WO2022209553A1 - フラックス及びソルダペースト - Google Patents
フラックス及びソルダペースト Download PDFInfo
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- WO2022209553A1 WO2022209553A1 PCT/JP2022/008913 JP2022008913W WO2022209553A1 WO 2022209553 A1 WO2022209553 A1 WO 2022209553A1 JP 2022008913 W JP2022008913 W JP 2022008913W WO 2022209553 A1 WO2022209553 A1 WO 2022209553A1
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- formula
- flux
- acid
- group
- solder
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- 150000004820 halides Chemical class 0.000 description 1
- 125000000755 henicosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002463 lignoceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 239000000113 methacrylic resin Substances 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical class NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FZPXKEPZZOEPGX-UHFFFAOYSA-N n,n-dibutylaniline Chemical compound CCCCN(CCCC)C1=CC=CC=C1 FZPXKEPZZOEPGX-UHFFFAOYSA-N 0.000 description 1
- JHOKTNSTUVKGJC-UHFFFAOYSA-N n-(hydroxymethyl)octadecanamide Chemical class CCCCCCCCCCCCCCCCCC(=O)NCO JHOKTNSTUVKGJC-UHFFFAOYSA-N 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- 229960004889 salicylic acid Drugs 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002469 tricosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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Images
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
-
- 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
- B23K35/3601—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 inorganic compounds as principal constituents
-
- 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
Definitions
- the present invention relates to flux and solder paste.
- BGA ball grid arrays
- Electronic parts that use BGA include, for example, semiconductor packages.
- a semiconductor package a semiconductor chip having electrodes is sealed with resin, and solder bumps are formed on the electrodes of the semiconductor package.
- the solder bumps are formed by bonding solder balls to the electrodes of the semiconductor package.
- solder bumps are placed in alignment with electrodes of a substrate coated with solder paste, and the solder paste is melted by heating to join the solder bumps and electrodes. mounted on the board.
- the solder paste used here is a composition containing solder powder and flux.
- the solder particles melt above the melting point and the oxide film on the surface of the solder particles is removed by the action of the flux. As a result, the solder particles are integrated and the bonding between the solder bump and the electrode is completed.
- solder bumps 2 are formed on the electrodes (not shown) of the semiconductor package 1 as shown in FIG. Further, the solder paste 5A is applied to the substrate electrodes 4 provided on the substrate 3. As shown in FIG. The solder bumps 2 of the semiconductor package 1 are placed on the substrate electrodes 4 coated with the solder paste 5A. In the process before reflow shown in FIG. 1A, the solder bumps 2 and the solder paste 5A applied to the substrate electrodes 4 are in contact with each other. In the subsequent reflow process, the semiconductor package 1 is first heated in a low-temperature region, and the entire semiconductor package 1 is warped due to the heating.
- the warp is large at the end of the component, so that most of the solder paste 5A remains on the board electrode 4, while the solder bump 2 with a part of the solder paste 5A attached peels off from the board electrode 4.
- An event occurs (FIG. 1(b)).
- a clearance is generated between the solder bumps 2 and the solder paste 5A applied to the substrate electrodes 4.
- solder bumps 2 are separated from the substrate electrodes 4 in this way, the solder paste 5A being melted and the substrate electrodes 4 cannot have a sufficient contact area or time for solder bonding during the main heating, or cannot be in contact with each other. Therefore, the metal oxide film on the surface of the substrate electrode 4 cannot sufficiently react with the activator component in the flux, and the metal oxide film on the surface of the substrate electrode 4 cannot be removed. As a result, the solder bumps and electrodes are not sufficiently bonded, resulting in defective bonding. Alternatively, if the soldering process ends with the solder bumps 2 and the substrate electrodes 4 separated from each other, the solder bumps 2 and the substrate electrodes 4 are not sufficiently bonded, resulting in poor bonding.
- the present invention has been made in view of such problems, and in particular, a solder paste solder paste that can suppress peeling of solder bumps from substrate electrodes due to warpage of parts that occurs in a lower temperature range than the main active temperature range of flux.
- the purpose is to provide flux and solder paste.
- the present inventor found that by using a solder joint failure inhibitor having a specific structure, it is possible to obtain a solder paste that can suppress peeling from the object to be joined even when stress due to warpage of the substrate is applied. perfected the invention.
- a flux comprising a base resin, an activator, a thixotropic agent, a solvent, and a solder joint failure inhibitor
- the solder joint defect inhibitor is a copolymer containing a structural unit represented by formula (1) and a structural unit represented by formula (2), The weight average molecular weight of the copolymer is 1000 or more and 100000 or less,
- a flux is provided in which the solder joint failure suppressor is in an amount of 1% by mass or more and 25% by mass or less with respect to the entire flux.
- R 1 is a saturated or unsaturated, linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, or a substituted or unsubstituted aryl group;
- R 2 is a group represented by formula (2-1), In formula (2-1), n is an integer of 1 to 20, R 21 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 22 is a straight chain having 1 to 6 carbon atoms. , a branched chain, or a cyclic alkylene group.
- a flux comprising a base resin, an activator, a thixotropic agent, a solvent, a polyoxyalkylene monoalkyl ether, and a solder joint failure inhibitor
- the solder joint defect inhibitor is a copolymer containing a structural unit represented by formula (1) and a structural unit represented by formula (2), The weight average molecular weight of the copolymer is 1000 or more and 100000 or less,
- a flux is provided in which the solder joint failure suppressor is in an amount of 1% by mass or more and 25% by mass or less with respect to the entire flux.
- R 1 is a saturated or unsaturated, linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, or a substituted or unsubstituted aryl group;
- R 2 is a group represented by formula (2-1), In formula (2-1), n is an integer of 1 to 20, R 21 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 22 is a straight chain having 1 to 6 carbon atoms. , a branched chain, or a cyclic alkylene group.
- solder paste containing solder powder and the flux is provided.
- the solder paste which can suppress peeling from a joining object even if the stress by the warp of a board
- X to Y in the description of numerical ranges means X or more and Y or less, unless otherwise specified.
- “1 to 5% by mass” means “1% by mass or more and 5% by mass or less”.
