component (D), the curing temperature of the thermosetting flux composition can be adjusted. Examples of the (D) component include imidazole-based hardeners, melamines, and dicyandiamides. These may be used individually by 1 type, and may mix and use 2 or more types. Examples of the imidazole-based curing agent include 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dimethylolimidazole, and 2,4-diamino- 6-[2'-Ethyl-4'-Methylimidazolyl-(1')]-Ethyl-Symmetric Tris, 2,4-Diamino-6-[2'-Methylimidazolyl-( 1')]-Ethyl-Symmetric Tris, 2,4-Diamino-6-[2'-Methylimidazolyl-(1')]-Ethyl-Symmetric Tris-Isocyanuric Acid Addition Compounds, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium triester, 1-cyanoethyl-2-undecylimidazole, and 2,4-di Amino-6-[2'-undecylimidazolyl-(1')]-ethyl-symmetric tris. Among them, it is preferable to use 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl -Symmetric triisocyanuric acid adducts, and 1-cyanoethyl-2-phenylimidazolium trimellitate, etc. These may be used individually by 1 type, and may mix and use 2 or more types. Commercial products of the above-mentioned imidazole-based hardeners include: 2P4MHZ, 2PHZ-PW, 2E4MZ-A, 2MZ-A, 2MA-OK, 2PZ-CN, 2PZCNS-PW, C11Z-CN, and C11Z-A (four Manufactured by Guohuacheng Industrial Co., Ltd., trade name). Examples of the above-mentioned melamines include melamine, betaguanidine, benzoguanamine, and the like. As said dicyandiamides, dicyandiamide, N-phenyl dicyandiamide, etc. are mentioned. In the case of using the above-mentioned (D) component, its blending amount is preferably 0.1% by mass or more and 10% by mass or less relative to the total solid content of the thermosetting flux composition. It is more preferably 0.2% by mass or more and 5% by mass or less, and particularly preferably 0.5% by mass or more and 3% by mass or less. If the blending amount of the component (D) is more than the above lower limit, the hardenability of the thermosetting flux composition can be improved. On the other hand, if the blending amount of the component (D) is equal to or less than the above upper limit, the storage stability of the thermosetting flux composition can be ensured. [(E) Component] Examples of the (E) thixotropic agent used in this embodiment include hydrogenated castor oil, amides, kaolin, colloidal silica, organic bentonite, and glass frit. These thixotropic agents may be used alone or in combination of two or more kinds. In the case of using the above-mentioned (E) component, the blending amount is preferably 0.1% by mass or more and 5% by mass or less, and more preferably 0.5% by mass or more and 2 Less than mass%. If the blending amount of the (E) component is within the above range, the thixotropy of the thermosetting flux composition can be adjusted to a preferable range. [Other components] The thermosetting flux composition of this embodiment may optionally also contain a surfactant, a coupling agent, a defoamer, a powder surface treatment agent, and a reaction in addition to the above (A) to (E) components. Additives such as inhibitors, anti-settling agents, and fillers. The blending amount of these additives is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.05% by mass or more and 5% by mass relative to the total solid content of the thermosetting flux composition. Moreover, the thermosetting flux composition of the present embodiment may contain a solvent from the viewpoint of adjustment of coatability and the like. In the case of using a solvent, there is no particular restriction on its blending amount. [The production method of the thermosetting flux composition] The thermosetting flux composition of the present embodiment can be produced by mixing the above-mentioned (A) component and the above-mentioned (B) component in the above-mentioned specific ratio, and stirring and mixing. [Method of Manufacturing Electronic Substrate] Next, a method of manufacturing the electronic substrate of this embodiment will be described. Furthermore, the method of using the thermosetting flux composition of this embodiment is not limited to the method of manufacturing an electronic substrate of this embodiment. The manufacturing method of the electronic substrate of this