CN113811420A - Composition for flux containing maleic acid-modified rosin ester or maleic acid-modified rosin amide, flux containing same, and solder paste - Google Patents
Composition for flux containing maleic acid-modified rosin ester or maleic acid-modified rosin amide, flux containing same, and solder paste Download PDFInfo
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- CN113811420A CN113811420A CN202080034898.8A CN202080034898A CN113811420A CN 113811420 A CN113811420 A CN 113811420A CN 202080034898 A CN202080034898 A CN 202080034898A CN 113811420 A CN113811420 A CN 113811420A
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- Prior art keywords
- flux
- acid
- maleic acid
- modified rosin
- mass ppm
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Classifications
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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
-
- 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
- B23K35/362—Selection of compositions of fluxes
Abstract
An object of the present invention is to provide: a flux for soldering, which suppresses residue cracking of flux residue and has excellent solder wettability. The invention provides a composition for soldering flux, which comprises the following components: 1 or more selected from the group consisting of a maleic acid-modified rosin ester, a maleic acid-modified rosin amide, a hydride of the maleic acid-modified rosin ester, and a hydride of the maleic acid-modified rosin amide.
Description
Technical Field
The present invention relates to: a composition for a flux, which contains a maleic acid-modified rosin ester or maleic acid-modified rosin amide, a flux containing the same, and a solder paste.
Background
The fixation and electrical connection with electronic components in electronic equipment, such as the mounting of electronic components to a printed board, are generally performed by soldering, which is most advantageous in terms of cost and reliability.
The method generally used in such soldering is: a flow soldering method in which a molten solder is brought into contact with a printed circuit board and an electronic component to perform soldering, and a reflow soldering method in which a solder in the form of a solder paste, a solder preform or a solder ball is remelted in a reflow furnace to perform soldering.
In this soldering, an auxiliary agent, that is, flux, is used to facilitate the solder to adhere to the printed circuit board and the electronic component. The flux exhibits many useful effects such as (1) a metal surface cleaning effect (an effect of chemically removing an oxide film on the metal surfaces of a printed circuit board and an electronic component to enable soldering and thereby cleaning the surfaces), (2) a re-oxidation preventing effect (an effect of covering the cleaned metal surfaces during soldering so as to block contact with oxygen and prevent re-oxidation of the metal surfaces by heating), and (3) an interfacial tension reducing effect (an effect of reducing the surface tension of molten solder and improving the wettability of the metal surfaces by the solder).
Patent document 1 describes the following: a rosin derivative compound obtained by dehydrating and condensing a rosin-based carboxyl group-containing resin and a dimer acid derivative flexible alcohol compound is used as a flux for soldering.
Further, patent document 2 discloses a method for producing a rosin ester with a good yield in a short time.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2014-185298
Patent document 2: japanese patent laid-open publication No. 2017-186324
Disclosure of Invention
Problems to be solved by the invention
However, the flux described in patent document 1 causes residue cracks in the flux residue after soldering, and is poor in reliability.
On the other hand, when the rosin ester described in patent document 2 is used as a flux, there are problems of low activity and poor solder wettability.
In view of the above circumstances, an object of the present invention is to provide: a flux for soldering, which suppresses residue cracking of flux residue and has excellent solder wettability.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: the above object can be achieved by using a flux composition containing 1 or more selected from the group consisting of a maleic acid-modified rosin ester, a maleic acid-modified rosin amide, a hydride of the maleic acid-modified rosin ester, and a hydride of the maleic acid-modified rosin amide, and the present invention has been completed. Namely, the present invention is as follows.
[1]
A composition for a solder flux, comprising: 1 or more selected from the group consisting of a maleic acid-modified rosin ester, a maleic acid-modified rosin amide, a hydride of the maleic acid-modified rosin ester, and a hydride of the maleic acid-modified rosin amide.
[2]
The composition for a flux according to the above [1], wherein the maleic acid-modified rosin ester or maleic acid-modified rosin amide is at least 1 selected from the group consisting of compounds represented by the following formulae (1) to (7).
(wherein, R's each independently represents an optionally substituted, linear or branched alkyl group, an alkylene glycol group, or a terminally modified polyalkylene oxide group; and R's each independently represents an optionally substituted, linear or branched alkylene group, or a 2-valent alkylene glycol group.)
[3]
A flux for soldering a solder alloy, comprising the composition for a flux according to [1] or [2 ].
[4]
The flux according to the above [3], wherein the content of the maleic acid-modified rosin ester and/or maleic acid-modified rosin amide is more than 0% by weight and 60% by weight or less with respect to the entire flux.
[5]
The flux according to the above [3] or [4], wherein the flux further comprises a thixotropic agent.
[6]
The flux according to any one of the above [3] to [5],
the flux further comprises:
0 to 20% by weight of an amine,
0 to 5% by weight of an organic halogen compound,
0 to 2% by weight of an amine hydrohalide salt, or
0 to 5 wt.% of an antioxidant,
0 to 80% by weight of a resin.
[7]
A solder paste, comprising: the flux according to any one of the above [3] to [6], and a solder alloy.
[8]
The solder paste according to the above [7], wherein,
the solder alloy had the following alloy composition:
as: 25 to 300 mass ppm, Bi: 0 to 25000 mass ppm inclusive, Pb: more than 0 mass ppm and 8000 mass ppm or less, and the balance being composed of Sn, and satisfying the following formulas (1) and (2):
275≤2As+Bi+Pb (1)
0<2.3×10-4×Bi+8.2×10-4×Pb≤7 (2)
[ in the above formulas (1) and (2), As, Bi and Pb are each the content (mass ppm) in the alloy composition ].
[9]
The solder paste according to the above [7], wherein,
the solder alloy had the following alloy composition:
as: 25 to 300 mass ppm; pb: more than 0 ppm by mass and 5100 ppm by mass or less; and Sb: more than 0 mass ppm and 3000 mass ppm or less and Bi: more than 0 mass ppm and 10000 mass ppm or less; the balance is composed of Sn, and satisfies the following formulae (3) and (4):
275≤2As+Sb+Bi+Pb (3)
0.01≤(2As+Sb)/(Bi+Pb)≤10.00 (4)
[ in the above formulas (3) and (4), As, Sb, Bi and Pb are each the content (mass ppm) in the alloy composition ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided: a flux for soldering, which suppresses residue cracking of flux residue and has excellent solder wettability.
Detailed Description
Hereinafter, an embodiment of the present invention (hereinafter, referred to as "the present embodiment") will be described in detail, but the present invention is not limited thereto, and various modifications can be made without departing from the gist thereof.
[ flux ]
The flux for soldering the solder alloy of the present embodiment includes: a composition for a flux comprising 1 or more selected from the group consisting of a maleic acid-modified rosin ester, a maleic acid-modified rosin amide, a hydride of the maleic acid-modified rosin ester, and a hydride of the maleic acid-modified rosin amide; and, a solvent.
By using the composition for a flux of the present embodiment, it is possible to sufficiently suppress residue cracking of flux residue and improve solder wettability. The soldering can be used for either of flow soldering and reflow soldering, but is preferably used for reflow soldering in order that the effect of the present invention becomes more remarkable.
