JP2023069920A - Flux and production method for joined body - Google Patents

Abstract

To provide a flux that can suppress the deposition of an activator in a flux residue after soldering and a production method for a joined body.SOLUTION: The present invention employs a flux that contains rosin, a terpene phenol resin, and an activator. The terpene phenol resin has a hydroxyl value greater than 130 mgKOH/g. The activator includes a halogenated salt of a primary amine.SELECTED DRAWING: None

Description

The present invention relates to a flux and a method for manufacturing a bonded body.

Fixing of parts to the board and electrical connection of parts to the board are generally performed by soldering. Soldering uses flux, solder, and solder paste that is a mixture of flux and solder.
Flux has the effect of chemically removing metal oxides present in the metal surface of the object to be soldered and the solder, and enabling the movement of metal elements at the boundary between the two. Therefore, by performing soldering using flux, an intermetallic compound is formed between the two, and a strong bond can be obtained.

In soldering, methods such as reflow soldering and flow soldering are adopted depending on the size of the object to be joined.
In reflow soldering, solder paste is first printed on the board. Then, soldering is performed by heating the board on which the components are mounted and the components are mounted in a heating furnace called a reflow furnace.
In flow soldering, flux is first applied to a board on which components are mounted. Next, soldering is performed by bringing molten solder jetted from below into contact with the soldering surface while conveying the board on which the components are mounted.

Flux used for soldering generally contains a resin component, a solvent, an activator, and the like. For example, Patent Document 1 describes a flux used for flow soldering containing rosin as a resin component and an organic acid, an organic halogen compound, or an amine hydrohalide as an activator. .

Japanese Patent No. 6617848

After soldering, the resin component and activator contained in the flux remain as flux residue at the junction between the component and the board. Depending on the activator contained in the flux, some activators tend to deposit in the flux residue after soldering. The activator thus deposited on the flux residue absorbs moisture in the air and ionizes. Ionized activators can corrode metals and cause migration.

Accordingly, an object of the present invention is to provide a flux and a method for producing a joined body, which can further suppress deposition of an activator in the flux residue after soldering.

The present invention includes the following aspects.
A first aspect of the present invention comprises a rosin, a terpene phenolic resin, and an activator, wherein the terpene phenolic resin has a hydroxyl value of greater than 130 mgKOH/g, and the activator is a primary amine. A flux containing a halide salt.

In the flux according to the first aspect, the halogenated salt of the primary amine is preferably a compound represented by the following general formula (1).

R ¹ —NH ₂ ·R ² (1)
[In the formula, R ¹ represents a hydrocarbon group which may have a substituent. ^R2 represents HX, _BX3 or _HBX4 . X represents a halogen atom. ]

In the flux according to the first aspect, the content of the terpene phenol resin is preferably 0.1% by mass or more and 10% by mass or less with respect to the total mass (100% by mass) of the flux.

In the flux according to the first aspect, the content of the halogenated salt of the primary amine is 0.01% by mass or more and 5% by mass or less with respect to the total mass (100% by mass) of the flux. is preferred.

In the flux according to the first aspect, the content ratio (mass ratio) of the halogenated salt of the primary amine is 5 parts by mass or more with respect to the content of the terpene phenol resin (100 parts by mass). It is preferably 150 parts by mass or less.

The flux according to the first aspect preferably further contains an organic acid having a solubility parameter (SP value) of 11.00 or more.

A second aspect of the present invention is a method for manufacturing a joined body, comprising a step of obtaining a joined body by soldering a solder alloy to the surface of the substrate treated with the flux according to the first aspect. is.

Advantageous Effects of Invention According to the present invention, it is possible to provide a method for manufacturing a flux and a joined body, which can further suppress deposition of an activator in the flux residue after soldering.

(flux)
The flux according to the first aspect contains rosin, terpene phenolic resin, and activator. The hydroxyl value of the terpene phenolic resin is greater than 130 mgKOH/g. The activator comprises a halide salt of a primary amine.

The flux according to the first aspect can be used for both flow soldering and reflow soldering, but is preferably used for flow soldering.
The substrates used in flow soldering are characterized by being inexpensive, being made of a material that is difficult to get wet, and being easily oxidized. Also, flow soldering has a short soldering time. For these reasons, highly active activators are used in flow soldering. A highly active activator becomes difficult to dissolve in a flux residue containing a resin or the like after soldering, and may precipitate on the flux residue. In flow soldering, a halogenated salt of a primary amine may be used as a highly active activator.
The flux according to the first aspect employs a terpene phenol resin having a hydroxyl value of more than 130 mgKOH/g with respect to the halogenated salt of the primary amine that is the activator. As a result, the activator can be uniformly dissolved in the flux residue and can be prevented from depositing on the flux residue.

As used herein, the solid content of the flux means all remaining components of the flux excluding the solvent.
In addition, in this specification, the hydroxyl value of the terpene phenol resin is JISK0070 “Acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponifiable substances of chemical products” 7.2 Potentiometric titration method means the hydroxyl value measured according to
The hydroxyl value measured by this method is the weighted average of the hydroxyl values of all kinds of terpene phenolic resins contained in the flux.

An embodiment in which the flux according to the first aspect is applied to flow soldering flux will be described below.
The flux of one embodiment described above contains a rosin, a terpene phenolic resin, an activator, a solvent, and optionally other ingredients.

<Rosin>
In the present invention, the term "rosin" includes natural resins containing abietic acid as a main component, mixtures of abietic acid and its isomers, and chemically modified natural resins (sometimes referred to as rosin derivatives). do.

The content of abietic acid in the natural resin is, for example, 40% by mass or more and 80% by mass or less relative to the natural resin.
As used herein, the term “main component” refers to a component whose content in the compound is 40% by mass or more among the components constituting the compound.

Typical isomers of abietic acid include neoabietic acid, parastric acid and levopimaric acid. The structure of abietic acid is shown below.

Examples of the "natural resin" include gum rosin, wood rosin and tall oil rosin.