embodiment is a method using the thermosetting flux composition of this embodiment described above, and the method includes the coating step, the mounting step, the reflow step, and the thermal hardening step described below. In the coating step, the above-mentioned thermosetting flux composition is coated on the wiring board. As the wiring board, a printed wiring board, a silicon substrate provided with wiring, etc. may be mentioned. Examples of coating devices include spin coaters, spray coaters, bar coaters, applicators, dispensers, and screen printers. Furthermore, when a spin coater, spray coater, etc. are used as the coating device, it is preferable to dilute the thermosetting flux composition with a solvent and use it. Examples of solvents include ketones (methyl ethyl ketone, cyclohexanone, etc.), aromatic hydrocarbons (toluene, xylene, etc.), alcohols (methanol, isopropanol, cyclohexanol, etc.), alicyclics Hydrocarbons (cyclohexane and methylcyclohexane, etc.), petroleum solvents (petroleum ether and naphtha, etc.), cellosolves (cellosolve and butyl cellosolve, etc.), carbitols (card Alcohol and butyl carbitol, etc.), and esters (e.g. ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate Ester, diethylene glycol ethyl ether acetate, diethylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate, etc.). These may be used individually by 1 type, and may mix and use 2 or more types. The thickness of the coating film (coating film thickness) can be appropriately set. In the mounting step, electronic components with solder bumps are mounted on the bonding pads of the wiring board. Examples of electronic components having solder bumps include BGA packages and square size packages. The solder bump includes a solder alloy with a melting point of 200°C or higher and 240°C or lower. Furthermore, the solder bumps can also be those whose surfaces are plated with solder alloys. Examples of solder alloys having a melting point of 200°C or higher and 240°C or lower include Sn-Ag-Cu-based solder alloys and Sn-Ag-based solder alloys. As the device used in the mounting step, a well-known chip mounting device can be suitably used. In addition, as the material of the bonding pad, a known conductive material (copper, silver, etc.) can be suitably used. In the reflow step, the solder bumps are melted by heating the wiring board on which the electronic components are mounted, thereby joining the solder bumps to the bonding pads. As the device used here, a well-known reflow furnace can be suitably used. The reflow conditions only need to be set appropriately depending on the melting point of the solder. For example, when a Sn-Ag-Cu-based solder alloy is used, it is only necessary to preheat for 60 to 120 seconds at a temperature of 150 to 180°C, and set the peak temperature to 220 to 260°C. In the thermal hardening step, the above-mentioned thermosetting flux composition is heated to harden it. As heating conditions, the heating temperature is preferably 150°C or higher and 220°C or lower, more preferably 180°C or higher and 200°C or lower. If the heating temperature is within the above range, the thermosetting flux composition can be sufficiently hardened, and the adverse effects on the electronic parts mounted on the electronic substrate are also less. The heating time is preferably 10 minutes or more and 3 hours or less, more preferably 30 minutes or more and 90 minutes or less. If the heating time is within the above range, the thermosetting flux composition can be sufficiently hardened, and there will be less adverse effects on the electronic parts mounted on the electronic substrate. According to the method of manufacturing an electronic substrate as described above, the joint portion using the solder bump can be reinforced by the hardened product of the thermosetting flux composition. Furthermore, the manufacturing method of the electronic substrate of the present embodiment is not limited to the above-mentioned embodiment, and the present invention includes changes, improvements, etc. within the scope of achieving the purpose of the present invention. Examples Next, the present invention will be described in further detail with examples and comparative