JP5697641B2 - Surface treatment agent for Sn and Sn alloy - Google Patents
Surface treatment agent for Sn and Sn alloy Download PDFInfo
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- JP5697641B2 JP5697641B2 JP2012224710A JP2012224710A JP5697641B2 JP 5697641 B2 JP5697641 B2 JP 5697641B2 JP 2012224710 A JP2012224710 A JP 2012224710A JP 2012224710 A JP2012224710 A JP 2012224710A JP 5697641 B2 JP5697641 B2 JP 5697641B2
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- alloy
- solder
- surface treatment
- treatment agent
- plating
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- 229910001128 Sn alloy Inorganic materials 0.000 title claims description 36
- 239000012756 surface treatment agent Substances 0.000 title claims description 24
- 229910052718 tin Inorganic materials 0.000 title claims description 19
- 229910000679 solder Inorganic materials 0.000 claims description 79
- 239000000843 powder Substances 0.000 claims description 22
- 238000004381 surface treatment Methods 0.000 claims description 21
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 18
- 239000001263 FEMA 3042 Substances 0.000 claims description 18
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 18
- 235000015523 tannic acid Nutrition 0.000 claims description 18
- 229920002258 tannic acid Polymers 0.000 claims description 18
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 18
- 229940033123 tannic acid Drugs 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000004020 conductor Substances 0.000 claims description 5
- 239000003125 aqueous solvent Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 description 21
- 238000007747 plating Methods 0.000 description 20
- 238000007254 oxidation reaction Methods 0.000 description 17
- 230000003647 oxidation Effects 0.000 description 16
- 239000000956 alloy Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 229910045601 alloy Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 229910020994 Sn-Zn Inorganic materials 0.000 description 11
- 229910009069 Sn—Zn Inorganic materials 0.000 description 11
- 229920001864 tannin Polymers 0.000 description 11
- 239000001648 tannin Substances 0.000 description 11
- 235000018553 tannin Nutrition 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- 235000006708 antioxidants Nutrition 0.000 description 9
- 230000004907 flux Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000010949 copper Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910020816 Sn Pb Inorganic materials 0.000 description 5
- 229910020922 Sn-Pb Inorganic materials 0.000 description 5
- 229910008783 Sn—Pb Inorganic materials 0.000 description 5
- 239000012190 activator Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000005476 soldering Methods 0.000 description 4
- 239000013008 thixotropic agent Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
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- 239000002245 particle Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 229910020836 Sn-Ag Inorganic materials 0.000 description 2
- 229910020830 Sn-Bi Inorganic materials 0.000 description 2
- 229910020988 Sn—Ag Inorganic materials 0.000 description 2
- 229910018728 Sn—Bi Inorganic materials 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- -1 phosphate ester Chemical class 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- CSTRPYAGFNTOEQ-MGMRMFRLSA-N (2r)-2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one;octadecanoic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O.CCCCCCCCCCCCCCCCCC(O)=O CSTRPYAGFNTOEQ-MGMRMFRLSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- FARHYDJOXLCMRP-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]pyrazol-3-yl]oxyacetic acid Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(N1CC2=C(CC1)NN=N2)=O)OCC(=O)O FARHYDJOXLCMRP-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-araboascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 1
- 239000011627 DL-alpha-tocopherol Substances 0.000 description 1
- 235000001815 DL-alpha-tocopherol Nutrition 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000002310 Isopropyl citrate Substances 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 150000000996 L-ascorbic acids Chemical class 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 241000208225 Rhus Species 0.000 description 1
- 235000014220 Rhus chinensis Nutrition 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- VLSOAXRVHARBEQ-UHFFFAOYSA-N [4-fluoro-2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(F)C=C1CO VLSOAXRVHARBEQ-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- YPHMISFOHDHNIV-FSZOTQKASA-N cycloheximide Chemical compound C1[C@@H](C)C[C@H](C)C(=O)[C@@H]1[C@H](O)CC1CC(=O)NC(=O)C1 YPHMISFOHDHNIV-FSZOTQKASA-N 0.000 description 1
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000010350 erythorbic acid Nutrition 0.000 description 1
- 239000004318 erythorbic acid Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001461 hydrolysable tannin Polymers 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229940026239 isoascorbic acid Drugs 0.000 description 1
- SKHXHUZZFVMERR-UHFFFAOYSA-L isopropyl citrate Chemical compound CC(C)OC(=O)CC(O)(C([O-])=O)CC([O-])=O SKHXHUZZFVMERR-UHFFFAOYSA-L 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 235000010263 potassium metabisulphite Nutrition 0.000 description 1
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- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 239000004320 sodium erythorbate Substances 0.000 description 1
- 235000010352 sodium erythorbate Nutrition 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- RBWSWDPRDBEWCR-RKJRWTFHSA-N sodium;(2r)-2-[(2r)-3,4-dihydroxy-5-oxo-2h-furan-2-yl]-2-hydroxyethanolate Chemical compound [Na+].[O-]C[C@@H](O)[C@H]1OC(=O)C(O)=C1O RBWSWDPRDBEWCR-RKJRWTFHSA-N 0.000 description 1
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- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
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- 229960000984 tocofersolan Drugs 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
Description
本発明は、Ｓｎ及びＳｎ合金に対する表面処理剤、及びそれを用いた表面処理方法に関する。更に、本発明は、その表面処理方法で処理を行った電子部品、Ｓｎ合金はんだボール、Ｓｎ合金はんだ粉末、及び該はんだボールを用いたボールグリッドアレイ、該はんだ粉末を用いたはんだペースト、それらを用いた実装品に関する。 The present invention relates to a surface treatment agent for Sn and an Sn alloy, and a surface treatment method using the same. Furthermore, the present invention relates to an electronic component treated by the surface treatment method, an Sn alloy solder ball, an Sn alloy solder powder, a ball grid array using the solder ball, a solder paste using the solder powder, It relates to the mounted product used.