In the present invention, "a chemically modified natural resin (rosin derivative)" refers to hydrogenation, dehydrogenation, neutralization, alkylene oxide addition, amidation, dimerization and multimerization of the above "natural resin", It includes those subjected to one or more treatments selected from the group consisting of esterification and Diels-Alder cycloaddition.

Examples of rosin derivatives include purified rosin and modified rosin.
Modified rosins include hydrogenated rosin, polymerized rosin, polymerized hydrogenated rosin, disproportionated rosin, acid-modified rosin, rosin ester, acid-modified hydrogenated rosin, acid-modified hydrogenated rosin, acid-modified disproportionated rosin, anhydrous Acid-modified disproportionated rosin, phenol-modified rosin and α,β unsaturated carboxylic acid-modified products (acrylated rosin, maleated rosin, fumarated rosin, etc.), and purified products, hydrides and disproportionated products of the polymerized rosin, and refined products, hydrides and disproportions of the α,β-unsaturated carboxylic acid-modified products, rosin alcohol, rosin amines, hydrogenated rosin alcohols, rosin esters, hydrogenated rosin esters, rosin soaps, hydrogenated rosin soaps, acid-modified Rosin soap etc. are mentioned.

One type of rosin may be used alone, or two or more types may be mixed and used.
A rosin derivative is preferably used as the rosin.
As the rosin derivative, it is preferable to use one or more selected from the group consisting of acid-modified hydrogenated rosin, acid-modified rosin, hydrogenated rosin, polymerized rosin, and rosin ester.
As the acid-modified hydrogenated rosin, it is preferable to use acrylic acid-modified hydrogenated rosin.
As the acid-modified rosin, it is preferable to use acrylic acid-modified rosin.

The content of the rosin in the flux is preferably 1% by mass or more and 50% by mass or less, and 2% by mass or more and 35% by mass or less with respect to the total amount (100% by mass) of the flux. is more preferable, and more preferably 4.5% by mass or more and 20% by mass or less.

In the solid content of the flux, the content of the rosin is preferably 30% by mass or more and 95% by mass or less, and 45% by mass or more and 95% by mass or less with respect to the total solid content (100% by mass). and more preferably 50% by mass or more and 95% by mass or less.

<Terpene phenolic resin>
In the present specification, the terpene phenol resin is a copolymer of a terpene monomer and a phenol, a hydrogenated product of the copolymer, and a copolymer of a terpene monomer and a monomer other than the terpene monomer and a phenol, and It means a hydrogenated product of the copolymer.
Terpene phenol resins include, for example, terpene resins, modified terpene resins, terpene phenol resins, and modified terpene phenol resins.
Examples of modified terpene resins include hydrogenated terpene resins, aromatic modified terpene resins, and hydrogenated aromatic modified terpene resins.
Examples of modified terpene phenol resins include hydrogenated terpene phenol resins.

Terpene monomers include, for example, hemiterpenes having 5 carbon atoms such as isoprene, monoterpenes having 10 carbon atoms, sesquiterpenes having 15 carbon atoms, diterpenes having 20 carbon atoms, sestateterpenes having 25 carbon atoms, triterpenes with 30 carbon atoms, tetraterpenes with 40 carbon atoms, and the like.
Examples of phenols include phenol, cresol, xylenol and the like.

The hydroxyl value of the terpene phenol resin is more than 130 mgKOH/g, preferably 140 mgKOH/g or more, more preferably 150 mgKOH/g or more, still more preferably 160 mgKOH/g or more, and 170 mgKOH/g. It is particularly preferably 180 mgKOH/g or more, and most preferably 180 mgKOH/g or more.
The upper limit of the hydroxyl value of the terpene phenol resin is not particularly limited as long as the effect of the present invention is exhibited. /g or less.
For example, the hydroxyl value of the terpene phenol resin may be more than 130 mgKOH/g and 300 mgKOH/g or less, preferably 140 mgKOH/g or more and 300 mgKOH/g or less, and 150 mgKOH/g or more and 300 mgKOH/g or less. It is more preferably 160 mgKOH/g or more and 300 mgKOH/g or less, particularly preferably 170 mgKOH/g or more and 300 mgKOH/g or less, and most preferably 180 mgKOH/g or more and 300 mgKOH/g or less.
Alternatively, the hydroxyl value of the terpene phenol resin may be more than 130 mgKOH/g and 250 mgKOH/g or less, preferably 140 mgKOH/g or more and 250 mgKOH/g or less, and 150 mgKOH/g or more and 250 mgKOH/g or less. It is more preferably 160 mgKOH/g or more and 250 mgKOH/g or less, particularly preferably 170 mgKOH/g or more and 250 mgKOH/g or less, and most preferably 180 mgKOH/g or more and 250 mgKOH/g or less.

When the hydroxyl value of the terpene phenol resin exceeds the above lower limit, the highly active primary amine halide salt is uniformly dissolved in the flux residue, and the effect of suppressing precipitation on the flux residue is obtained. be heightened.
When the hydroxyl value of the terpene phenol resin is equal to or less than the upper limit, moisture absorption of the flux residue can be further reduced. This makes it possible to further suppress the decrease in the insulation resistance value of the flux and to further suppress the occurrence of migration.

Examples of terpene phenol resins include YS Polyster (terpene phenol resin: manufactured by Yasuhara Chemical Co., Ltd.), Tamanol (terpene phenol resin: manufactured by Arakawa Chemical Industries, Ltd.), Tertac 80 (terpene phenol resin: manufactured by Nippon Terpene Chemical Co., Ltd.), SylvaresTP (terpene Phenolic resin: manufactured by Air Braun Co.) and the like are easily available. The terpene phenol resin may be selected from among these so as to have a desired hydroxyl value.

Terpene phenol resins may be used singly or in combination of two or more.
The flux according to this embodiment may contain one type of terpene phenolic resin having a hydroxyl value of more than 130 mgKOH/g. Alternatively, the flux according to the present embodiment uses two or more terpene phenolic resins with different hydroxyl values or structures in combination, and the weighted average hydroxyl value of those hydroxyl values is more than 130 mgKOH/g. good.