- alkyl group includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).
- the flux in the first embodiment includes a base resin, an activator, a thixotropic agent, a solvent, and a solder joint failure inhibitor.
- the solder joint defect inhibitor is a copolymer containing a structural unit represented by formula (1) and a structural unit represented by formula (2).
- R 1 is a saturated or unsaturated, linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, or a substituted or unsubstituted aryl group.
- R 2 is a group represented by formula (2-1).
- n is an integer of 1 to 20
- R 21 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- R 22 is a straight chain having 1 to 6 carbon atoms. , a branched chain, or a cyclic alkylene group.
- solder joint failure is suppressed.
- “poor joint” means, for example, non-wet open (NWO) joint formation between the solder and the object to be soldered.
- “Poor bonding” can be measured, for example, by electrical resistance measurement.
- “suppression of poor joining” means, for example, when joining is performed using a control solder or solder paste having a similar composition except that it does not contain the inhibitor of the present invention, the frequency of occurrence of poor joining is significantly means that the The occurrence frequency of the joint failure can be determined based on the NWO evaluation test described later.
- the flux of the present embodiment contains the above copolymer, it has excellent adhesion to the solder bumps and realizes strong connection between the semiconductor package electrodes and the substrate electrodes. Therefore, the solder paste containing the flux of the present embodiment does not separate from the object to be bonded even when stress due to warping of the substrate is applied, and as a result, defective bonding between the solder bumps of the semiconductor package and the electrodes of the substrate is suppressed. be. More specifically, when the solder paste containing the flux of this embodiment is used, even if the semiconductor package 1 is warped due to heating in the reflow process, the solder bumps 2 as shown in FIG. An event of detachment from the electrode 4 does not occur.
- solder paste containing the flux of the present embodiment By using the solder paste containing the flux of the present embodiment, even if the semiconductor package 1 warps, the solder paste 5A separates from both the substrate electrodes 4 and the solder bumps 2 as shown in FIG. Therefore, no clearance is generated between the solder bumps 2 and the substrate electrodes 4 . Therefore, bonding between the solder bumps 2 and the substrate electrodes 4 is ensured.
- the flux in the second embodiment contains a base resin, an activator, a thixotropic agent, a solvent, a polyoxyalkylene monoalkyl ether and a solder joint failure inhibitor.
- the flux of the second embodiment differs from the flux of the first embodiment in that it contains polyoxyalkylene monoalkyl ether.
- copolymer Polymer P (Solder joint failure suppressor)
- copolymer Polymer P a copolymer (herein referred to as "copolymer Polymer P”).
- R 1 is a saturated or unsaturated, linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, or a substituted or unsubstituted aryl group.
- R 2 is a group represented by formula (2-1).
- n is an integer of 1 to 20
- R 21 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- R 22 is a straight chain having 1 to 6 carbon atoms. , a branched chain, or a cyclic alkylene group.
- the flux of the present embodiment suppresses poor solder joints. More specifically, since the flux of the present embodiment contains the copolymer P described above, it has excellent adhesion to both the substrate electrodes and the solder bumps. Thereby, a robust connection between the semiconductor package and the substrate electrode is realized. Therefore, the solder paste containing the flux of the present embodiment does not separate from the object to be bonded even when stress due to warping of the substrate is applied, and as a result, defective bonding between the solder bumps of the semiconductor package and the electrodes of the substrate is suppressed. be. The reason why the above effect is obtained by using the above copolymer P is not necessarily clear.
- the adhesiveness to the substrate electrodes and solder bumps can be maintained.
- the copolymer P has a high heat resistance and therefore has the effect of uniforming the dispersibility of the solder powder in the solder paste even in a high temperature environment.
- R 1 is a saturated or unsaturated linear, branched or cyclic structure having 1 to 24 carbon atoms. or a substituted or unsubstituted aryl group.
- R 1 is preferably a saturated linear alkyl group having 1 to 24 carbon atoms or an unsubstituted aryl group, more preferably R 1 is a saturated linear alkyl group having 6 to 18 carbon atoms, a phenyl group or It is an alkylphenyl group.
- saturated or unsaturated linear, branched or cyclic alkyl groups having 1 to 24 carbon atoms that can constitute R 1 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, (n-)hexyl group, (n-) heptyl group, (n-) octyl group, (n-) nonyl group, (n-) decyl group, (n-) udecyl group, (n-) dodecyl group, (n-) tridecyl group, (n-) tetradecyl group, (n-) pentadecyl group, (n-) hexade
- R 1 is a hexyl group, an octadecyl group, or an (n-)octyl group (--C 8 H 17 ) because the copolymer P has an excellent effect of suppressing defective solder joints.
- Examples of the substituted or unsubstituted aryl group that can constitute R 1 include a phenyl group and an alkylphenyl group, preferably a phenyl group and a methylphenyl group.
- the alkyl group in the alkylphenyl group is, for example, a saturated or unsaturated linear, branched or cyclic alkyl group having 1 to 5 carbon atoms, preferably a saturated linear alkyl group having 1 to 5 carbon atoms. is the base.
- Examples of the alkyl group in the alkylphenyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group and the like.
- a hydrogen atom of an aromatic ring such as a benzene ring may be substituted with, for example, other substituents.
- substituents include a hydroxy group, a halogen group, an amino group, an alkyl group, and the like. mentioned.
- the halogen group includes, for example, a chlorine atom, a bromine atom, and the like.
- the ratio of the structural unit represented by formula (1) in the total structural units of the copolymer P is, for example, 20 to 80 mol%, preferably 30 to 70 mol%, more preferably 40 ⁇ 60 mol%.
- R 2 is a group represented by the above formula (2-1).
- n is an integer of 1 to 30
- R 21 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- R 22 is a straight It is a chain, branched, or cyclic alkylene group.
- n is preferably an integer of 1-20, more preferably an integer of 4-15, even more preferably an integer of 8-13.
- R 21 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms (methyl group or ethyl group).
- R 22 is preferably a linear alkylene group having 1 to 6 carbon atoms, more preferably alkylene having 2 or 3 carbon atoms.
