Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
  • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
  • B23K35/24—Selection of soldering or welding materials proper
  • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
  • B23K35/262—Sn as the principal constituent
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
  • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
  • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
  • B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
  • B23K35/3618—Carboxylic acids or salts
• • 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
• • 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
  • B23K35/368—Selection of non-metallic compositions of core materials either alone or conjoint with selection of soldering or welding materials
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C13/00—Alloys based on tin
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C13/00—Alloys based on tin
  • C22C13/02—Alloys based on tin with antimony or bismuth as the next major constituent

Definitions

• the present invention relates to a lead-free solder flux composition, a lead-free solder composition, and a flux cored solder.
• Inner solder has a structure with solid flux in the center of linear solder.
• the flux cored solder is used when mounting electronic components such as resistors, capacitors, and ICs on a printed circuit board.
• Flux for flux cored solder is usually produced by mixing a base resin, an activator and other additives.
• a base resin it has excellent performance such as corrosiveness and insulation resistance, and has the effect of preventing reoxidation of metals after soldering, so natural rosin, polymerized rosin, hydrogenated rosin, disproportionated rosin, maleic acid modified rosin
• rosin resins such as acrylic acid-modified rosin and esterified rosin are used (Non-patent Document 1).
• the activator amine halogen salts, amine organic acid salts, organic acids, organic halides, amines and the like are used (Non-patent Document 1).
• a softening point depressant, a rust inhibitor, an antioxidant, a stabilizer, a matting agent, and the like are used in the flux for flux cored solder as necessary.
• the solder flux removes and cleans the solder metal that joins the electronic component and the substrate electrode and the surface oxide film on the substrate electrode, reduces the interfacial tension of the solder, and promotes wetting and spreading. These effects greatly depend on the activity of amine halogen salts, amine organic acid salts, organic acids, organic halides, amines, etc. in the flux composition and rosin as the base resin.
• An object of the present invention is to provide a solder composition having good insulation resistance and wet spreadability of a flux residue and a flux composition used therefor even when the activator content is low.
• the present invention provides a solder composition in which a flux residue attached to a solder joint does not hinder the hardening of the sealing resin when coated with a sealing resin after soldering, and a flux composition used therefor Intended to provide
• the present inventors have found that the above problem can be solved by setting the composition of the rosin resin to be used within a specific range.
• the present invention has been completed based on the above findings, and provides the following lead-free solder flux composition, lead-free solder composition, and flux cored solder.
• Item 1 A lead-free solder flux composition comprising 8 to 65% by weight of dehydroabietic acid and 8 to 67% by weight of dihydroabietic acid based on the total amount of the composition.
• Item 2. The flux composition for lead-free solder according to Item 1, comprising 5 to 25% by weight of tetrahydroabietic acid based on the total amount of the composition.
• Item 3. Item 2. The lead-free solder flux composition according to Item 1, wherein the activator is contained in an amount of 0.05 to 20% by weight based on the total amount of the composition.
• Item 4. Item 4.
• a lead-free solder composition comprising the flux composition for lead-free solder according to any one of Items 1 to 3 and a lead-free solder alloy.
• Item 5. Item 5.
• Item 6. Item 3. A cored solder containing the flux composition for lead-free solder according to any one of Items 1 to 3 and a solder alloy.
• Item 7. Item 7. The cored solder according to Item 6, wherein the lead-free solder flux composition is present in a tubular lead-free solder alloy tube.
• the lead-free solder flux composition of the present invention even when the amount of the activator used is reduced, the insulation resistance of the flux residue is sufficiently high in practice, and the wet spreadability is good, that is, solderability Can obtain a good solder composition.
• the lead-free solder flux composition of the present invention can provide a solder composition that does not inhibit the curing of the sealing resin when sealed with various sealing resins after soldering.
• the flux composition of the present invention is a lead-free solder flux composition, which contains dehydroabietic acid and dihydroabietic acid, the content of dehydroabietic acid is about 8 to 65% by weight, and dihydroabietic acid Is a composition having a content of about 8 to 67% by weight.
• the content of dehydroabietic acid is preferably about 10 to 62% by weight, more preferably about 20 to 50% by weight.
• the content of dihydroabietic acid is preferably about 10 to 50% by weight, more preferably about 15 to 40% by weight. If the content of dihydroabietic acid is too small, the wettability of the solder is lowered, and if it is too much, the insulation resistance is lowered. However, such a problem does not occur within the above range.
• the solder flux composition of the present invention preferably contains tetrahydroabietic acid. The content is preferably about 5 to 25% by weight, more preferably about 10 to 20% by weight. When the content of tetrahydroabietic acid is within the above range, the wettability of the solder is improved and the insulation resistance is improved.