[ maleic acid-modified rosin ester/maleic acid-modified rosin amide ]
The flux composition of the present embodiment includes: 1 or more selected from the group consisting of a maleic acid-modified rosin ester, a maleic acid-modified rosin amide, a hydride of the maleic acid-modified rosin ester, and a hydride of the maleic acid-modified rosin amide.
The maleic acid-modified rosin ester is not particularly limited, and examples thereof include: maleic acid-modified rosin monoesters such as maleic acid-modified rosin monomethyl ester, maleic acid-modified rosin monoethyl ester, maleic acid-modified rosin monoisopropyl ester, and maleic acid-modified rosin monoethyl glycol ester; and maleic acid-modified rosin diesters such as maleic acid-modified rosin dimethyl ester. Among them, monoester remaining with carboxylic acid is preferable, and isopropyl ester is particularly preferable, from the viewpoint of flux activity and compatibility.
Examples of the maleic acid-modified rosin ester include compounds represented by the following formula (1) or (2).
(wherein R represents an optionally substituted, linear or branched alkyl group, an alkylene glycol group, or a terminally modified polyalkylene oxide group.)
Wherein the alkylene glycol group represents a 1-valent group represented by the following formula (i) wherein R is1Each independently represents a linear or branched alkylene group having 1 to 4 carbon atoms, and n represents an integer of 1 to 500.
h(OR1)n- (i)
The terminal-modified polyoxyalkylene group represents a 1-valent group represented by the following formula (ii) wherein R is1Each independently represents a linear or branched alkylene group having 1 to 4 carbon atoms, X represents an amino group, a linear or branched alkyl ester group having 1 to 40 carbon atoms, or a linear or branched alkyl ether group having 1 to 40 carbon atoms, and n represents an integer of 0 to 500.
X-R1-(OR1)n- (ii)
The number of carbon atoms of the alkyl group represented by R is not particularly limited, and is preferably 1 to 54. The number of carbon atoms of the alkylene glycol group and the terminal-modified polyalkylene oxide group represented by R is not particularly limited, and is preferably 1 to 500. In the formulae (i) and (ii), the number of carbon atoms in the alkyl moiety of X is preferably 1 to 24, and R is preferably1The carbon number of (C) is preferably 1 to 3. In the formulae (i) and (ii), n is preferably 1 to 500, more preferably 1 to 100, and still more preferably 1 to 10. Examples of the terminal-modified polyalkylene oxide group include: a group obtained by adding an alcohol having 1 to 40 carbon atoms such as cetyl alcohol, stearyl alcohol and behenyl alcohol or a carboxylic acid having 1 to 40 carbon atoms such as palmitic acid, stearic acid and behenic acid to the hydroxyl terminal of a polyalkylene glycol such as polyethylene glycol, polypropylene glycol and a copolymer of ethylene oxide and propylene oxide; and a group obtained by modifying the hydroxyl group terminal of a polyalkylene glycol such as a copolymer of ethylene oxide and propylene oxide with an amino group.
Further, the maleic acid-modified rosin ester also includes: and (3) a compound obtained by condensing or bonding 2 or more species of a maleic acid-modified rosin ester such as a maleic acid-modified rosin ester dimer or a maleic acid-modified rosin ester multimer with an alcohol or the like.
(wherein R' represents an optionally substituted, linear or branched alkylene group, or a 2-valent alkylene glycol group.)
Wherein the alkylene glycol group having a valence of 2 represents a group having a valence of 2 represented by the following formula (iii) wherein R represents2And R3Each independently represents a linear or branched alkylene group having 1 to 4 carbon atoms, and n represents an integer of 0 to 500.
-R2-(OR3)n- (iii)
The number of carbon atoms of the alkylene group represented by R' is not particularly limited, but is preferably 1 to 54. The number of carbon atoms of the alkylene glycol group having a valence of 2 represented by R' is not particularly limited, but is preferably 1 to 500. In the formula (iii), R2And R3The carbon number of (C) is preferably 1 to 3. In the formula (iii), n is preferably 1 to 500, more preferably 1 to 100, and further preferably 1 to 10.
The maleic acid-modified rosin amide is not particularly limited, and examples thereof include a dehydration condensate of maleic acid-modified rosin and cyclohexylamine, and cyclohexylamine salts of the dehydration condensate of maleic acid-modified rosin and cyclohexylamine. Specifically, for example, compounds represented by the following formula (4) or (5) can be mentioned. Among them, maleic acid-modified rosin monocyclohexylamide and maleic acid-modified hydrogenated rosin cyclohexylamide are preferable from the viewpoint of flux activity and compatibility.
(wherein R is as defined above.)
Further, the maleic acid-modified rosin amide further contains: and compounds obtained by condensation or bonding of 2 or more species of maleic acid-modified rosin amides via amines, such as maleic acid-modified rosin amide dimers or maleic acid-modified rosin amide multimers represented by the following formula (6).
(wherein R' has the same meaning as defined above.)
Further, the maleic acid-modified rosin acid amide also includes: a compound obtained by bonding a maleic acid-modified rosin amide represented by the following formula (7) and a maleic acid-modified rosin ester directly or via an amine, an alcohol or the like.
(wherein R' has the same meaning as defined above.)
Further, the maleic acid-modified rosin ester and the maleic acid-modified rosin amide also include: various isomers (structural isomers, optical isomers, etc.) of the above compounds, and salts (amine salts, etc.) of the above compounds.
The maleic acid-modified rosin ester and the maleic acid-modified rosin amide may be used alone in 1 kind or in combination of 2 or more kinds.
The hydrogenated products of the maleic acid-modified rosin ester and the maleic acid-modified rosin amide mean compounds in which the carbon-carbon double bond present in these compounds is hydrogenated. For example, the hydrogenated product of a maleic acid-modified rosin ester represented by the above formula (1) has a structure represented by the following formula (8).
(wherein R is as defined above.)
The various maleic acid-modified rosin esters and maleic acid-modified rosin amides described above can be produced by known methods. As known methods, for example, the following methods can be adopted: the solvent-free reaction described in example 1 of Japanese patent application laid-open No. 2017-186324, or the reaction in a hydrophobic solvent of example 6. Examples of the raw material rosin used for synthesizing the maleic acid-modified rosin ester and the maleic acid-modified rosin amide include gum rosin, tall oil rosin, wood rosin, and purified products thereof (purified rosin). Further, as the raw material rosin, for example, raw rosin and commercially available gum rosin described in "df. zinkel, j. russell editors of kuchuangji hong, (1993), chemical production, chemistry and use of pine, 361-. That is, the maleic acid-modified rosin ester and the maleic acid-modified rosin amide of the present embodiment may include compounds obtained by esterifying or amidating the various raw material rosins and rosin derivatives obtained from raw material rosins such as (hydrogenated) maleic acid-modified rosins.
The content of the maleic acid-modified rosin ester and the maleic acid-modified rosin amide is preferably more than 0% by weight and 60% by weight or less, more preferably 5% by weight or more, further preferably 10% by weight or more, further more preferably 20% by weight or more, and particularly preferably 30% by weight or more, with respect to the entire flux, as an upper limit, more preferably 50% by weight or less, and further preferably 40% by weight or less. The larger the contents of the maleic acid-modified rosin ester and the maleic acid-modified rosin amide are, the more significant the effect of suppressing the residue cracking of the flux residue tends to be.