- the —R 21 O— group in formula (2) is preferably an oxyethylene group or an oxypropylene group.
- the ratio of the structural unit represented by formula (2) in the total structural units of the copolymer P is, for example, 20 to 80 mol%, preferably 30 to 70 mol%, more preferably 40 ⁇ 60 mol%.
- the copolymer P is a copolymer (p1) having a repeating structure represented by formula (p1).
- l and m represent the molar content in the copolymer (p1), l is greater than 0 and less than 1, m is greater than 0 and less than 1, R 1 is a saturated or unsaturated linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, R 2 has the same definition as in formula (2) above.
- the copolymer (p1) represented by the formula (p1) may be an alternating copolymer in which each structural unit is alternately bonded, or may be a random copolymer in which the structural units are randomly formed. , may be a block copolymer in which block units are combined.
- the copolymer P is a copolymer (p2) having a repeating structure represented by formula (p2).
- l and m represent the molar content in the copolymer (p2), l is greater than 0 and less than 1, m is greater than 0 and less than 1, R 2 has the same definition as in formula (2) above.
- the copolymer (p2) represented by the formula (p2) may also be an alternating copolymer in which each structural unit is alternately bonded, or may be a random copolymer in which the structural units are randomly formed. However, it may be a block copolymer in which block units are combined.
- the copolymer (p2) corresponds to the case where the above formula (1) is a structural unit represented by formula (6).
- the structural unit represented by formula (6) is chemically robust. Therefore, the copolymer (p2) containing this as a structural unit has the effect of suppressing defective solder joints and can have high heat resistance.
- the weight average molecular weight (Mw) of the copolymer P is, for example, 1000-100000.
- the lower limit of the weight average molecular weight (Mw) of the copolymer P is preferably 2000 or more, more preferably 4000 or more, still more preferably 6000 or more, and particularly preferably 7000 or more.
- the lower limit of the weight average molecular weight (Mw) of the copolymer P is preferably 50,000 or less, more preferably 40,000 or less, still more preferably 30,000 or less, and particularly preferably 20,000 or less. .
- the number average molecular weight (Mn) of the copolymer P is, for example, 1000-4000, preferably 2000-3000.
- the polydispersity (Mw/Mn) of the copolymer P is, for example, 1.0 to 5.0, preferably 2.0 to 4.0, more preferably 3.0. 0 to 4.0.
- the copolymer P used in the present embodiment is, for example, a copolymer of an olefin and/or a vinyl aromatic compound and maleic anhydride represented by the formula (p3) (hereinafter referred to as "precursor polymer” ) by introducing a group represented by the above formula (2-1).
- R 1 has the same definition as in formula (1) above, l and m indicate the molar content in the precursor polymer (p3), and l is greater than 0 and less than 1. , m is greater than 0 and less than 1.
- the copolymer P is a precursor polymer (p3), which is a copolymer of an olefin and/or a vinyl aromatic compound and maleic anhydride, in the presence of a basic catalyst according to the following formula (7 ) can be produced by reacting with an alcohol represented by By reacting the precursor polymer (p3) with the compound of formula (7), the maleic anhydride moiety in the precursor polymer (p3) is esterified to obtain the desired copolymer represented by formula (p). P is obtained.
- the precursor polymer (p3) may be any of random copolymer, alternating copolymer and block copolymer. Since maleic anhydride is generally known as a monomer having strong alternating copolymerizability, the precursor polymer (p3) is typically an alternating copolymer.
- l and m represent the molar content in the copolymer P, l is greater than 0 and less than 1, m is greater than 0 and less than 1, and R 1 is the above formula ( 1), and R 2 has the same definition as in formula (2) above.
- the precursor polymer (p3) represented by formula (p3) may be produced by a polymerization reaction between an olefin or vinyl aromatic compound and maleic anhydride, or may be a commercially available product.
- a polymerization reaction of the olefin or vinyl aromatic compound and maleic anhydride a known method of reacting the olefin or vinyl aromatic compound and maleic anhydride in the presence of a polymerization initiator can be used.
- Olefins used to prepare the precursor polymer (p3) include ethylene, propylene, 1-butene, isobutene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, Alpha-olefins such as 1-dodecene are preferred.
- Vinyl aromatic compounds used for producing the precursor polymer (p3) include styrene, ⁇ -methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p-amino ethylstyrene, N,N-diethyl-p-aminoethylstyrene and the like. It is preferable to use styrene from the viewpoint of production cost. Also, the olefins or vinyl aromatic compounds may be used singly or in combination of two or more. Examples of the styrene-maleic anhydride copolymer used as the precursor polymer (p3) include Xiran series (manufactured by Polyscope).
- the precursor polymer (p3) and a compound represented by the following formula (7) are reacted with a basic catalyst. is carried out by reacting in the presence of
- n, R 21 and R 22 in formula (7) have the same definitions as in formula (2-1).
- Examples of the compound represented by formula (7) used in the above step include polyoxyalkylene monoalkyl ethers, preferably polyethylene glycol monomethyl ether or polyethylene glycol monoethyl ether where n is 1 to 30, or n is 1 to 30 polypropylene glycol monomethyl ether or polypropylene glycol monoethyl ether.
- n is more preferably an integer of 1 to 20, more preferably an integer of 4 to 15, even more preferably an integer of 8 to 13. .
- the copolymer P may contain a structural unit represented by formula (8), a structural unit represented by formula (9), or a structural unit represented by formula (10).
- R 2 has the same definition as in formula (2) above.
- the copolymer P contains a structural unit represented by the formula (8), a structural unit represented by the formula (9), or a structural unit represented by the formula (10), the content is It is 1 to 10 mol % with respect to the total structural units of coalescence P.
- the content of the copolymer P in the flux is 1% by mass or more and 25% by mass or less with respect to the entire flux.
- the lower limit of the content of the copolymer P in the flux is preferably 1.5% by mass or more, more preferably 2% by mass or more, and further It is preferably 5% by mass or more, still more preferably 8% by mass or more, and particularly preferably 10% by mass or more.
