WO2014103751A1 - フラックスおよびはんだペースト - Google Patents
フラックスおよびはんだペースト Download PDFInfo
- Publication number
- WO2014103751A1 WO2014103751A1 PCT/JP2013/083463 JP2013083463W WO2014103751A1 WO 2014103751 A1 WO2014103751 A1 WO 2014103751A1 JP 2013083463 W JP2013083463 W JP 2013083463W WO 2014103751 A1 WO2014103751 A1 WO 2014103751A1
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- WO
- WIPO (PCT)
- Prior art keywords
- acrylic resin
- flux
- meth
- acrylate
- mass
- Prior art date
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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
- B23K35/24—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
-
- 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
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
-
- 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
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
-
- 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
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
- B23K35/025—Pastes, creams, slurries
-
- 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
-
- 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
- B23K35/36—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
- B23K35/3613—Polymers, e.g. resins
-
- 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
- B23K35/365—Selection of non-metallic compositions of coating 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3489—Composition of fluxes; Methods of application thereof; Other methods of activating the contact surfaces
Definitions
- the present invention relates to a soldering flux used when soldering circuit components to a circuit board such as a printed circuit board of an electronic device, and a solder paste composition using the same.
- soldering fluxes and solder paste compositions have been used for soldering electronic circuit components and the like.
- the flux removes the solder and the metal oxide on the substrate surface, and prevents reoxidation of the metal during soldering. Therefore, it is indispensable for reducing the surface tension of the solder and performing the soldering well.
- solder paste application methods can be broadly divided into printing methods and ejection methods.
- the printing method is a method in which a metal mask or a silk screen provided with a hole in a soldering portion is placed on a printed circuit board, and a solder paste is applied thereon.
- the discharge method is a method in which a solder paste is applied to the soldering portion one by one using a dispenser or the like.
- the fine pitch pattern has a drawback that it cannot be applied by a discharge method. For example, when an electronic circuit component or the like is solder-connected to a fine pitch circuit board, a printing method is used.
- the solder paste is required to have excellent printability (transferability) in addition to conventionally required characteristics (stability, reliability, etc.).
- the printability is to efficiently transfer the solder paste attached to the wall surface of the metal mask opening to the substrate.
- improvement in printability means such as refinement of the metal particle size and increase in the amount of wax have been proposed.
- the metal particle size is reduced, printability is improved, but “storage stability”, “wetability” and the like are decreased.
- the amount of wax increases, it is difficult to adjust the viscosity, and the wettability tends to decrease.
- thermoplastic acrylic resin having a glass transition temperature of less than ⁇ 50 ° C. as the base resin, and an acid value of the thermoplastic acrylic resin of 50 mgKOH. It has been found that the active action can be promoted when it is at least / g (Patent Document 1).
- Patent Document 2 discloses a rosin obtained by adding a resin having an acid value of 50 mgKOH / g or less to a solder paste in order to improve the cleaning property of a flux residue after soldering.
- a resin having a high acid value is mixed in order to supplement the activity of the resin having a low acid value.
- An object of the present invention is to provide a soldering flux that exhibits excellent effects in all of printability, wettability, and crack resistance of a flux residue of a solder paste, and a solder paste composition using the same. .
- an acrylic resin (A) having an acid value of 0 to 70 obtained by polymerizing a monomer mixture containing an alkyl (meth) acrylate having an alkyl group having 12 to 23 carbon atoms, and an alkyl group having a carbon number of A soldering flux containing, as a base resin, an acrylic resin (B) having an acid value of 30 to 230, which is obtained by polymerizing a monomer mixture containing 6 to 10 alkyl (meth) acrylates.
- a soldering flux wherein the acid value of the resin (B) is higher than the acid value of the acrylic resin (A), and the difference is 15 or more.
- the acrylic resin (A) is contained in a proportion of 10 to 30% by mass with respect to the total amount of flux, and the acrylic resin (B) is contained in a proportion of 10 to 30% by mass with respect to the total amount of flux.
- the acrylic resin (A) is an acrylic resin obtained by polymerizing a monomer mixture containing at least 50% by mass of an alkyl (meth) acrylate having an alkyl group having 12 to 23 carbon atoms, (1) or The soldering flux according to (2).
- the acrylic resin (B) is an acrylic resin obtained by polymerizing a monomer mixture containing at least 50% by mass of an alkyl (meth) acrylate having an alkyl group having 6 to 10 carbon atoms.