The flux of the present embodiment may contain a resin other than the above-described maleic acid-modified rosin ester, maleic acid-modified rosin amide, and hydride thereof. As the resin, various resins used in conventional soldering fluxes can be used. Examples of such a resin include rosin resins, acrylic resins, polyesters, polyethylene, polypropylene, polyamides, styrene-maleic acid copolymers, acrylic resins, epoxy resins, phenol resins, phenoxy resins, terpene phenol resins, and mixtures thereof, and among these, rosin resins are usually used. Examples of the rosin-based resin include natural rosins such as gum rosin and wood rosin, and derivatives thereof (polymerized rosin, hydrogenated rosin, disproportionated rosin, acid-modified rosin, rosin ester, and the like).
The content of the resin in the flux is not limited, and when the flux is used as a flux for reflow soldering, the content may be, for example, in the range of 10 to 80 wt%, or 20 to 70 wt%, or 30 to 60 wt%. When used as a flux for flow soldering, the flux may be used, for example, in the range of 3 to 18 wt%, or 6 to 15 wt%, or 9 to 12 wt%.
Examples of the solvent contained in the flux of the present embodiment include water, alcohol solvents, glycol ether solvents, terpineol, and the like. Examples of the alcohol solvent include isopropanol, 1, 2-butanediol, isobornyl cyclohexanol, 2, 4-diethyl-1, 5-pentanediol, 2-dimethyl-1, 3-propanediol, 2, 5-dimethyl-2, 5-hexanediol, 2, 5-dimethyl-3-hexyne-2, 5-diol, 2, 3-dimethyl-2, 3-butanediol, 1,1, 1-tris (hydroxymethyl) ethane, 2-ethyl-2-hydroxymethyl-1, 3-propanediol, 2 '-oxybis (methylene) bis (2-ethyl-1, 3-propanediol), 2-bis (hydroxymethyl) -1, 3-propanediol, isobornyl cyclohexanol, 2, 4-diethyl-1, 5-pentanediol, 2-dimethyl-1, 3-propanediol, 2, 1, 1-tris (hydroxymethyl) ethane, 2-ethyl-2-hydroxymethyl-1, 3-propanediol, 2' -oxybis (methylene) bis (2-ethyl-1, 3-propanediol, 2-bis (hydroxymethyl) -1, 3-propanediol, and the like, 1,2, 6-trihydroxyhexane, bis [2,2, 2-tris (hydroxymethyl) ethyl ] ether, 1-ethynyl-1-cyclohexanol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, erythritol, threitol, guaifenesin, 3, 6-dimethyl-4-octyne-3, 6-diol, 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, and the like. Examples of the glycol ether solvent include hexyldiglycol, diethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, 2-methylpentane-2, 4-diol, diethylene glycol monohexyl ether, diethylene glycol dibutyl ether, triethylene glycol monobutyl ether, and tetraethylene glycol monomethyl ether.
The flux of the present embodiment may further include an organic acid, an amine, and a halogen (organic halogen compound, amine hydrohalide) as an active agent.
When the flux of the present embodiment is used as a flux for reflow soldering, it preferably contains 0 wt% to 10 wt% of an organic acid. When the flux of the present embodiment is used as a flux for reflow soldering, the amine is contained preferably in an amount of 0 wt% to 20 wt%, more preferably in an amount of 0 wt% to 5 wt%. When the flux of the present embodiment is used as a flux for reflow soldering, the halogen preferably contains an organic halogen compound in an amount of 0 wt% to 5 wt%, and the amine hydrohalide salt in an amount of 0 wt% to 2 wt%.
When the flux of the present embodiment is used as a flux for flow soldering, the active agent is preferably contained in an amount of 0.1 wt% or more and 12.0 wt% or less, more preferably 0.3 wt% or more and 8.0 wt% or less, and still more preferably 0.5 wt% or more and 4.0 wt% or less.
Examples of the organic acid include glutaric acid, adipic acid, azelaic acid, eicosanedioic acid, citric acid, glycolic acid, succinic acid, salicylic acid, diglycolic acid, dipicolinic acid, dibutylanilide diglycolic acid, suberic acid, sebacic acid, thioglycolic acid, terephthalic acid, dodecanedioic acid, p-hydroxyphenylacetic acid, phenylsuccinic acid, phthalic acid, fumaric acid, maleic acid, malonic acid, lauric acid, benzoic acid, tartaric acid, tris (2-carboxyethyl) isocyanurate, glycine, 1, 3-cyclohexanedicarboxylic acid, 2-bis (hydroxymethyl) propionic acid, 2-bis (hydroxymethyl) butyric acid, 2, 3-dihydroxybenzoic acid, 2, 4-diethylglutaric acid, 2-quinolinecarboxylic acid, 3-hydroxybenzoic acid, malic acid, p-anisic acid, stearic acid, maleic acid, malonic acid, lauric acid, benzoic acid, tartaric acid, tris (2-carboxyethyl) isocyanurate, glycine, 1, 3-cyclohexanedicarboxylic acid, malic acid, p-anisic acid, stearic acid, and the like, 12-hydroxystearic acid, oleic acid, linoleic acid, linolenic acid, etc.
Examples of the organic acid include a dimer acid, a trimer acid, a hydrogenated dimer acid which is a hydrogenated product of a dimer acid to which hydrogen is added, and a hydrogenated trimer acid which is a hydrogenated product of a trimer acid to which hydrogen is added.
Examples thereof include: dimer acid, which is a reactant of oleic acid and linoleic acid, trimer acid, which is a reactant of oleic acid and linoleic acid, dimer acid, which is a reactant of acrylic acid, trimer acid, which is a reactant of acrylic acid, dimer acid, which is a reactant of methacrylic acid, dimer acid, which is a reactant of acrylic acid and methacrylic acid, trimer acid, which is a reactant of acrylic acid and methacrylic acid, dimer acid, which is a reactant of oleic acid, trimer acid, which is a reactant of oleic acid, dimer acid, which is a reactant of linoleic acid, trimer acid, which is a reactant of linolenic acid, trimer acid, which is a reactant of acrylic acid and oleic acid, dimer acid, which is a reactant of acrylic acid and linoleic acid, trimer acid, which is a reactant of acrylic acid and linoleic acid, dimer acid, which is a reactant of acrylic acid, linolenic acid, which is a reactant of acrylic acid and linolenic acid, dimer acid, and trimer acid, which is a reactant of acrylic acid, and linolenic acid, dimer acid, and dimer acid, Trimer acid which is a reaction product of acrylic acid and linolenic acid, dimer acid which is a reaction product of methacrylic acid and oleic acid, trimer acid which is a reaction product of methacrylic acid and oleic acid, dimer acid which is a reaction product of methacrylic acid and linoleic acid, trimer acid which is a reaction product of methacrylic acid and linoleic acid, dimer acid which is a reaction product of methacrylic acid and linolenic acid, trimer acid which is a reaction product of methacrylic acid and linolenic acid, dimer acid which is a reaction product of oleic acid and linolenic acid, trimer acid which is a reaction product of oleic acid and linolenic acid, dimer acid which is a reaction product of linoleic acid and linolenic acid, trimer acid which is a reaction product of linoleic acid and linolenic acid, hydrogenated dimer acid which is a hydrogenated product of each of the above dimer acids, hydrogenated trimer acid which is a hydrogenated product of each of the above trimer acids, and the like.
