CN1307024C - High adhesion leadless soldering tin grease - Google Patents
High adhesion leadless soldering tin grease Download PDFInfo
- Publication number
- CN1307024C CN1307024C CNB2004100231816A CN200410023181A CN1307024C CN 1307024 C CN1307024 C CN 1307024C CN B2004100231816 A CNB2004100231816 A CN B2004100231816A CN 200410023181 A CN200410023181 A CN 200410023181A CN 1307024 C CN1307024 C CN 1307024C
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- China
- Prior art keywords
- acid
- quality
- resin
- solder flux
- leadless soldering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000005476 soldering Methods 0.000 title claims abstract description 31
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000004519 grease Substances 0.000 title 1
- 230000004907 flux Effects 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- -1 succinic acid, tetrabutyl hydrobromic acid amine Chemical class 0.000 claims abstract description 20
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 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 claims abstract description 15
- 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 claims abstract description 15
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 10
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 10
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004359 castor oil Substances 0.000 claims abstract description 9
- 235000019438 castor oil Nutrition 0.000 claims abstract description 9
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 9
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003112 inhibitor Substances 0.000 claims abstract description 6
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims abstract description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000005456 glyceride group Chemical group 0.000 claims abstract description 3
- 229910000679 solder Inorganic materials 0.000 claims description 56
- 229910052718 tin Inorganic materials 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 27
- 239000000853 adhesive Substances 0.000 claims description 26
- 230000001070 adhesive effect Effects 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 14
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 claims description 12
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- AFVOMBDKBIFCLB-UHFFFAOYSA-N 2-ethylpentane-1,1-diol Chemical compound CCCC(CC)C(O)O AFVOMBDKBIFCLB-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 239000012190 activator Substances 0.000 claims description 7
- DYHGIZFXHVQIEA-UHFFFAOYSA-N 2-methylhexane-1,6-diol Chemical compound OCC(C)CCCCO DYHGIZFXHVQIEA-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- 229940057402 undecyl alcohol Drugs 0.000 claims description 6
- YAQLSKVCTLCIIE-UHFFFAOYSA-N 2-bromobutyric acid Chemical compound CCC(Br)C(O)=O YAQLSKVCTLCIIE-UHFFFAOYSA-N 0.000 claims description 5
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 5
- FJWGRXKOBIVTFA-UHFFFAOYSA-N 2,3-dibromobutanedioic acid Chemical compound OC(=O)C(Br)C(Br)C(O)=O FJWGRXKOBIVTFA-UHFFFAOYSA-N 0.000 claims description 4
- 229960000789 guanidine hydrochloride Drugs 0.000 claims description 4
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- GTYLEVMOSBBKCQ-UHFFFAOYSA-N acetic acid;2-(2-ethoxyethoxy)ethanol Chemical class CC(O)=O.CCOCCOCCO GTYLEVMOSBBKCQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000180 alkyd Polymers 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 3
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- PDBMKOUAWURVBE-UHFFFAOYSA-N 2-methyl-2-(2-methylpentan-2-yloxy)pentane Chemical compound CCCC(C)(C)OC(C)(C)CCC PDBMKOUAWURVBE-UHFFFAOYSA-N 0.000 claims description 2
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims description 2
- FUECIDVNGAUMGJ-UHFFFAOYSA-N acetic acid;2-(2-butoxyethoxy)ethanol Chemical class CC(O)=O.CCCCOCCOCCO FUECIDVNGAUMGJ-UHFFFAOYSA-N 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 235000014121 butter Nutrition 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 2
- XHFGWHUWQXTGAT-UHFFFAOYSA-N dimethylamine hydrochloride Natural products CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 0.000 claims description 2
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229960005323 phenoxyethanol Drugs 0.000 claims description 2
- CBPYOHALYYGNOE-UHFFFAOYSA-M potassium;3,5-dinitrobenzoate Chemical compound [K+].[O-]C(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 CBPYOHALYYGNOE-UHFFFAOYSA-M 0.000 claims description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 150000003505 terpenes Chemical class 0.000 claims description 2
- 235000007586 terpenes Nutrition 0.000 claims description 2
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 238000003466 welding Methods 0.000 abstract description 10
- 238000007639 printing Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- IRLDRDAUVNWOKZ-UHFFFAOYSA-N 2-methylhexane-1,1-diol Chemical compound CCCCC(C)C(O)O IRLDRDAUVNWOKZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000013543 active substance Substances 0.000 abstract 1