- a solder paste composition comprising the soldering flux according to any one of (1) to (6) above and a solder alloy powder.
- the soldering flux of the present invention exhibits excellent effects in all of the printability and wettability of the solder paste and the crack resistance of the flux residue.
- soldering flux of the present invention contains an acrylic resin (A) and an acrylic resin (B) having different acid values as a base resin.
- the acrylic resins (A) and (B) are both polymers obtained by polymerizing a monomer mixture containing an alkyl (meth) acrylate.
- (meth) acrylate means acrylate or methacrylate.
- the acrylic resin (A) is obtained by polymerizing a monomer mixture containing at least 50% by mass of an alkyl (meth) acrylate having an alkyl group having 12 to 23 carbon atoms, the effects of the present invention can be exhibited.
- the acrylic resin (B) is obtained by polymerizing a monomer mixture containing at least 50% by mass of an alkyl (meth) acrylate having an alkyl group having 6 to 10 carbon atoms, the effect of the present invention is exhibited. it can.
- alkyl (meth) acrylate having an alkyl group having 12 to 23 carbon atoms examples include 2,2-dimethyllauryl (meth) acrylate, 2,3-dimethyllauryl (meth) acrylate, and 2,2-dimethylstearyl (meth) acrylate.
- These alkyl (meth) acrylates may be used alone or in combination of two or more. Among these, alkyl (meth) acrylates having 12 to 20 carbon atoms in the alkyl group are preferable.
- alkyl (meth) acrylate having 6 to 10 carbon atoms in the alkyl group examples include hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, and nonyl (meth) acrylate. These alkyl (meth) acrylates may be used alone or in combination of two or more.
- alkyl (meth) acrylate In addition to the above alkyl (meth) acrylate, other monomers that can be copolymerized with these alkyl (meth) acrylates may be used.
- Other monomers include nonionic monomers (for example, acrylamide, styrene, ⁇ -olefins, alkyl (meth) acrylates having 1 to 5 carbon atoms in the alkyl group (for example, methyl (meth) acrylate, ethyl (meth) acrylate, Hydroxyethyl (meth) acrylate, butyl (meth) acrylate, etc.)) and anionic monomers (for example, acrylic acid, methacrylic acid, itaconic acid, etc.).
- nonionic monomers for example, acrylamide, styrene, ⁇ -olefins
- alkyl (meth) acrylates having 1 to 5 carbon atoms in the alkyl group for example,
- the acid value of the acrylic resin is determined by the ratio of organic acid monomers (for example, acrylic acid, methacrylic acid, etc.) in the monomer component. That is, when the monomer component contains only an alkyl (meth) acrylate and a nonionic monomer, the acid value of the resulting acrylic resin is 0 mgKOH / g, and the acid value increases as the proportion of the organic acid monomer increases.
- organic acid monomers for example, acrylic acid, methacrylic acid, etc.
- the present invention is characterized in that the acid value of the acrylic resin (B) is higher than the acid value of the acrylic resin (A), and the difference is 15 or more.
- the acrylic resin (A) has an acid value of 0 to 70 mgKOH / g, preferably 20 to 50 mgKOH / g.
- the acrylic resin (B) has an acid value of 30 to 230 mgKOH / g, preferably 60 to 150 mgKOH / g.
- the method for synthesizing the acrylic resins (A) and (B) is not particularly limited, and a known method is employed.
- the monomer components constituting the acrylic resins (A) and (B) may be subjected to radical polymerization using a solvent, a polymerization initiator, a chain transfer agent, or the like as necessary.
- the polymerization initiator used for radical polymerization is not particularly limited as long as it is a compound that decomposes to generate radicals. Examples thereof include azo initiators and peroxide initiators. Among these, azo initiators such as azobisisobutyronitrile (AIBN), azobismethylbutyronitrile (ABNE), and azobisdimethylvaleronitrile (ABNV) are preferable.
- the acrylic resins (A) and (B) preferably have a weight average molecular weight of 30000 or less, more preferably 5000 to 30000.
- the acrylic resins (A) and (B) may have different weight average molecular weights.
- the weight average molecular weight is usually measured using a gel permeation chromatograph (GPC).
- the acrylic resin (A) is contained in a proportion of 10 to 30% by mass, preferably in a proportion of 10 to 25% by mass with respect to the total amount of flux.
- the acrylic resin (B) is also contained in a proportion of 10 to 30% by mass, preferably 10 to 25% by mass, based on the total amount of flux.
