US20190030656A1 - Flux - Google Patents

Flux Download PDF

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Publication number
US20190030656A1
US20190030656A1 US16/070,022 US201716070022A US2019030656A1 US 20190030656 A1 US20190030656 A1 US 20190030656A1 US 201716070022 A US201716070022 A US 201716070022A US 2019030656 A1 US2019030656 A1 US 2019030656A1
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United States
Prior art keywords
mass
salt
less
flux
examination
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US16/070,022
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English (en)
Inventor
Takahiro Nishizaki
Takashi Hagiwara
Hiroyoshi Kawasaki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Senju Metal Industry Co Ltd
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Senju Metal Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Senju Metal Industry Co Ltd filed Critical Senju Metal Industry Co Ltd
Assigned to SENJU METAL INDUSTRY CO., LTD. reassignment SENJU METAL INDUSTRY CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HAGIWARA, TAKASHI, KAWASAKI, HIROYOSHI, NISHIZAKI, TAKAHIRO
Publication of US20190030656A1 publication Critical patent/US20190030656A1/en
Abandoned legal-status Critical Current

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Classifications

    • 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
    • B23K35/36Selection 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
    • B23K35/362Selection of compositions of fluxes
    • 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
    • B23K35/36Selection 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
    • B23K35/3612Selection 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56Encapsulations, e.g. encapsulation layers, coatings
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151Die mounting substrate
    • H01L2924/153Connection portion
    • H01L2924/1531Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface
    • H01L2924/15311Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface being a ball array, e.g. BGA
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151Die mounting substrate
    • H01L2924/156Material
    • H01L2924/157Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2924/15738Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950 C and less than 1550 C
    • H01L2924/15747Copper [Cu] as principal constituent