はんだ付けは、融点が比較的低い物質を用いて物体同士を接合する技術であり、現代産業において、電子機器の接合、組み立て等に幅広く用いられている。一般的に用いられているはんだはＳｎ−Ｐｂ合金であり、その共晶組成（６３％Ｓｎ−残部Ｐｂ）の融点が１８３℃と低いものであることから、そのはんだ付けは２２０〜２３０℃で行われるため、電子部品や基板に対しほとんど熱損傷を与えない。しかも、Ｓｎ−Ｐｂ合金は、はんだ付け性が良好であるとともに、はんだ付け時にすぐに凝固して、はんだ付け部に振動が加わっても割れや剥離を起こし難いという優れた特徴も有している。 Soldering is a technique for joining objects using a material having a relatively low melting point, and is widely used in joining and assembling electronic devices in the modern industry. The commonly used solder is Sn—Pb alloy, and its eutectic composition (63% Sn—remainder Pb) has a melting point as low as 183 ° C., so the soldering is performed at 220 to 230 ° C. As a result, almost no thermal damage is caused to the electronic components and the substrate. In addition, the Sn-Pb alloy has excellent characteristics that it has good solderability and is solidified immediately during soldering, and hardly cracks or peels even if vibration is applied to the soldered portion. .
一般に電子機器は、外枠や基板等の合成樹脂と導体部やフレーム等の金属により形成されており、廃棄処分された場合は、焼却処分されず、ほとんどが地中に埋め立てられる。近年、地上に降る雨は酸性を示す傾向にあり（酸性雨）、地中に埋められた電子機器のはんだを溶出させて、地下水を汚染することが問題化している。このため、特に電子機器業界において、鉛を含まないはんだ（鉛フリーはんだ）への代替の動きが急速に進んでいる。 In general, an electronic device is formed of a synthetic resin such as an outer frame or a substrate and a metal such as a conductor or a frame. When discarded, the electronic device is not incinerated and mostly buried in the ground. In recent years, rain on the ground tends to be acidic (acid rain), and it has become a problem that the solder of electronic devices buried in the ground is eluted to contaminate groundwater. For this reason, particularly in the electronic equipment industry, an alternative movement to lead-free solder (lead-free solder) is rapidly progressing.
電子部品の外部リード端子には、そのはんだ濡れ性と耐食性を向上させるため、主にはんだめっき（９０％Ｓｎ−残部Ｐｂ）が施されており、その鉛フリー化への対応が望まれている。鉛フリーはんだめっきの候補としては、純Ｓｎ、Ｓｎ−Ａｇ（Ｃｕ）系、Ｓｎ−Ｚｎ系、Ｓｎ−Ｂｉ系に大別されるが、それぞれ一長一短がありＳｎ−Ｐｂ合金を完全に代替するには未だ至っていない。 External lead terminals of electronic components are mainly subjected to solder plating (90% Sn-remainder Pb) in order to improve solder wettability and corrosion resistance, and it is desired to cope with lead-free. . Candidates for lead-free solder plating are broadly divided into pure Sn, Sn-Ag (Cu), Sn-Zn, and Sn-Bi, but each has its merits and demerits to completely replace Sn-Pb alloys. Has not yet reached.
純Ｓｎめっきは、コストやめっきの作業性等、総合的にみて鉛フリーめっきとしては最有力と考えられる。しかし、Ｓｎめっきは表面の酸化や内部応力に起因して、ウィスカーが発生し易いことに加え、経時的にはんだ濡れ性が劣化し易いという課題があり、その改善が強く要望されている。 Pure Sn plating is considered to be the most powerful lead-free plating in terms of cost and workability of plating. However, Sn plating has a problem that solder wettability tends to deteriorate with time in addition to the fact that whiskers are likely to occur due to surface oxidation and internal stress, and there is a strong demand for improvement.
Ｓｎ−Ｚｎ系合金は、従来のＳｎ−Ｐｂ系合金と融点が近いことから、現在の設備や工程を変える必要がないという点で有利である。また、めっき被膜の機械的強度に優れコスト的にも優れている。しかし、Ｚｎは活性な金属種であることから酸化され易く、Ｓｎ−Ｚｎ系合金は酸化により、はんだ濡れ性が非常に悪くなるため、現時点では、実用化される可能性は最も低いと考えられている。 The Sn—Zn alloy is advantageous in that it does not need to change current facilities and processes because it has a melting point close to that of a conventional Sn—Pb alloy. Moreover, it is excellent in the mechanical strength of a plating film, and is excellent also in cost. However, since Zn is an active metal species, it is likely to be oxidized, and Sn—Zn-based alloys have a very poor solder wettability due to oxidation. ing.
はんだペーストは、電子部品を基板に表面実装するために用いられ、近年その使用量が増大している。はんだペーストは、一般には、はんだ合金粉末を主体とし、粘着剤、活性剤、チクソトロピック剤、界面活性剤、溶剤等を含むフラックスを加えたものである。はんだペーストの鉛フリー化として、Ｓｎ−Ａｇ（Ｃｕ）系合金、Ｓｎ−Ｚｎ系合金、Ｓｎ−Ｂｉ系合金が検討されているが、Ｓｎ−Ｚｎ系合金は前述した通り、従来のＳｎ−Ｐｂ系はんだの共晶温度に近いことから、代替の有力な候補として考えられている。しかし、前述の通りＺｎの酸化されやすさから、Ｓｎ−Ｚｎ系合金をはんだ粉末として用いたはんだペーストはフラックスに含まれる活性剤と酸化反応を起こし、はんだ濡れ性、保存安定性が著しく悪く、またリフロー時に不活性ガス雰囲気が必要という欠点がある。 Solder paste is used to surface-mount electronic components on a substrate, and the amount of use has increased in recent years. The solder paste is generally composed of a solder alloy powder as a main component and added with a flux containing an adhesive, an activator, a thixotropic agent, a surfactant, a solvent, and the like. As a lead-free solder paste, Sn—Ag (Cu) alloy, Sn—Zn alloy, and Sn—Bi alloy have been studied. As described above, Sn—Zn alloy is a conventional Sn—Pb alloy. Because it is close to the eutectic temperature of a solder, it is considered as a promising alternative candidate. However, because of the ease of oxidation of Zn as described above, the solder paste using the Sn—Zn alloy as the solder powder causes an oxidation reaction with the activator contained in the flux, and the solder wettability and storage stability are remarkably poor. In addition, there is a disadvantage that an inert gas atmosphere is required during reflow.