- the flux of the present invention usually contains an activator, a thixotropic agent, an organic solvent, etc., and may contain other base resins as long as the effects of the present invention are not impaired.
- base resins include styrene-maleic acid resin, epoxy resin, urethane resin, polyester resin, phenoxy resin, terpene resin, rosin resin, and the like.
- rosins include gum rosin, tall rosin, wood rosin, and derivatives thereof.
- these derivatives include polymerized rosin, acrylated rosin, hydrogenated rosin, disproportionated rosin, formylated rosin, rosin ester, rosin modified maleic resin, rosin modified phenolic resin, rosin modified alkyd resin and the like.
- the activator examples include amines (diphenylguanidine, naphthylamine, diphenylamine, triethanolamine, monoethanolamine, etc.), amine salts (polyamines such as ethylenediamine, and organic acid salts of amines such as cyclohexylamine, ethylamine, and diethylamine) Inorganic acids (mineral acids such as hydrochloric acid and sulfuric acid) salts, organic acids (dicarboxylic acids such as succinic acid, adipic acid, glutaric acid, sebacic acid, maleic acid; myristic acid, palmitic acid, stearic acid, oleic acid, etc.
- amines diphenylguanidine, naphthylamine, diphenylamine, triethanolamine, monoethanolamine, etc.
- amine salts polyamines such as ethylenediamine, and organic acid salts of amines such as cyclohexylamine, ethylamine
- Fatty acids Hydroxycarboxylic acids such as lactic acid, dimethylolpropionic acid and malic acid; benzoic acid, phthalic acid, trimellitic acid, etc.), amino acids (glycine, alanine, aspartic acid, glutamic acid, valine, etc.), aniline hydrogen halide And the like salts (such as aniline hydrobromide).
- thixotropic agent examples include hardened castor oil, beeswax, carnauba wax, stearic acid amide, hydroxy stearic acid ethylene bisamide, and the like.
- organic solvent examples include alcohol solvents (ethyl alcohol, isopropyl alcohol, ethyl cellosolve, butyl carbitol, hexyl carbitol, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), hydrocarbon solvents (toluene, terpine) Oil).
- alcohol solvents ethyl alcohol, isopropyl alcohol, ethyl cellosolve, butyl carbitol, hexyl carbitol, etc.
- ester solvents ethyl acetate, butyl acetate, etc.
- hydrocarbon solvents toluene, terpine
- isopropyl alcohol, butyl carbitol, hexyl carbitol and the like are preferable.
- Isopropyl alcohol is excellent in volatility and solubility of the active agent, and is preferably used for, for example, a liquid flux.
- an ether of a polyhydric alcohol having a high boiling point such as butyl carbitol and hexyl carbitol is preferably used.
- the flux of the present invention contains acrylic resin (A), acrylic resin (B), other base resin, activator, thixotropic agent and organic solvent in the following proportion with respect to the total amount of flux.
- the flux of the present invention may contain additives such as an antioxidant, a chelating agent, and a rust preventive as necessary, as long as the effects of the present invention are not impaired. These additives may be added, for example, when the flux and the solder alloy powder are mixed.
- solder paste composition contains the flux of the present invention and a solder alloy powder.
- the solder alloy powder is not particularly limited.
- an Sn—Pb alloy an alloy obtained by adding silver, bismuth, indium or the like to an Sn—Pb alloy, an Sn—Ag alloy, an Sn—Cu alloy, an Sn—Ag—Cu Based alloys.
- lead-free alloys such as Sn—Ag alloy, Sn—Cu alloy, Sn—Ag—Cu alloy are preferable.
- the average particle size of the solder alloy powder is not particularly limited, but is preferably about 10 to 40 ⁇ m, for example.
- the mass ratio of the flux to the solder alloy powder is not particularly limited as long as it is appropriately set according to the use of the solder paste, but is preferably about 8:92 to 15:85.
- the solder paste composition of the present invention is applied onto a substrate by a dispenser, screen printing or the like when soldering an electronic device part or the like. After coating, preheating is performed at about 150 to 200 ° C., and reflow is performed at a maximum temperature of about 170 to 250 ° C.
- the application and reflow on the substrate may be performed in the air or in an inert atmosphere such as nitrogen, argon, helium.
- an acrylic resin (A1) (acid value: 0 mg KOH / g, weight average molecular weight (Mw): 10,000, glass transition temperature (Tg): 27 ° C).