• the content of these resin acids in the composition affects the reactivity between the resin acid and the metal oxide contained in the rosin and the aqueous solution specific resistance related to the insulation resistance.
• rosin and various known rosin derivatives may be mixed and used as necessary.
• rosin gum rosin, wood rosin, tall oil rosin and the like can be used.
• the rosin derivative examples include unsaturated acid-modified rosin, polymerized rosin, disproportionated rosin, and hydrogenated rosin.
• the unsaturated acid-modified rosin is obtained by modifying the rosin with an unsaturated acid such as (meth) acrylic acid, (anhydrous) maleic acid or fumaric acid.
• the polymerized rosin is obtained by polymerizing rosin.
• Disproportionated rosin is obtained by disproportionating rosin.
• Hydrogenated rosin is obtained by hydrogenating rosin. Since rosin and rosin derivatives have different resin acid compositions depending on the species, rosin and rosin derivatives are appropriately selected and used according to the purpose.
• the amount of disproportionated rosin used may be increased.
• the disproportionated rosin usually contains about 40 to 55% by weight of dehydroabietic acid.
• the amount of hydrogenated rosin used should be increased.
• the content of each component varies depending on the degree of hydrogenation in hydrogenated rosin, but usually 5 to 40% by weight of dehydroabietic acid, 20 to 70% by weight of dihydroabietic acid, and 5 to 60% by weight. Of tetrahydroabietic acid.
• the flux composition has good wettability and excellent compatibility with the sealing resin.
• (meth) acrylic acid-modified rosin and / or the above-mentioned hydrogenated rosin In order to adjust the content of the resin acid component to the above range, it is preferable to use (meth) acrylic acid-modified rosin and / or the above-mentioned hydrogenated rosin.
• the (meth) acrylic acid-modified rosin usually contains about 10 to 20% by weight of dehydroabietic acid, about 1 to 10% by weight of dihydroabietic acid, and about 1 to 10% by weight of tetrahydroabietic acid. Yes. When these components are used, they may be appropriately selected and used so that the content of dehydroabietic acid is within the above-mentioned range.
• the lead-free solder flux composition of the present invention contains a known base resin for solder flux as required so that the content of each resin acid component is in the above-mentioned range. It's okay.
• solder flux base resin other than rosin include polyester resin, phenoxy resin, terpene resin, and polyamide resin.
• the solder flux base resin other than rosin can be used alone or in combination of two or more.
• the content in the case of using a flux base resin other than rosin is not particularly limited, but may be, for example, about 1 to 10% by weight of the total amount of the flux composition.
• An activator can be used in the lead-free solder flux composition of the present invention as necessary.
• an activator it does not specifically limit but a well-known thing can be used.
• Specific examples include amine hydrohalides, organic acids, organic halogens, and organic amines. Of these, organic acids and organic halogens are preferred. Of the organic acids, dibasic acids are preferable, and glutaric acid, adipic acid, suberic acid, and the like are particularly preferable.
• organic halogens nonionic organic halogen activators are preferable in terms of low solder wettability and corrosion, and specifically, trans-2,3-dibromo-1,4-butenediol, tetrabromobutane. Etc. are preferred.
• an activator can be used individually by 1 type or in combination of 2 or more types.
• the content may be, for example, about 0.05 to 20% by weight, preferably about 0.5 to 10% by weight, based on the total amount of the flux composition.
• the content may be, for example, about 0.05 to 10% by weight, and preferably about 0.5 to 10% by weight, based on the total amount of the flux.
• additives such as an antioxidant, a solvent, a thixo agent, and a plasticizer may be added to the lead-free solder flux of the present invention as necessary.
• An additive can be used individually by 1 type or in combination of 2 or more types.
• the antioxidant is not particularly limited, and a known product can be used. Specific examples include 2,6-di-tert-butyl-p-cresol, para-tert-amylphenol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), and the like.
• the content of the antioxidant is not particularly limited, but is usually about 0.5 to 3% by weight of the total amount of the flux composition.
• the solvent is not particularly limited and a known solvent can be used.
• the solvent include alcohols, glycol ethers, and ester hydrocarbons.
• alcohols include ethanol, n-propanol, isopropanol, and isobutanol.
• glycol ethers include butyl carbitol and hexyl carbitol.
• the esters include isopropyl acetate, ethyl propionate, butyl benzoate, diethyl adipate and the like.
• hydrocarbons include n-hexane, dodecane, and tetradecene.