Examples of the amine include: monoethanolamine, diphenylguanidine, ditolylbuanidine, ethylamine, triethylamine, cyclohexylamine, ethylenediamine, triethylenetetramine, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, cyclohexylamine, tetramethylammonium chloride, ammonium chloride, and the like, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2 ' -undecylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2 ' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, 2, 4-diamino-6-vinyl-s-triazine isocyanuric acid adduct, 2, 4-diamino-6-methacryloyloxyethyl-s-triazine, epoxy-imidazole adduct, 2-methylbenzimidazole, 2-octylbenzimidazole, 2-pentylbenzimidazole, 2-dimethylbenzimidazole, dimethylimidazole, 2- (1-ethylpentyl) benzimidazole, 2-nonylbenzimidazole, 2- (4-thiazolyl) benzimidazole, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, 2- (2 '-hydroxy-3' -tert-butyl-5 '-methylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ', 5' -di-tert-amylphenyl) benzotriazole, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole, 2 '-methylenebis [6- (2H-benzotriazol-2-yl) -4-tert-octylphenol ], 6- (2-benzotriazolyl) -4-tert-octyl-6' -tert-butyl- 4 ' -methyl-2, 2 ' -methylenebisphenol, 1,2, 3-benzotriazole, 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] benzotriazole, carboxybenzotriazole, 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] methylbenzotriazole, 2 ' - [ [ (methyl-1H-benzotriazol-1-yl) methyl ] imino ] diethanol, 1- (1 ', 2 ' -dicarboxyethyl) benzotriazole, 1- (2, 3-dicarboxypropyl) benzotriazole, 1- [ (2-ethylhexylamino) methyl ] benzotriazole, 2, 6-bis [ (1H-benzotriazol-1-yl) methyl ] -4-methylphenol, and mixtures thereof, 5-methylbenzotriazole, 5-phenyltetrazole, and the like.
Examples of the organic halogen compound include: trans-2, 3-dibromo-2-butene-1, 4-diol, triallyl isocyanurate hexabromide, 1-bromo-2-butanol, 1-bromo-2-propanol, 3-bromo-1, 2-propanediol, 1, 4-dibromo-2-butanol, 1, 3-dibromo-2-propanol, 2, 3-dibromo-1, 4-butanediol, 2, 3-dibromo-2-butene-1, 4-diol, tris (2, 3-dibromopropyl) isocyanurate, chlorendic anhydride, and the like.
Amine hydrohalides are compounds obtained by reacting amines with hydrogen halides.
As the amine of the amine hydrohalide salt, the above-mentioned amines can be used, and examples thereof include ethylamine, cyclohexylamine, ethylenediamine, triethylamine, diphenylguanidine, ditolylbutylguanidine, methylimidazole, 2-ethyl-4-methylimidazole and the like. Examples of the hydrogen halide include hydrides of chlorine, bromine, iodine, and fluorine (hydrogen chloride, hydrogen bromide, hydrogen iodide, and hydrogen fluoride). Further, a borofluoride may be contained instead of or together with the amine hydrohalide salt, and examples of the borofluoride include borofluoric acid and the like.
Examples of the amine hydrohalide salt include aniline hydrogen chloride, cyclohexylamine hydrogen chloride, aniline hydrogen bromide, diphenylguanidine hydrogen bromide, ditolyguanidinium hydrogen bromide, and ethylamine hydrogen bromide.
The flux of the present embodiment may further contain an antioxidant, and examples of the antioxidant include a hindered phenol-based antioxidant, and when used as a reflow flux, the antioxidant is preferably contained in an amount of 0 wt% to 5 wt%, and when used as a flow solder flux, the antioxidant is preferably contained in an amount of 0 wt% to 5 wt%, and more preferably contained in an amount of 0 wt% to 2 wt%.
The flux of the present embodiment may include a thixotropic agent.
Examples of the thixotropic agent include wax-based thixotropic agents, amide-based thixotropic agents, and sorbitol-based thixotropic agents. Examples of the wax thixotropic agent include hydrogenated castor oil and the like. Examples of the amide-based thixotropic agent include monoamide-based thixotropic agents, bisamide-based thixotropic agents, and polyamide-based thixotropic agents, and specific examples thereof include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, saturated fatty acid amide, oleic acid amide, erucic acid amide, unsaturated fatty acid amide, p-tolylmethane amide, aromatic amide, methylene bisstearic acid amide, ethylene bislauric acid amide, ethylene bishydroxystearic acid amide, saturated fatty acid bisamide, methylene bisoleic acid amide, unsaturated fatty acid bisamide, m-xylylene bisstearic acid amide, aromatic bisamide, saturated fatty acid polyamide, unsaturated fatty acid polyamide, aromatic polyamide, substituted amide, methylol stearic acid amide, methylolamide, and fatty acid ester amide. Examples of the sorbitol thixotropic agent include dibenzylidene-D-sorbitol and bis (4-methylbenzylidene) -D-sorbitol.
In addition, the flux of the present embodiment may contain an ester compound as a thixotropic agent. Examples of the ester compound include hydrogenated castor oil and the like.
When the total amount of the thixotropic agent contained in the flux is used as a reflow flux, the total amount is preferably 0 wt% or more and 15 wt% or less, and more preferably 0 wt% or more and 10 wt% or less. The content of the amide thixotropic agent is preferably 0 wt% or more and 12 wt% or less when used as a reflow flux, and the content of the ester compound is preferably 0 wt% or more and 8.0 wt% or less, more preferably 0 wt% or more and 4.0 wt% or less when used as a reflow flux.
When the total amount of the thixotropic agent contained in the flux is used as a flux for flow soldering, the total amount is preferably 0 wt% or more and 3 wt% or less, and more preferably 0 wt% or more and 1 wt% or less.
[ solder paste ]
The flux of the present embodiment can be used for either flow soldering or reflow soldering, but is preferably used for reflow soldering in order to make the effects of the present invention more remarkable.
The solder paste of the present embodiment 1 includes: the flux and the solder alloy.
The solder alloy is not particularly limited, and preferably has the following alloy composition:
as: 25 to 300 mass ppm, Bi: 0 to 25000 mass ppm inclusive, Pb: more than 0 mass ppm and 8000 mass ppm or less, and the balance being composed of Sn, and satisfying the following formulas (1) and (2):
275≤2As+Bi+Pb (1)
0<2.3×10-4×Bi+8.2×10-4×Pb≤7 (2)
[ in the above formulas (1) and (2), As, Bi and Pb are each the content (mass ppm) in the alloy composition ].