Definitions

  • the present invention relates to a flux containing a benzimidazole-based compound.
  • the flux used for soldering it is necessary for the flux used for soldering to have properties of removing any metal oxide, inhibiting reoxidation when the solder melts, reducing surface tension of the solder and the like.
  • a flux containing an activator for removing an oxide film from a metal surface to improve its wettability and base material such as rosin for protecting the activator from heat is used.
  • Patent Document 1 discloses a flux composition for soldering which contains a solvent, an aromatic carboxylic acid and an imidazole compound.
  • Patent Document 2 discloses a flux composition for soldering which contains as an activator a benzimidazole compound having an alkyl group in 2-position.
  • Patent Document 3 discloses a processing method of contacting processing liquid, which contains a first imidazole compound, on a surface of copper or copper alloy of the printed circuit board, and contacting processing liquid, which contains a second imidazole compound, thereon.
  • BGA ball grid allay
  • a back surface of which has electrodes is applied to cope with narrowing of the connection terminal and/or reduction of mounting area along with the miniaturization.
  • a semiconductor package is exemplified.
  • a Cu-OSP substrate is used in which Cu electrodes are processed by organic solderability preservative (OSP) processing with water-soluble preflux to inhibit the electrode from being oxidized.
  • OSP organic solderability preservative
  • Patent Document 4 discloses an OSP processed substrate and a method of forming a solder ball mounted on the substrate.
  • a step of removing an OSP film from the substrate is generally required before a step of mounting the solder ball and after the step of removing the OSP film from the substrate, the surface mounted components are soldered on the substrate.
  • Patent Document 1 Japanese Patent Application Publication No. 2015-160244
  • Patent Document 2 Japanese Patent Application Publication No. H05-237688
  • Patent Document 3 Japanese Patent Application Publication No. 2014-101553
  • Patent Document 4 Japanese Patent Application Publication No. 2006-54467
  • This invention solves the above-mentioned problem and has an object to provide a flux which can solder the Cu-OSP processed substrate without requiring a step of removing the Cu-OSP film.
  • a flux containing rosin, an organic acid, a benzimidazole-based compound, and a solvent is characterized in that 30% by mass or more and 70% by mass or less of the rosin; 1% by mass or more and 10% by mass or less of the organic acid; 0.2% by mass or more and 10% by mass or less of the benzimidazole-based compound; and 20% by mass or more and 60% by mass or less of the solvent, wherein the benzimidazole-based compound includes at least one species selected from a group consisting of 2-alkylbenzimidazole and a salt of 2-alkylbenzimidazole hydrohalide.
  • the flux according to the above-mentioned item (1) or (2) characterized in that the flux further contains 5% by mass or less of the imidazole-based compound (a total amount of the imidazole-based compound and the salt of hydrohalogenic acid when containing the imidazole-based compound and the salt of hydrohalogenic acid) wherein an addition amount of the imidazole-based compound is equal to or less than an addition amount of the benzimidazole-based compound.
  • the flux of the present embodiment contains rosin, an organic acid, a solvent and a benzimidazole-based compound.
  • rosin 30% by mass or more and 70% by mass or less of the rosin is added to protect an activator component from heat and prevent the activator component from volatilizing.
  • rosin for example, hydrogenated rosin, acid-modified rosin, polymerized rosin, rosin ester or the like is used.
  • organic acid 1% by mass or more and 10% by mass or less of the organic acid is added as an activator component in the flux.
  • the organic acid succinic acid, glutaric acid, adipic acid or the like is used.
  • thixotropic agent More than 0% by mass and 10% by mass or less of the thixotropic agent may be added to give thixotropic property.
  • thixotropic agent higher fatty acid amide, hydrogenated castor oil or the like is exemplified.
  • the solvent is selected from generally-known glycol-ether-based compounds. It is preferable that the solvent does not volatilize at a low-temperature range of 120 degrees C. and 150 degrees C., in order to allow the activator to efficiently act. When the solvent volatilizes, fluidity of the flux deteriorates so that it may be difficult to wetly spread out the flux to a portion to be joined. Accordingly, the solvent preferably has 200 degrees C. or more, more preferably 240 degrees C. or more, of a boiling point.