The content of the terpene phenol resin in the flux is preferably 0.1% by mass or more and 10% by mass or less, and 0.2% by mass or more and 5% by mass with respect to the total amount (100% by mass) of the flux. % or less, and more preferably 0.5 mass % or more and 4 mass % or less.

In the solid content of the flux, the content of the terpene phenol resin is preferably 3% by mass or more and 50% by mass or less, and 5% by mass or more and 40% by mass with respect to the total amount (100% by mass) of the solid content. % or less, and more preferably 5 mass % or more and 35 mass % or less.

When the content of the terpene phenol resin is at least the above lower limit, it is possible to further suppress the deposition of the activator in the flux residue after soldering.
When the content of the terpene phenol resin is equal to or less than the upper limit, it is possible to reduce the possibility that the viscosity of the flux becomes too high.

The mixing ratio of rosin and terpene phenol resin is 0.5 or more and 20 or less as a mass ratio represented by rosin/terpene phenol resin, that is, the ratio (mass ratio) of the content of rosin to the content of terpene phenol resin. , more preferably 1 or more and 16 or less, and even more preferably 2 or more and 16 or less.

<Activator>
《Specific activator》
The flux of this embodiment contains a halogenated salt of a primary amine as a specific activator.

Examples of the halogenated salt of the primary amine include hydrohalide, tetrafluoroborate, and trifluoroborate.
The halogenated salt of the primary amine is preferably a hydrohalide or a tetrafluoroborate.

Examples of the substituent (that is, R in R—NH ₂ ) possessed by the primary amine include a hydrocarbon group which may have a substituent.
The hydrocarbon group which may have a substituent may be linear, branched or cyclic.
The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.

When the hydrocarbon group which may have a substituent is a linear or branched hydrocarbon group, the number of carbon atoms in the hydrocarbon group is preferably 1 to 10, preferably 1 to 6. is more preferred, and 2 to 4 is even more preferred.

When the hydrocarbon group is linear or branched, examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and sec-butyl group. group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, etc. mentioned.

When the hydrocarbon group which may have a substituent is a cyclic hydrocarbon group, the number of carbon atoms in the hydrocarbon group is preferably 3 to 20, more preferably 4 to 12. , 4 to 8.

When the hydrocarbon group is cyclic, examples of the hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, and a cycloundecyl group. etc.

Examples of the substituent that the hydrocarbon group may have include a halogen atom, a hydroxyl group, and a carboxy group.

The halogenated salt of the primary amine may be used alone or in combination of two or more.
Examples of the primary amine include ethylamine and cyclohexylamine.

[Compound represented by general formula (1)]
The halogenated salt of the primary amine is preferably a compound represented by the following general formula (1).

R ¹ —NH ₂ ·R ² (1)
[In the formula, R ¹ represents a hydrocarbon group which may have a substituent. ^R2 represents HX, _BX3 or _HBX4 . X represents a halogen atom. ]

In general formula (1), examples of the hydrocarbon group for R ¹ include those described above for the substituent (R) of the primary amine.

^R2 represents HX, _BX3 or _HBX4 . X represents a halogen atom.
X includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
BX ₃ is preferably boron trifluoride (BF ₃ ).
HBX ₄ is preferably tetrafluoroboric acid (HBF ₄ ).
^R2 is preferably HX.

Examples of the compound represented by the general formula (1) include ethylamine hydrofluoride, ethylamine hydrochloride, ethylamine hydrobromide, cyclohexylamine tetrafluoroborate and the like.
The specific active agent may be used singly or in combination of two or more.

The content of the primary amine halide salt in the flux is preferably 0.01% by mass or more and 5% by mass or less with respect to the total mass (100% by mass) of the flux. It is more preferably 1% by mass or more and 2% by mass or less, and even more preferably 0.15% by mass or more and 1.5% by mass or less.

In the solid content of the flux, the content of the halogenated salt of the primary amine is preferably 0.2% by mass or more and 20% by mass or less with respect to the total solid content (100% by mass). , more preferably 0.5% by mass or more and 15% by mass or less, and even more preferably 1% by mass or more and 10% by mass or less.

When the content of the halogenated salt of the primary amine is at least the lower limit, the wettability of the flux can be further enhanced.
When the content of the halogenated salt of the primary amine is equal to or less than the upper limit, it becomes possible to further suppress deposition of the activator in the flux residue after soldering.

The mixing ratio of the halogenated salt of the primary amine and the terpene phenol resin is the mass ratio represented by the halogenated salt of the primary amine/terpene phenol resin, that is, the content of the terpene phenol resin (100 mass The ratio of the halogenated salt of the primary amine to the (parts) is preferably 5 parts by mass or more and 150 parts by mass or less, more preferably 5 parts by mass or more and 100 parts by mass or less, and 5 parts by mass or more and 100 parts by mass It is more preferably less than 1 part, and most preferably 5 parts by mass or more and 50 parts by mass or less.
Solderability can be improved by setting the content ratio of the halogenated salt of the primary amine to be equal to or higher than the lower limit.
When the content ratio of the halogenated salt of the primary amine is equal to or less than the upper limit, it is possible to further suppress deposition of the activator in the flux residue after soldering.

《Other activators》
The activator contained in the flux of this embodiment may contain other activators in addition to the specific activator described above.
Examples of other activators include halogen-based activators, organic acid-based activators, and amine-based activators other than the above halogenated salts of primary amines.

[Other halogen-based activators]
Other halogen-based activators include, for example, amine halide salts other than those mentioned above (other amine halide salts), organic halogen compounds other than amine halide salts, and the like.

Other Amine Halide Salts:
Other amine halide salts include, for example, hydrohalides, tetrafluoroborates, trifluoroborates and the like.
Hydrogen halides include, for example, hydrides of chlorine, bromine and iodine.

Examples of the amine in the amine halide salt include alkylamine compounds, azoles, guanidines, aminoalcohol compounds, rosinamine, etc. other than the primary amines described above.

