CN110936063A - Flux composition for soldering and soldering method - Google Patents

Flux composition for soldering and soldering method Download PDF

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Publication number
CN110936063A
CN110936063A CN201910880647.0A CN201910880647A CN110936063A CN 110936063 A CN110936063 A CN 110936063A CN 201910880647 A CN201910880647 A CN 201910880647A CN 110936063 A CN110936063 A CN 110936063A
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flux composition
acid
component
mass
welding
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CN110936063B (en
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网野大辉
熊仓市朗
小川泰贵
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Tamura Corp
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Tamura Corp
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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
    • B23K35/36Selection 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

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)

Abstract

The present invention provides a welding flux composition, which contains (A) rosin resin, (B) activating agent, (C) solvent, and (D) higher fatty acid ester formed by aliphatic carboxylic acid with 12-24 carbon atoms and alcohol with 1-4 carbon atoms.

Description

Flux composition for soldering and soldering method
Technical Field
The present invention relates to a solder composition for soldering.
Background
As a method for soldering an electronic substrate and an electronic component, a method of soldering an electronic component temporarily fixed to an electronic substrate by bringing the electronic component into contact with a molten solder in a jet flow, a so-called flow soldering (reflow) method, is used in addition to the so-called reflow soldering method. In this flow soldering method, a flux composition described in, for example, document 1 (japanese patent application laid-open No. 8-243787) is used before being brought into contact with a molten solder of a jet flow.
On the other hand, with the recent lead-free solder, there is a tendency to use a solder having a high melting point. The most commonly used lead-free solder alloys are tin (Sn) -silver (Ag) -copper (Su) based solder alloys, so-called SAC based solder alloys. The SAC-based solder alloy is inferior in wet spreading of the oxidized copper foil to conventional tin-lead eutectic solder. Therefore, the flux composition used in the solder spreading test using SAC-based solder alloy does not reach 80% or more.
Disclosure of Invention
The purpose of the present invention is to provide a solder composition for soldering which has sufficiently excellent solder wettability even when a lead-free solder is used.
In order to solve the above problems, the present invention provides the following solder composition for soldering.
The flux composition for welding contains (A) a rosin resin, (B) an activator, (C) a solvent, and (D) a higher fatty acid ester formed by an aliphatic carboxylic acid with 12-24 carbon atoms and an alcohol with 1-4 carbon atoms.
In the flux composition for soldering of the present invention, the amount of the component (D) is preferably 0.1 mass% or more and 5 mass% or less with respect to 100 mass% of the flux composition.
According to the present invention, a solder composition for soldering which is sufficiently excellent in solder wettability even when a lead-free solder is used can be provided.
Detailed Description
The flux composition for welding of the present embodiment (hereinafter, also simply referred to as "flux composition") contains (a) a rosin-based resin, (B) an activator, (C) a solvent, and (D) a higher fatty acid ester, which are described below.
In this specification, lead-free solder refers to a solder metal or alloy to which no lead is added. Among them, lead is allowed to exist as an inevitable impurity in the lead-free solder, but in this case, the amount of lead is preferably 300 mass ppm or less.
Specific examples of the solder alloy in the lead-free solder include: Sn-Ag, Sn-Ag-Cu, Sn-Ag-Bi, Sn-Ag-Cu-Bi, Sn-Sb, Sn-Zn-Bi, Sn-Zn-Al, Sn-Ag-Bi-In, Sn-Ag-Cu-Bi-In-Sb, In-Ag and the like. Among them, Sn — Ag — Cu based solder alloys are preferably used from the viewpoint of the strength of soldering. The melting point of Sn — Ag — Cu based solder is usually 200 ℃ or higher and 250 ℃ or lower. In Sn — Ag — Cu based solders, a solder having a low silver content has a melting point of 210 ℃ to 250 ℃ (more preferably 220 ℃ to 240 ℃).
[ (A) component ]
Examples of the rosin-based resin (a) used in the present embodiment include rosins and rosin-based modified resins, examples of the rosins include gum rosin, wood rosin, tall oil rosin, and the like, examples of the rosin-based modified resin include disproportionated rosin, polymerized rosin, hydrogenated rosin, and derivatives thereof, examples of the hydrogenated rosin include fully hydrogenated rosin, partially hydrogenated rosin, and hydrogenated products of unsaturated organic acid-modified rosins (also referred to as "hydrogenated acid-modified rosins") of modified rosins of unsaturated organic acids such as unsaturated aliphatic monocarboxylic acids such as (meth) acrylic acid, unsaturated aliphatic dibasic acids such as α -unsaturated carboxylic acids such as fumaric acid and maleic acid, and unsaturated carboxylic acids having an aromatic ring such as cinnamic acid).