- the upper limit of the content of the copolymer P in the flux is preferably 24% by mass or less, more preferably 22% by mass or less, and still more preferably , 20% by mass or less, and particularly preferably 18% by mass or less.
- Base resins used in the flux of the present embodiment include, for example, rosin-based resins, (meth)acrylic-based resins, urethane-based resins, polyester-based resins, phenoxy resins, vinyl ether-based resins, terpene resins, and modified terpene resins (e.g., aromatic modified terpene resin, hydrogenated terpene resin, hydrogenated aromatic modified terpene resin, etc.), terpene phenol resin, modified terpene phenol resin (e.g., hydrogenated terpene phenol resin, etc.), styrene resin, modified styrene resin (e.g., styrene acrylic resin, styrene maleic resin, etc.), xylene resin, modified xylene resin (e.g., phenol-modified xylene resin, alkylphenol-modified xylene resin, phenol-modified resol-type xylene resin,
- the base resin preferably contains a rosin-based resin.
- rosin-based resins include starting rosins such as gum rosin, wood rosin and tall oil rosin, and derivatives obtained from starting rosins. Derivatives include, for example, purified rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, ⁇ , ⁇ unsaturated carboxylic acid-modified products (acrylated rosin), maleated rosin, fumarated rosin, etc.), and polymerized rosin. Purified products, hydrides and disproportionated products, and purified products, hydrides and disproportionated products of ⁇ , ⁇ -unsaturated carboxylic acid-modified products are included. These rosin-based resins are used singly or in combination of two or more.
- the content of the base resin in the flux is, for example, 10-60% by mass, preferably 20-50% by mass, relative to the entire flux.
- the flux of this embodiment contains an active agent having a flux action.
- the flux action means a reduction action to remove the oxide film formed on the metal surface to which the solder paste is applied, and a reduction action to lower the surface tension of the molten solder to promote the wettability of the solder to the joint metal surface.
- the activator include organic acids, organic halogen compounds, amine hydrohalides, and the like.
- organic acids examples include monocarboxylic acids, dicarboxylic acids, anhydrides of dicarboxylic acids, and oxyacids. These may be used alone or in combination of two or more. Among these, polyvalent organic acids having two or more of at least one of hydroxy groups and carboxy groups in the molecule may be used.
- organic acids include glutaric acid, adipic acid, azelaic acid, eicosanedioic acid, citric acid, glycolic acid, succinic acid, salicylic acid, diglycolic acid, dipicolinic acid, dibutylaniline diglycolic acid, suberic acid, Sebacic acid, thioglycolic acid, terephthalic acid, dodecanedioic acid, p-hydroxyphenylacetic acid, picolinic acid, phenylsuccinic acid, phthalic acid, fumaric acid, maleic acid, malonic acid, lauric acid, benzoic acid, tartaric acid, tris isocyanurate ( 2-carboxyethyl), glycine, 1,3-cyclohexanedicarboxylic acid, 2,2-bis(hydroxymethyl)propionic acid, 2,2-bis(hydroxymethyl)butanoic acid, 2,3-dihydroxybenzoic acid, 2, 4-diethylglutaric
- dimer acid dimer acid
- trimer acid hydrogenated dimer acid which is a hydrogenated product of dimer acid to which hydrogen is added
- trimer acid hydrogenated product of trimer acid to which hydrogen is added
- Examples include dimer acid which is the reactant of oleic acid and linoleic acid, trimer acid which is the reactant of oleic acid and linoleic acid, dimer acid which is the reactant of acrylic acid, trimer acid which is the reactant of acrylic acid, Reaction of dimer acid, a reaction product of methacrylic acid, trimer acid, a reaction product of methacrylic acid, dimer acid, a reaction product of acrylic acid and methacrylic acid, trimer acid, a reaction product of acrylic acid and methacrylic acid, and 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, dimer acid, a reactant of linolenic acid, linolenic acid trimer acid, a reaction product of acrylic acid and oleic acid, dim
- the organic halide preferably has a polar group such as a hydroxyl group or a carboxyl group, such as a halogenated alcohol or a halogenated carboxyl compound, in order to improve the solubility in an aqueous solvent.
- a polar group such as a hydroxyl group or a carboxyl group, such as a halogenated alcohol or a halogenated carboxyl compound, in order to improve the solubility in an aqueous solvent.
- halogenated alcohols examples include 2,3-dibromopropanol, 2,3-dibromobutanediol, trans-2,3-dibromo-2-butene-1,4-diol, 1,4-dibromo-2-butanol, and brominated alcohols such as tribromoneopentyl alcohol, chlorinated alcohols such as 1,3-dichloro-2-propanol and 1,4-dichloro-2-butanol, fluorinated alcohols such as 3-fluorocatechol, and In addition, compounds similar to these may be mentioned.
- Halogenated carboxyl compounds include iodinated carboxyl compounds such as 2-iodobenzoic acid, 3-iodobenzoic acid, 2-iodopropionic acid, 5-iodosalicylic acid, and 5-iodoanthranilic acid, 2-chlorobenzoic acid, and Examples include chlorinated carboxyl compounds such as 3-chloropropionic acid, brominated carboxyl compounds such as 2,3-dibromopropionic acid, 2,3-dibromosuccinic acid, and 2-bromobenzoic acid.
- Amine hydrohalides include reaction products of amines and hydrogen halides.
- the amines include ethylamine, diethylamine, triethylamine, ethylenediamine, cyclohexylamine, 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, 1-o-tolylbiguanide and the like.
- Examples include hydrides of chlorine, bromine and iodine.
- the content of the activator in the flux is, for example, 1-20% by mass, preferably 5-15% by mass, relative to the entire flux.
- the flux of this embodiment contains a thixotropic agent.
- a thixotropic agent has the effect of improving the fluidity of the flux and the solder paste obtained using the same.
- thixotropic agents include wax-based thixotropic agents and amide-based thixotropic agents.
- wax-based thixotropic agents include castor hardened oil.
- Amide thixotropic agents include, for example, lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, saturated fatty acid amide, oleic acid amide, erucic acid amide, unsaturated fatty acid amide, p-toluene methanamides, aromatic amides, substituted amides, methylol stearamides, methylol amides, fatty acid ester amides, and the like.