The solder alloy according to embodiment 2 is not particularly limited, and preferably has the following alloy composition:
as: 25-300 mass ppm, Pb: more than 0 ppm by mass and 5100 ppm by mass or less, and Sb: more than 0 mass ppm and 3000 mass ppm or less and Bi: more than 0 ppm by mass and 10000 ppm by mass or less, the balance being Sn, and satisfying the following formulae (3) and (4):
275≤2As+Sb+Bi+Pb (3)
0.01≤(2As+Sb)/(Bi+Pb)≤10.00 (4)
[ in the above formulas (3) and (4), As, Sb, Bi and Pb are each the content (mass ppm) in the alloy composition ].
As is an element that can suppress a change in viscosity of the solder paste with time. As is an element that has low reactivity with flux and is more expensive than Sn, and therefore is presumed to exhibit a thickening suppression effect. When As is less than 25 ppm by mass, the thickening-inhibiting effect cannot be sufficiently exhibited. The lower limit of the As content is 25 mass ppm or more, preferably 50 mass ppm or more, and more preferably 100 mass ppm or more. On the other hand, if As is too large, the wettability of the solder alloy deteriorates. The upper limit of the As content is 300 mass ppm or less, preferably 250 mass ppm or less, and more preferably 200 mass ppm or less.
Sb is an element having low reactivity with the flux and showing a thickening suppressing effect. When the solder alloy of the present embodiment contains Sb, the lower limit of the Sb content is more than 0 mass ppm, preferably 25 mass ppm or more, more preferably 50 mass ppm or more, further preferably 100 mass ppm or more, and particularly preferably 300 mass ppm or more. On the other hand, if the Sb content is too large, the wettability deteriorates, and therefore, an appropriate content is required. The upper limit of the Sb content is 3000 mass ppm or less, preferably 1150 mass ppm or less, more preferably 500 mass ppm or less.
Like Sb, Bi and Pb are elements that have low reactivity with flux and exhibit thickening suppression effect. In addition, Bi and Pb are elements that can suppress deterioration of wettability by As by lowering the liquidus temperature of the solder alloy.
If at least 1 element of Sb, Bi, and Pb is present, deterioration of wettability based on As can be suppressed. When the solder alloy of the present embodiment contains Bi, the lower limit of the Bi content exceeds 0 mass ppm, preferably 25 mass ppm or more, more preferably 50 mass ppm or more, still more preferably 75 mass ppm or more, particularly preferably 100 mass ppm or more, and most preferably 250 mass ppm or more. When the solder alloy of the present embodiment contains Pb, the lower limit of the Pb content exceeds 0 mass ppm, preferably 25 mass ppm or more, more preferably 50 mass ppm or more, further preferably 75 mass ppm or more, particularly preferably 100 mass ppm or more, and most preferably 250 mass ppm or more.
On the other hand, if the contents of these elements are too large, the solidus temperature is significantly lowered, and therefore, the temperature difference between the liquidus temperature and the solidus temperature, i.e., Δ T, becomes excessively wide. If the Δ T is excessively large, a high-melting-point crystal phase containing a small amount of Bi and Pb precipitates during solidification of the molten solder, and Bi and Pb in the liquid phase are concentrated. Then, if the temperature of the molten solder is further lowered, a low melting point crystal phase having high Bi and Pb concentrations segregates. Therefore, the solder alloy has deteriorated mechanical strength and the like, and the reliability is deteriorated. In particular, since a crystal phase having a high Bi concentration is hard and brittle, if segregation occurs in the solder alloy, the mechanical strength and the like are significantly reduced.
From this viewpoint, when the solder alloy of the present embodiment contains Bi, the upper limit of the Bi content is 25000 mass ppm or less, preferably 10000 mass ppm or less, more preferably 1000 mass ppm or less, further preferably 600 mass ppm or less, and particularly preferably 500 mass ppm or less. When the solder alloy of the present embodiment contains Pb, the upper limit of the Pb content is 8000 mass ppm or less, preferably 5100 mass ppm or less, more preferably 5000 mass ppm or less, further preferably 1000 mass ppm or less, particularly preferably 850 mass ppm or less, and most preferably 500 mass ppm or less.
1 st solder alloy according to the present embodiment preferably satisfies the following expression (1).
275≤2As+Bi+Pb (1)
In the above formula (1), As, Bi and Pb each represent the content (mass ppm) in the alloy composition.
As, Bi and Pb are all elements showing a thickening suppressing effect. The total amount of these is preferably 230 mass ppm or more. (1) In the formula, the content of As is 2 times that of Bi or Pb, and As has a higher thickening-suppressing effect than Bi or Pb.
(1) If the value of the formula is less than 275, the thickening-inhibiting effect cannot be sufficiently exhibited. (1) The lower limit of the formula is 275 or more, preferably 300 or more, more preferably 700 or more, and further preferably 900 or more. On the other hand, the upper limit of (1) is not particularly limited from the viewpoint of the thickening suppressing effect, but from the viewpoint of forming a range suitable for Δ T, it is preferably 25200 or less, more preferably 15200 or less, further preferably 10200 or less, particularly preferably 8200 or less, and most preferably 5300 or less.
When the upper limit and the lower limit are appropriately selected from the above-described preferred embodiments, the following formulae (1a) and (1b) are given.
275≤2As+Bi+Pb≤25200 (1a)
275≤2As+Bi+Pb≤5300 (1b)
In the above formulae (1a) and (1b), As, Bi and Pb represent the contents (mass ppm) in the alloy composition, respectively.
1 st solder alloy according to the present embodiment preferably satisfies the following expression (2).
0<2.3×10-4×Bi+8.2×10-4×Pb≤7 (2)
In the above formula (2), Bi and Pb each represent the content (mass ppm) in the alloy composition.
Bi and Pb suppress the deterioration of wettability due to the inclusion of As, but if the content is too large, the Δ T increases, and therefore strict control is required. Particularly, in an alloy composition containing Bi and Pb at the same time, Δ T is likely to increase. In embodiment 1, the increase in Δ T can be suppressed by limiting the total of the values obtained by multiplying the contents of Bi and Pb by a predetermined coefficient. (2) In the formula, the coefficient of Pb is larger than that of Bi. This is because Pb has a higher degree of contribution to Δ T than Bi, and Δ T is greatly increased by a slight increase in the content.
(2) The solder alloy of formula 0 does not contain both Bi and Pb, and cannot suppress the deterioration of wettability due to the inclusion of As. (2) The lower limit of the formula (iii) is more than 0, preferably 0.02 or more, more preferably 0.03 or more, still more preferably 0.05 or more, particularly preferably 0.06 or more, and most preferably 0.11 or more. On the other hand, if the value of equation (2) exceeds 7, the temperature range of Δ T becomes excessively wide, so that a crystal phase having a high Bi and Pb concentration is segregated when the molten solder is solidified, and the mechanical strength and the like deteriorate. (2) The upper limit of (b) is 7 or less, preferably 6.56 or less, more preferably 6.40 or less, further preferably 5.75 or less, further more preferably 4.18 or less, particularly preferably 2.30 or less, most preferably 0.90 or less.
When the upper limit and the lower limit are appropriately selected from the above-described preferred embodiments, the following formula (2a) is used.
0.02≤2.3×10-4×Bi+8.2×10-4×Pb≤0.9 (2a)
In the above formula (2a), Bi and Pb each represent the content (mass ppm) in the alloy composition.