  • benzimidazole-based compound 0.2% by mass or more and 10% by mass or less of 2-alkylbenzimidazole or a salt of 2-alkylbenzimidazole hydrohalide is used.
  • 2-alkylbenzimidazole 2-pentylbenzimidazole, 2-octylbenzimidazole, 2-nonylbenzimidazole, 2-(1-ethylpentyl)benzimidazole or the like is exemplified.
  • 2-alkylbenzimidazole in the salt of 2-alkylbenzimidazole hydrohalide is identical to the above-mentioned compounds and as the hydrohalogenic acid, hydrochloric acid, hydrobromic acid, hydriodic acid or the like is exemplified.
  • imidazole-based compound for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-methyl-2-phenylimidazole, 1-benzil-2-methylimidazole, 1-benzil-2-phenylimidazole or the like is exemplified.
  • a salt of amine hydrohalide other than the salt of 2-alkylbenzimidazole hydrohalide may be added.
  • the amine compound in the addible salt of amine hydrohalide for example, ethylamine, diethylamine, dibutyl amine, isopropylamine, diphenylguanidine, cyclohexyl amine or the like is exemplified.
  • hydrohalogenic acid hydrochloric acid, hydrobromic acid, hydriodic acid or the like is exemplified.
  • both of the above-mentioned additives may be added. Namely, to the flux containing the benzimidazole-based compound, another imidazole-based compound and a salt of amine hydrohalide excluding the salt of 2-alkylbenzimidazole hydrohalide may be added.
  • an antioxidant for example, an antioxidant, a surface-active agent, an antifoam and/or the like may be suitably added unless it (they) impair(s) any flux property.
  • fluxes of the Executed Examples and the Comparison Examples having compositions shown in following Tables were prepared to find out an ingredient of each composition contained in the fluxes and the following overall appearance examination and a wetly-spreading-out examination of the solder were performed. It is to be noted that the fluxes of the Executed Examples and the Comparison Examples contained the rosin, the organic acid, the thixotropic agent and the solvent in the ratios of Tables 1 and 2 but we will not specifically describe them in the following (The numerals in the flux compositions represent % by mass).
  • Cu-OSP process was first performed on a copper plate having 0.3 mm of a thickness and 30 mm by 30 mm of a dimension. After the Cu-OSP processed copper plate was heated at 250 degrees C. for 30 minutes, it was baked at 175 degrees C. for 12 hours.
  • the fluxes prepared in the ratios shown in each of the Executed Examples and the Comparison Examples in Tables were applied to the Cu-OSP processed copper plates. After the fluxes were applied to the Cu-OSP processed copper plates, the baked copper plates were heated at a heating speed of 2.5 degrees C./second up to a peak of 250 degrees C. and then, cooled to a room temperature.
  • the copper plates were washed by hydrocarbon-based cleaner and their overall appearances were examined whether or not there was any residue around a soldered portion using a magnifying microscope.
  • any or both of the Cu-OSP and flux residue remain on the substrate.
  • Any residue of Cu-OSP and any residue such as the flux residue cause contact failure and/or conduction failure. It is possible to suppress contact failure and/or conduction failure by removing the residue from the substrate. It has been determined that the Executed Examples indicating good washability in the overall appearance examination could suitably remove such residue of Cu-OSP and the flux residue without a step of removing Cu-OSP.
  • Cu-OSP process was first performed on a copper plate having 0.3 mm of a thickness and 30 mm by 30 mm of a dimension. After the Cu-OSP processed copper plate was heated at 250 degrees C. for 30 minutes, it was baked at 175 degrees C. for 12 hours.
  • the fluxes prepared in the ratios shown in each of the Executed Examples and the Comparison Examples in Tables were applied to the Cu-OSP processed copper plates.
  • Solder balls each having a composition of Sn-3Ag-0.5Cu and a diameter of 500 pm were mounted on each of the flux-applied copper plates.
  • the copper plates were heated at a heating speed of 2.5 degrees C./second up to a peak of 250 degrees C. and then, cooled to a room temperature.
  • the copper plates were washed by hydrocarbon-based cleaner and wetly-spread-out diameters of solder were measured therein.
  • 2-octylbenzimidazole, 2-pentylbenzimidazole, 2-nonylbenzimidazole, 2-(1-ethylpentyl)benzimidazole were selected and added as the 2-alkylbenzimidazole.
  • 2-ethyl-4-methylimidazole, 2-phenylimidazole and 1-benzil-2-methylimidazole were selected as another imidazole-based compound.
  • Diphenylguanidine was selected as another amine compound.
  • Comparison Example 8 Only the rosin, the organic acid, the thixotropic agent and the solvent were contained in the Comparison Example 8. The Comparison Example 8 did not indicate any good results in the overall appearance examination and the wetly-spreading-out examination.