- the amide-based thixotropic agent may be a bisamide-based thixotropic agent and/or a polyamide-based thixotropic agent.
- fatty acid bisamides examples include saturated fatty acid polyamides, unsaturated fatty acid polyamides, and aromatic polyamides. etc.
- the content of the thixotropic agent in the flux is, for example, 1-15% by mass, preferably 5-10% by mass, relative to the entire flux.
- the flux of this embodiment contains a solvent.
- Solvents are used to adjust the viscosity of the flux to a level suitable for application.
- Solvents used include alcohol solvents, glycol ether solvents, terpineols, hydrocarbons, esters, water and the like. These may be used alone or in combination of two or more. Among these, at least one of alcohol-based solvents and glycol ether-based solvents may be used.
- alcohol solvents include 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, 1,1,1-tris ( hydroxymethyl)ethane, 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, bis[2,2,2-tris(hydroxymethyl)ethyl]ether, 1-ethynyl-1-
- glycol ether solvents include hexyl diglycol, diethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, 2-methylpentane-2,4-diol, diethylene glycol monohexyl ether, diethylene glycol dibutyl ether, and triethylene glycol. monobutyl ether, tetraethylene glycol monomethyl ether, and the like.
- Ester solvents include diisobutyl succinate, dibutyl succinate, dimethyl adipate, diethyl adipate, dibutyl adipate, diisopropyl adipate, diisobutyl adipate, diisodecyl adipate, dibutyl maleate, dimethyl sebacate, diethyl sebacate, dibutyl sebacate, dioctyl sebacate, diisopropyl decanedioate and the like.
- the content of the solvent in the flux can be selected in consideration of the properties and addition amount of the base resin and the organic acid so that the coating work can be carried out smoothly. % by mass, preferably 25 to 50% by mass.
- the flux in the second embodiment contains polyoxyalkylene monoalkyl ethers.
- polyoxyalkylene monoalkyl ethers include polyethylene glycol monomethyl ether having a weight average molecular weight of 76 to 5000, polyethylene glycol monoethyl ether having a weight average molecular weight of 90 to 5000, or polypropylene glycol monomethyl ether having a weight average molecular weight of 90 to 5000.
- Ether or polypropylene glycol monoethyl ether having a weight average molecular weight of 104 to 5,000 can be mentioned.
- the lower limit of the weight average molecular weight of the polyoxyalkylene monoalkyl ether used is preferably 200 or more, more preferably 300 or more, still more preferably 400 or more.
- the upper limit of the weight average molecular weight of the polyoxyalkylene monoalkyl ether used is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,500 or less.
- the use of polyoxyalkylene monoalkyl ether improves the applicability and handleability of the obtained solder paste, and thus the electronic circuit mounting board manufactured using it has excellent connection reliability.
- the content of the polyoxyalkylene monoalkyl ether in the flux of the second embodiment is, for example, 0.1% by mass to 10% by mass, preferably 2% by mass to 8% by mass, relative to the entire flux. be.
- the flux of this embodiment may further contain an amine.
- Amines can function as flux activators.
- Examples of amines include ethylamine, diethylamine, triethylamine, ethylenediamine, cyclohexylamine, 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, 1-o-tolylbiguanide, imidazole, 2-ethylimidazole, 2 -methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-methyl-2-phenylimidazole, 1-benzyl- 2-methylimidazole, 1-benzyl-2-phenylimidazole and the like.
- the content of the amine is 0.1% by mass or more and 5% by mass or less, preferably 1% by mass or more and 5% by mass or less, relative to the entire flux.
- the flux of the present invention may further contain an antioxidant.
- the antioxidant can suppress oxidation of the solder powder.
- antioxidants include hindered phenol-based antioxidants, phenol-based antioxidants, bisphenol-based antioxidants, polymer-type antioxidants, and the like.
- antioxidant may be used individually by 1 type, and may use two or more types together.
- the amount of the antioxidant compounded in the flux is not particularly limited, and is, for example, 1% by mass or more and 10% by mass or less, preferably 1% by mass or more and 5% by mass or less based on the total amount of the flux.
- the flux of the present embodiment may further contain additives other than those described above within a range that does not impair the effects of the present invention.
- additives include coloring agents, antifoaming agents, surfactants, matting agents, and the like.
- a blending amount of the additive is not particularly limited, and can be, for example, 0% by mass or more and 5% by mass or less based on the total amount of the flux.
- solder paste contains the above-described flux and solder powder.
- solder powder is not particularly limited. Specifically, Sn--Ag alloy, Sn--Cu alloy, Sn--Ag--Cu alloy, Sn--In alloy, Sn--Pb alloy, Sn--Bi alloy, Sn--Ag--Cu--Bi alloy, and the above alloy composition to which Ag, Cu, In, Ni, Co, Sb, Ge, P, Fe, Zn, Ga and the like are further added.
- the solder paste of this embodiment can usually be produced by mixing the above flux and solder powder (metal powder).
- the mixing ratio of the flux and the solder powder is not particularly limited as long as the finally obtained solder paste has a practically acceptable viscosity.
- solder paste of the present embodiment can suppress solder joint failure by using the flux described above. Therefore, by using the solder paste of this embodiment, a highly reliable electronic circuit mounting board can be provided.
- (Poor bonding inhibitor) Inhibitor 1 a copolymer having a structural unit of formula (p1) below (weight average molecular weight (Mw): 7855, number average molecular weight (Mn): 2058, Mw/Mn: 3.8).
- Inhibitor 2 a copolymer having a structural unit of the following formula (p2) (weight average molecular weight (Mw): 8495, number average molecular weight (Mn): 2397, Mw/Mn: 3.5)
- solder paste was prepared using the fluxes having the compositions shown in the above examples and comparative examples. Specifically, 12% by mass of each flux and 88% by mass of Sn-3Ag-0.5Cu (melting point 217° C.) solder powder (particle size: 20 to 38 ⁇ m) are mixed with respect to the entire solder paste. By doing so, solder pastes of Examples 1 to 11 and Comparative Example 1 were prepared.