2 nd solder alloy of the present embodiment preferably satisfies the following expression (3).
275≤2As+Sb+Bi+Pb (3)
In the above formula (3), As, Sb, Bi and Pb each represent the content (mass ppm) in the alloy composition.
As, Sb, Bi and Pb are all elements showing a thickening suppressing effect. The total amount of these components must be 275 mass ppm or more. (3) In the formula, the content of As is 2 times that of Sb, Bi and Pb, and As has a higher thickening-suppressing effect.
(1) If the value of the formula is less than 275, the thickening-inhibiting effect cannot be sufficiently exhibited. (1) The lower limit of the formula is 275 or more, preferably 350 or more, and more preferably 1200 or more. On the other hand, the upper limit of (1) is not particularly limited from the viewpoint of the thickening suppressing effect, but from the viewpoint of forming a range suitable for Δ T, it is preferably 25200 or less, more preferably 10200 or less, further preferably 5300 or less, and particularly preferably 3800 or less.
When the upper limit and the lower limit are appropriately selected from the above-described preferred embodiments, the following formulae (3a) and (3b) are given.
275≤2As+Sb+Bi+Pb≤25200 (3a)
275≤2As+Sb+Bi+Pb≤5300 (3b)
In the above formulae (3a) and (3b), As, Sb, Bi and Pb each represent the content (mass ppm) in the alloy composition.
2 nd solder alloy of the present embodiment preferably satisfies the following expression (4).
0.01≤(2As+Sb)/(Bi+Pb)≤10.00 (4)
In the above formula (2), As, Sb, Bi and Pb each represent the content (mass ppm) in the alloy composition.
If the content of As and Sb is large, the wettability of the solder alloy deteriorates. On the other hand, Bi and Pb suppress the deterioration of wettability by containing As, but if the content is too large, Δ T increases, and therefore strict management is required. In particular, in an alloy composition containing both Bi and Pb, Δ T is likely to increase. Therefore, when the wettability is intended to be improved excessively by increasing the contents of Bi and Pb, Δ T is enlarged. On the other hand, when the content of As or Sb is increased to improve the thickening suppressing effect, the wettability is deteriorated. Therefore, in embodiment 2, the thickening effect, the narrowing of Δ T, and the wettability are all satisfied at the same time when the total amount of the two groups is within an appropriate predetermined range.
(4) If the amount of the compound represented by the formula is less than 0.01, the total content of Bi and Pb becomes relatively larger than the total content of As and Pb, and thus Δ T increases. (4) The lower limit of the formula is 0.01 or more, preferably 0.02 or more, more preferably 0.41 or more, further preferably 0.90 or more, particularly preferably 1.00 or more, most preferably 1.40 or more. On the other hand, if the formula (4) exceeds 10.00, the total content of As and Sb becomes relatively larger than the total content of Bi and Pb, and thus the wettability deteriorates. (4) The upper limit of (b) is 10.00 or less, preferably 5.33 or less, more preferably 4.50 or less, further preferably 2.67 or less, further more preferably 4.18 or less, particularly preferably 2.30 or less.
The denominator of the formula (4) is "Bi + Pb", and if they are not contained, the formula (4) does not hold. That is, the solder alloy of embodiment 2 must contain at least 1 of Bi and Pb. As described above, the alloy composition containing no Bi and Pb is poor in wettability.
The upper limit and the lower limit are appropriately selected from the above-described preferred embodiments and defined by the following formula (4 a).
0.31≤(2As+Sb)/(Bi+Pb)≤10.00(4a)
In the above formula (4a), As, Sb, Bi and Pb each represent the content (mass ppm) in the alloy composition.
Ag is formed at grain boundary3Sn and any element capable of improving the reliability, mechanical strength and the like of the solder alloy. Ag is an element having a higher ionization tendency than Sn, and contributes to the thickening suppression effect of As, Pb, and Bi by coexisting therewith. The Ag content is preferably 0 to 4%, more preferably 0.5 to 3.5%, and further preferably 1.0 to 3.0%.
Cu is any element that can improve the bonding strength of the soldered joint. Cu is an element having a higher ionization tendency than Sn, and contributes to the thickening suppression effect thereof by coexisting with As, Pb, and Bi. The Cu content is preferably 0 to 0.9%, more preferably 0.1 to 0.8%, and further preferably 0.2 to 0.7%.
The solder alloy of the present embodiment has Sn as the remainder. Inevitable impurities may be contained in addition to the aforementioned elements. Even when unavoidable impurities are contained, the aforementioned effects are not affected. As described later, the elements not contained in the present embodiment are contained as inevitable impurities and do not affect the above-described effects. If the In content is too large, Δ T increases, so that the effect is not affected if the In content is 1000 ppm by mass or less.
The contents of the solder alloy and the flux in the solder paste are not limited, and for example, the solder alloy may be 5 to 95 wt% and the flux may be 5 to 95 wt%.
The solder paste of the present embodiment preferably contains zirconia powder. The zirconia can suppress the increase in viscosity of the paste with time. This is presumably because the oxide film thickness on the solder powder surface was maintained before being put into the flux by the zirconia. The details are not clear, but are presumed as follows. In general, the active ingredients of the flux remain slightly active even at normal temperature, and therefore, the oxide film on the surface of the solder powder is reduced to be thin, which causes the powder to aggregate. Therefore, it is presumed that: by adding zirconia powder to the solder paste, the active component of the flux and the zirconia powder preferentially react with each other, and the oxide film on the solder powder surface is maintained at a level not to aggregate.
In order to sufficiently exhibit such an action and effect, the content of the zirconia powder in the solder paste is preferably 0.05 to 20.0% with respect to the total mass of the solder paste. If the content is 0.05% or more, the above-mentioned effects can be exhibited, and if the content is 20.0% or less, the content of the metal powder can be secured, and the thickening-preventing effect can be exhibited. The content of zirconia is preferably 0.05 to 10.0%, and more preferably 0.1 to 3%.
The particle size of the zirconia powder in the solder paste is preferably 5 μm or less. If the particle size is 5 μm or less, the printability of the paste can be maintained. The lower limit is not particularly limited as long as it is 0.5 μm or more. The particle size is as follows: the SEM photographs of the zirconia powder were taken, and the projected circle equivalent diameters were obtained as the average value of the projected circle equivalent diameters by image analysis for each powder having a diameter of 0.1 μm or more.
The shape of zirconia is not particularly limited, and if it is irregularly shaped, the contact area with the flux is large, and the thickening suppressing effect is obtained. Since good fluidity can be obtained if the ink is spherical, excellent printability as a paste can be obtained. The shape can be appropriately selected according to the desired characteristics.
Examples
The present invention will be described in more detail below with reference to examples and comparative examples, but the scope of the present invention is not limited thereto.
The flux of examples A1 to 45 and comparative examples A1 to 3 was mixed with the compositions shown in tables 1 to 6 below, and the wetting rate of the flux was verified by using the flux to mix solder paste.
The composition ratios in the following tables are weight (mass)%, with the total amount of flux being 100.
In the solder paste, the flux was 11 wt% and the metal powder was 89 wt%. In addition, the metal powder in the solder paste is as follows: 3.0 wt% of Ag, 0.5 wt% of Cu, and the balance Sn, and the average particle diameter of the metal powder is 20 μm.