これらの問題に対処するため、本発明者らは特許文献１（特開２００４−１３７５７４号公報）にて、一つもしくは二つの、飽和もしくは不飽和アルキル基をもつ酸性リン酸エステル及びその塩を含むことを特徴とする表面処理剤を提案した。 In order to cope with these problems, the present inventors have disclosed, in Patent Document 1 (Japanese Patent Application Laid-Open No. 2004-137574), one or two acidic phosphate esters having a saturated or unsaturated alkyl group and salts thereof. A surface treatment agent characterized by containing was proposed.
また、特許文献２（特開平７−１８８９４２号公報）には、特に、リン酸ジフェニルエステル及び／又は亜リン酸ジフェニルエステルからなることを特徴とする酸化防止剤が提案されている。 Patent Document 2 (Japanese Patent Laid-Open No. 7-188942) proposes an antioxidant characterized in that it is composed of phosphoric acid diphenyl ester and / or phosphorous acid diphenyl ester.
しかし、上記の技術におけるリン酸エステルもしくは亜リン酸エステルは、比較的高温（２００℃以上）の熱処理によってエステル結合が分解することにより、充分な酸化防止効果が得られない。このため、上記の技術では、一般的にはんだ付け温度が従来より上がる鉛フリーはんだ対応のＳｎ及びＳｎ合金材の酸化を防止することは困難であった。 However, the phosphoric acid ester or phosphite ester in the above technique cannot obtain a sufficient antioxidant effect because the ester bond is decomposed by heat treatment at a relatively high temperature (200 ° C. or higher). For this reason, it has been difficult to prevent the oxidation of Sn and Sn alloy materials corresponding to lead-free solder, in which the soldering temperature is generally higher than in the prior art.
この高温酸化防止を目的に、本発明者らは特許文献３（特願２００４−０６１６３５）において、一分子中に２個以上のホスホン酸基を持ち、分子内にエステル結合を含まない化合物、及び／又はその塩の一種もしくは二種以上を合計で０．０１ｇ／Ｌ以上含む表面処理剤を提案した。 For the purpose of preventing this high temperature oxidation, the present inventors disclosed in Patent Document 3 (Japanese Patent Application No. 2004-061635) a compound having two or more phosphonic acid groups in one molecule and no ester bond in the molecule, and A surface treatment agent containing at least 0.01 g / L of one or more of its salts in total has been proposed.
しかし、この表面処理剤は、強酸領域（ｐＨ２以下）で最大の効果を発揮することから、チップコンデンサー等の酸に弱い素材の部品には適用することが困難であった。 However, since this surface treatment agent exhibits the maximum effect in a strong acid region (pH 2 or less), it has been difficult to apply it to parts made of materials that are vulnerable to acids such as chip capacitors.
本発明は、酸に弱い素材の部品にも適用することができ、Ｓｎ及びＳｎ合金に耐酸化性を付与し、はんだ濡れ性を改善する表面処理剤を提供することを目的とする。更に、本発明は、Ｓｎ及びＳｎ合金のウィスカーの発生を抑制する表面処理剤を提供することを目的とする。 The present invention can be applied to parts made of a material that is weak against acid, and an object thereof is to provide a surface treatment agent that imparts oxidation resistance to Sn and Sn alloy and improves solder wettability. Furthermore, an object of this invention is to provide the surface treating agent which suppresses generation | occurrence | production of the whisker of Sn and Sn alloy.
そこで、本発明者は、鋭意検討を重ねた結果、タンニン酸を０．０１ｇ／Ｌ以上含む表面処理剤でＳｎ及びＳｎ合金を表面処理することにより、ｐＨ３〜５の領域でも耐酸化性を付与し、はんだ濡れ性が改善されることを見出した。また、この表面処理を施したＳｎ合金を含むはんだペーストは、その保存安定性に顕著な改善効果が見られた。更に、この表面処理を施したＳｎ及びＳｎ合金めっきからは、ウィスカーの発生が大幅に抑制されることを確認した。 Therefore, as a result of intensive studies, the present inventor imparts oxidation resistance even in a pH range of 3 to 5 by surface-treating Sn and Sn alloy with a surface treatment agent containing 0.01 g / L or more of tannic acid. And found that the solder wettability is improved. Further, the solder paste containing the Sn alloy subjected to the surface treatment showed a remarkable improvement effect on the storage stability. Furthermore, it was confirmed that the generation of whiskers was significantly suppressed from the Sn and Sn alloy plating subjected to this surface treatment.
即ち本発明は、以下のとおりである。
（１） 接続端子部の導体表面にＳｎまたはＳｎ合金めっきを施した電子部品、はんだボール、はんだ粉末からなる群から選ばれるＳｎ及びＳｎ合金表面に被膜を形成する表面処理を行うための、タンニン酸を０．０１ｇ／Ｌ以上含むみ、水系溶媒を用い、溶液のｐＨを３〜５に調整したことを特徴とする表面処理剤。
（２） 更に酸化防止剤を含むことを特徴とする前記（１）に記載の表面処理剤。
（３） 前記（１）〜（２）のいずれかに記載の表面処理剤による表面処理方法。
（４） 前記（３）に記載の表面処理方法により表面処理を行ったＳｎ合金はんだボール、又ははんだ粉末。
（５） 前記（４）に記載のＳｎ合金はんだボールを電気的接続部材として用いたことを特徴とするボールグリッドアレイ。
（６） 前記（４）に記載のＳｎ合金はんだボールを電子部品に配置し、これを回路基板に接続したことを特徴とする実装品。
（７） 前記（４）に記載のＳｎ合金はんだ粉末を用いたことを特徴とするはんだペースト。
（８） 前記（７）に記載のはんだペーストを用いたことを特徴とする実装品。
That is, the present invention is as follows.