The amount of component (a) is preferably 0.5 mass% or more and 20 mass% or less, more preferably 1 mass% or more and 10 mass% or less, and particularly preferably 2 mass% or more and 6 mass% or less, based on 100 mass% of the flux composition. (A) When the amount of the component is not less than the lower limit, the occurrence of bridging and welding burr can be more reliably suppressed. On the other hand, when the amount of the component (a) is not more than the upper limit, the flux residue can be reduced.
[ (B) component ]
Examples of the activator include: an organic acid, a non-dissociative activator composed of a non-dissociative halogen-containing compound, and an amine activator. These activators may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
Examples of the organic acid include monocarboxylic acids, dicarboxylic acids, and the like.
Examples of monocarboxylic acids include: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, tuberculostearic acid, arachidic acid, behenic acid, lignoceric acid, and glycolic acid.
Examples of the dicarboxylic acid 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, diglycolic acid, and the like.
Examples of other organic acids include: dimer acid, levulinic acid, lactic acid, acrylic acid, benzoic acid, salicylic acid, anisic acid, citric acid, picolinic acid, and the like.
In the present embodiment, component (B) preferably contains succinic acid from the viewpoint of wetting of the through-holes.
Examples of the non-dissociative activator composed of a non-dissociative halogen-containing compound include non-salt-like organic compounds to which a halogen atom is bonded by a covalent bond. The halogen-containing compound may be a compound formed by covalent bonds of individual elements such as chlorine, bromine, and fluorine, such as chloride, bromide, and fluoride, or may be a compound having covalent bonds of any 2 or all of chlorine, bromine, and fluorine. In order to improve the solubility in an aqueous solvent, these compounds preferably have a polar group such as a hydroxyl group or a carboxyl group, like a halogenated alcohol or a halogenated carboxylic acid. Examples of the halogenated alcohol include: bromoalcohols (2, 3-dibromopropanol, 2, 3-dibromobutanediol, trans-2, 3-dibromo-2-butene-1, 4-diol (TDBD), 1, 4-dibromo-2-butanol, tribromoneopentyl alcohol and the like), chlorohydrins (1, 3-dichloro-2-propanol, 1, 4-dichloro-2-butanol and the like), fluoroalcohols (3-fluorocatechol and the like), and other compounds similar thereto. Examples of the halogenated carboxylic acid include: iodocarboxylic acids (2-iodobenzoic acid, 3-iodobenzoic acid, 2-iodopropionic acid, 5-iodosalicylic acid, and 5-iodoanthranilic acid, etc.), chlorocarboxylic acids (2-chlorobenzoic acid, and 3-chloropropionic acid, etc.), bromocarboxylic acids (2, 3-dibromopropionic acid, 2, 3-dibromosuccinic acid, 2-bromobenzoic acid, etc.), and other similar compounds.
Examples of the amine activator include: amines (such as polyamines including ethylenediamine), amine salts (such as amines including trimethylolamine, cyclohexylamine, and diethylamine, organic acid salts such as aminoalcohols, and inorganic acid salts (such as hydrochloric acid, sulfuric acid, and hydrobromic acid)), amino acids (such as glycine, alanine, aspartic acid, glutamic acid, and valine), and amide compounds. Specifically, there may be mentioned: diphenylguanidine hydrobromide, cyclohexylamine hydrobromide, diethylamine salts (hydrochloride, succinate, adipate, sebacate, etc.), triethanolamine, monoethanolamine, and hydrobromide salts of these amines, and the like.
The amount of component (B) is preferably 0.5% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 8% by mass or less, and particularly preferably 2% by mass or more and 5% by mass or less, based on 100% by mass of the flux composition. When the amount is not less than the lower limit, the solderability can be improved, while when the amount is not more than the upper limit, the insulation property of the flux composition can be ensured.
[ (C) ingredient ]
As the solvent (C) used in the present embodiment, a known solvent can be suitably used. As the component (C), a water-soluble solvent having a boiling point of 100 ℃ or lower (C1) is preferably used.
Examples of the component (C1) include ethanol and isopropanol. These solvents may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The component (C) may contain, in addition to the water-soluble solvent having a boiling point of 100 ℃ or lower, (C2) a glycol-based solvent or terpene-based solvent having a boiling point of 120 ℃ or higher and 320 ℃ or lower (preferably 240 ℃ or higher and 320 ℃ or lower) at 1013 hPa. In the case of such a (C2) component, it can contribute to suppression of thermal deterioration of the activator.