- solder pastes of Examples and Comparative Examples obtained by the above method were evaluated for the following performances.
- NWO evaluation Each of the solder pastes described above was evaluated for the occurrence of non-wet open (NWO) bonding. Specifically, using a metal mask with an opening diameter of 0.30 mm, a mask thickness of 0.12 mm (120 ⁇ m), and an opening number of 132 on a substrate (Cu-OSP treated glass epoxy substrate), each solder paste is printed. A 0.5 mm pitch BGA on which solder bumps were formed was mounted.
- the BGA warps due to heating in the reflow process, and an event occurs in which the solder bumps peel off from the substrate electrodes.
- the soldering process ends with the solder bumps and the substrate electrodes separated from each other, the solder bumps and the substrate electrodes are not sufficiently bonded to each other, resulting in defective bonding.
- this evaluation method makes it possible to estimate latent locations where NWO may occur.
- each solder paste was printed on a substrate (Cu-OSP treated glass epoxy substrate) using a metal mask having an opening diameter of 0.28 mm, a mask thickness of 0.1 mm, and an opening number of 64.
- This substrate was heated at a rate of 4°C/sec from 50°C to 170°C, and at a rate of temperature increase from 170°C to 195°C at a rate of about 0.2°C/sec for 118 seconds, peak temperature: 236.5°C.
- Melting time at 220° C. or higher Air reflow was performed with a reflow profile of 43 seconds to melt the solder alloy.
- a case where all 64 printed points were melted was evaluated as " ⁇ "
- a case where even one point was not melted was evaluated as "X”. Table 1 shows the results.
- the viscosity was measured using PCU-205 manufactured by Malcom Co., Ltd. in accordance with JIS Z3284-3 spiral method at a rotation speed of 10 rpm, 25° C., and in the air for 10 hours. If the viscosity after 10 hours is 1.3 times or less as compared to the initial viscosity of the solder paste, it is evaluated as " ⁇ " as indicating sufficient stability over time, and if it exceeds 1.3 times was evaluated as " ⁇ ".
- the initial viscosity means the viscosity at the start of continuous stirring. Table 1 shows the results.
- solder paste (adhesiveness (tackiness)) Each solder paste described above was measured according to JIS3284-3. Measurement was performed four times, and an average value of 1.1 N or more of the force required to peel off the probe was evaluated as "good", and less than 1.1 N was evaluated as “poor”. Higher force required to peel off the probe indicates higher tack and better tip retention.
- the NWO evaluation value of the joint was 35, whereas when each of the solder pastes of Examples 1 to 11 was used, , the NWO evaluation value of the joint was 20 or less, and the occurrence of joint failure was suppressed.
- the NWO evaluation values of the solder pastes of Examples 3 to 11 were 7 or less, and the occurrence of defective joints was more effectively suppressed.
- the evaluation value of NWO for the solder pastes of Examples 5 to 11 was 0, and the occurrence of defective joints was completely suppressed.
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Abstract