(1) Tannin for performing a surface treatment for forming a coating on the surface of Sn and Sn alloy selected from the group consisting of electronic parts, solder balls and solder powder plated with Sn or Sn alloy on the conductor surface of the connection terminal portion using only containing an acid 0.01 g / L or more, a water-based solvent, a surface treatment agent characterized in that the pH of the solution was adjusted to 3-5.
Front surface treatment agent according to (1), characterized in that it comprises (2) more antioxidants.
(3) the (1) to (2) front surface processing method that by the surface treatment agent according to any one of.
( 4 ) An Sn alloy solder ball or solder powder that has been surface-treated by the surface treatment method described in ( 3 ) above.
( 5 ) A ball grid array using the Sn alloy solder ball according to ( 4 ) as an electrical connection member.
( 6 ) A mounted product comprising the Sn alloy solder balls described in ( 4 ) above arranged on an electronic component and connected to a circuit board.
( 7 ) A solder paste using the Sn alloy solder powder according to ( 4 ).
( 8 ) A mounted product using the solder paste according to ( 7 ).
タンニン酸を０．０１ｇ／Ｌ以上含む表面処理剤でＳｎ又はＳｎ合金を表面処理することにより、耐酸化性を付与し、はんだ濡れ性を改善することができる。 By surface-treating Sn or Sn alloy with a surface treatment agent containing 0.01 g / L or more of tannic acid, oxidation resistance can be imparted and solder wettability can be improved.
また、本発明の表面処理剤を用いて表面処理を施したＳｎ合金はんだ粉末を含むはんだペーストは、その保存安定性が著しく改善される。更に、Ｓｎ及びＳｎ合金めっきを本発明の表面処理剤を用いて処理することにより、ウィスカーの発生を大幅に抑制することができる。 Moreover, the storage stability of the solder paste containing the Sn alloy solder powder subjected to the surface treatment using the surface treating agent of the present invention is remarkably improved. Furthermore, by processing Sn and Sn alloy plating using the surface treating agent of the present invention, the generation of whiskers can be significantly suppressed.
以下に本発明の表面処理剤について詳述する。 The surface treatment agent of the present invention is described in detail below.
本発明の表面処理剤で処理される金属としては、Ｓｎ及びＳｎ合金が挙げられ、Ｓｎ合金としては、環境汚染等の問題から鉛を含まないＳｎ合金がより好ましい。鉛を含まないＳｎ合金としては、ＳｎにＺｎ、Ｂｉ、Ｃｕ、Ｉｎ、Ａｇ、Ｓｂのいずれか一つもしくは二つ以上を含むはんだ合金等が挙げられる。 Examples of the metal to be treated with the surface treating agent of the present invention include Sn and Sn alloy. As the Sn alloy, an Sn alloy containing no lead is more preferable from the viewpoint of environmental pollution. Examples of the Sn alloy not containing lead include a solder alloy containing one or more of Zn, Bi, Cu, In, Ag, and Sb in Sn.
本発明の表面処理剤は、タンニン酸を溶媒に溶解して用いることができる。 The surface treating agent of the present invention can be used by dissolving tannic acid in a solvent.
タンニンは、通例、没食子や五倍子等の植物に含まれる多価フェノール成分であって、一つのベンゼン環に複数のＯＨ基を持つ化合物であり、本発明においては、このタンニン及び／又はその誘導体を含めタンニン酸と称する。タンニンとしては、没食子タンニン、五倍子タンニン、トルコタンニン、スーマックタンニン等の加水分解型タンニンと、ケプラチョタンニン、ワルトタンニン等の縮合型タンニンが、本用途に有効であるが、Ｓｎ及びＳｎ合金との反応性の点では、加水分解型タンニンを使用することが望ましい。 Tannin is a polyhydric phenol component usually contained in plants such as gallic and pentaploid, and is a compound having a plurality of OH groups in one benzene ring. In the present invention, tannin and / or a derivative thereof is used. Including tannic acid. As tannins, hydrolyzable tannins such as gallic tannin, pentaploid tannin, turkey tannin, sumac tannin, and condensed tannins such as kepracho tannin and walt tannin are effective for this application, but Sn and Sn alloys From the viewpoint of reactivity, it is desirable to use hydrolyzed tannin.
タンニン酸は複雑な構造のため、分解温度が比較的高く（２２５〜２３５℃）、耐熱性が高い。従って、リン酸エステルや亜リン酸エステルを用いる場合より耐熱性に優れている。 Tannic acid has a complex structure, and therefore has a relatively high decomposition temperature (225 to 235 ° C.) and high heat resistance. Accordingly, the heat resistance is superior to the case of using phosphate ester or phosphite ester.
使用される溶媒としては、可溶であれば特に制限されるものでない。例えば、水や、アルコール、グリコール等の極性溶媒が挙げられるが、溶解度、コスト等を考慮すると水が好ましい。 The solvent used is not particularly limited as long as it is soluble. For example, water and polar solvents such as alcohol and glycol can be mentioned, but water is preferable in consideration of solubility, cost and the like.
タンニン酸を０．０１ｇ／Ｌ以上含有する表面処理剤でＳｎ又はＳｎ合金を表面処理することにより、被処理材表面に耐酸化性を付与し、はんだ濡れ性を向上させることができる。 By surface-treating Sn or an Sn alloy with a surface treatment agent containing 0.01 g / L or more of tannic acid, it is possible to impart oxidation resistance to the surface of the material to be treated and improve solder wettability.
タンニン酸の量が０．０１ｇ／Ｌ未満であるとその効果が小さい。また、逆に添加量が多過ぎると特性が劣化することはないため、添加量の上限はないが、コスト的な問題から、添加量は０．０１〜５００ｇ／Ｌが望ましく、より好ましくは０．１〜１００ｇ／Ｌである。 The effect is small when the amount of tannic acid is less than 0.01 g / L. On the other hand, if the amount added is too large, the properties will not deteriorate, so there is no upper limit for the amount added. .1 to 100 g / L.