  • the flux containing 5% by mass of 2-octylbenzimidazole and 5% by mass of 2-ethyl-4-methylimidazole has obtained good results in the overall appearance examination and the wetly-spreading-out examination but the flux containing 5% by mass of 2-octylbenzimidazole and 10% by mass of 2-phenylimidazole has not obtained any good result in the overall appearance examination.
  • the flux containing 5% by mass of 2-octylbenzimidazole and 5% by mass or less of imidazole-based compound in which an addition amount of the imidazole-based compound is equal to or less than that of 2-octylbenzimidazole has obtained good results in the overall appearance examination and the wetly-spreading-out examination.
  • EXAMPLE 11 EXAMPLE 12 EXAMPLE 13 EXAMPLE 14 ROSIN 50 50 50 50 50 ORGANIC ACID 6 6 6 6 6 6 2-OCTYLBENZIMIDAZOLE 5 5 5 2-PENTYLBENZIMIDAZOLE 2-(1-ETHYLPENTYL) BENZIMIDAZOLE 2-NONYLBENZIMIDAZOLE 2-ETHYL-4- METHYLIMIDAZOLE 2-PHENYLIMIDAZOLE SALT OF 2- 5 0.2 10 5 5 OCTYLBENZIMIDAZOLE HYDROBROMIC ACID SALT OF ETHYL AMINE 1 5 1 HYDROBROMIC ACID SALT OF DIPHENYLGUANIDINE HYDROBROMIC ACID SALT OF 2-PHENYLIMIDAZOLE HY
  • Comparison Examples 9 and 10 0.01% by mass and 20% by mass of a salt of 2-octylbenzimidazole hydrobromic acid were respectively contained in the Comparison Examples 9 and 10.
  • the Comparison Example 9 did not indicate any good results in the overall appearance examination and the wetly-spreading-out examination.
  • the Comparison Example 10 indicated good result in the wetly-spreading-out examination but did not indicate any good result in the overall appearance examination.
  • the flux containing 0.2% by mass or more and 10% by mass or less of a salt of 2-octylbenzimidazole hydrobromic acid as an example of the salt of 2-alkylbenzimidazole hydrohalide has obtained good results in the overall appearance examination and the wetly-spreading-out examination.
  • the flux containing 5% by mass or less of a salt of ethyl amine hydrobromic acid, a salt of diphenylguanidine hydrobromic acid or a salt of 2-phenylimidazole hydrobromic acid as an example of the salt of amine hydrohalide in addition to 5% by mass of a salt of 2-octylbenzimidazole hydrobromic acid has obtained good results in the overall appearance examination and the wetly-spreading-out examination.
  • EXAMPLE 21 ROSIN 30 40 60 70 ORGANIC ACID 2 10 6 1 2-OCTYLBENZIMIDAZOLE 3 5 5 2 2-PENTYLBENZIMIDAZOLE 2-(1-ETHYLPENTYL)BENZIMIDAZOLE 2-NONYLBENZIMIDAZOLE 2-ETHYL-4-METHYLIMIDAZOLE 2-PHENYLIMIDAZOLE SALT OF 2-OCTYLBENZIMIDAZOLE HYDROBROMIC ACID SALT Of ETHYL AMINE HYDROBROMIC ACID SALT OF DIPHENYLGUANIDINE HYDROBROMIC ACID SALT OF 2-PHENYLIMIDAZOLE HYDROBROMIC ACID THIXOTROPIC AGENT 10 7 0 1 SOLVENT 55 38 29 26 TOTAL AMOUNT 100 100 100 100 100 OVERALL APPEARANCE EXA
  • the flux containing 2-octylbenzimidazole, 30% by mass or more and 70% by mass or less of the rosin, 1% by mass or more and 10% by mass or less of the organic acid, more than 0% by mass and 10% by mass or less of the thixotropic agent and 20% by mass or more and 60% by mass or less of the solvent has also obtained good results in the overall appearance examination and the wetly-spreading-out examination.
  • the flux containing 5% by mass or less of imidazole-based compound in addition to the above-mentioned flux (i) or (ii) has obtained good results in the overall appearance examination and the wetly-spreading-out examination.
  • an addition amount of the imidazole-based compound is equal to or less than that of benzimidazole-based compound.
  • the total amount thereof is equal to or less than 5% by mass.
  • the flux may contain more than 0% by mass and 10% by mass or less of the thixotropic agent.
  • contents of the rosin, the organic acid, the thixotropic agent and the solvent are not limited to the contents described in the above-mentioned Tables 1 through 3.
  • the solder balls were mounted, a color of each of the copper plates was visually confirmed but any discoloration was not seen in each of the copper plates of the Executed Examples. Even when a reflow process was performed in the atmosphere, not inert gas such as nitrogen gas, any discoloration was not seen in each of the copper plates of the Executed Examples. Therefore, it is understood that OSP film processing the copper plate may inhibit any oxidation and the OSP film on only a portion to which the flux is applied may be removed.
  • the flux of this invention is applicable to a substrate other than the Cu-OSP processed substrate.
  • the present invention is applicable to a flux used for soldering.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
US16/070,022 2016-01-15 2017-01-12 Flux Abandoned US20190030656A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JPPCT/JP2016/051108 2016-01-15
PCT/JP2016/051108 WO2017122341A1 (ja) 2016-01-15 2016-01-15 フラックス
PCT/JP2017/000890 WO2017122750A1 (ja) 2016-01-15 2017-01-12 フラックス