- 239000012964 benzotriazole Substances 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 4
- 229910018100 Ni-Sn Inorganic materials 0.000 description 3
- 229910018532 Ni—Sn Inorganic materials 0.000 description 3
- 229910020836 Sn-Ag Inorganic materials 0.000 description 3
- 229910020988 Sn—Ag Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 3
- 230000003026 anti-oxygenic effect Effects 0.000 description 3
- 239000006071 cream Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- 229910020830 Sn-Bi Inorganic materials 0.000 description 2
- 229910020935 Sn-Sb Inorganic materials 0.000 description 2
- 229910020994 Sn-Zn Inorganic materials 0.000 description 2
- 229910018728 Sn—Bi Inorganic materials 0.000 description 2
- 229910008757 Sn—Sb Inorganic materials 0.000 description 2
- 229910009069 Sn—Zn Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000006253 efflorescence Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 206010037844 rash Diseases 0.000 description 2
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- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
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- Electric Connection Of Electric Components To Printed Circuits (AREA)
Abstract
The present invention discloses a high adhesion leadless soldering paste which is used for pasting the surface of electronic products. The leadless soldering paste comprises Sn-Ag-Cu-Bi-Ni based leadless soldering tin powder which is mixed with welding flux. The welding flux is basically prepared from the following ingredients by the mass percentage: 35 to 50% of resin (such as modified rosin resin and toxilic acid resin), 1 to 10 % of thixotropic agent (modified hydrogenated castor oil and fatty glyceride), 35 to 55% of solvent (undecanol, 2-methyl-hexanediol), and 1.5 to 5% of active agent (succinic acid, tetrabutyl hydrobromic acid amine). The welding flux can also comprise 0.01 to 0.9 mass% of corrosion inhibitors for copper, and the corrosion inhibitors comprise one or more than one of benzothiazole, benzotriazole, benzimidazole, etc. The leadless soldering paste of the present invention has obvious effects on increasing adhesion, and the welding performance and the properties of printing and demoulding are not changed.
Description
Affiliated technical field
The present invention relates to a kind of electronic product surface mount leadless soldering tin paste that is used for, be particularly useful for pasting the high adhesive force leadless soldering tin paste of inserting the electronic product that loads in mixture and use a solder reflow process.
Background technology
Traditional solder(ing) paste product is made up of tin-lead solder powder and solder flux, and tin-lead solder powder wherein is generally 63%Sn, the 37%Pb of 25 μ m ∽, 75 μ m or 62%Sn, 36%Pb, the 2%Ag spherical powder constitutes; Solder flux generally is made of resin, activator, thixotropic agent, solvent, additive.On the one hand, heavy metal lead in the solder(ing) paste is after welding PCB, can intersperse among in the environment with discarded later on electronic product, long-term etch through acid rain, lead can permeate the ground, dissolve in ground water regime, long-term accumulation in human body can cause the harm to nervous system, fertility system etc. after drinking.For ensureing human body health, guarantee economic, social sustainable development, regulation in " electronics and IT products production prevention and cure of pollution management method " that China's Ministry of Information Industry puts into effect " the electronics and IT products producer should guarantee: carry out the minimizing production measure of harmful and noxious substance from July 1st, 2003; Electronics and IT products in the state key supervision catalogue of putting on market on July 1st, 2006 can not contain lead, mercury, cadmium, Cr VI, polymerization bromination biphenyl (PBB), polymerization bromination biphenyl ether (PBDE) etc. ".The NEDO of the IDEALS in NCMS, the NEMI of each the electronics industry developed country of west such as the U.S., Europe, the ITRI of Britain and Japan etc., research and development and large-scale production can substitute the lead-free solder of traditional tin-kupper solder.
Usually the alloy as lead-free solder has Sn-Ag system, Sn-Sb system, Sn-Zn system, Sn-Bi system.Sn-Bi is that mechanical performance can not be satisfactory, and Sn-Zn is easy oxidation, and Sn-Sb is that welding temperature is had relatively high expectations.For above-mentioned reasons, everybody concentrates on Sn-Ag system to sight, and its higher anti-aging, creep-resistant property and favorable mechanical performance, weldability can determine it to possess commercial basic fundamental condition.Consider the cost-performance factor,, need carry out the quality % of Ag preferably, also need to add the fusion temperature that other suitable metals improve solder powder as countermeasure.