水系溶媒を用いた場合、表面処理剤のｐＨは、素材等への影響を鑑み、好ましくはｐＨ３〜５であり、より好ましくはｐＨ３〜４である。ｐＨが４を超えると、分解しやすくなるが、酸化防止剤を添加することにより抑制することができる。ｐＨ調整剤としては、一般的に入手可能な酸、アルカリが使用可能である。 When an aqueous solvent is used, the pH of the surface treatment agent is preferably pH 3 to 5 and more preferably pH 3 to 4 in view of the influence on the material and the like. When pH exceeds 4, it becomes easy to decompose | disassemble, but it can suppress by adding antioxidant. As the pH adjuster, generally available acids and alkalis can be used.
上述したように、本発明の表面処理剤は、更に酸化防止剤（溶液安定化剤）を添加することによりタンニン酸の分解を抑制することができる。酸化防止剤は、タンニン酸の量に対し５ｗｔ％以上添加することが好ましい。酸化防止剤の添加量がタンニン酸の５ｗｔ％未満であると、添加することによるタンニン酸の分解抑制効果が得られない。酸化防止剤の添加量は、好ましくはタンニン酸の量に対し５〜２０ｗｔ％である。 As described above, the surface treatment agent of the present invention can suppress decomposition of tannic acid by adding an antioxidant (solution stabilizer). The antioxidant is preferably added in an amount of 5 wt% or more based on the amount of tannic acid. When the addition amount of the antioxidant is less than 5 wt% of the tannic acid, the effect of suppressing the decomposition of tannic acid due to the addition cannot be obtained. The addition amount of the antioxidant is preferably 5 to 20 wt% with respect to the amount of tannic acid.
酸化防止剤としては、通常の酸化防止剤を用いることができ、例えば、
１）フェノール性水酸基を分子内に持つdl−α−トコフェロール、ジブチルヒドロキシトルエン、ブチルヒドロキシアニソール、没食子酸などと、Ｌ−アスコルビン酸、Ｌ−アスコルビン酸ステアリン酸エステル等のアスコルビン酸誘導体、エリソルビン酸、エリソルビン酸ナトリウム、Ｌ−システイン塩酸塩などのラジカルや活性酸素を消去するもの、
２）ピロ亜硫酸カリウム、ピロ亜硫酸ナトリウム、亜硫酸ナトリウム、次亜硫酸ナトリウム、二酸化硫黄などの無機系還元作用が強いもの、
３）エチレンジアミン四酢酸カルシウム二ナトリウム、エチレンジアミン四酢酸二ナトリウム、クエン酸イソプロピルなどのキレート作用が強いもの
がある。
As the antioxidant, a normal antioxidant can be used, for example,
1) dl-α-tocopherol having a phenolic hydroxyl group in the molecule, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid and the like, ascorbic acid derivatives such as L-ascorbic acid and L-ascorbic acid stearate, erythorbic acid, Eliminate radicals and active oxygen such as sodium erythorbate and L-cysteine hydrochloride
2) Strong inorganic reducing action such as potassium pyrosulfite, sodium pyrosulfite, sodium sulfite, sodium hyposulfite, sulfur dioxide,
3) Some have strong chelating action such as disodium ethylenediaminetetraacetate, disodium ethylenediaminetetraacetate, isopropyl citrate and the like.
また、本発明の表面処理剤は、所望の性能を付与させる目的で本来の性質を損なわない範囲の量の添加剤を含んでいてもよい。添加剤としては、防腐剤、ｐＨ緩衝剤等が挙げられ、これらは従来公知のものを用いることができる。 In addition, the surface treatment agent of the present invention may contain an amount of an additive in a range that does not impair the original properties for the purpose of imparting desired performance. Examples of the additive include preservatives and pH buffering agents, and conventionally known additives can be used.
本発明の表面処理剤を用いてＳｎ又はＳｎ合金を表面処理するには、Ｓｎ又はＳｎ合金の表面に被膜を形成する方法であればよく、例えば、Ｓｎ又はＳｎ合金を単に表面処理剤に浸漬させる方法、表面処理剤を、シャワー、又はエアードコータ、ブレードコータ、ロッドコータ、ナイフコータ、グラビアコータ、リバースコータ、キャストコータなどの装置を用いて塗布する方法等が挙げられる。 In order to surface-treat Sn or Sn alloy using the surface treatment agent of the present invention, any method can be used as long as it is a method of forming a film on the surface of Sn or Sn alloy. For example, Sn or Sn alloy is simply immersed in the surface treatment agent. And a method of applying the surface treatment agent using a shower or an apparatus such as an air coater, a blade coater, a rod coater, a knife coater, a gravure coater, a reverse coater, and a cast coater.
表面処理する際の溶液の温度としては、水系で使用する場合は、反応性、設備耐熱温度及び作業性の観点から２０〜６０℃が好ましく、より好ましくは３０〜５０℃である。 The temperature of the solution for the surface treatment is preferably 20 to 60 ° C., more preferably 30 to 50 ° C. from the viewpoint of reactivity, equipment heat resistance temperature and workability when used in an aqueous system.
本発明の表面処理剤で表面処理をする金属の形状は、線状、板・帯・箔状、粒状、粉末状等いずれの形状であってもよく、本発明の表面処理剤は、電子部品、はんだボール、はんだ粉末等を処理することができる。尚、本発明における電子部品としては、基板も含むものである。 The shape of the metal surface-treated with the surface treatment agent of the present invention may be any shape such as linear, plate / strip / foil, granular, powder, etc. The surface treatment agent of the present invention is an electronic component. Solder balls, solder powder, etc. can be processed. The electronic component in the present invention includes a substrate.
本発明の表面処理剤を用い、電子部品の接続端子部の導体表面を表面処理する、またはその導体表面にめっきを施した後に、表面処理することにより、耐酸化性に優れ、はんだ濡れ性が改善された電子部品とすることができる。また、はんだ濡れ性が改善されることにより、はんだ付け性も改善される。 The surface treatment agent of the present invention is used to surface-treat the conductor surface of the connection terminal portion of the electronic component, or after plating the conductor surface, it is excellent in oxidation resistance and solder wettability. It can be an improved electronic component. Moreover, solderability is also improved by improving solder wettability.