- the acid value and the weight average molecular weight were measured by the following methods.
- Acid value (A ⁇ f ⁇ 5.611) / S (In the formula, A represents the titration amount (mL), f represents the factor of the potassium hydroxide ethanol solution, and S represents the mass (g) of the sample.) ⁇ Measurement of weight average molecular weight> The molecular weight distribution of the resin was measured by gel permeation chromatography (GPC), and the weight average molecular weight was determined.
- Acrylic resins (A2) to (A6) and Acrylic resins (B1) to (B8) were prepared in the same manner as in Synthesis Example 1 except that the components shown in Table 1 were used in the proportions shown in Table 1. And acrylic resins 1 to 4 were obtained.
- the acid value, Mw and Tg of the obtained acrylic resin are shown in Table 1.
- the acrylic resins (A1) to (A6) obtained in Synthesis Examples 1 to 6 are included in the acrylic resin (A), and the acrylic resins (B1) to (B8) obtained in Synthesis Examples 7 to 14 are acrylic resins ( B).
- Example 1 As shown in Table 2, 20% by mass of acrylic resin (A1), 20% by mass of acrylic resin (B1), 8% by mass of adipic acid, 0.5% by mass of tributylamine hydrobromide, hexylcarbyl 30% by mass of Toll and 6.5% by mass of Custer wax were put in a container. Next, the container was heated to dissolve and mix the components, and then cooled to obtain a flux. The obtained flux and solder alloy powder (Sn-3.0Ag-0.5Cu) were mixed with flux: solder metal powder in a ratio of 11:89 (mass ratio) to obtain a solder paste composition.
- solder paste composition As shown in Table 2, 20% by mass of acrylic resin (A1), 20% by mass of acrylic resin (B1), 8% by mass of adipic acid, 0.5% by mass of tributylamine hydrobromide, hexylcarbyl 30% by mass of Toll and 6.5% by mass of Custer wax were put in a container. Next, the container was heated to dissolve
- Examples 2 to 23 and Comparative Examples 1 to 15 Flux was obtained in the same procedure as in Example 1 except that the components shown in Tables 2 and 3 were used in the proportions shown in Tables 2 and 3. Next, a solder paste composition was obtained in the same manner as in Example 1 except that each obtained flux was used.
- solder paste compositions of Examples 1 to 23 showed good results in all of (1) solder paste printability, (2) wettability, and (3) cracking resistance of the flux residue. It turns out that it is obtained.