On the other hand, some electronic product considers that thermal shock may cause damage to it, wish that weld interval is short, welding temperature is low as far as possible, again because the needs of the microminiaturized multifunction of electronic product, these electronic products require slotting the loading in mixture once of two-sided subsides to finish, this has just produced a kind of new welding manner: slice component, ventilating hole element all with behind the metal matrix printing lead-free tin cream, are implemented to mount and plug-in mounting, implement a reflow soldering of lead-free tin cream afterwards.This just needs lead-free tin cream that adhesive force is preferably arranged, and is unlikely to moving, causing device to come off in the welding process or weld preceding soldering paste coming off on the via pad.As countermeasure, need improve the component of the solder flux of solder(ing) paste, to increase the adhesive force of solder(ing) paste.
Summary of the invention
The purpose of this invention is to provide a kind of favorable mechanical performance that has, anti-aging, creep resistant, antioxygenic property improve, electronic product surface mount leadless soldering tin paste with good adhesive force is particularly useful for pasting the high adhesive force leadless soldering tin paste of inserting the electronic product that loads in mixture and use a solder reflow process.
Unleaded glass putty alloy composition among the present invention is main composition with Sn, Ag, Cu, Bi, Ni mainly, to wherein adding Ce, In, P, Ga, Sm, Pr, Eu, La, Pm rare earth and adding element and improve its machinery and antioxygenic property.
Lead-free solder based on Sn-Ag has gratifying mechanical performance, ageing resistace, solderability, but its eutectic alloy Sn-3.5Ag cost is higher, commercialization acquires a certain degree of difficulty, therefore, we suitably reduce the content of silver, the actual 0.1-3.0% scope of finding, effect is comparatively desirable, for keeping its favorable mechanical performance, we add Ni, Cu compensates, Sn, the eutectic point Sn-0.7Cu of Cu, 227 ℃ of eutectic temperatures, show high melt point again, such soldering paste welding temperature requires about 260 ℃, and is too big to the thermal shock of components and parts, also kept original mechanical performance, through the experiment contrast, the nickel of 0.01-1.0%, the copper of 0.01-1.5%, the Ag of 0.1-3.0%, the bismuth of 0.1-2.0% is comparatively desirable as the alloy effect of main composition, and its liquidus temperature is less than 220 ℃, percentage elongation＞20%, shear strength＞30mPa, tensile strength＞40N/mm
2, it is anti-aging in order further to improve, creep resistant, antioxygenic property, and we are selective to add one or more additions among P, Ga, Se, Ce, Pr, Pm, Nd, Sm, Eu, Tm, the Tb between 0.01=0.05%, satisfactory for result.
The traditional material of resin in the solder flux is generally newtrex, Foral, disproportionation rosin etc., find that in practice its postwelding residue is more, residual color is darker, adhesion is also good inadequately, for increasing the adhesion of soldering paste, we have screened other several resins: the Foral glyceride, rosin pentaerythritol ester, modified rosin resin, terpene resin, the maleficent acid resin, alkyd resins etc., add wherein one or more, content is the 35-50% of flux quality, exceed this scope or adhesion is not enough, the solder(ing) paste life-span is bad, or adhesion influences printing too by force.The present invention has improved the adhesive force of solder(ing) paste by the adjustment to resin, because the decomposability of part resin, postwelding is residual very low.
Components contents has no particular limits in the resin, but in quality %, the modified rosin resin of preferred 55.0-75.0% respectively with the combination of the rosin pentaerythritol ester of 25.0-45.0%, maleficent acid resin, rosin pentaerythritol ester, account for the preferred 40.0-45.0% of amount of solder flux as resin.
Thixotropic agent is selected: rilanit special, castor oil, butter, modified hydrogenated castor oil, palmitic amide, glycerine monofatty ester, fatty acid glyceryl ester, select wherein one or more, and content is the 1.0-10.0% of flux quality.
Components contents has no particular limits in the thixotropic agent, but in quality %, the combination of preferred rilanit special, the modified hydrogenated castor oil of 45.0-55.0% and 45.0-55.0% palmitic amide; The combination of 45.0-55.0% glycerine monofatty ester and fat 45.0-55.0% fat acid glyceryl ester; Account for the preferred 5.0-7.0% of amount of solder flux as thixotropic agent.
Solvent is selected: diethylene glycol monoethyl ether acetic acid esters, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetic acid esters, diglycol monotertiary hexyl ether, diglycol monotertiary hexyl ether acetic acid esters, ethylene glycol monobutyl ether, ethyleneglycol monophenylether, propylene glycol monobutyl ether, propane diols monophenyl ether, undecyl alcohol, 2-ethyl-pentanediol, 2-methyl-hexylene glycol, alkyl replace one or more in pentanediol, alkyl replacement hexylene glycol, the modification terpinol etc., and content is the 35.0-55.0% of flux quality.