本発明の表面処理剤で処理されたＳｎ合金を用いたはんだボールは、耐酸化性に優れ、電気的接続部材であるボールグリッドアレイとして、また、電子部品に配置し、これを回路基板に接続した実装品として良好に用いることができる。 Solder balls using an Sn alloy treated with the surface treating agent of the present invention have excellent oxidation resistance, and are arranged on electronic components as a ball grid array which is an electrical connection member, and this is connected to a circuit board. It can be used satisfactorily as a mounted product.
また、Ｓｎ合金粉末を本発明の表面処理剤を用いて処理し、これに粘着剤、活性剤、チクソトロピック剤、界面活性剤、溶剤等を含むフラックスを加えてはんだペーストとして用いることもできる。このはんだペーストは、その保存安定性に顕著な改善効果が見られる。上記粘着剤、活性剤、チクソトロピック剤、界面活性剤、溶剤としては従来公知のものを用いることができる。 Further, the Sn alloy powder can be treated with the surface treating agent of the present invention, and a flux containing an adhesive, an activator, a thixotropic agent, a surfactant, a solvent and the like can be added thereto to be used as a solder paste. This solder paste has a remarkable improvement effect on its storage stability. Conventionally known pressure-sensitive adhesives, activators, thixotropic agents, surfactants and solvents can be used.
以下に実施例を挙げて本発明を詳細に説明する。
参考例１〜２、実施例３〜７、及び比較例１
タンニン酸（タンニン酸ＡＬ、富士化学工業（株）製）を主成分とするイソプロピルアルコール（ＩＰＡ）溶液又は水溶液を７種類調製した（参考例１〜２、実施例３〜７）。内訳を表１に示す。
Hereinafter, the present invention will be described in detail with reference to examples.
Reference Example 1-2, Example 3-7, and Comparative Example 1
Tannic acid (tannic acid AL, manufactured by Fuji Chemical Industry Co., Ltd.) was isopropyl alcohol (IPA) solution or aqueous seven preparation mainly comprising (Reference Examples 1-2, Example 3-7). The breakdown is shown in Table 1.
他方、銅材（Ｃ１０２０Ｐ、１０ｍｍ×２５ｍｍ×０．２tｍｍ）に対し、以下の前処理を行った。 On the other hand, the following pretreatment was performed on the copper material (C1020P, 10 mm × 25 mm × 0.2 t mm).
アルカリ電解脱脂(常温、１５Ａ／ｄｍ2、約３０秒程度処理)→水洗→酸浸漬（１０％硫酸、常温、５秒）→水洗→化学研磨（ＣＰＢ−４０、常温、１分浸漬）→水洗→酸浸漬（１０％硫酸、常温、５秒）→水洗
この基材に対し、膜厚約５μｍのＳｎめっきを行った（めっき浴：ティンコートＫ（日鉱メタルプレーティング（株）製）、めっき条件：陰極電流密度２Ａ／ｄｍ2、温度２０℃、液流動及びカソード揺動めっき）。
Alkaline electrolytic degreasing (room temperature, 15 A / dm 2 , treatment for about 30 seconds) → water washing → acid immersion (10% sulfuric acid, room temperature, 5 seconds) → water washing → chemical polishing (CPB-40, room temperature, 1 minute immersion) → water washing → Acid soaking (10% sulfuric acid, room temperature, 5 seconds) → Washing This substrate was Sn plated with a film thickness of about 5 μm (plating bath: Tincoat K (manufactured by Nikko Metal Plating Co., Ltd.)), plating Conditions: cathode current density 2 A / dm 2 , temperature 20 ° C., liquid flow and cathode swing plating).
このＳｎめっきを施した基材（以下Ｓｎ基材）を、上記のアルコール溶液に、室温で１０秒間浸漬した後、乾燥させたものを試験基板とした（参考例１、２）。他方、このＳｎ基材を、上記の水溶液に、浴温４０℃で１０秒間浸漬した後、水洗し、乾燥させたものも併せて試験基板とした（実施例３〜７）。 The substrate subjected to Sn plating (hereinafter referred to as Sn substrate) was immersed in the above alcohol solution for 10 seconds at room temperature and then dried to obtain a test substrate ( Reference Examples 1 and 2). On the other hand, the Sn substrate was immersed in the above aqueous solution at a bath temperature of 40 ° C. for 10 seconds, then washed with water and dried to obtain a test substrate (Examples 3 to 7).
これらの試験基板に対し、以下の評価を行った。 The following evaluations were performed on these test substrates.
また、更に比較例として、未処理の上記Ｓｎ基材（比較例１）も併せて評価した。
耐熱酸化性
これらの試験基板を、２２０℃に保持した電気炉において、大気雰囲気で１時間熱処理した後、鉛フリーはんだとのはんだ付け性（ゼロクロスタイム）をメニスコグラフ法で以下の測定条件に基づき測定し、下記の基準に沿って評価した。
Further, as a comparative example, the untreated Sn base material (Comparative Example 1) was also evaluated.
Thermal oxidation resistance These test boards were heat-treated in an electric furnace maintained at 220 ° C. for 1 hour in air, and then solderability with lead-free solder (zero cross time) was measured by the meniscograph method based on the following measurement conditions And evaluated according to the following criteria.