- solder paste compositions of Comparative Examples 1 to 15 are inferior in at least one of (1) solder paste printability, (2) wettability, and (3) flux residue. .
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- Organic Chemistry (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
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Abstract
Description
(1)アルキル基の炭素数が12~23のアルキル(メタ)アクリレートを含有するモノマー混合物を重合して得られる、酸価が0~70のアクリル樹脂(A)と、アルキル基の炭素数が6~10のアルキル(メタ)アクリレートを含有するモノマー混合物を重合して得られる、酸価が30~230のアクリル樹脂(B)とをベース樹脂として含有するはんだ付け用フラックスであって、前記アクリル樹脂(B)の酸価が、前記アクリル樹脂(A)の酸価よりも高く、その差が15以上であることを特徴とするはんだ付け用フラックス。
(2)前記アクリル樹脂(A)が、フラックス総量に対して10~30質量%の割合で含有され、前記アクリル樹脂(B)が、フラックス総量に対して10~30質量%の割合で含有される、(1)に記載のはんだ付け用フラックス。
(3)前記アクリル樹脂(A)は、アルキル基の炭素数が12~23のアルキル(メタ)アクリレートを少なくとも50質量%含有するモノマー混合物を重合して得られるアクリル樹脂である、(1)または(2)に記載のはんだ付け用フラックス。
(4)前記アクリル樹脂(B)は、アルキル基の炭素数が6~10のアルキル(メタ)アクリレートを少なくとも50質量%含有するモノマー混合物を重合して得られるアクリル樹脂である、(1)~(3)のいずれかに記載のはんだ付け用フラックス。
(5)前記アクリル樹脂(A)が、30000以下の重量平均分子量を有する、(1)~(4)のいずれかに記載のはんだ付け用フラックス。
(6)前記アクリル樹脂(B)が、30000以下の重量平均分子量を有する、(1)~(5)のいずれかに記載のはんだ付け用フラックス。
(7)上記(1)~(6)のいずれかに記載のはんだ付け用フラックスと、はんだ合金粉末とを含有する、はんだペースト組成物。
本発明のはんだ付け用フラックス(以下、単に「フラックス」と記載する場合がある)は、酸価が異なるアクリル樹脂(A)およびアクリル樹脂(B)を、ベース樹脂として含有する。
重量平均分子量は、通常、ゲル浸透クロマトグラフ(GPC)を用いて測定される。
アクリル樹脂(B):10~30質量%、好ましくは10~25質量%
他のベース樹脂 :0~20質量%、好ましくは5~15質量%
活性剤 :0~30質量%、好ましくは5~25質量%
チキソ剤 :0~13質量%、好ましくは1~8質量%
有機溶剤 :0~35質量%、好ましくは10~30質量%
本発明のはんだペースト組成物は、本発明のフラックスとはんだ合金粉末とを含有する。はんだ合金粉末は特に限定されず、例えば、Sn-Pb合金や、Sn-Pb合金に銀、ビスマス、インジウムなどを添加した合金、Sn-Ag系合金、Sn-Cu系合金、Sn-Ag-Cu系合金などが挙げられる。環境への影響を考慮すると、Sn-Ag系合金、Sn-Cu系合金、Sn-Ag-Cu系合金などの鉛フリー合金が好ましい。はんだ合金粉末の平均粒子径は特に限定されないが、例えば10~40μm程度が好ましい。
(合成例1)
温度計および窒素導入管を備えた反応容器(ガラス製フラスコ)に、反応溶媒として30質量部のヘキシルカルビトールを入れて、窒素雰囲気下で撹拌しながら120℃まで加熱した。次いで、モノマー成分として65質量部のステアリルメタクリレート、重合開始剤として5質量部のAIBNを混合してモノマー溶液を調製した。このモノマー溶液を2時間かけて反応容器内に滴下して、120℃で反応を行った。全てのモノマー溶液を滴下した後、さらに120℃で2時間熟成し、アクリル樹脂(A1)を得た(酸価:0mgKOH/g、重量平均分子量(Mw):10000、ガラス転移温度(Tg):27℃)。酸価および重量平均分子量は、以下の方法によって測定した。
JIS 0070の酸価中和滴定法に基づいて行った。試料となる樹脂1gを三角フラスコに入れ、100mLの溶剤(トルエンとエタノールとの混合溶液、混合比1:1)および数滴のフェノールフタレイン溶液(指示薬)を加え、試料を完全に溶解させた。その後、0.1mol/Lの水酸化カリウムエタノール溶液で滴定を行い、指示薬の薄い紅色が30秒間着色した時点を終点とした。以下の式を用いて酸価を求めた。
酸価=(A×f×5.611)/S
(式中、Aは滴定量(mL)、fは水酸化カリウムエタノール溶液のファクター、およびSは試料の質量(g)を示す。)
<重量平均分子量の測定>
ゲル浸透クロマトグラフ(GPC)にて樹脂の分子量分布を測定し、重量平均分子量を求めた。
表1に記載の成分を表1に記載の割合で用いたこと以外は、合成例1と同様の手順で、それぞれアクリル樹脂アクリル樹脂(A2)~(A6)、アクリル樹脂(B1)~(B8)、およびアクリル樹脂1~4を得た。得られたアクリル樹脂の酸価、MwおよびTgを表1に示す。
合成例1~6で得られたアクリル樹脂(A1)~(A6)はアクリル樹脂(A)に包含され、合成例7~14で得られたアクリル樹脂(B1)~(B8)はアクリル樹脂(B)に包含される。