Examples of alkylamine compounds include ethylenediamine, triethylenetetramine, hexadecylamine, stearylamine, and the like.

Examples of azoles include 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino -6-[2′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-undecylimidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-methylimidazolyl-(1′ )]-ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 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, 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-(1-ethylpentyl)benzimidazole, 2-nonylbenzimidazole, 2-(4-thiazolyl)benzimidazole, benzimidazole, 1,2,4-triazole , 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, 2,2'-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, 2,2′-[[(methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol, 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, 5 -methylbenzotriazole, 5-phenyltetrazole and the like.

Examples of guanidines include 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, 1-o-tolylbiguanide, 1,3-di-o-cumenylguanidine, 1,3-di- and o-cumenyl-2-propionylguanidine.

Examples of aminoalcohol compounds include N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine and the like.

Rosinamines include, for example, dehydroabiethylamine and dihydroabiethylamine.
Rosinamine means so-called disproportionated rosinamine.
The structures of dehydroabiethylamine and dihydroabiethylamine are shown below.

More specifically, amine hydrohalides include, for example, hexadecylamine hydrobromide, stearylamine hydrobromide, diphenylguanidine hydrobromide, stearylamine hydrochloride, and diethylaniline hydrochloride. salt, diethanolamine hydrochloride, pyridine hydrobromide, diethylamine hydrobromide, dimethylamine hydrobromide, dimethylamine hydrochloride, rosinamine hydrobromide, 2-pipecholine hydrobromide, 1 , 3-diphenylguanidine hydrochloride, dimethylbenzylamine hydrochloride, hydrazine hydrate hydrobromide, trinonylamine hydrobromide, diethylaniline hydrobromide, 2-diethylaminoethanol hydrobromide, 2-diethylaminoethanol hydrochloride, ammonium chloride, diallylamine hydrochloride, diallylamine hydrobromide, diethylamine hydrochloride, triethylamine hydrobromide, triethylamine hydrochloride, hydrazine monohydrochloride, hydrazine dihydrochloride, hydrazine monobromide hydrochloride, hydrazine dihydrobromide, pyridine hydrochloride, aniline hydrobromide, n-octylamine hydrochloride, dodecylamine hydrochloride, ethylenediamine dihydrobromide, rosinamine hydrobromide, 2-phenylimidazole hydrobromide, 4-benzylpyridine hydrobromide, L-glutamate hydrochloride, N-methylmorpholine hydrochloride, betaine hydrochloride, 2-pipecoline hydroiodide, 1,3-diphenyl guanidine hydrofluoride, diethylamine hydrofluoride, rosinamine hydrofluoride, dicyclohexylamine tetrafluoroborate, boron trifluoride piperidine and the like.

Organic halogen compounds:
Examples of organic halogen compounds other than amine hydrohalides include halogenated aliphatic compounds. A halogenated aliphatic hydrocarbon group refers to an aliphatic hydrocarbon group in which some or all of the hydrogen atoms constituting the aliphatic hydrocarbon group are substituted with halogen atoms.
Halogenated aliphatic compounds include halogenated aliphatic alcohols and halogenated heterocyclic compounds.

Halogenated aliphatic alcohols include, for example, 1-bromo-2-propanol, 3-bromo-1-propanol, 3-bromo-1,2-propanediol, 1-bromo-2-butanol, 1,3-dibromo -2-propanol, 2,3-dibromo-1-propanol, 1,4-dibromo-2-butanol, trans-2,3-dibromo-2-butene-1,4-diol and the like.

Examples of halogenated heterocyclic compounds include compounds represented by the following general formula (3).

R ¹¹ -(R ¹² ) _n (3)
[In the formula, R ¹¹ represents an n-valent heterocyclic group. R ¹² represents a halogenated aliphatic hydrocarbon group. ]

The heterocyclic ring of the n-valent heterocyclic group for R ¹¹ includes a ring structure in which part of carbon atoms constituting an aliphatic hydrocarbon or aromatic hydrocarbon ring is substituted with a heteroatom. Heteroatoms in this heterocyclic ring include an oxygen atom, a sulfur atom, a nitrogen atom and the like. This heterocyclic ring is preferably a 3- to 10-membered ring, more preferably a 5- to 7-membered ring. Examples of this heterocyclic ring include an isocyanurate ring.
The halogenated aliphatic hydrocarbon group for R ¹² preferably has 1 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 3 to 5 carbon atoms. R ¹² is preferably a brominated aliphatic hydrocarbon group or a chlorinated aliphatic hydrocarbon group, more preferably a brominated aliphatic hydrocarbon group, and still more preferably a brominated saturated aliphatic hydrocarbon group.

Halogenated heterocyclic compounds include, for example, tris-(2,3-dibromopropyl)isocyanurate.

Examples of organic halogen compounds other than amine hydrohalides include iodides such as 2-iodobenzoic acid, 3-iodobenzoic acid, 2-iodopropionic acid, 5-iodosalicylic acid, and 5-iodoanthranilic acid. Carboxyl compounds; Carboxyl chloride compounds such as 2-chlorobenzoic acid and 3-chloropropionic acid; Halogens such as brominated carboxyl compounds such as 2,3-dibromopropionic acid, 2,3-dibromosuccinic acid and 2-bromobenzoic acid carboxyl compounds, hydrobromic acid, carbon tetrabromide, chlorinated fatty acid methyl esters (chlorinated paraffins), tetrabromoethane and the like.

Other halogen-based activators may be used singly or in combination of two or more.