• the content of the solvent is not particularly limited, but it may be usually about 20 to 40% by weight of the total amount of the flux composition.
• the thixotropic agent is not particularly limited, and known ones can be used. Specific examples include hardened castor oil, beeswax, carnauba wax, stearamide, hydroxy stearic acid ethylene bisamide, and the like.
• the content of the thixotropic agent is not particularly limited, but is usually about 3 to 10% by weight of the total amount of the flux composition.
• the plasticizer is not particularly limited, and a known plasticizer can be used. Specific examples include carboxylic acid esters such as dioctyl phthalate and dioctyl adipate.
• the content of the plasticizer is not particularly limited, but is usually 5 to 10% by weight of the total amount of the flux composition.
• solder composition of the present invention is a lead-free solder composition, and the above-mentioned lead-free solder flux composition of the present invention and a lead-free solder alloy are mixed, particularly uniformly or substantially uniformly. Or by combining them.
• the solder alloy used in the present invention is not particularly limited as long as it is an alloy used for lead-free solder, and a known alloy can be used.
• it is an alloy based on Sn, which is mainly composed of an alloy of Sn—Ag, Sn—Cu, Sn—Sb, Sn—Zn, etc., and if necessary, Ag, One, two or more of Al, Au, Bi, Co, Cu, Fe, Ga, Ge, In, Ni, P, Pt, Sb, and Zn may be added.
• Sn95Sb5 solidus temperature 238 ° C., liquidus temperature 241 ° C.
• Sn99.3Cu0.7 solidus temperature 227 ° C., liquidus temperature 228 ° C.
• Sn97Cu3 solidus line
• Sn92Cu6Ag2 solidus temperature 217 ° C, liquidus temperature 373 ° C
• Sn99Cu0.7Ag0.3 solidus temperature 217 ° C, liquidus temperature 226 ° C
• Sn95Cu4Ag1 solidus temperature 217 ° C, liquidus temperature 335 ° C
• Sn97Ag3 solidus temperature 221 ° C, liquidus temperature 222 ° C
• Sn96.3Ag3.7 solidus temperature 221 ° C, liquidus temperature
• the content ratio of the two is not particularly limited.
• the solder alloy is about 80 to 99% by weight in the total amount of the lead-free solder composition.
• the solder flux composition is preferably contained in an amount of about 1 to 20% by weight, more preferably about 85 to 95% by weight of the solder alloy and about 5 to 15% by weight of the solder flux composition.
• the solder alloy is extruded into a tubular rod and sucked into the tube by suction. It can be prepared by putting the composition.
• the use ratio of the flux composition to the solder alloy in this case is not particularly limited, but the linear solder alloy is about 95 to 99% by weight and the solder flux composition is 1 to 1% with respect to the total amount of the solder composition. It is preferable to use about 5% by weight, more preferably about 96 to 98% by weight of solder alloy and about 2 to 4% by weight of solder flux composition.
• the solder alloy is preferably a wire solder having a wire diameter (outer diameter) of about 0.05 to 2.0 mm.
• the cored solder of the present invention has good compatibility with various sealing resins, but particularly shows good compatibility with epoxy resins, urethane resins, acrylic resins and the like.
• solderability test Insert five 2.5-pitch, 18-pin, Sn-plated connectors into a single-sided phenolic board, and use a soldering iron with a soldering tip temperature of about 380 ° C. At the same time, soldering was performed at a constant speed of 1 sec / mm. The results were expressed according to the following criteria. ⁇ : Soldering was good. X: Wetting failure such as not getting wet or insufficient wetting of copper land exposure occurred.
• the test method was performed according to JIS Z 3197. The results were expressed according to the following criteria.
• ⁇ The specific resistance value is 1000 ⁇ ⁇ m (JIS standard AA class) or more.
• X The specific resistance value is lower than 1000 ⁇ ⁇ m (JIS standard AA class).
• Acrylic rosin (Arakawa Chemical Industries, Ltd., dehydroabietic acid content 19% by weight, dihydroabietic acid content 10% by weight, tetrahydroabietic acid content 10% by weight), disproportionated rosin containing a lot of dehydroabietic acid ( Arakawa Chemical Industries, Ltd. Dehydroabietic acid content 80 wt%, dihydroabietic acid 8 wt%, tetrahydroabietic acid 12 wt% each 49 wt%, activator (Tokyo Kasei Co., Ltd., glutaric acid 1 wt%) , Trans-2,3-dibromo-1,3-butenediol (1 wt%) was mixed to prepare a flux composition for solder.