Description
前記はんだ接合不良抑制剤は、式(1)で表される構造単位と、式(2)で表される構造単位とを含む共重合体であり、
前記共重合体の重量平均分子量は、1000以上100000以下であり、
前記はんだ接合不良抑制剤は、当該フラックス全体に対して、1質量%以上25質量%以下の量である、フラックスが提供される。
前記はんだ接合不良抑制剤は、式(1)で表される構造単位と、式(2)で表される構造単位とを含む共重合体であり、
前記共重合体の重量平均分子量は、1000以上100000以下であり、
前記はんだ接合不良抑制剤は、当該フラックス全体に対して、1質量%以上25質量%以下の量である、フラックスが提供される。
本明細書における基(原子団)の表記において、置換か無置換かを記していない表記は、置換基を有しないものと置換基を有するものの両方を包含するものである。例えば「アルキル基」とは、置換基を有しないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含するものである。
(第一の実施形態)
第一の実施形態におけるフラックスは、ベース樹脂、活性剤、チクソ剤、溶剤、及びはんだ接合不良抑制剤を含む。第一の実施形態のフラックスにおいて、はんだ接合不良抑制剤は、式(1)で表される構造単位と、式(2)で表される構造単位とを含む共重合体である。
より詳細には、本実施形態のフラックスを含むソルダペーストを使用した場合、リフロー工程による加熱により半導体パッケージ1に反りが発生しても、図1(b)に示すような、はんだバンプ2が基板電極4から剥離する事象が生じない。本実施形態のフラックスを含むソルダペーストを使用することにより、半導体パッケージ1に反りが発生しても、図2に示すように、ソルダペースト5Aが基板電極4とはんだバンプ2との両方から剥離することなく、よってはんだバンプ2と基板電極4との間にクリアランスが生じない。よって、はんだバンプ2と基板電極4との間の接合が確保される。
第二の実施形態におけるフラックスは、ベース樹脂、活性剤、チクソ剤、溶剤、ポリオキシアルキレンモノアルキルエーテル及びはんだ接合不良抑制剤を含む。第二の実施形態のフラックスは、ポリオキシアルキレンモノアルキルエーテルを含む点で、上記第一の実施形態のフラックスと相違する。
本実施形態のフラックスは、はんだ接合不良抑制剤として、式(1)で表される構造単位と、式(2)で表される構造単位とを含む共重合体(本明細書中、「共重合体P」と称する)を含む。
R1は、炭素数1~24の飽和もしくは不飽和の直鎖、分枝状もしくは環状のアルキル基であり、
R2は、上記式(2)における定義と同義である。
R2は、上記式(2)における定義と同義である。
式(p2)で表される共重合体(p2)もまた、各構造単位が交互に結合した交互共重合体であってもよいし、ランダムに決層したランダム共重合体であってもよいし、ブロック単位で結合したブロック共重合体であってもよい。
以下に、はんだ接合不良抑制剤として使用される共重合体Pの製造方法にて記載する。
本実施形態で用いられる共重合体Pは、例えば、式(p3)で表される、オレフィン及び/又はビニル芳香族化合物と無水マレイン酸との共重合体(以下、「前駆体ポリマー」と称する)に、上記式(2-1)で表される基を導入することにより得られる。
本実施形態のフラックスに用いられるベース樹脂としては、例えば、ロジン系樹脂、(メタ)アクリル系樹脂、ウレタン系樹脂、ポリエステル系樹脂、フェノキシ樹脂、ビニルエーテル系樹脂、テルペン樹脂、変性テルペン樹脂(例えば、芳香族変性テルペン樹脂、水添テルペン樹脂、水添芳香族変性テルペン樹脂等)、テルペンフェノール樹脂、変性テルペンフェノール樹脂(例えば、水添テルペンフェノール樹脂等)、スチレン樹脂、変性スチレン樹脂(例えば、スチレンアクリル樹脂、スチレンマレイン樹脂等)、キシレン樹脂、変性キシレン樹脂(例えば、フェノール変性キシレン樹脂、アルキルフェノール変性キシレン樹脂、フェノール変性レゾール型キシレン樹脂、ポリオール変性キシレン樹脂、ポリオキシエチレン付加キシレン樹脂等)等が挙げられる。これらを単独で用いても2種以上を組み合わせて用いてもよい。なお、本明細書中、「(メタ)アクリル系樹脂」とは、メタクリル系樹脂及びアクリル系樹脂を包含する概念をいう。
本実施形態のフラックスは、フラックス作用を有する活性剤を含む。ここでフラックス作用とは、ソルダペーストが塗布される金属表面に生じた酸化皮膜を除去するという還元作用、及び、溶融はんだの表面張力を低下させて、はんだの接合金属表面への濡れ性を促進する作用を意味する。活性剤としては、有機酸、有機ハロゲン化合物、アミンハロゲン化水素酸塩等が挙げられる。
本実施形態のフラックスは、チクソ剤を含む。チクソ剤は、フラックス及びこれを用いて得られるソルダペーストの流動特性を改善する作用を有する。チクソ剤としては、例えば、ワックス系チクソ剤、アマイド系チクソ剤等が挙げられる。ワックス系チクソ剤としては、例えば、ヒマシ硬化油等が挙げられる。アマイド系チクソ剤としては、例えば、ラウリン酸アマイド、パルミチン酸アマイド、ステアリン酸アマイド、ベヘン酸アマイド、ヒドロキシステアリン酸アマイド、飽和脂肪酸アマイド、オレイン酸アマイド、エルカ酸アマイド、不飽和脂肪酸アマイド、p-トルエンメタンアマイド、芳香族アマイド、置換アマイド、メチロールステアリン酸アマイド、メチロールアマイド、脂肪酸エステルアマイド等が挙げられる。アマイド系チクソ剤は、ビスアマイド系チクソ剤及び/又はポリアマイド系チクソ剤であってもよく、ビスアマイド系チクソ剤としては、メチレンビスステアリン酸アマイド、エチレンビスラウリン酸アマイド、エチレンビスヒドロキシステアリン酸アマイド、飽和脂肪酸ビスアマイド、メチレンビスオレイン酸アマイド、不飽和脂肪酸ビスアマイド、m-キシリレンビスステアリン酸アマイド、芳香族ビスアマイド等が挙げられ、ポリアマイド系チクソ剤としては、飽和脂肪酸ポリアマイド、不飽和脂肪酸ポリアマイド、芳香族ポリアマイド等が挙げられる。
本実施形態のフラックスは、溶剤を含む。溶剤は、フラックスの粘度を、塗布に適切な程度に調整するために用いられる。用いられる溶剤としては、アルコール系溶剤、グリコールエーテル系溶剤、テルピネオール類、炭化水素類、エステル類、水等などが挙げられる。これらを単独で用いても2種以上を組み合わせて用いてもよい。この中でも、アルコール系溶剤又はグリコールエーテル系溶剤の少なくとも一方を用いてもよい。
第二の実施形態におけるフラックスは、ポリオキシアルキレンモノアルキルエーテルを含む。ポリオキシアルキレンモノアルキルエーテルとしては、例えば、重量平均分子量が76~5000のポリエチレングリコールモノメチルエーテル又は重量平均分子量が90~5000のポリエチレングリコールモノエチルエーテル、あるいは重量平均分子量が90~5000のポリプロピレングリコールモノメチルエーテル又は重量平均分子量が104~5000のポリプロピレングリコールモノエチルエーテルが挙げられる。
用いられるポリオキシアルキレンモノアルキルエーテルの重量平均分子量の下限値は、好ましくは、200以上であり、より好ましくは、300以上であり、さらに好ましくは、400以上ある。用いられるポリオキシアルキレンモノアルキルエーテルの重量平均分子量の上限値は、好ましくは、3000以下であり、より好ましくは、2000以下であり、さらに好ましくは、1500以下である。