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/000890 A-371-Of-International WO2017122750A1 (ja) 2016-01-15 2017-01-12 フラックス

Related Child Applications (1)

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US16/751,330 Continuation US11571772B2 (en) 2016-01-15 2020-01-24 Flux

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US20190030656A1 true US20190030656A1 (en) 2019-01-31

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Family Applications (2)

Application Number Title Priority Date Filing Date
US16/070,022 Abandoned US20190030656A1 (en) 2016-01-15 2017-01-12 Flux
US16/751,330 Active 2037-05-23 US11571772B2 (en) 2016-01-15 2020-01-24 Flux

Family Applications After (1)

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US16/751,330 Active 2037-05-23 US11571772B2 (en) 2016-01-15 2020-01-24 Flux

Country Status (10)

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US (2) US20190030656A1 (ja)
EP (1) EP3409412B1 (ja)
JP (1) JP6222412B1 (ja)
KR (1) KR101923877B1 (ja)
CN (1) CN108472771B (ja)
ES (1) ES2816001T3 (ja)
HU (1) HUE051886T2 (ja)
PT (1) PT3409412T (ja)
TW (1) TWI681953B (ja)
WO (2) WO2017122341A1 (ja)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11167380B2 (en) 2018-06-01 2021-11-09 Senju Metal Industry Co., Ltd. Flux for solder paste and solder paste

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JP6688267B2 (ja) * 2017-09-06 2020-04-28 千住金属工業株式会社 フラックスの製造方法
JP6681566B1 (ja) * 2019-05-27 2020-04-15 千住金属工業株式会社 はんだペースト及びフラックス
JP6681567B1 (ja) * 2019-05-27 2020-04-15 千住金属工業株式会社 はんだペースト及びフラックス
CN111001965B (zh) * 2019-10-28 2022-03-11 东莞市吉田焊接材料有限公司 一种有铅锡膏助焊剂及其制备方法与锡膏
JP6845452B1 (ja) * 2020-03-30 2021-03-17 千住金属工業株式会社 はんだ接合不良抑制剤、フラックスおよびソルダペースト
CN114590045B (zh) * 2021-12-31 2023-01-06 南通威斯派尔半导体技术有限公司 一种高精度焊料图形的印刷方法

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Publication number Priority date Publication date Assignee Title
US11167380B2 (en) 2018-06-01 2021-11-09 Senju Metal Industry Co., Ltd. Flux for solder paste and solder paste

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TW201825464A (zh) 2018-07-16
PT3409412T (pt) 2020-08-27
JPWO2017122750A1 (ja) 2018-01-18
EP3409412B1 (en) 2020-07-29
WO2017122750A1 (ja) 2017-07-20
CN108472771A (zh) 2018-08-31
CN108472771B (zh) 2019-05-28
WO2017122341A1 (ja) 2017-07-20
HUE051886T2 (hu) 2021-03-29
EP3409412A1 (en) 2018-12-05
KR20180096798A (ko) 2018-08-29
JP6222412B1 (ja) 2017-11-01
ES2816001T3 (es) 2021-03-31
KR101923877B1 (ko) 2018-11-29
US20200156192A1 (en) 2020-05-21
US11571772B2 (en) 2023-02-07
TWI681953B (zh) 2020-01-11
EP3409412A4 (en) 2019-06-19

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