Examples of the component (C2) include: ethylene glycol monomethyl ether (124 ℃), triethylene glycol monomethyl ether (249 ℃), polyethylene glycol monomethyl ether (295 ℃), triethylene glycol monobutyl ether (271 ℃), diethylene glycol monohexyl ether (259 ℃), diethylene glycol 2-ethylhexyl ether (272 ℃), ethylene glycol monophenyl ether (245 ℃), diethylene glycol monophenyl ether (283 ℃), ethylene glycol monobenzyl ether (256 ℃), diethylene glycol monobenzyl ether (302 ℃), tripropylene glycol monoethyl ether (242 ℃), tripropylene glycol monobutyl ether (274 ℃), propylene glycol monophenyl ether (243 ℃), diethylene glycol dibutyl ether (255 ℃), tetraethylene glycol dimethyl ether (275 ℃), Isobornyl cyclohexanol (310-318 ℃), and the like. Of these, tripropylene glycol monobutyl ether, propylene glycol monophenyl ether, diethylene glycol mono 2-ethylhexyl ether, isobornyl cyclohexanol are preferable. These compounds may be used alone in 1 kind, or may be mixed in 2 or more kinds. The temperature indicated in parentheses is the boiling point of the solvent.
The amount of component (C) is preferably 70% by mass or more and 95% by mass or less, more preferably 75% by mass or more and 92% by mass or less, and particularly preferably 80% by mass or more and 90% by mass or less, based on 100% by mass of the flux composition. When the amount is within the above range, the coatability of the flux composition can be adjusted to an appropriate range.
[ (D) component ]
The higher fatty acid ester (D) used in the present embodiment is a higher fatty acid ester comprising an aliphatic carboxylic acid having 12 to 24 carbon atoms and an alcohol having 1 to 4 carbon atoms. Since the active action of the component (D) is not easily deactivated even at high temperatures, the solder wettability can be improved when a lead-free solder is used. When the aliphatic carboxylic acid has 11 or less carbon atoms, the solder wettability improving effect is insufficient. On the other hand, a carboxylic acid having 25 or more carbon atoms is difficult to obtain as an aliphatic carboxylic acid. In addition, when the carbon number of the alcohol is 5 or more, the solder wettability improving effect is insufficient. The aliphatic carboxylic acid preferably has 12 to 18 carbon atoms, and particularly preferably has 18 carbon atoms. The number of carbon atoms of the alcohol is preferably 2 to 4, and particularly preferably 4.
These higher fatty acid esters may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Here, the aliphatic carboxylic acid may be saturated or unsaturated. In addition, the aliphatic carboxylic acid may have a branch.
Examples of the aliphatic carboxylic acid include lauric acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachic acid, heneicosanic acid, behenic acid, tricosanic acid, lignoceric acid, α -linolenic acid, linoleic acid, and oleic acid.
Examples of the alcohol include: methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, and the like.
The amount of component (D) is preferably 0.1 to 5 mass%, more preferably 0.2 to 3 mass%, and particularly preferably 0.5 to 2 mass% with respect to 100 mass% of the flux composition. When the amount is not less than the lower limit, solder wettability can be further improved, and when the amount is not more than the upper limit, insulation reliability can be maintained.
The flux composition of the present embodiment may contain, in addition to the components (a) to (D), additives such as a thixotropic agent, an antioxidant, an antifoaming agent, a rust inhibitor, and a surfactant, as necessary. The amount of these additives is preferably 0.01 mass% or more and 5 mass% or less with respect to 100 mass% of the flux composition.
[ welding method ]
Next, a welding method using the flux composition of the present embodiment will be described. The welding method of the present embodiment includes a component mounting step, a flux applying step, and a welding step described below.
In the component mounting step, first, the electronic component is inserted into the electronic substrate and mounted.
Examples of the electronic substrate include a printed wiring board.
The electronic component can be inserted into a through hole of an electronic substrate and used in a method of mounting by soldering after insertion (so-called through hole mounting). Examples of the electronic component include an integrated circuit, a transistor, a diode, a resistor, a capacitor, and the like.
In the flux coating step, the flux composition is coated on the bonding surface of the electronic substrate.
As the applicator for the flux composition, a Spray Fluxer (Spray Fluxer), a foam Fluxer, and the like can be used. Among them, a spray fluxer is preferable from the viewpoint of stability of the coating amount.
The amount of the flux composition to be applied is preferably 30mL/m from the viewpoint of weldability2Above and 180mL/m2Hereinafter, more preferably 40mL/m2Above and 150mL/m2The concentration is preferably 50mL/m2Above and 120mL/m2The following.
In the soldering step, the soldering surface of the electronic substrate is brought into contact with the molten solder to perform soldering.
The method of bringing the molten solder into contact with the electronic substrate is not particularly limited as long as the molten solder can be brought into contact with the electronic substrate. As such a method, for example, a method (flow soldering method) of bringing an electronic substrate into contact with a molten solder of a jet flow can be employed. Further, a method of bringing a solder bath containing molten solder into contact with an electronic substrate may be employed.