Components contents has no particular limits in the solvent, but in quality %, preferred undecyl alcohol; 2-ethyl-pentanediol; 2-methyl-hexylene glycol; The diethylene glycol monoethyl ether acetic acid esters of 30.0-40.0% respectively with the combination of the undecyl alcohol of 60.0-70.0%, 2-ethyl-pentanediol, 2-methyl-hexylene glycol; Account for the preferred 40.0-50.0% of amount of solder flux as solvent.
Activator is selected: succinic acid, glutaric acid, adipic acid, azelaic acid, decanedioic acid, salicylic acid, phthalic acid, terephthalic acid (TPA), dimethylamine hydrochloride, diethylamine hydrochloride, tetrabutylammonium hydrogen bromic acid amine, diphenylguanidine hydrobromate, 1,3 one two bromo-2-propyl alcohol, 1,2 one two bromo-1-propyl alcohol, 1,4 one two bromo-2-butylene, 2,3 one two bromo-2-butene-1s, the mixture of one or more of 4-glycol, dibromosuccinic acid, α one bromo-butyric acid, guanidine hydrochloride, content is the 1.5-5.0%. of flux quality
Components contents has no particular limits in the activator, but in quality %, 2, the 3 one two bromo-2-butene-1s of 1, the 3 one two bromo-2-propyl alcohol of the succinic acid of 20.0-30.0% and the adipic acid of 20.0-30.0%, 20-30%, 20-30%, the combination of 4-glycol; The combination of the guanidine hydrochloride of the adipic acid of 20.0-30.0% and the dibromosuccinic acid of 20.0-30.0%, 40.0-50.0%; The combination of the tetrabutylammonium hydrogen bromic acid amine of the decanedioic acid of 20.0-30.0% and the α of 20.0-30.0% one bromo-butyric acid, 40.0-50.0%; Account for the preferred 4.0-5.0% of amount of solder flux as activator.
For preventing that corrosion from can add copper inhibitor: as benzothiazole, BTA, benzimidazole one or more, content is the 0.01-0.9% of flux quality.
The preparation method of the high adhesive force leadless soldering tin paste of the present invention:
Shape to invention Pb-free solder powder has no particular limits, but globular powder normally.This powder can prepare by methods such as centrifugal efflorescence method or gas efflorescence methods.The particle size of this Pb-free solder powder can be identical with the solder(ing) paste of routine, and its order of magnitude is generally the 200-400 order, but also can use 500 orders or thinner powder.
Resin among the present invention, activator, thixotropic agent are joined in the stainless steel cauldron in proportion, add the solvent of remaining proportion, add thermal agitation at 100-150 ℃, up to dissolving fully, cooling rapidly, the solvent part of additional volatilization, airtight placement is standby.Get the Pb-free solder powder of 88-92% ratio and put in the planetary stirrer, the solder flux that adds remaining proportion stirs, and little plastic bottle packing gets final product.
The specific embodiment
Embodiment 1; Calculate by percentage to the quality, the globular powder of the Pb-free solder powder that consists of 2.0%Ag-1.0%Cu-0.5%Bi-0.5%Ni-Sn (surplus) with 90.0%, with 10% solder flux, with the high adhesive force leadless soldering tin paste of preparation the present invention with 1 composition of embodiment shown in the table 1.
Embodiment 2; Calculate by percentage to the quality, the globular powder of the Pb-free solder powder that consists of 2.5%Ag-1.2%Cu-1.5%Bi-0.8%Ni-Sn (surplus) with 88.0%, with 12.0% solder flux, with the high adhesive force leadless soldering tin paste of preparation the present invention with 2 compositions of embodiment shown in the table 1.
Embodiment 3; Calculate by percentage to the quality, the globular powder of the Pb-free solder powder that consists of 1.5%Ag-0.7%Cu-0.9%Bi-0.1%Ni-Sn (surplus) with 92.0%, with 8.0% solder flux, with the high adhesive force leadless soldering tin paste of preparation the present invention with 3 compositions of embodiment shown in the table 1.
Embodiment 4; Calculate by percentage to the quality, the globular powder of the Pb-free solder powder that consists of 96.1%Sn-1.3%Ag-0.8%Cu-0.7%Bi-0.1%Ni-1.0%Ga with 92.0%, with 8.0% solder flux, with the high adhesive force leadless soldering tin paste of preparation the present invention with 1 composition of embodiment shown in the table 1.