各実施例および比較例では、活性剤としてトリブチルアミン臭化水素酸塩(表2および3では「HBr」と記載)およびアジピン酸、チキソ剤としてカスターワックス(表2および3では「ワックス」と記載)、および有機溶剤としてヘキシルカルビトール(表2および3では「カルビトール」と記載)を用いた。
表2に示すように、アクリル樹脂(A1)を20質量%、アクリル樹脂(B1)を20質量%、アジピン酸を8質量%、トリブチルアミン臭化水素酸塩を0.5質量%、ヘキシルカルビトールを30質量%、およびカスターワックスを6.5質量%の割合で容器に入れた。次いで、容器を加熱し成分を溶解して混合した後、冷却してフラックスを得た。得られたフラックスとはんだ合金粉末(Sn-3.0Ag-0.5Cu)とを、フラックス:はんだ金属粉末を11:89(質量比)の割合で混合して、はんだペースト組成物を得た。
表2および3に記載の各成分を表2および3に記載の割合で用いたこと以外は、実施例1と同様の手順で、それぞれフラックスを得た。次いで、得られた各フラックスを用いたこと以外は、実施例1と同様にしてはんだペースト組成物を得た。
印刷性評価用基板(10×10ピンの0.5mmピッチ、BGA(Ball Grid Array)0.25mmφの開口パターンを有するガラスエポキシ基板)を用い、対応する厚み150μmのマスクを使用して、20枚の連続印刷性を以下の基準で評価した。
○:全ての基板において、10×10ピンのうち、欠けが2割未満の場合。
×:全ての基板において、10×10ピンのうち、欠けが2割以上の場合。
0.8mmピッチのQFP(Quad Flat Package)パターンが存在する基板に、同じパターンを有する厚み200μmのメタルマスクを用いてはんだペースト組成物を印刷した。印刷後10分以内に、大気下において175±5℃で80±5秒間プリヒートを行い、最高温度235±5℃でリフローを行った。そして、指標となるはんだボールの発生状況を、20倍の実体顕微鏡を用いて80パッド(80個のはんだ付け部)の周囲に発生したはんだボール数(個)をカウントし、はんだボールの数が10個以下の場合に、優れた濡れ性を有すると評価した。
○:はんだボールの数が10個以下である場合。
×:はんだボールの数が10個を超える場合。
上記の濡れ性試験を行った後の基板を試験片とし、該試験片に、-40℃×30分→125℃×30分を1サイクルとして、1000サイクルの条件で冷熱サイクル負荷をかけた後、基板上のはんだ付け部における残渣亀裂発生状態を目視観察し、以下の基準で評価した。
○:亀裂が認められない場合。
×:亀裂が観察される場合。
Claims (7)
- アルキル基の炭素数が12~23のアルキル(メタ)アクリレートを含有するモノマー混合物を重合して得られる、酸価が0~70のアクリル樹脂(A)と、
アルキル基の炭素数が6~10のアルキル(メタ)アクリレートを含有するモノマー混合物を重合して得られる、酸価が30~230のアクリル樹脂(B)と、
をベース樹脂として含有するはんだ付け用フラックスであって、
前記アクリル樹脂(B)の酸価が、前記アクリル樹脂(A)の酸価よりも高く、その差が15以上であることを特徴とする、はんだ付け用フラックス。 - 前記アクリル樹脂(A)が、フラックス総量に対して10~30質量%の割合で含有され、前記アクリル樹脂(B)が、フラックス総量に対して10~30質量%の割合で含有される、請求項1に記載のはんだ付け用フラックス。
- 前記アクリル樹脂(A)は、アルキル基の炭素数が12~23のアルキル(メタ)アクリレートを少なくとも50質量%含有するモノマー混合物を重合して得られるアクリル樹脂である、請求項1または2に記載のはんだ付け用フラックス。
- 前記アクリル樹脂(B)は、アルキル基の炭素数が6~10のアルキル(メタ)アクリレートを少なくとも50質量%含有するモノマー混合物を重合して得られるアクリル樹脂である、請求項1~3のいずれかに記載のはんだ付け用フラックス。
- 前記アクリル樹脂(A)が、30000以下の重量平均分子量を有する、請求項1~4のいずれかに記載のはんだ付け用フラックス。
- 前記アクリル樹脂(B)が、30000以下の重量平均分子量を有する、請求項1~5のいずれかに記載のはんだ付け用フラックス。
- 請求項1~6のいずれかに記載のはんだ付け用フラックスと、はんだ合金粉末とを含有する、はんだペースト組成物。
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EP3263272A4 (en) * | 2015-02-27 | 2018-10-10 | Senju Metal Industry Co., Ltd. | Flux |
WO2024009843A1 (ja) * | 2022-07-06 | 2024-01-11 | デクセリアルズ株式会社 | 回路装置の製造方法及び封止用樹脂組成物 |
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JP6268507B1 (ja) * | 2017-06-07 | 2018-01-31 | 千住金属工業株式会社 | やに入りはんだ用フラックス、フラックスコートはんだ用フラックス、やに入りはんだ、及びフラックスコートはんだ |
JP6583391B2 (ja) * | 2017-11-14 | 2019-10-02 | 千住金属工業株式会社 | フラックス、やに入りはんだおよびフラックスコートペレット |
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