The conditions for soldering may be set appropriately according to the melting point of the solder. For example, when a Sn — Au — Cu-based solder alloy is used, the temperature of the molten solder may be set to 230 ℃ or higher and 280 ℃ or lower (preferably 250 ℃ or higher and 270 ℃ or lower). The preheating temperature may be set to 80 ℃ or higher and 130 ℃ or lower (preferably 90 ℃ or higher and 120 ℃ or lower).
Examples
The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. Materials used in examples and comparative examples are shown below.
(component (A))
Rosin resin: trade name "Chinese rosin X", manufactured by Mitsuwa chemical industry Co., Ltd
(component (B))
An activator A: succinic acid
An activator B: adipic acid
An activator C: trans-2, 3-dibromo-2-butene-1, 4-diol (TDBD) manufactured by Takayasu petrochemical Co., Ltd
((C1) component)
Solvent A: isopropanol (I-propanol)
((C2) component)
Solvent B: tripropylene glycol monobutyl ether
(component (D))
Higher fatty acid ester A: butyl stearate, trade name "EXCEPARL BS", manufactured by Ishikaki Kaisha
Higher fatty acid ester B: stearic acid ethyl ester
Higher fatty acid ester C: palmitic acid isopropyl ester
Higher fatty acid ester D: lauric acid methyl ester
(other Components)
Dibasic acid ester: diisopropyl succinate, Bolus oil chemical Co Ltd
[ example 1]
3 mass% of rosin resin, 1.5 mass% of activator a, 0.5 mass% of activator B, 1 mass% of activator C, 0.5 mass% of higher fatty acid ester a, 90.5 mass% of solvent a, and 3 mass% of solvent B were put into a container and mixed to obtain a flux composition.
Examples 2 to 5 and comparative examples 1 to 2
Flux compositions were obtained in the same manner as in example 1, except that the respective materials were blended in the compositions shown in table 1.
< evaluation of flux composition >
The characteristics (solder spreading, wetting) of the flux composition were evaluated by the following methods. The obtained results are shown in table 1.
(1) Solder spreading
A test piece was obtained by polishing a copper plate (size: 50 mm. times.50 mm, thickness: 0.5mm) with No. 600 waterproof abrasive paper, further washing with isopropyl alcohol, and then subjecting to oxidation treatment in a dryer at 150 ℃ for 1 hour.
Next, 0.05mL of the flux composition was applied to a test piece, and a solder ring (1 roll of wire-like solder having a diameter of 1.6mm wound around a rod having a diameter of 3.2 mm) was placed on the test piece and placed on a ceramic plate. Then, the ceramic plate was placed on a solder bath set to 255 ℃, and the test piece was heated. Then, the heating was continued for 30 seconds from the melting of the solder, and the sample was lifted up horizontally and naturally cooled to obtain a sample for evaluation.
The height (H) of the solder spread was measured with a micrometer for this evaluation sample, and the spreading ratio (Sr) was obtained from the following formula (F1).
Sr=(D-H)/D×100···(F1)
D=1.24V1/3···(F2)
Sr: spreading Rate (%)
H: height (mm) of solder spread
D: the diameter (mm) of the solder used in the test was regarded as a sphere
V: quality/density of solder used in the test
The test was performed on (i) the solder ring 1 and (ii) the solder ring 2.
(i) Solder alloy composition of solder ring 1: Sn3.0Ag0.5Cu
(ii) Solder alloy composition of solder ring 2: Sn0.3Ag0.7Cu
Then, based on the spreading rate, the solder spreading was evaluated according to the following criteria. The spreading rate (%) is also shown in table 1.
B: the spreading rate is more than 80%.
C: the spreading rate was less than 80%.
(2) Moistening
A substrate (thickness: 1.6mm) having through holes of 1.0mm and 0.8mm in diameter was subjected to 3 reflow treatment, to thereby obtain a test piece. The reflow conditions here are: the preheating temperature is 150-200 deg.C (80 seconds), the time of 200 deg.C or more is 80 seconds, and the peak temperature is 250 deg.C.
Next, the flux composition (coating amount: 110 mL/m) was applied by a spray fluxer2) The test piece was coated with the coating solution and then subjected to flow soldering to obtain a sample for evaluation. The flow welding conditions here are: the preheating temperature is 100-120 ℃ (30-60 seconds), the solder temperature is 250 ℃, and the solder alloy comprises Sn3.0Ag0.5Cu.
The evaluation sample was observed at 120 sites each having a diameter of 1.0mm and 0.8mm, and the site wetted with the solder over the entire circumference of the end face of the through hole was "OK", and the wetting rate was obtained from the following formula (F3).
(OK number/< 120 > of phi 1.0) + (OK number/< 120 > of phi 0.8) } × 100 · (F3)
Then, the wetting was evaluated based on the wetting rate according to the following criteria. The wet yield (%) is also shown in table 1.
A: the wetting rate is more than 80%.
B: the wet yield is 70% or more and 80% or less.
C: the wetting rate is lower than 70%.
Figure BDA0002205795380000091
From the results shown in table 1, it is understood that solder spreading and wetting were good in the case of using the flux composition of the present invention (examples 1 to 5). Therefore, it was confirmed that, according to the present invention, solder wettability was sufficiently excellent even in the case of using a lead-free solder.