Embodiment 5; Calculate by percentage to the quality, the globular powder of the Pb-free solder powder that consists of 95.7%Sn-1.3%Ag-0.8%Cu-0.7%Bi-0.1%Ni-1.0%Ga-0.4%In with 90.0%, with 10.0% solder flux, with the high adhesive force leadless soldering tin paste of preparation the present invention with composition shown in the table 1.
Embodiment 6; Calculate by percentage to the quality, the globular powder of the Pb-free solder powder that consists of 96.0%Sn-1.5%Ag-0.7%Cu-0.9%Bi-0.1%Ni-0.03%Ce-0.15%In-0.02 %P-0.5%Ga-0.02%Sm-0.02%Pr-0.02%Eu-0.02%La-0.02%Pm with 88.0%, with 12.0% solder flux, with the high adhesive force leadless soldering tin paste of preparation the present invention with composition shown in the table 1.
Embodiment 7; Calculate by percentage to the quality, the globular powder of the Pb-free solder powder that consists of 95.5%Sn-1.5%Ag-0.8%Cu-0.7%Bi-0.1%Ni-1.0%Ga-0.4%In with 89.0%, 11.0% solder flux of forming with 30.0% modified rosin resin, 16.0% maleficent acid resin, 1.0% decanedioic acid, α-bromo-butyric acid of 1.0%, 1.5% four butyl bromation amine, 4.0% modified hydrogenated castor oil, 3.0% palmitic amide, 2-ethyl-pentanediol of 43.5%, 0.5% copper inhibitor is with the high adhesive force leadless soldering tin paste of preparation the present invention.Copper inhibitor is made up of 30.0-40.0% benzothiazole, 30.0-40.0% BTA, 30.0-40.0% benzimidazole.
Table 1 is embodiment and comparative example component and the table of comparisons of content by mass percentage.
Table 1
| Title | Comparative example 1 | Comparative example 2 | Comparative example 3 | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Modified rosin resin | 25.0 | 25.0 | 25.0 | 25.0 | 30.0 | 30.0 |
| Foral | 20.0 | 20.0 | 20.0 | |||
| Alkyd resins | 20.0 | |||||
| The maleficent acid resin | 16.0 | |||||
| Rosin pentaerythritol ester | 14.0 | |||||
| Succinic acid | 1.0 | 1.0 | ||||
| Adipic acid | 1.0 | 1.0 | 1.0 | 1.0 | ||
| Decanedioic acid | 1.0 | 1.0 | ||||
| α-bromo-butyric acid | 1.0 | 1.0 | ||||
| Dibromosuccinic acid | 1.0 | 1.0 | ||||
| Guanidine hydrochloride | 2.0 | 2.0 | ||||
| Four butyl bromation amine | 1.5 | 1.5 | ||||
| 1,3-two bromo-2-propyl alcohol | 1.0 | 1.0 | ||||
| 2,3-two bromo-2-butene-1s, 4-glycol | 1.0 | 1.0 |
| Modified hydrogenated castor oil | 4.0 | 4.0 | ||||
| Glyceryl monostearate | 3.0 | 3.0 | ||||
| Glycerol stearate | 3.0 | 3.0 | ||||
| Rilanit special | 6.0 | 6.0 | ||||
| Palmitic amide | 3.0 | 3.0 | ||||
| 2-ethyl-pentanediol | 43.5 | 43.5 | ||||
| 2-methyl-hexylene glycol | 46.0 | 46.0 | ||||
| Undecyl alcohol | 45.0 | 45.0 |
Through to the test of the rate of spread of above-mentioned comparative example and embodiment, printing test, adhesive force test, the results are shown in Table 2, table 2 is the table of comparisons of embodiment and the comparative example rate of spread, printing, adhesive force.
Table 2
| Project | Comparative example 1 | Comparative example 2 | Comparative example 3 | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Rate of spread % | 90 | 88 | 89 | 89 | 89 | 90 |
| Adhesive force, initial stage gf | 109 | 106 | 107 | 116 | 118 | 121 |
| The limit 0.2mm thick template 0.3 * 2.0mm figure, spacing 〉=0.25mm do not collapse | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified |
By table 2 as seen, add to add the effect that the leadless soldering tin paste of resin has tangible adhesive force to increase, and its weldability, printing release property do not change.