• the flux composition thus obtained was used with a solder alloy having an alloy composition of Sn 98.0 wt% -Ag 1.2 wt% -copper 0.8 wt%, with a wire diameter of 0.8 mm and a flux composition content of 3 % Of cored solder was prepared.
• Example 1 the rosin composition in the flux composition for flux cored solder was acrylated rosin (manufactured by Arakawa Chemical Industries, Ltd .; dehydroabietic acid content 19% by weight, dihydroabietic acid content 10% by weight, tetrahydroabietic acid Disproportionated rosin (content 10% by weight) 28% by weight, rich in dehydroabietic acid (manufactured by Arakawa Chemical Industries, Ltd .; dehydroabietic acid content 80% by weight, dihydroabietic acid 8% by weight, tetrahydroabietic acid 12 In the same manner as in Example 1 except that 70% by weight) was obtained, a cored solder was obtained.
• the rosin composition in the flux composition for flux cored solder is a disproportionated rosin containing a large amount of dehydroabietic acid (manufactured by Arakawa Chemical Industries, Ltd .; dehydroabietic acid content 80% by weight, dihydroabietic acid 8% %, 17% by weight of tetrahydroabietic acid (12% by weight), hydrogenated rosin (manufactured by Arakawa Chemical Industries, Ltd.); 10% by weight of dehydroabietic acid, 70% by weight of dihydroabietic acid, 17% by weight of tetrahydroabietic acid ) Was changed to 81% by weight, and a cored solder was obtained in the same manner as in Example 1.
• dehydroabietic acid manufactured by Arakawa Chemical Industries, Ltd .
• dehydroabietic acid content 80% by weight, dihydroabietic acid 8% %, 17% by weight of tetrahydroabietic acid (12% by weight)
• hydrogenated rosin manufactured by Arak
• the rosin composition in the flux composition for flux cored solder is a disproportionated rosin containing a large amount of dehydroabietic acid (manufactured by Arakawa Chemical Industries, Ltd .; dehydroabietic acid content 80% by weight, dihydroabietic acid 8% %, Tetrahydroabietic acid 12% by weight), hydrogenated rosin (manufactured by Arakawa Chemical Industries, Ltd .; dehydroabietic acid content 10%, dihydroabietic acid content 70%, tetrahydroabietic acid 17% by weight) 49 each In the same manner as in Example 1 except that the amount was changed to% by weight, a hollow solder was obtained.
• Example 1 the rosin composition in the flux composition for flux cored solder was hydrogenated rosin (manufactured by Arakawa Chemical Industries, Ltd .; dehydroabietic acid content 10% by weight, dihydroabietic acid content 70% by weight, tetrahydroabietic acid 17% by weight) 95% by weight, acrylated rosin (Arakawa Chemical Industries, Ltd .; dehydroabietic acid content 19% by weight, dihydroabietic acid content 10% by weight, tetrahydroabietic acid content 10% by weight) 3% %, Solder was obtained in the same manner as in Example 1.
• Example 1 disproportionated rosin containing a large amount of dehydroabietic acid (made by Arakawa Chemical Industries, Ltd .; dehydroabietic acid content: 80% by weight, dihydroabietic acid 8) A flux-filled solder was obtained in the same manner as in Example 1 except that 98% by weight (wt%, tetrahydroabietic acid 12% by weight) was used.
• Example 1 the rosin composition in the flux composition for flux cored solder was changed to an acrylated rosin (manufactured by Arakawa Chemical Industries, Ltd .; dehydroabietic acid content 19% by weight, dihydroabietic acid content 10% by weight, tetrahydroabietin Disproportionated rosin (produced by Arakawa Chemical Co., Ltd .; dehydroabietic acid content 80% by weight, dihydroabietic acid 8% by weight, tetrahydroabietic acid 12%, acid content 10% by weight) 13% by weight, dehydroabietic acid-rich
• a cored solder was obtained.
• a test was conducted in the same manner as in Example 1 using this cored solder.
• Example 1 rosin-hydrogenated rosin in flux composition for flux cored solder (manufactured by Arakawa Chemical Industries, Ltd .; dehydroabietic acid content 10% by weight, dihydroabietic acid content 70% by weight, tetrahydroabietic acid 17% by weight %) was obtained in the same manner as in Example 1 except that 98% by weight was used.
• Tables 1 and 2 below show the compositions, solderability (wettability), aqueous solution specific resistance, and compatibility with the sealing resin of each of the above examples and comparative examples.
• the flux composition of the present invention provides a solder composition in which the insulation resistance of the flux residue is sufficiently high in practice, the wet spreadability is good, that is, the solderability is good, and the curing of the sealing resin is not hindered. Is.

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• 2010
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