[Organic acid activator]
Examples of organic acid surfactants include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecane. diacid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, citric acid, glycolic acid, salicylic acid, diglycolic acid, dipicolinic acid, dibutylaniline diglycolic acid, thioglycol acid, dithioglycolic acid, terephthalic acid, p-hydroxyphenylacetic acid, picolinic acid, phenylsuccinic acid, phthalic acid, fumaric acid, maleic acid, lauric acid, benzoic acid, tartaric acid, tris(2-carboxyethyl) isocyanurate, glycine, 1,3-cyclohexanedicarboxylic acid, 2,2-bis(hydroxymethyl)propionic acid, 2,2-bis(hydroxymethyl)butanoic acid, 2,3-dihydroxybenzoic acid, 2,4-diethylglutaric acid, 2- quinolinecarboxylic acid, 3-hydroxybenzoic acid, 4-tert-butylbenzoic acid, propionic acid, malic acid, p-anisic acid, stearic acid, 12-hydroxystearic acid, oleic acid, linoleic acid, linolenic acid, palmitic acid, Mono-2-ethylhexyl 2-ethylhexylphosphonate, dimer acid, trimer acid, hydrogenated dimer acid which is hydrogenated dimer acid, hydrogenated trimer acid which is hydrogenated trimer acid etc.

Examples of dimer acid and trimer acid include dimer acid which is a reaction product of oleic acid and linoleic acid, trimer acid which is a reaction product of oleic acid and linoleic acid, dimer acid which is a reaction product of acrylic acid, and acrylic acid. trimer acid which is the reactant of methacrylic acid, dimer acid which is the reactant of methacrylic acid, trimer acid which is the reactant of methacrylic acid, dimer acid which is the reactant of acrylic acid and methacrylic acid, reaction of acrylic acid and methacrylic acid trimer acid, a reactant of oleic acid, dimer acid, a reactant of oleic acid, trimer acid, a reactant of oleic acid, dimer acid, a reactant of linoleic acid, trimer acid, a reactant of linoleic acid, linolenic acid trimer acid, which is a reaction product of linolenic acid, dimer acid, which is a reaction product of acrylic acid and oleic acid, trimer acid, which is a reaction product of acrylic acid and oleic acid, acrylic acid and linoleic acid dimer acid that is the reaction product of acrylic acid and linoleic acid, trimer acid that is the reaction product of acrylic acid and linolenic acid, dimer acid that is the reaction product of acrylic acid and linolenic acid, trimer acid that is the 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, reaction of methacrylic acid and linoleic acid trimer acid, a reaction product of methacrylic acid and linolenic acid; trimer acid, a reaction product of methacrylic acid and linolenic acid; dimer acid, a reaction product of oleic acid and linolenic acid; Trimer acid which is a reaction product of 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, hydrogenation products of each dimer acid described above Certain hydrogenated dimer acids, hydrogenated trimer acids which are hydrogenated products of the trimer acids described above, and the like.
For example, dimer acid, which is a reaction product of oleic acid and linoleic acid, is a dimer with 36 carbon atoms. Trimer acid, which is a reaction product of oleic acid and linoleic acid, is a trimer having 54 carbon atoms.
The organic acid-based activators may be used singly or in combination of two or more.

From the viewpoint of further enhancing the wettability of the substrate, the flux according to the present embodiment preferably contains a highly polar organic acid in addition to the above-described primary amine halide salt as a highly active activator. . Examples of highly polar organic acids include organic acids having a solubility parameter (SP value) of 11 or more.

As used herein, the solubility parameter (SP value) means a value calculated from the molecular structure based on the Fedors method. The SP value (δ) can be obtained from the following formula (sp).
δ=(ΔE/ΔV) ^1/2 (cal/cm ³ ) ^1/2 (sp)
In the formula (sp), ΔE represents the sum of the evaporation energies (cal/mol) of the atoms and atomic groups possessed by the molecule of the organic acid (A1).
ΔV represents the total molar volume (cm ³ /mol) at 25° C. of atoms and atomic groups possessed by molecules of the organic acid (A1).
As the evaporation energy and molar volume, values described in Robert F. Fedors, A method for estimating both the solubility parameters and molar volumes of liquids. Polymer Engineering and Science, 14, 147-154 (1974).

Examples of organic acids having a solubility parameter (SP value) of 11 or more include oxalic acid (15.22), malonic acid (14.03), succinic acid (13.21), glutaric acid (12.61), adipic acid (12.15), pimelic acid (11.79), suberic acid (11.49), azelaic acid (11.25), sebacic acid (11.04), 2,4-diethylglutaric acid (14. 89), 1,3-cyclohexanedicarboxylic acid (12.80), picolinic acid (12.78), 2,2-bis(hydroxymethyl)propionic acid (16.12), 2,2-bis(hydroxymethyl) butanoic acid (19.07) and the like. The numbers in parentheses represent the SP value of each organic acid.
Even if the flux according to the present embodiment contains a highly polar organic acid in addition to the halogenated salt of the primary amine, the deposition of the activator in the flux residue after soldering can be further suppressed. .

The content of the organic acid activator in the flux is preferably 0.05% by mass or more and 5% by mass or less, and 0.1% by mass or more, relative to the total mass (100% by mass) of the flux. It is more preferably 4% by mass or less, and even more preferably 0.1% by mass or more and 3% by mass or less.

[Amine activator]
Examples of amine-based activators include amines exemplified as raw materials for halogen-based activators in <<Halogen-based activators>>.
Amine-based activators may be, for example, ethylamine, triethylamine, cyclohexylamine.
Amine-based activators may be used singly or in combination of two or more.

<Solvent>
Examples of solvents include water, alcohol solvents, glycol ether solvents, terpineols and the like.
Examples of alcohol solvents include ethanol, 1-propanol, 2-propanol (isopropyl alcohol), 1,2-butanediol, isobornylcyclohexanol, 2,4-diethyl-1,5-pentanediol, 2, 2-dimethyl-1,3-propanediol, 2,5-dimethyl-2,5-hexanediol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,3-dimethyl-2,3- butanediol, 2-methylpentane-2,4-diol, 1,1,1-tris(hydroxymethyl)propane, 2-ethyl-2-hydroxymethyl-1,3-propanediol, 2,2′-oxybis( methylene)bis(2-ethyl-1,3-propanediol), 2,2-bis(hydroxymethyl)-1,3-propanediol, 1,2,6-trihydroxyhexane, 1-ethynyl-1-cyclo hexanol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol and the like.
Examples of glycol ether solvents include diethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, diethylene glycol monohexyl ether (hexyl diglycol), diethylene glycol dibutyl ether, triethylene glycol monobutyl ether, methylpropylene triglycol, butyl Propylene triglycol, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether and the like.