Claims (7)
1, a kind ofly be used for the high adhesive force leadless soldering tin paste that the electronic product surface mount is used, it is characterized in that:
(1), described leadless soldering tin paste is made up of the Pb-free solder powder of 88.0-92.0 quality % and the solder flux of 8.0-12.0 quality %;
(2), described Pb-free solder powder is made up of Bi, the Ni of 0.01-1.0 quality % of Cu, the 0.1-2.0 quality % of Ag, the 0.01-1.5 quality % of Sn, the 0.1-3.0 quality % of 93.5-99.7 quality % basically;
(3) described solder flux is made up of the resin of 35.0-50.0 quality %, the thixotropic agent of 1.0-10.0 quality %, the solvent of 35.0-55.0 quality %, the activating agent of 1.5-5.0 quality % basically;
(4) the described resin of solder flux is made up of one or more of Foral glyceride, rosin pentaerythritol ester, modified rosin resin, terpene resin, maleficent acid resin, alkyd resins;
(5) the described thixotropic agent of solder flux is made up of one or more of rilanit special, castor oil, butter, modified hydrogenated castor oil, palmitic amide, glycerine monofatty ester, fatty acid glyceryl ester;
(6) the described solvent of solder flux is made up of one or more of diethylene glycol monoethyl ether acetic acid esters, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetic acid esters, diglycol monotertiary hexyl ether, diglycol monotertiary hexyl ether acetic acid esters, ethylene glycol monobutyl ether, ethyleneglycol monophenylether, propylene glycol monobutyl ether, propane diols monophenyl ether, undecyl alcohol, 2-methyl-hexylene glycol, 2-ethyl-pentanediol, modification terpinol;
(7) the described activating agent of solder flux is by succinic acid, glutaric acid, adipic acid, azelaic acid, decanedioic acid, salicylic acid, phthalic acid, terephthalic acid (TPA), dimethylamine hydrochloride, diethylamine hydrochloride, tetrabutylammonium hydrogen bromic acid amine, diphenylguanidine hydrobromate, 1,3 one two bromo-2-propyl alcohol, 1,2 one two bromo-1-propyl alcohol, 1,4 one two bromo-2-butylene, 2,3 one two bromo-2-butene-1s, one or more compositions of 4-glycol, dibromosuccinic acid, α one bromo-butyric acid, guanidine hydrochloride.
2, according to the described high adhesive force leadless soldering tin paste of claim 1, it is characterized in that: the Pb-free solder powder at least also contains one or more of Ce, In, P, Ga, Sm, Pr, Eu, La, Pm, and its content is 0.8-1.4 quality %.
3, according to the described high adhesive force leadless soldering tin paste of claim 1, it is characterized in that: also include the copper inhibitor that one or more one-tenth by benzothiazole, BTA, benzimidazole are grouped in the solder flux, its content is 0.01-0.9 quality %.
4, according to the described high adhesive force leadless soldering tin paste of claim 1, it is characterized in that: resin be 55.0-75%.0 modified rosin resin respectively with more than one the combination of the rosin pentaerythritol ester of 25.0-45.0%, maleficent acid resin, rosin pentaerythritol ester, the amount that resin accounts for solder flux is 40.0-45.0%.
5, according to the described high adhesive force leadless soldering tin paste of claim 1, it is characterized in that: thixotropic agent is the combination of rilanit special or modified hydrogenated castor oil of 45.0-55.0% and 45.0-55.0% palmitic amide, and the amount that thixotropic agent accounts for solder flux is 5.0-7.0%.
6, according to the described high adhesive force leadless soldering tin paste of claim 1, it is characterized in that: solvent is undecyl alcohol or 2-ethyl-pentanediol or 2-methyl-hexylene glycol, and the amount that solvent accounts for solder flux is 40.0-50.0%.
7, according to the described high adhesive force leadless soldering tin paste of claim 1, it is characterized in that: activator be the succinic acid of 20.0-30.0% and 20.0-30.0% adipic acid, 20.0-30.0% 1,2 of 3 one two bromo-2-propyl alcohol, 20.0-30.0%, 3 one two bromo-2-butene-1s, the amount that the combination of 4-glycol, activator account for solder flux is 4.0-5.0%.
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| JP6795777B1 (en) * | 2020-03-27 | 2020-12-02 | 千住金属工業株式会社 | Flux for cleaning and solder paste for cleaning |
| CN115070259A (en) * | 2022-07-15 | 2022-09-20 | 深圳市同方电子新材料有限公司 | Novel environment-friendly lead-free soldering paste of superfine soldering tin powder |
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