examples, but the present invention is not limited by these examples at all. Furthermore, the materials used in the examples and comparative examples are shown below. (Component (A1)) Difunctional oxetane compound A: Trade name "ETERNACOLL OXBP", manufactured by Ube Industries Co., Ltd. Difunctional oxetane compound B: Trade name "ARON OXETANE OXT-121", East Asia Synthetic Company-manufactured difunctional oxetane compound C: brand name "ARON OXETANE OXT-221", manufactured by Toagosei Co., Ltd. ((A2) component) Monofunctional oxetane compound A: brand name "ETERNACOLL OXMA", Ube Monofunctional oxetane compound B manufactured by Kosan Co., Ltd.: brand name "ARON OXETANE OXT-212", manufactured by Toagosei Co., Ltd. ((B1) component) Active agent A: Adipic acid ((B2) component) Active agent B : Benzylamine adipate (component (C)) Epoxy resin A: Bisphenol A type epoxy resin, trade name "EPICLON EXA-850CRP", manufactured by DIC Corporation Epoxy resin B: Naphthalene type epoxy resin, product Name "EPICLON HP-4032D", manufactured by DIC Corporation ((D) component) Hardener A: 2-Phenyl-4-methyl-5-hydroxymethylimidazole, trade name "2P4MHZ", manufactured by Shikoku Kasei Kogyo Co., Ltd. Hardener B: Betaguanidine Hardener C: N-phenyldicyandiamide ((E) component) Thixotropic agent: Brand name "GEL ALL D", manufactured by Nippon Rika Co., Ltd. [Example 1] Difunctional oxygen was added 80 parts by mass of cyclobutane compound A, 10 parts by mass of epoxy resin A, 5 parts by mass of active agent A, and 5 parts by mass of active agent B are put into the container, and the pulverizing mixer is used for pulverization and mixing to disperse these to obtain thermosetting properties. Flux composition. Moreover, 10 mass parts of solvents (propylene glycol monomethyl ether acetate) were added with respect to 100 mass parts of the obtained thermosetting flux composition, and the coating liquid for spin coaters was prepared. Next, prepare a substrate capable of mounting chip components, apply solder paste (manufactured by Tamura Manufacturing Co., Ltd., SAC-based solder paste) on the electrodes of the substrate by screen printing, and perform reflow processing to form solder bumps. Cleaning is then carried out. Then, a spin coater is used to coat the coating liquid for a spin coater on the obtained substrate. The coating film thickness of the coating film is 30 μm. Next, the chip parts (1005 chip, solder alloy: Sn-Ag3.0-Cu0.5, solder melting point: 217°C to 220°C) are mounted on the bonding pads of the substrate after the coating film is formed, and pass through the reflow furnace (Manufactured by Tamura Manufacturing Co., Ltd.) for heating. The reflow conditions here are that the preheating temperature is 150-180°C (60 seconds), the time when the temperature is above 220°C is 50 seconds, and the peak temperature is 230°C. After that, the reflowed substrate was put into a heating furnace, and a heating treatment was performed at a temperature of 200° C. for 1 hour to produce a substrate for a cold-heat cycle test. [Examples 2 to 5 and Comparative Examples 1 to 3] The materials were prepared according to the composition shown in Table 1, except that the thermosetting flux composition and spin coater coating were obtained in the same manner as in Example 1 liquid. Furthermore, regarding Example 5, each material was prepared according to the composition shown in Table 1, and except for that, the same method as Example 1 was carried out to produce a substrate for the cold and heat cycle test. <Evaluation of the thermosetting flux composition> The evaluation of the thermosetting flux composition was carried out by the following method (the viscosity of the thermosetting flux composition at 200°C and 250°C, the solder composition at 200°C and 250°C Viscosity, solder fusion, insulation, thermal cycle test). The results obtained are shown in Table 1. (1) The viscosity of the thermosetting flux composition was measured using a rheometer (manufactured by HAAKE, trade name "MARS-III"), while the temperature was raised from 25°C to the melting point of the solder at a heating rate of 5°C/min. The viscosity of the flux composition. Calculate (i) the viscosity at a temperature of 200°C, and (ii) the viscosity at a temperature of 250°C from the obtained results. Then, the viscosity is divided according to the following criteria. A: The viscosity is less than 5 Pa·s. B: The viscosity exceeds 5 Pa·s and does not reach 50 Pa·s. C: The viscosity is 50 Pa·s or more. (2) The viscosity of the solder composition is 50% by mass of the thermosetting flux composition and the solder powder (solder alloy: Sn-Ag3.0-Cu0.5, average particle size: 20 μm, particle size distribution: 10-40 μm ) 50% by mass is mixed to obtain a solder composition. The viscosity of the obtained solder composition at 200°C and 250°C was measured by the same method as the above (1) the viscosity of the thermosetting flux composition. Then, the viscosity is divided according to the following criteria. A: The viscosity is less than 5 Pa·s. B: The viscosity exceeds 5 Pa·s and does not reach 50 Pa·s. C: The viscosity is 50 Pa·s or more. (3) Solder melting property: 50% by mass of thermosetting flux composition and solder powder (solder alloy: Sn-Ag3.0-Cu0.5, average particle size: 20 μm, particle size distribution: 10-40 μm) 50% The mass% is mixed to obtain a solder composition. The obtained solder composition was formed into a coating film with a diameter of 1 cm and a thickness of 50 μm on a substrate (surface material: copper) by the screen printing method, and heated it on a hot plate set at a temperature of 250°C for 30 seconds . Then, the molten state of the solder was visually observed, and the solder meltability was evaluated based on the following criteria. A: The solder has melted. B: The solder is not melted. (4) Insulation: 50% by mass of thermosetting flux composition and 50% by mass of solder powder (solder alloy: Sn-Ag3.0-Cu0.5, average particle size: 20 μm, particle size distribution: 10-40 μm) % Is mixed to obtain a solder composition. For the obtained solder composition, the insulation resistance value was measured in accordance with the insulation resistance test described in 8.5.3 of JIS Z3284-1 and JIS Z3197. That is, use a metal mask on the comb-shaped electrode substrate (conductor width: 0.318 mm, conductor spacing: 0.318 mm, size: 30 mm×30 mm) (one that matches the comb-shaped electrode pattern and is processed into a slit shape, thickness: 100 μm) Printing solder composition. After that, reflow was performed under the conditions of preheating at 150°C for 60 seconds and the melting time at a temperature of 250°C for 30 seconds to produce a test substrate. The test substrate was put into a high temperature and high humidity tester set at a temperature of 85°C and a relative humidity of 95%, and the insulation resistance value after 500 hours was measured. Then, the insulation was evaluated based on the following criteria. A: The insulation resistance value is 1.0×10 9 or more. B: The insulation resistance value does not reach 1.0×10 9 . (5) Thermal cycle test Put the substrate for thermal cycle test into the thermal cycle tester, and perform the following thermal cycle test (according to the thermal cycle test of vehicle solder paste), that is, after placing it at -40°C for 10 minutes Leave it at 125°C for 10 minutes as 1 cycle, and repeat it for 2000 cycles. Observe the substrate after the thermal cycle test with a microscope to confirm whether there are solder cracks in the chip parts, and evaluate the resistance to the thermal cycle test according to the following criteria. A: Less than 50% of the solder cracks occurred. B: The area where solder cracks are generated is 50% or more and less than 90%. C: 90% or more of solder cracks. [Table 1]
Figure 106132755-A0304-0001
 From the results shown in Table 1, it was clearly confirmed that when the thermosetting flux composition of the present invention was used (Examples 1 to 5), the solder meltability and insulation were good. In addition, it was confirmed that the solderability and auto-calibration during reflow are excellent due to the good solder meltability. In contrast, when using a thermosetting flux composition that does not contain the (A1) component or the (B1) component (Comparative Examples 1 to 3), it can be seen that at least one of solder meltability and insulation properties is insufficient.