A solvent may be used individually by 1 type, and may be used in mixture of 2 or more types.
The solvent preferably contains a solvent having a boiling point of 100° C. or lower from the viewpoint of increasing the volatility in preheating.
The solvent having a boiling point of 100° C. or lower is preferably an alcohol-based solvent from the viewpoint of solubility of the specific active agent.
The alcohol-based solvent preferably contains 2-propanol (isopropyl alcohol) from the viewpoint of being industrially inexpensive.

The content of the solvent in the flux is preferably 40% by mass or more and 98% by mass or less, and 60% by mass or more and 98% by mass or less with respect to the total amount (100% by mass) of the flux. is more preferable, and more preferably 70% by mass or more and 98% by mass or less.

<Other ingredients>
The flux according to the present embodiment may optionally contain other components in addition to the rosin, terpene phenolic resin, activator and solvent.
Other components include thixotropic agents, resin components other than rosin and terpene phenol resins, metal deactivators, surfactants, silane coupling agents, antioxidants, colorants, and the like.

<<Resin components other than rosin and terpene phenol resin (other resin components)>>
Examples of other resin components include styrene resins, modified styrene resins, xylene resins, modified xylene resins, acrylic resins, polyethylene resins, acrylic-polyethylene copolymer resins, epoxy resins, and silicone resins.
Modified styrene resins include styrene acrylic resins, styrene maleic acid resins, and the like. Modified xylene resins include phenol-modified xylene resins, alkylphenol-modified xylene resins, phenol-modified resol-type xylene resins, polyol-modified xylene resins, and polyoxyethylene-added xylene resins.

《Metal deactivator》
Examples of metal deactivators include hindered phenol compounds and nitrogen compounds.
The term "metal deactivator" as used herein refers to a compound that has the ability to prevent metals from deteriorating due to contact with certain compounds.

A hindered phenolic compound refers to a phenolic compound having a bulky substituent (for example, a branched or cyclic alkyl group such as a t-butyl group) on at least one of the ortho positions of phenol.
The hindered phenol compound is not particularly limited, and examples thereof include bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)], N, N '-Hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide], 1,6-hexanediolbis[3-(3,5-di-tert-butyl-4 -hydroxyphenyl)propionate], 2,2′-methylenebis[6-(1-methylcyclohexyl)-p-cresol], 2,2′-methylenebis(6-tert-butyl-p-cresol), 2,2′ -methylenebis(6-tert-butyl-4-ethylphenol), triethyleneglycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis -[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t- butylanilino)-1,3,5-triazine, pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-( 3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N′-hexamethylenebis(3 ,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2, 4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N'-bis[2-[2-(3,5-di-tert-butyl-4-hydroxyphenyl ) ethylcarbonyloxy]ethyl]oxamide, compounds represented by the following chemical formulas, and the like.

（式中、Ｚは、置換されてもよいアルキレン基である。Ｒ^１０１及びＲ^１０２は、それぞれ独立して、置換されてもよい、アルキル基、アラルキル基、アリール基、ヘテロアリール基、シクロアルキル基又はヘテロシクロアルキル基である。Ｒ^１０３及びＲ^１０４は、それぞれ独立して、置換されてもよいアルキル基である。）

(In the formula, Z is an optionally substituted alkylene group. R ¹⁰¹ and R ¹⁰² are each independently an optionally substituted alkyl group, aralkyl group, aryl group, heteroaryl group, cycloalkyl or a heterocycloalkyl group.R ¹⁰³ and R ¹⁰⁴ are each independently an optionally substituted alkyl group.)

Examples of the nitrogen compound in the metal deactivator include hydrazide nitrogen compounds, amide nitrogen compounds, triazole nitrogen compounds, and melamine nitrogen compounds.

As the hydrazide-based nitrogen compound, any nitrogen compound having a hydrazide skeleton may be used. -butyl-4-hydroxyphenyl)propionyl]hydrazine, decanedicarboxylic acid disalicyloyl hydrazide, N-salicylidene-N'-salicylhydrazide, m-nitrobenzhydrazide, 3-aminophthalhydrazide, phthalic acid dihydrazide, adipic acid hydrazide , oxalobis(2-hydroxy-5-octylbenzylidene hydrazide), N'-benzoylpyrrolidonecarboxylic acid hydrazide, N,N'-bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl) hydrazine and the like.

The amide nitrogen compound may be any nitrogen compound having an amide skeleton, and N,N'-bis{2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyl]ethyl } oxamide and the like.

The triazole nitrogen compound may be any nitrogen compound having a triazole skeleton, such as N-(2H-1,2,4-triazol-5-yl) salicylamide, 3-amino-1,2,4-triazole, 3-(N-salicyloyl)amino-1,2,4-triazole and the like.

The melamine-based nitrogen compound may be any nitrogen compound having a melamine skeleton, and examples thereof include melamine and melamine derivatives. More specifically, for example, trisaminotriazine, alkylated trisaminotriazine, alkoxyalkylated trisaminotriazine, melamine, alkylated melamine, alkoxyalkylated melamine, N2-butylmelamine, N2,N2-diethylmelamine, N, N,N',N',N'',N''-hexakis(methoxymethyl)melamine and the like.

Preferably, the metal deactivator comprises bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)].
The content of the metal deactivator is preferably 0% by mass or more and 10.0% by mass or less, and 0.6% by mass or more and 3.0% by mass with respect to the total amount (100% by mass) of the flux. The following are more preferable.

《Surfactant》
Examples of surfactants include nonionic surfactants and weak cationic surfactants.
Examples of nonionic surfactants include polyethylene glycol, polyethylene glycol-polypropylene glycol copolymers, aliphatic alcohol polyoxyethylene adducts, aromatic alcohol polyoxyethylene adducts, and polyhydric alcohol polyoxyethylene adducts. be done.
Examples of weak cationic surfactants include terminal diamine polyethylene glycol, terminal diamine polyethylene glycol-polypropylene glycol copolymer, aliphatic amine polyoxyethylene adduct, aromatic amine polyoxyethylene adduct, polyvalent amine polyoxy Ethylene adducts can be mentioned.