装置；ソルダーチェッカー ＳＡＴ−５１００（レスカ製）
はんだ槽；すず：銀：銅＝９６．５：３：０．５（浴温２４５℃）
フラックス；ＮＡ−２００（タムラ化研製）
浸漬深さ；２ｍｍ
浸漬速度；４ｍｍ／ｓｅｃ．
浸漬時間；５ｓｅｃ．
評価基準
◎： ゼロクロスタイム1秒未満
○： ゼロクロスタイム1秒以上３秒未満
△： ゼロクロスタイム３秒以上５秒未満
×： ゼロクロスタイム５秒以上
表１に試験結果を示す。
耐湿酸化性
これらの試験基板に対し、ＰＣＴ処理（温度１０５℃、湿度１００％の密閉釜内にて１６時間放置）を施した後、鉛フリーはんだとのはんだ付け性（ゼロクロスタイム）をメニスコグラフ法で耐熱酸化性の項と同様に測定し、評価した。表１に試験結果を示す。
溶液の安定性
参考例１〜２、実施例３〜７で調製した溶液をネジ口ビンに入れ、蓋を閉めて、４０℃に保持したウォーターバスに浸漬して、溶液の経時劣化（沈殿の発生）を確認した。結果を併せて表１に示す。
Equipment: Solder Checker SAT-5100 (Resca)
Solder bath; tin: silver: copper = 96.5: 3: 0.5 (bath temperature 245 ° C.)
Flux: NA-200 (Tamura Kaken)
Immersion depth: 2mm
Immersion speed: 4 mm / sec.
Immersion time: 5 sec.
Evaluation criteria A: Zero cross time less than 1 second ○: Zero cross time 1 second or more and less than 3 seconds Δ: Zero cross time 3 seconds or more and less than 5 seconds X: Zero cross time 5 seconds or more Table 1 shows the test results.
Moisture oxidation resistance These test substrates were subjected to PCT treatment (left in a sealed kettle with a temperature of 105 ° C and a humidity of 100% for 16 hours) and then soldered with lead-free solder (zero cross time) by meniscograph method Measured and evaluated in the same manner as in the section of heat and oxidation resistance. Table 1 shows the test results.
Solution stability
Reference Example 1-2, was placed a solution prepared in Example 3-7 in screw-cap bottle, closes the lid, is immersed in a water bath kept at 40 ° C., check the aging of the solution (the occurrence of precipitation) did. The results are also shown in Table 1.
参考例８〜９、実施例１０〜１３、及び比較例２
前記参考例１〜２、実施例３〜７と同様な前処理を行った銅材（Ｃ１０２０Ｐ、１０ｍｍ×２５ｍｍ×０．２tｍｍ）に対し、膜厚約５μｍのＳｎ−Ｚｎめっきを行った（めっき浴：日鉱メタルプレーティング（株）製、めっき条件：陰極電流密度３Ａ／ｄｍ2、温度３５℃、ｐＨ４．０、液流動及びカソード揺動めっき）。
Reference Example 8-9, Example 10-13, and Comparative Example 2
Sn—Zn plating with a film thickness of about 5 μm was performed on the copper material (C1020P, 10 mm × 25 mm × 0.2 t mm) subjected to the same pretreatment as in Reference Examples 1 and 2 and Examples 3 to 7. (Plating bath: manufactured by Nikko Metal Plating Co., Ltd., plating conditions: cathode current density 3 A / dm 2 , temperature 35 ° C., pH 4.0, liquid flow and cathode swing plating).
このＳｎ−Ｚｎめっきを施した基材（以下Ｓｎ−Ｚｎ基材）を、前記参考例１、２にて調製したアルコール溶液に、室温で１０秒間浸漬した後、乾燥させたものを試験基板とした（参考例８、９）。他方、このＳｎ−Ｚｎ基材を、前記実施例３、４、６、７で調製した水溶液に、浴温４０℃で１０秒間浸漬した後、水洗し、乾燥させたものも併せて試験基板とした（実施例１０〜１３）。 The substrate subjected to Sn—Zn plating (hereinafter referred to as “Sn—Zn substrate”) was immersed in the alcohol solution prepared in Reference Examples 1 and 2 for 10 seconds at room temperature, and then dried, and the test substrate and ( Reference Examples 8 and 9 ). On the other hand, the Sn—Zn base material was immersed in the aqueous solutions prepared in Examples 3, 4, 6, and 7 at a bath temperature of 40 ° C. for 10 seconds, washed with water, and dried, together with the test substrate. (Examples 10 to 13).
これらの試験基板に対し、前記参考例１〜２、実施例３〜７、及び比較例１と同様に、耐熱酸化性、耐湿酸化性の評価を行った。試験結果を表２に示す。 These test substrates were evaluated for heat oxidation resistance and moisture oxidation resistance in the same manner as in Reference Examples 1 and 2, Examples 3 to 7, and Comparative Example 1. The test results are shown in Table 2.
また、更に比較例として、未処理の上記Ｓｎ−Ｚｎ基材（比較例２）も併せて評価した。試験結果を併せて表２に示す。 Further, as a comparative example, the untreated Sn—Zn base material (Comparative Example 2) was also evaluated. The test results are also shown in Table 2.
参考例１４、及び比較例３
参考例１４では、Ｓｎめっきに対し表面処理したもののウィスカー発生が、表面処理しなかったものと比べて、著しく抑制された結果を示す。
Reference Example 14 and Comparative Example 3
Reference Example 14 shows a result in which whisker generation of the surface-treated Sn plating was significantly suppressed as compared with the case where the surface treatment was not performed.
前記参考例２と同等の処理をしたＳｎめっき基板と、表面処理をしなかった基板を、温度８５℃、湿度８５％の恒温恒湿雰囲気下において、２４時間放置した。その後、基板を充分に乾燥した後、走査型電子顕微鏡（ＳＥＭ）にて表面観察したところ、表面処理をしなかったものは、ウィスカーが多く観察された（比較例３）のに対し、表面処理をしたものからは、ウィスカーが全く観察されなかった（参考例１４）。
参考例１５、及び比較例４
参考例１５では、表面処理したＳｎ−９％Ｚｎ合金粉を用いたペーストの保存安定性が、表面処理しなかったものと比べて、著しく抑制された結果を示す。
The Sn-plated substrate that was treated in the same manner as in Reference Example 2 and the substrate that was not surface-treated were left for 24 hours in a constant temperature and humidity atmosphere at a temperature of 85 ° C. and a humidity of 85%. Then, after fully drying the substrate, the surface was observed with a scanning electron microscope (SEM). When the surface treatment was not performed, many whiskers were observed (Comparative Example 3), whereas the surface treatment was performed. No whisker was observed from those subjected to ( Reference Example 14).