Claims (12)

一種熱固性助焊劑組合物，其特徵在於：其係於藉由回流焊接使具有包含熔點為200℃以上且240℃以下之焊料合金的焊料凸塊之電子零件接合於電子基板之情形時所使用者，且含有(A)氧雜環丁烷化合物、(B)活性劑、與(C)環氧樹脂，上述(A)成分含有(A1)於1分子中具有2個氧雜環丁烷環之二官能氧雜環丁烷化合物，上述(B)成分含有(B1)有機酸，上述(A)成分之調配量相對於上述熱固性助焊劑組合物之固形物成分總量，為40質量%以上且95質量%以下，且該熱固性助焊劑組合物於以5℃/min之升溫速度自溫度25℃升溫之情形時，於溫度200℃下之黏度為5Pa‧s以下，且於溫度250℃下之黏度為50Pa‧s以上。 A thermosetting flux composition, characterized in that it is used when reflow soldering is used to bond electronic parts having solder bumps containing solder alloys with a melting point of 200°C or more and 240°C or less to an electronic substrate. , And contains (A) oxetane compound, (B) activator, and (C) epoxy resin. The above-mentioned (A) component contains (A1) having two oxetane rings in one molecule The bifunctional oxetane compound, the (B) component contains (B1) an organic acid, and the blending amount of the (A) component is 40% by mass or more relative to the total solid content of the thermosetting flux composition, and 95% by mass or less, and when the thermosetting flux composition is heated from a temperature of 25°C at a heating rate of 5°C/min, the viscosity at a temperature of 200°C is less than 5Pa‧s and the temperature is 250°C The viscosity is above 50Pa‧s. 一種熱固性助焊劑組合物，其特徵在於：其係於藉由回流焊接使具有包含熔點為200℃以上且240℃以下之焊料合金的焊料凸塊之電子零件接合於電子基板之情形時所使用者，且含有(A)氧雜環丁烷化合物、與(B)活性劑，上述(A)成分含有(A1)於1分子中具有2個氧雜環丁烷環之二官能氧雜環丁烷化合物、與(A2)於1分子中具有1個氧雜環丁烷環之單官能氧雜環丁烷化合物，上述(B)成分含有(B1)有機酸， 上述(A)成分之調配量相對於上述熱固性助焊劑組合物之固形物成分總量，為40質量%以上且95質量%以下，且該熱固性助焊劑組合物於以5℃/min之升溫速度自溫度25℃升溫之情形時，於溫度200℃下之黏度為5Pa‧s以下，且於溫度250℃下之黏度為50Pa‧s以上。 A thermosetting flux composition, characterized in that it is used when reflow soldering is used to bond electronic parts having solder bumps containing solder alloys with a melting point of 200°C or more and 240°C or less to an electronic substrate. , And contains (A) an oxetane compound, and (B) an active agent. The above (A) component contains (A1) a bifunctional oxetane having two oxetane rings in one molecule A compound, and (A2) a monofunctional oxetane compound having one oxetane ring in one molecule, the above-mentioned (B) component contains (B1) an organic acid, The blending amount of the above-mentioned (A) component relative to the total solid content of the above-mentioned thermosetting flux composition is 40% by mass or more and 95% by mass or less, and the thermosetting flux composition is set at a heating rate of 5°C/min When the temperature is raised from 25℃, the viscosity at 200℃ is less than 5Pa‧s, and the viscosity at 250℃ is more than 50Pa‧s. 如請求項2之熱固性助焊劑組合物，其進而含有(C)環氧樹脂。 Such as the thermosetting flux composition of claim 2, which further contains (C) epoxy resin. 如請求項1或3之熱固性助焊劑組合物，其中上述(C)成分之調配量相對於上述熱固性助焊劑組合物之固形物成分總量，為1質量%以上且30質量%以下。 The thermosetting flux composition of claim 1 or 3, wherein the blending amount of the above-mentioned component (C) is 1% by mass to 30% by mass relative to the total solid content of the thermosetting flux composition. 如請求項1之熱固性助焊劑組合物，其中上述(A)成分進而含有(A2)於1分子中具有1個氧雜環丁烷環之單官能氧雜環丁烷化合物。 The thermosetting flux composition according to claim 1, wherein the component (A) further contains (A2) a monofunctional oxetane compound having one oxetane ring in one molecule. 如請求項2或5之熱固性助焊劑組合物，其中上述(A1)成分相對於上述(A2)成分之質量比((A1)/(A2))為2以上且20以下。 The thermosetting flux composition according to claim 2 or 5, wherein the mass ratio ((A1)/(A2)) of the above-mentioned (A1) component to the above-mentioned (A2) component is 2 or more and 20 or less. 