Examples of surfactants other than the above include polyoxyalkylene acetylene glycols, polyoxyalkylene glyceryl ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene esters, polyoxyalkylene alkylamines, polyoxyalkylene alkylamides, and the like. .

The flux of one embodiment described above contains a rosin, a terpene phenol resin, a halogenated salt of a primary amine as a specific activator, and a solvent, and is suitable for flow soldering.
The specific activator has high activity and tends to precipitate in the flux residue. However, even if the flux of this embodiment contains a halogenated salt of a primary amine, in addition to rosin, by containing a terpene phenol resin having a hydroxyl value of more than 130 mgKOH/g, In the flux residue, it becomes possible to further suppress deposition of the activator.
The reason why such an effect is obtained is not clear, but by using the flux of the present embodiment, the activator is uniformly dissolved and confined in the flux residue containing rosin and terpene phenolic resin after soldering. Therefore, it is assumed that

(Manufacturing method of joined body)
A method for manufacturing a joined body according to the second aspect includes a step of obtaining a joined body by soldering a solder alloy to the surface of the substrate treated with the flux according to the first aspect.
An embodiment of the method for manufacturing a joined body according to the second aspect will be described below.
The manufacturing method of the joined body according to the present embodiment is a method having a component mounting process, a flux application process, a preheating process and a soldering process in this order.

In the component mounting process, the component is mounted on the board.
Examples of substrates include printed wiring boards.
Components include, for example, integrated circuits, transistors, diodes, resistors, and capacitors.

In the flux application step, the flux of the above embodiment is applied to the soldering surface of the substrate on which the components are mounted.
Flux applicators include spray fluxers and foaming fluxers. Among these, the spray fluxer is preferable from the viewpoint of the stability of the coating amount.
From the viewpoint of solderability, the flux coating amount is preferably 30 to 180 mL/m ² , more preferably 40 to 150 mL/m ² , and particularly preferably 50 to 120 mL/m ² . .

In the preheating step, the board on which the components are mounted is preheated. The temperature for heating the substrate in the preheating step is preferably 80 to 130.degree. C., more preferably 90 to 120.degree.

In the soldering process, the soldering surface of the board on which the component is mounted is brought into contact with molten solder in which the solder alloy is melted.
The method of bringing the molten solder into contact with the soldering surface is not particularly limited as long as the method can bring the molten solder into contact with the substrate. Examples of such a method include a jet method and an immersion method.
The jet method is a method in which the soldering surface of a circuit board on which components are mounted is brought into contact with jetting molten solder. The immersion method is a method in which the soldering surface of a substrate on which components are mounted is brought into contact with the liquid surface of stationary molten solder.

As the solder alloy, a solder alloy having a known composition can be used.
The solder alloy is Sn single solder, Sn-Ag system, Sn-Cu system, Sn-Ag-Cu system, Sn-Bi system, Sn-In system, etc., or these alloys containing Sb, Bi, In , Cu, Zn, As, Ag, Cd, Fe, Ni, Co, Au, Ge, P or the like may be added.
The solder alloy is a Sn--Pb system or a solder alloy in which Sb, Bi, In, Cu, Zn, As, Ag, Cd, Fe, Ni, Co, Au, Ge, P, etc. are added to the Sn--Pb system. There may be.
The solder alloy is preferably a Pb-free solder.

Soldering conditions in the soldering process may be appropriately set according to the melting point of the solder. For example, when a Sn--Ag--Cu based solder alloy is used, the temperature of the molten solder is preferably 230-280.degree. C., more preferably 250-270.degree.

According to the method for manufacturing a joined body according to the present embodiment described above, it is possible to further suppress the precipitation of the activator in the flux residue on the resulting joined body. This makes it possible to reduce the risk of migration occurring in the resulting joined body.

Other embodiments:
The flux according to one embodiment described above is suitable for flow soldering, but the flux according to the first aspect is not limited to this, and can also be used for reflow soldering.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the following examples.

<Preparation of mixed solution>
(Test Examples 1 to 30)
Mixtures of test examples were prepared with the compositions shown in Tables 1 to 6. In Tables 1 to 6, the numerical values represent the mass (g) of each component.
The raw materials used are shown below.

Specific activator: Ethylamine/HBr, Cyclohexylamine/HBF ₄
Other activators: diphenylguanidine/HBr, dicyclohexylamine/HBF ₄

Terpene Phenolic Resin:
Resin A 200±10 mg KOH/g
Resin B 150±10 mg KOH/g
Resin C 120±10 mg KOH/g
Resin D 100±10 mg KOH/g
Resin E 60±10 mg KOH/g

<Evaluation>
<<Evaluation of solubility of activator>>
To Resins AE, activator was added to form a mixture. The mixed solution was heated to the softening point of the resin or above, and then cooled to room temperature. Presence or absence of precipitates was confirmed in the mixed solution during heating and after cooling, and evaluation was performed based on the following criteria. The results are shown in Tables 1-6.

criterion:
A: The activator was dissolved in the mixed liquid by heating, and no precipitate was observed after cooling.
B: Even when heated, the activator did not dissolve in the mixed liquid, and a precipitate was observed after cooling.

As shown in Table 1, in Test Example 1 containing ethylamine·HBr and resin A, no precipitate was observed after cooling.
On the other hand, in Test Examples 2 to 5 containing ethylamine·HBr and any of resins B to E, ethylamine·HBr did not dissolve in the mixture even when heated.

As shown in Table 2, Test Examples 6 to 7 containing cyclohexylamine·HBF ₄ and resin A or resin B did not show any precipitate after cooling.
On the other hand, in Test Examples 8 to 10 containing cyclohexylamine·HBF ₄ and any of Resins C to E, cyclohexylamine·HBF ₄ did not dissolve in the mixed solution even when heated.