< research on flux >
(1) Evaluation of solder wettability (wetting Rate)
(verification method)
The Solder paste wetting rate was evaluated by a method of a cambered tin-plating test (meniscograph test) in which a copper plate having a width of 5mm, a length of 25mm and a thickness of 0.5mm was oxidized at 150 ℃ for 1 hour to obtain a copper oxide plate as a test plate, and Sn-3Ag-0.5Cu (each value is weight%) was used as a Solder by using a Solder Checker SAT-5200 (manufactured by RHESCA corporation) as a test device, as follows.
First, a test plate was dipped in each of the fluxes of examples and comparative examples measured in a beaker by 5mm, and the flux was applied to the test plate. Next, after the flux was applied, the test plate coated with the flux was rapidly immersed in a solder bath to obtain a zero crossing time (sec). Next, 5 measurements were performed on each flux of examples and comparative examples, and an average value of the obtained 5 zero crossing times (seconds) was calculated. The test conditions were set as follows.
Dipping speed for the soft solder pot: 5 mm/sec (JIS Z3198-4: 2003)
Dipping depth of the soft solder groove: 2mm (JIS Z3198-4: 2003)
Dipping time for the soft solder pot: 10 seconds (JIS Z3198-4: 2003)
Temperature of the soft solder groove: 245 ℃ (JIS C60068-2-69: 2019)
The shorter the average value of the zero crossing time (seconds), the higher the wetting rate, and the better the solder wettability.
(criteria for determination)
Good: the average value of the zero crossing time (seconds) is 6 seconds or less.
X: the average of the zero crossing times (seconds) exceeds 6 seconds.
(2) Evaluation of residual crack inhibition
A substrate having a size of 1.5X 0.25mm and 64 rows of electrode pads arranged at a pitch of 0.4mm was printed with a paste using a metal mask having a thickness of 0.15mm and soldered using a reflow furnace (the reflow peak temperature was 240 ℃). After reflow, after leaving at room temperature for 24 hours or more, the number of cracks in the flux residue existing between the pads was counted and evaluated as follows.
Good: the number of cracks in the residue is 15 or less
X: more than 15 cracks in the residue
In the table, the maleic acid-modified rosin ester and the maleic acid-modified rosin amide compound each include an isomer (structural isomer/stereoisomer) thereof.
[ Table 1]
[ Table 2]
[ Table 3]
[ Table 4]
[ Table 5]
[ Table 6]
The flux of the present embodiment contains 1 or more selected from the group consisting of a maleic acid-modified rosin ester, a maleic acid-modified rosin amide, a hydride of the maleic acid-modified rosin ester, and a hydride of the maleic acid-modified rosin amide, whereby residue cracking of the flux residue is suppressed, and solder wettability is also excellent.
< study of solder alloy >
The flux adjusted in example a1 was mixed with a solder alloy having an alloy composition shown in tables 7 to 18 and satisfying JIS Z3284-1: size of symbol 4 (particle size distribution) in classification of powder sizes in 2014 (table 2). The mass ratio of the soldering flux to the soft solder alloy is that the soldering flux: solder powder 11: 89. for each solder paste, the change in viscosity with time was measured. In addition, the liquidus temperature and solidus temperature of the solder powder were measured. Further, evaluation of wettability was performed using the solder paste immediately after the production. The details are as described below.
(3) Change with time
For each solder paste immediately after the production, a paste was prepared by using Malcolm co., ltd: PCU-205, at rotational speed: the viscosity was measured at 10rpm and 25 ℃ for 12 hours in the air. When the viscosity after 12 hours was 1.2 times or less as high as the viscosity after 30 minutes from the production of the solder paste, it was judged that a sufficient thickening suppressing effect was obtained, and the evaluation was "o", and when it exceeded 1.2 times, the evaluation was "x".
(4)ΔT
For the solder alloy before mixing with the flux, the solder alloy was prepared by SII nanoechnolgy inc, model: EXSTAR DSC7020, at sample size: about 30mg, rate of temperature rise: DSC measurement was performed at 15 ℃/min to obtain the solidus temperature and the liquidus temperature. The solidus temperature was subtracted from the obtained liquidus temperature to determine Δ T. When Δ T is 10 ℃ or lower, the value is "O", and when Δ T exceeds 10 ℃, the value is "X".
(5) Wettability
Printing each solder paste just after the preparation on a Cu plate, and performing N in a reflow furnace2The mixture was heated from 25 ℃ to 260 ℃ at a temperature rising rate of 1 ℃/sec in the atmosphere, and then cooled to room temperature. The appearance of the solder bump after cooling was observed with an optical microscope to evaluate wettability. The case where the incompletely melted solder powder was not observed was evaluated as "O", and the case where the incompletely melted solder powder was observed was evaluated as "OThe condition was evaluated as "x".
(6) Comprehensive evaluation
Good: all the above evaluations were good
X: the above evaluations are
[ Table 7]
[ Table 8]
[ Table 9]
[ Table 10]
[ Table 11]
[ Table 12]
[ Table 13]
[ Table 14]
[ Table 15]
[ Table 16]
[ Table 17]
[ Table 18]
As shown in tables 7 to 18, evaluation of the solder pastes including the flux of example A1 and the solder alloy of example B revealed that all of examples B (examples B2 to B95; and examples B2-1 to B2-108) exhibited good results in terms of the thickening-inhibiting effect, Δ T, and wettability.
In contrast, comparative examples B1, B10, B19, B28, B37, and B46 do not contain As, and therefore, the thickening-suppressing effect cannot be exhibited.
In comparative examples B2, B11, B20, B29, B38, and B47, the formula (1) is less than the lower limit, and therefore, the thickening-inhibiting effect cannot be exhibited.
Comparative examples B3, B4, B12, B13, B21, B22, B30, B31, B39, B40, B48, and B49 had As contents exceeding the upper limit values, and thus showed poor wettability results.
Comparative examples B5, B7, B9, B14, B16, B18, B23, B25, B27, B32, B34, B36, B41, B43, B45, B50, B52, and B54 have Pb contents and formula (2) exceeding the upper limit value, and therefore show a result in which Δ T exceeds 10 ℃.
Comparative examples B6, B15, B24, B33, B42, and B51 show the result that Δ T exceeds 10 ℃, because formula (2) exceeds the upper limit value.
Comparative examples B8, B17, B26, B35, B44, and B53 have Bi contents and formula (2) exceeding the upper limit value, and therefore show results in which Δ T exceeds 10 ℃.
Comparative examples B2-1, B2-14, B2-27, B2-40, B2-53 and B2-66 did not contain As, and therefore, the thickening-inhibiting effect was not exhibited.
In comparative examples B2-2, B2-15, B2-28, B2-41, B2-54 and B2-67, the lower limit of formula (3) was not satisfied, and therefore the thickening-inhibiting effect was not exhibited.
In comparative examples B2-3, B2-16, B2-29, B2-42, B2-55 and B2-68, the wettability was poor because the formula (4) exceeded the upper limit.