如請求項1或2之熱固性助焊劑組合物，其中上述(B1)成分為選自由戊二酸、己二酸、庚二酸及辛二酸所組成之 群中之至少1種。 The thermosetting flux composition of claim 1 or 2, wherein the above component (B1) is selected from the group consisting of glutaric acid, adipic acid, pimelic acid and suberic acid At least 1 species in the group. 如請求項1或2之熱固性助焊劑組合物，其中上述(B1)成分之調配量相對於上述熱固性助焊劑組合物之固形物成分總量，為1質量%以上且15質量%以下。 The thermosetting flux composition of claim 1 or 2, wherein the blending amount of the above-mentioned (B1) component is 1% by mass or more and 15% by mass or less relative to the total solid content of the thermosetting flux composition. 如請求項1或2之熱固性助焊劑組合物，其中上述(A1)成分為選自由苯二甲基雙氧雜環丁烷、3-乙基-3{[(3-乙基氧雜環丁烷-3-基)甲氧基]甲基}氧雜環丁烷、及具有聯苯骨架之二官能氧雜環丁烷化合物所組成之群中之至少1種。 The thermosetting flux composition of claim 1 or 2, wherein the above-mentioned (A1) component is selected from the group consisting of xylylene dioxetane, 3-ethyl-3{[(3-ethyloxetane Alk-3-yl)methoxy]methyl}oxetane and at least one of the group consisting of a bifunctional oxetane compound having a biphenyl skeleton. 如請求項1或2之熱固性助焊劑組合物，其中製作將包含錫96.5質量%、銀3.0質量%及銅0.5質量%之焊料合金且平均粒徑為30μm之焊料粉末、與上述熱固性助焊劑組合物以質量比成為1：1之方式進行混合而成之焊料組合物，於將上述焊料組合物以5℃/min之升溫速度自溫度25℃升溫之情形時，於溫度200℃下之黏度為5Pa‧s以下，且於溫度250℃下之黏度為50Pa‧s以上。 The thermosetting flux composition of claim 1 or 2, in which a solder alloy containing 96.5 mass% of tin, 3.0 mass% of silver and 0.5 mass% of copper and a solder powder with an average particle size of 30μm is produced in combination with the above thermosetting flux When the solder composition is mixed with a mass ratio of 1:1, when the above solder composition is heated from a temperature of 25°C at a temperature increase rate of 5°C/min, the viscosity at a temperature of 200°C is Below 5Pa‧s, and the viscosity at a temperature of 250℃ is above 50Pa‧s. 一種電子基板之製造方法，其特徵在於包括：塗佈步驟，其係於配線基板上塗佈如請求項1至9中任一項之熱固性助焊劑組合物；搭載步驟，其係將具有焊料凸塊之電子零件搭載於上述配線基板之接合用焊墊上； 回焊步驟，其係藉由對搭載有上述電子零件之配線基板進行加熱，而使上述焊料凸塊熔融，從而將上述焊料凸塊接合於上述接合用焊墊；及熱硬化步驟，其係對上述熱固性助焊劑組合物進行加熱而使之硬化。 An electronic substrate manufacturing method, characterized by comprising: a coating step, which is to coat a thermosetting flux composition as claimed in any one of claims 1 to 9 on a wiring substrate; and a mounting step, which will have solder bumps The electronic parts of the block are mounted on the bonding pads of the above-mentioned wiring board; A reflow step, which is to melt the solder bumps by heating the wiring board on which the electronic components are mounted, thereby joining the solder bumps to the bonding pads; and a thermal hardening step, which is The above-mentioned thermosetting flux composition is heated to harden it. 一種電子基板之製造方法，其特徵在於包括：塗佈步驟，其係於配線基板上塗佈如請求項10之熱固性助焊劑組合物；搭載步驟，其係將具有焊料凸塊之電子零件搭載於上述配線基板之接合用焊墊上；回焊步驟，其係藉由對搭載有上述電子零件之配線基板進行加熱，而使上述焊料凸塊熔融，從而將上述焊料凸塊接合於上述接合用焊墊；及熱硬化步驟，其係對上述熱固性助焊劑組合物進行加熱而使之硬化。 A method of manufacturing an electronic substrate, characterized by comprising: a coating step, which is to coat the thermosetting flux composition of claim 10 on a wiring substrate; and a mounting step, which is to mount an electronic component with solder bumps on On the bonding pad of the wiring board; a reflow step of heating the wiring board on which the electronic components are mounted to melt the solder bumps, thereby bonding the solder bumps to the bonding pads ; And a thermal hardening step, which is to heat the above-mentioned thermosetting flux composition to harden it.
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