As shown in Table 3, Test Examples 11-14 containing diphenylguanidine.HBr and any of Resins A-D showed no precipitate after cooling.
In contrast, in Test Example 15 containing diphenylguanidine·HBr and resin E, diphenylguanidine·HBr did not dissolve in the mixed solution even when heated.

As shown in Table 4, Test Examples 16-20 containing dicyclohexylamine.HBF ₄ and any of Resins A-E showed no precipitate after cooling.

As shown in Table 5, Test Examples 21-22 containing ethylamine.HBr and cyclohexylamine.HBF ₄ and any of Resins A-B showed no deposits after cooling.
On the other hand, in Test Examples 23 to 25 containing ethylamine·HBr and cyclohexylamine·HBF ₄ and any of resins C to E, ethylamine·HBr and cyclohexylamine·HBF ₄ were did not dissolve.

As shown in Table 6, Test Examples 26-29 containing diphenylguanidine.HBr and dicyclohexylamine.HBF ₄ and any of Resins A-D showed no deposits after cooling.
On the other hand, in Test Example 30 containing diphenylguanidine·HBr and dicyclohexylamine·HBF ₄ and any of resins C to E, diphenylguanidine·HBr and dicyclohexylamine·HBF ₄ were did not dissolve.

From the above results, it was clarified that the halogenated salt of the primary amine was dissolved by selecting a terpene phenol resin having a hydroxyl value of more than 130 mgKOH/g.
It was also found that the halogenated salts of primary amines cannot be dissolved in terpene phenol resins having a hydroxyl value of 130 mgKOH/g or less.

<Preparation of Flux>
(Examples 1 to 15, Comparative Examples 1 to 3)
Example and comparative example fluxes were formulated with the compositions shown in Tables 7-8 below. The compositions in Tables 7 and 8 are mass % when the total amount of flux is 100 mass %.

Specific activator: Ethylamine/HBr, Cyclohexylamine/HBF ₄
Other active agents: diphenylguanidine/HBr, dicyclohexylamine/ _HBF4 , succinic acid

Terpene Phenolic Resin:
Resin A 200±10 mg KOH/g
Resin B 150±10 mg KOH/g
Resin C 120±10 mg KOH/g
Resin D 100±10 mg KOH/g
Resin E 60±10 mg KOH/g

Rosin: acrylic acid-modified hydrogenated rosin, acrylic acid-modified rosin, hydrogenated rosin, polymerized rosin, rosin ester

Solvent: 2-propanol

Other resin components: Silicone Antioxidant: Quinoline compound

<Preparation of molten solder>
An ingot made of an alloy containing 3% by mass of Ag, 0.5% by mass of Cu, and the balance of Sn was prepared as a master alloy.
This ingot was melted to prepare molten solder.

<<Evaluation of Precipitation on Surface of Flux Residue>>
Method of verification:
A pretreated substrate was obtained by spraying the flux of each example onto the substrate.
Next, flow soldering was performed by bringing molten solder into contact with the pretreated substrate in a nitrogen atmosphere.
Presence or absence of precipitation on the surface of the flux residue on the substrate was confirmed, and evaluation was performed based on the following criteria. The results are shown in Tables 7-8.

criterion:
A: No precipitate was observed on the surface of the flux residue.
B: A small amount of precipitate was observed on the surface of the flux residue.
C: A large amount of deposits were observed on the surface of the flux residue.
In the evaluation results, the amount of precipitates on the surface of the flux residue increases in order from A to C. Fluxes with evaluation results of A to B were regarded as acceptable, and fluxes with evaluation results of C were regarded as unacceptable.

The fluxes of Examples 1 to 14 containing a primary amine halide salt and a terpene phenolic resin having a hydroxyl value of more than 130 mgKOH/g had an evaluation of A or B for deposition of flux residue on the surface. rice field.
The flux of Example 15, which contains a primary amine halide salt, an organic acid, and a terpene phenolic resin having a hydroxyl value of greater than 130 mg KOH/g, had a rating of B for deposition of flux residue on the surface. .
On the other hand, the fluxes of Comparative Examples 1 to 3 containing a halogenated salt of a primary amine and a terpene phenol resin having a hydroxyl value of 130 mgKOH/g or less evaluated the precipitation on the surface of the flux residue as C Met.

Advantageous Effects of Invention According to the present invention, it is possible to provide a method for manufacturing a flux and a joined body, which can further suppress deposition of an activator in the flux residue after soldering. This flux can be suitably used for flow soldering and soldering of electronic substrates used in a hot and humid environment.

Claims (7)

containing a rosin, a terpene phenolic resin, and an activator;
The hydroxyl value of the terpene phenol resin is greater than 130 mgKOH/g,
The flux, wherein the activator comprises a halide salt of a primary amine. 2. The flux according to claim 1, wherein the halogenated salt of the primary amine is a compound represented by the following general formula (1).
R ¹ —NH ₂ ·R ² (1)
[In the formula, R ¹ represents a hydrocarbon group which may have a substituent. ^R2 represents HX, _BX3 or _HBX4 . X represents a halogen atom. ] The flux according to claim 1 or 2, wherein the content of said terpene phenol resin is 0.1% by mass or more and 10% by mass or less with respect to the total mass (100% by mass) of the flux. 4. Any one of claims 1 to 3, wherein the content of the halogenated salt of the primary amine is 0.01% by mass or more and 5% by mass or less with respect to the total mass (100% by mass) of the flux. Flux as described in . The content ratio (mass ratio) of the halogenated salt of the primary amine is (5 parts by mass) or more and (150 parts by mass) or less with respect to the content (100 parts by mass) of the terpene phenol resin. , the flux according to any one of claims 1 to 4. The flux according to any one of claims 1 to 5, further comprising an organic acid having a solubility parameter (SP value) of 11.00 or more. A method for manufacturing a joined body, comprising the step of obtaining a joined body by soldering a solder alloy to the surface of a substrate treated with the flux according to any one of claims 1 to 6.