Reference Example 15 and Comparative Example 4
Reference Example 15 shows a result in which the storage stability of the paste using the surface-treated Sn-9% Zn alloy powder was remarkably suppressed as compared with the case where the surface treatment was not performed.
タンニン酸を有効成分とする１ｗｔ％イソプロパノール溶液（参考例２と同じ溶液）を調製し、Ｓｎ−９％Ｚｎはんだ粉（粒径２５〜４５μｍ）に表面処理を行った。 A 1 wt% isopropanol solution containing tannic acid as an active ingredient (the same solution as in Reference Example 2) was prepared, and surface treatment was performed on Sn-9% Zn solder powder (particle size: 25 to 45 μm).
この表面処理を施したはんだ粉末とフラックスを重量比で９：１でよく混合し、はんだペーストとした。尚、フラックスとしては重合ロジン３０部、水添ロジン３０部、グリコール系溶剤３０部、活性剤（炭素数１〜３０の有機酸、及びアミン臭化水素酸塩）５部、チキソ剤（硬化ヒマシ油）５部を用いたはんだペースト用フラックスを用いた。 This surface-treated solder powder and flux were well mixed at a weight ratio of 9: 1 to obtain a solder paste. The flux includes 30 parts of polymerized rosin, 30 parts of hydrogenated rosin, 30 parts of glycol solvent, 5 parts of activator (organic acid having 1 to 30 carbon atoms and amine hydrobromide), thixotropic agent (cured castor) Oil) Flux for solder paste using 5 parts was used.
５℃で冷蔵保存し、保存安定性の評価を行ったところ、未処理粉によるはんだペーストは、１週間後に固化し、粘度が測定不能になった（比較例４）のに対し、表面処理粉によるはんだペーストは、３ヶ月後でも粘度に大きな差はなかった（参考例１５）。
参考例１６、及び比較例５
参考例１６では、表面処理したＳｎ−３％Ａｇ−０．５％Ｃｕ合金微粉を用いたペーストの保存安定性が、表面処理しなかったものと比べて、著しく抑制された結果を示す。
When the storage stability was evaluated by refrigerated storage at 5 ° C., the solder paste made of untreated powder solidified after one week, and the viscosity became unmeasurable (Comparative Example 4). The solder paste according to No. 3 showed no significant difference in viscosity even after 3 months ( Reference Example 15).
Reference Example 16 and Comparative Example 5
Reference Example 16 shows a result in which the storage stability of the paste using the surface-treated Sn-3% Ag-0.5% Cu alloy fine powder was remarkably suppressed as compared with the case where the surface treatment was not performed.
タンニン酸を有効成分とする１ｗｔ％イソプロパノール溶液（参考例２と同じ溶液）を調製し、Ｓｎ−３％Ａｇ−０．５％Ｃｕはんだ粉（粒径５〜１５μｍ）に表面処理を行った。 A 1 wt% isopropanol solution containing tannic acid as an active ingredient (the same solution as in Reference Example 2) was prepared, and surface treatment was performed on Sn-3% Ag-0.5% Cu solder powder (particle size 5-15 μm).
この表面処理を施したはんだ粉末と参考例１５で用いたはんだペースト用フラックスを重量比で９：１でよく混合し、はんだペーストとした。 The solder powder subjected to the surface treatment and the solder paste flux used in Reference Example 15 were thoroughly mixed at a weight ratio of 9: 1 to obtain a solder paste.
５℃で冷蔵保存し、保存安定性の評価を行ったところ、未処理粉によるはんだペーストは、２週間後に固化し、粘度が測定不能になった（比較例５）のに対し、表面処理粉によるはんだペーストは、３ヶ月後でも粘度に大きな差はなかった（参考例１６）。
参考例１７、及び比較例６
参考例１７では、表面処理したＳｎ−３％Ａｇ−０．５％Ｃｕ合金を用いたはんだボールの耐酸化性能が、表面処理しなかったものと比べて、著しく改善された結果を示す。
When the storage stability was evaluated by refrigerated storage at 5 ° C., the solder paste made of untreated powder solidified after 2 weeks, and the viscosity became unmeasurable (Comparative Example 5). The solder paste according to No. 3 showed no significant difference in viscosity even after 3 months ( Reference Example 16).
Reference Example 17 and Comparative Example 6
Reference Example 17 shows a result in which the oxidation resistance performance of the solder balls using the surface-treated Sn-3% Ag-0.5% Cu alloy is remarkably improved as compared with the case where the surface treatment is not performed.
タンニン酸を有効成分とする１ｗｔ％イソプロパノール溶液（参考例２と同じ溶液）を調製し、Ｓｎ−３％Ａｇ−０．５％Ｃｕはんだボール（粒径６００μｍ）に表面処理を行った。 A 1 wt% isopropanol solution containing tannic acid as an active ingredient (the same solution as in Reference Example 2) was prepared, and surface treatment was performed on Sn-3% Ag-0.5% Cu solder balls (particle size 600 μm).
この表面処理を施したはんだボール及び未処理のはんだボールを、２２０℃に保持した電気炉において、大気雰囲気で１時間熱処理した後、以下の測定条件に基づき、参考例１で作製したＳｎめっき基板上でリフロー処理を行った。 The surface-treated solder balls and untreated solder balls were heat-treated in an air atmosphere for 1 hour in an electric furnace maintained at 220 ° C., and then Sn-plated substrate produced in Reference Example 1 based on the following measurement conditions The reflow process was performed above.
リフロー条件；２６０℃×３０秒（ホットプレートで実施）
フラックス：ＮＡ−２００、タムラ化研製
それぞれのはんだ部を上方から写真撮影し、はんだ部の濡れ広がり面積を算出し、はんだボールの濡れ広がり性を評価した。表３に結果を示す。
Reflow conditions: 260 ° C x 30 seconds (implemented on a hot plate)
Flux: NA-200, manufactured by Tamura Chemical Co., Ltd. Each solder part was photographed from above, the wet spread area of the solder part was calculated, and the wet spread characteristic of the solder ball was evaluated. Table 3 shows the results.
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