ポリオキシアルキレンモノアルキルエーテルを用いることにより、得られるソルダペーストの塗布性および取り扱い性が改善され、よってこれを用いて製造された電子回路実装基板は、優れた接続信頼性を備える。
本実施形態のフラックスは、さらにアミンを含んでもよい。アミンは、フラックス活性剤として機能し得る。アミンとしては、例えば、エチルアミン、ジエチルアミン、トリエチルアミン、エチレンジアミン、シクロヘキシルアミン、1,3-ジフェニルグアニジン、1,3-ジ-o-トリルグアニジン、1-o-トリルビグアニド、イミダゾール、2-エチルイミダゾール、2-メチルイミダゾール、2-ウンデシルイミダゾール、2-ヘプタデシルイミダゾール、1,2-ジメチルイミダゾール、2-エチル-4-メチルイミダゾール、2-フェニルイミダゾール、4-メチル-2-フェニルイミダゾール、1-ベンジル-2-メチルイミダゾール、1-ベンジル-2-フェニルイミダゾール等が挙げられる。
本実施形態のソルダペーストは、上述のフラックスと、はんだ粉末とを含む。
下記表1に、実施例1~11及び比較例1の組成を示す。下記表1に示す配合量の各材料をそれぞれ混合し、加熱溶融することにより、均一に分散された実施例1~11及び比較例1のフラックスを得た。
(ベース樹脂)
・ベース樹脂1:アクリル酸変性水添ロジン
・ベース樹脂2:マレイン酸変性水添ロジン
(活性剤)
・活性剤1:グルタル酸
・活性剤2:スベリン酸
・活性剤3:アゼライン酸
・活性剤4:コハク酸
・活性剤5:セバシン酸
・活性剤6:トランス-2,3-ジブロモ-2-ブテン-1,4-ジオール
・活性剤7:2-フェニル-4-メチルイミダゾール
(チクソ剤)
・チクソ剤1:ポリアマイド
・チクソ剤2:硬化ひまし油
(溶剤)
・溶剤1:ジエチレングリコールモノヘキシルエーテル
(酸化防止剤)
・酸化防止剤1:ヒンダードフェノール系酸化防止剤
(添加剤)
・添加剤1:重量平均分子量が400~800のポリエチレングリコールモノメチルエーテルの混合物
・抑制剤1:以下式(p1)の構造単位を有する共重合体(重量平均分子量(Mw):7855、数平均分子量(Mn):2058、Mw/Mn:3.8)。
前述の各実施例及び比較例で示した組成のフラックスを用いて、ソルダペーストを作製した。具体的には、ソルダペースト全体に対して、12質量%の各フラックスと、88質量%のSn-3Ag-0.5Cu(融点217℃)のはんだ粉末(粒径:20~38μm)とを混合することにより、実施例1~11及び比較例1の各ソルダペーストを作製した。
上述の方法で得られた各実施例及び比較例のソルダペーストを、以下の性能について評価した。
(NWO評価)
上述の各ソルダペーストについて、接合不良(Non Wet Open:NWO)が生じるかを評価した。具体的には、基板(Cu-OSP処理ガラスエポキシ基板)に開口径:0.30mm、マスク厚0.12mm(120μm)、開口数:132個のメタルマスクを用いて、前記各ソルダペーストを印刷し、はんだバンプを形成した、0.5mmピッチのBGAを搭載した。これを、リフロー炉にて、25℃から130℃の昇温速度を、3℃/sec、130℃から190℃の昇温速度を1.0℃/sec、ピーク温度を200℃に設定して加熱し、その後冷却した。冷却後、基板とBGAとを剥離させた。剥離後に、印刷したソルダペーストが、はんだバンプに付着し、且つ基板側にソルダペーストが付着していない箇所を、NWOが発生した箇所とみなした。NWOが発生した箇所の個数を数え、表1に、「NWO発生数」(個)として記載する。また、NWO発生数が20個以下であるものを接合良好であると評価し、表1において「〇」と記載する。NWO発生数が20個を超えるものを、接合不良と評価し、表1において「×」と記載する。
上述の各ソルダペーストの溶融性を以下の方法により評価した。まず、基板(Cu-OSP処理ガラスエポキシ基板)に開口径:0.28mm、マスク厚0.1mm、開口数:64個のメタルマスクを用いて、前記各ソルダペーストを印刷した。この基板を、50℃から170℃の昇温速度を、4℃/sec、170℃から195℃の昇温速度を、約0.2℃/secで、118秒、ピーク温度:236.5℃、220℃以上の溶融時間:43秒のリフロープロファイルで大気リフローをし、はんだ合金を溶融させた。溶融性の評価について、印刷した64点のすべてが溶融したものを「〇」と評価し、1点でも溶融していないものを「×」と評価した。結果を表1に示す。
上述の各ソルダペーストについて、株式会社マルコム社製:PCU-205を用い、JISZ3284-3スパイラル方式に準拠して、回転数:10rpm、25℃、大気中で10時間、粘度を測定した。そして、10時間後の粘度が、ソルダペーストの初期粘度と比較して1.3倍以下であれば、十分な経時安定性を示すものとして「○」と評価し、1.3倍を超える場合には「×」と評価した。なお初期粘度は、連続撹拌開始時点の粘度を意味する。結果を表1に示す。
上述の各ソルダペーストについて、JIS3284-3に準拠し、リフロー工程の加熱時でのだれ挙動の測定を行った。なお、メタルマスクとしては、JISZ3284-3の図6において、より孔径が小さいメタルマスクを使用した。各パターンのうち印刷されたソルダペースト全てが一体にならない最小間隔を目視により測定した。最小間隔が小さいほど、加熱時の形状保持性が良好であることを表す。最小間隔の測定結果が0.4mm以下を「〇」と評価し、0.5mm以上を「×」と評価した。
上述の各ソルダペーストについて、JIS3284-3に準拠し測定を行った。4回測定を行い、プローブを引き剥がすのに必要な力の平均値が1.1N以上を「〇」と評価し、1.1N未満を「×」と評価した。プローブを引き剥がすのに必要な力が高いほど、粘着性が高く、チップ保持力が優れることを表す。
Claims (6)
- ベース樹脂、活性剤、チクソ剤、溶剤、及びはんだ接合不良抑制剤を含む、フラックスであって、
前記はんだ接合不良抑制剤は、式(1)で表される構造単位と、式(2)で表される構造単位とを含む共重合体であり、
前記共重合体の重量平均分子量は、1000以上100000以下であり、
前記はんだ接合不良抑制剤は、当該フラックス全体に対して、1質量%以上25質量%以下の量である、フラックス:
- ベース樹脂、活性剤、チクソ剤、溶剤、ポリオキシアルキレンモノアルキルエーテル及びはんだ接合不良抑制剤を含む、フラックスであって、
前記はんだ接合不良抑制剤は、式(1)で表される構造単位と、式(2)で表される構造単位とを含む共重合体であり、
前記共重合体の重量平均分子量は、1000以上100000以下であり、
前記はんだ接合不良抑制剤は、当該フラックス全体に対して、1質量%以上25質量%以下の量である、フラックス:
- 前記式(1)において、R1は、置換もしくは無置換のアリール基である、請求項1又は2に記載のフラックス。
- 前記式(2-1)において、R22は、炭素数2又は3のアルキレン基である、請求項1乃至4のいずれか一項に記載のフラックス。
- はんだ粉末と、
請求項1乃至5のいずれか一項に記載のフラックスと、を含むソルダペースト。
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