Claims (12)

1. A welding flux composition contains (A) a rosin resin, (B) an activator, (C) a solvent, and (D) a higher fatty acid ester formed by an aliphatic carboxylic acid with 12-24 carbon atoms and an alcohol with 1-4 carbon atoms.
2. The flux composition for welding according to claim 1,
the component (B) contains a dicarboxylic acid and a halohydrin.
3. The flux composition for welding according to claim 1,
the component (B) contains succinic acid and trans-2, 3-dibromo-2-butene-1, 4-diol.
4. The flux composition for welding according to claim 1,
the component (C) contains (C1) a water-soluble solvent having a boiling point of 100 ℃ or lower, and (C2) a glycol-based solvent or terpene-based solvent having a boiling point of 120 ℃ to 320 ℃ at 1013 hPa.
5. The flux composition for welding according to claim 4,
the boiling point of the component (C2) at 1013hPa is 240-320 ℃.
6. The flux composition for welding according to claim 1,
the component (D) is a higher fatty acid ester formed by aliphatic carboxylic acid with 12-18 carbon atoms and alcohol with 2-4 carbon atoms.
7. The flux composition for welding according to claim 1,
the component (D) is a higher fatty acid ester formed by aliphatic carboxylic acid with 18 carbon atoms and alcohol with 2-4 carbon atoms.
8. The flux composition for welding according to claim 1,
the amount of the component (A) is 0.5 to 20 mass% based on 100 mass% of the flux composition,
the amount of the component (B) is 0.5 to 10 mass% based on 100 mass% of the flux composition,
the amount of the component (C) is 70 to 95 mass% based on 100 mass% of the flux composition.
9. The flux composition for welding according to any one of claims 1 to 8,
the amount of the component (D) is 0.1 to 5 mass% based on 100 mass% of the flux composition.
10. A method of welding, the method comprising:
inserting an electronic component into an electronic substrate and mounting the electronic component;
applying the flux composition for soldering according to any one of claims 1 to 9 to a soldering surface of the electronic substrate;
and a step of bringing the soldering surface of the electronic substrate into contact with molten solder to perform soldering.
11. The welding method according to claim 10,
the coating device for the welding flux composition is a spray fluxer,
the coating weight of the flux composition for welding is 30mL/m2Above and 180mL/m2The following.
12. The welding method according to claim 10 or 11,
the molten solder is Sn-Au-Cu solder alloy,
in the step of soldering, the temperature of the molten solder is 230 ℃ to 280 ℃, and the preheating temperature is 80 ℃ to 130 ℃.
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JP6967050B2 (en) * 2019-09-27 2021-11-17 株式会社タムラ製作所 Flux composition for soldering
JP6928295B1 (en) * 2020-10-02 2021-09-01 千住金属工業株式会社 Flux and solder paste

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JP2003225795A (en) * 2002-01-30 2003-08-12 Showa Denko Kk Flux for soldering and solder paste
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JP2015208770A (en) * 2014-04-28 2015-11-24 株式会社タムラ製作所 Flux composition for soldering and electronic circuit board using the same
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