Comparative examples B2-4, B2-5, B2-17, B2-18, B2-30, B2-31, B2-43, B2-44, B2-56, B2-57, B2-69 and B2-70 were found to have As contents and formula (4) exceeding the upper limit, and therefore, the results of poor wettability were shown.
Comparative examples B2-6 to B2-8; b2-19 to B2-21; b2-32 to B2-34; B2-45-B2-47; b2-58 to B2-60; and B2-71 to B2-73 have an Sb content exceeding the upper limit, and therefore have poor wettability.
Comparative examples B2-9, B2-10, B2-22, B2-23, B2-35, B2-36, B2-48, B2-49, B2-61, B2-62, B2-74 and B2-75 had a Bi content exceeding the upper limit, and therefore showed results in which Δ T exceeded 10 ℃.
Comparative examples B2-11, B2-13, B2-24, B2-26, B2-37, B2-39, B2-50, B2-52, B2-63, B2-65, B2-76 and B2-78 have Pb contents exceeding the upper limit, and thus show a result in which Δ T exceeds 10 ℃.
Comparative examples B2-12, B2-25, B2-38, B2-51, B2-64 and B2-77 did not contain Bi and Pb, and the formula (4) did not hold, and therefore, the wettability was poor.
Flux and solder alloy combination
When the various fluxes of examples A2 to A45 were used in place of the flux of example A1 and the various solder alloys of example B (examples B2 to B95; and examples B2-1 to B2-108) were combined, the thickening-inhibiting effect, Δ T, and wettability were also excellent.
< preparation of flux composition for flow soldering > < preparation of solder powder for flow soldering >
Flux compositions for flow soldering of reference examples C1 to C36 were formulated with the compositions shown in tables 13 to 15 below.
[ Table 19]
[ Table 20]
[ Table 21]
When the flux of the present embodiment is formed into a flux for flow soldering, residue cracking of flux residue is also suppressed, and solder wettability is also excellent.
The present application is based on japanese patent application filed on day 27 of 2019 (japanese patent application 2019-.
Claims (9)
1. A composition for a solder flux, comprising: 1 or more selected from the group consisting of a maleic acid-modified rosin ester, a maleic acid-modified rosin amide, a hydride of the maleic acid-modified rosin ester, and a hydride of the maleic acid-modified rosin amide.
2. The composition for a flux according to claim 1, wherein the maleic acid-modified rosin ester or maleic acid-modified rosin amide is at least 1 selected from the group consisting of compounds represented by the following formulas (1) to (7),
wherein R's each independently represent an optionally substituted, linear or branched alkyl group, an alkylene glycol group, or a terminal-modified polyalkylene oxide group, and R's each independently represent an optionally substituted, linear or branched alkylene group, or a 2-valent alkylene glycol group.
3. A flux for soldering a solder alloy, comprising the composition for a flux of claim 1 or 2.
4. The flux of claim 3, wherein the maleic acid-modified rosin ester and/or maleic acid-modified rosin amide is contained in an amount of more than 0 wt% and 60 wt% or less with respect to the entire flux.
5. The solder flux of claim 3 or 4, wherein the solder flux further comprises a thixotropic agent.
6. The flux of any one of claims 3 to 5,
the flux further comprises:
0 to 20% by weight of an amine,
0 to 5% by weight of an organic halogen compound,
0 to 2% by weight of an amine hydrohalide salt, or
0 to 5 wt.% of an antioxidant,
0 to 80% by weight of a resin.
7. A solder paste, comprising: the flux of any one of claims 3 to 6, and a solder alloy.
8. A solder paste according to claim 7,
the solder alloy has the following alloy composition:
as: 25 to 300 mass ppm, Bi: 0 to 25000 mass ppm inclusive, Pb: more than 0 mass ppm and 8000 mass ppm or less, and the balance being composed of Sn, and satisfying the following formulas (1) and (2):
275≤2As+Bi+Pb (1)
0<2.3×10-4×Bi+8.2×10-4×Pb≤7 (2)
in the formulas (1) and (2), As, Bi, and Pb respectively represent the contents (mass ppm) in the alloy composition.
9. A solder paste according to claim 7,
the solder alloy has the following alloy composition:
as: 25 to 300 mass ppm; pb: more than 0 ppm by mass and 5100 ppm by mass or less; and Sb: more than 0 mass ppm and 3000 mass ppm or less and Bi: more than 0 mass ppm and 10000 mass ppm or less; the balance is composed of Sn, and satisfies the following formulae (3) and (4):
275≤2As+Sb+Bi+Pb (3)
0.01≤(2As+Sb)/(Bi+Pb)≤10.00 (4)
in the formulas (3) and (4), As, Sb, Bi, and Pb respectively represent the contents (mass ppm) in the alloy composition.
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| JP2019098782 | 2019-05-27 | ||
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| JP2019098775 | 2019-05-27 | ||
| JP2019-098775 | 2019-05-27 | ||
| JP2020-091559 | 2020-05-26 | ||
| JP2020091571A JP2021079443A (en) | 2019-05-27 | 2020-05-26 | Flux composition containing maleic acid-modified rosin ester or maleic acid-modified rosin amide, flux containing that composition, and solder paste |
| JP2020-091571 | 2020-05-26 | ||
| JP2020091559A JP2021079442A (en) | 2019-05-27 | 2020-05-26 | Flux composition containing maleic acid-modified rosin ester or maleic acid-modified rosin amide, flux containing that composition, and solder paste |
| PCT/JP2020/020923 WO2020241687A1 (en) | 2019-05-27 | 2020-05-27 | Flux composition containing maleic acid-modified rosin ester or maleic acid-modified rosin amide, flux containing said composition, and solder paste |
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| CN1579698A (en) * | 2003-08-08 | 2005-02-16 | 株式会社东芝 | Thermal-setting welding-assistant, welding paste and welding method |
| CN102369083A (en) * | 2009-03-30 | 2012-03-07 | 荒川化学工业株式会社 | Flux composition for lead-free solder, and lead-free solder composition |
| CN104073167A (en) * | 2013-03-25 | 2014-10-01 | 株式会社田村制作所 | Soldering flux composition with abietate for soldering and soldering paste composition |
| CN104345555A (en) * | 2013-07-25 | 2015-02-11 | 山荣化学株式会社 | Resin composition for solder bump formation, solder bump formation method, and member having solder bumps |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1579698A (en) * | 2003-08-08 | 2005-02-16 | 株式会社东芝 | Thermal-setting welding-assistant, welding paste and welding method |
| US20070221712A1 (en) * | 2003-08-08 | 2007-09-27 | Kabushiki Kaisha Toshiba | Thermosetting flux and solder paste |
| CN102369083A (en) * | 2009-03-30 | 2012-03-07 | 荒川化学工业株式会社 | Flux composition for lead-free solder, and lead-free solder composition |
| CN104073167A (en) * | 2013-03-25 | 2014-10-01 | 株式会社田村制作所 | Soldering flux composition with abietate for soldering and soldering paste composition |
| CN104345555A (en) * | 2013-07-25 | 2015-02-11 | 山荣化学株式会社 | Resin composition for solder bump formation, solder bump formation method, and member having solder bumps |
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| TW202120636A (en) | 2021-06-01 |
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