CN1930323A - Metal surface treating agent - Google Patents
Metal surface treating agent Download PDFInfo
- Publication number
- CN1930323A CN1930323A CNA2005800070997A CN200580007099A CN1930323A CN 1930323 A CN1930323 A CN 1930323A CN A2005800070997 A CNA2005800070997 A CN A2005800070997A CN 200580007099 A CN200580007099 A CN 200580007099A CN 1930323 A CN1930323 A CN 1930323A
- Authority
- CN
- China
- Prior art keywords
- surface treatment
- salt
- treatment agent
- intramolecularly
- compound
- 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.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 16
- 239000002184 metal Substances 0.000 title claims abstract description 16
- 229910000679 solder Inorganic materials 0.000 claims abstract description 50
- 238000007747 plating Methods 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 229910001128 Sn alloy Inorganic materials 0.000 claims abstract description 19
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052718 tin Inorganic materials 0.000 claims abstract description 14
- 239000012756 surface treatment agent Substances 0.000 claims description 40
- -1 alkali metal salt Chemical class 0.000 claims description 31
- 239000000758 substrate Substances 0.000 claims description 29
- 238000004381 surface treatment Methods 0.000 claims description 19
- 239000013543 active substance Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 239000004094 surface-active agent Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- 239000002253 acid Substances 0.000 description 15
- 239000000956 alloy Substances 0.000 description 14
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 13
- 229910045601 alloy Inorganic materials 0.000 description 13
- 239000001103 potassium chloride Substances 0.000 description 13
- 235000011164 potassium chloride Nutrition 0.000 description 13
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 11
- 229910020994 Sn-Zn Inorganic materials 0.000 description 11
- 229910009069 Sn—Zn Inorganic materials 0.000 description 11
- HPEUEJRPDGMIMY-IFQPEPLCSA-N molybdopterin Chemical compound O([C@H]1N2)[C@H](COP(O)(O)=O)C(S)=C(S)[C@@H]1NC1=C2N=C(N)NC1=O HPEUEJRPDGMIMY-IFQPEPLCSA-N 0.000 description 11
- 238000003466 welding Methods 0.000 description 9
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- 230000004907 flux Effects 0.000 description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- QLYHVLWJJRLFJQ-UHFFFAOYSA-N CCC(CCCCC)(CC)P(O)(O)=O.OCC Chemical compound CCC(CCCCC)(CC)P(O)(O)=O.OCC QLYHVLWJJRLFJQ-UHFFFAOYSA-N 0.000 description 5
- 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
- 230000003078 antioxidant effect Effects 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000003750 conditioning effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000005499 phosphonyl group Chemical group 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000013008 thixotropic agent Substances 0.000 description 3
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 2
- 229910000952 Be alloy Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 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
- 239000003513 alkali Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 2
- SVMUEEINWGBIPD-UHFFFAOYSA-N dodecylphosphonic acid Chemical class CCCCCCCCCCCCP(O)(O)=O SVMUEEINWGBIPD-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 230000005499 meniscus Effects 0.000 description 2
- 229940055577 oleyl alcohol Drugs 0.000 description 2
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 241000276498 Pollachius virens Species 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FYOYCZHNDCCGCE-UHFFFAOYSA-N diphenyl hydrogen phosphite Chemical group C=1C=CC=CC=1OP(O)OC1=CC=CC=C1 FYOYCZHNDCCGCE-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- IYDNQWWOZQLMRH-UHFFFAOYSA-N octadec-1-yne Chemical compound CCCCCCCCCCCCCCCCC#C IYDNQWWOZQLMRH-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/58—Treatment of other metallic material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3457—Solder materials or compositions; Methods of application thereof
- H05K3/3478—Applying solder preforms; Transferring prefabricated solder patterns
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Chemical Treatment Of Metals (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Disclosed is a surface treating agent for imparting a metal, in particular an Sn and Sn alloy plating, with oxidation resistance and improving the solder wettability thereof. Also disclosed is a surface treating agent for suppressing generation of whiskers in the Sn and Sn alloy plating. The metal surface treating agent is characterized by containing one or more substances selected from compounds having two or more phosphonic acid groups and no ester bond in one molecule and/or salts thereof in an amount of not less than 0.01 g/L in total. It is preferable that the surface treating agent has a pH of not more than 5 and further contains 0.1-10 g/L of a surfactant. Metals preferably treated by this surface treating agent are Sn and Sn alloys.
Description
Technical field
The present invention relates to the surface treatment agent of metal, especially Sn and Sn alloy and used the surface treatment method of this surface treatment agent.And then, electronic unit, substrate, solder ball, solder powder, the ball grid array of having used this solder ball that the present invention relates to handle, used the solder paste of this solder powder and used their assembling part with this surface treatment method.
Background technology
Welding be a kind of lower material of fusing point that uses with the technology that couples together between the object, in modern industry, extensively be applied to joint, assembling of electronics etc.The general scolder that uses is the Sn-Pb alloy, because the fusing point of its eutectic composition (all the other are Pb for 63%Sn-) is lower 183 ℃, can carry out this welding under 220～230 ℃, therefore can not cause thermal damage to electronic unit, substrate substantially.And the Sn-Pb alloy also has following feature when having good weldability, that is, can solidify very soon when welding, also is difficult to split or peel off even apply vibration in the weld.
In general, electronics is that the metal by the synthetic resins of housing, substrate etc. and conductor portion, framework etc. forms, and when carrying out waste treatment, not by burning disposal, is buried in underground substantially.In recent years, the ground rainfall has and shows tart trend (acid rain), makes the scolder stripping of underground electronics of burying, and forms the problem of polluted underground water.Therefore, especially in the electronics industry, replace fast to lead-free scolder (lead-free solder).
For the solder wettability and the erosion resistance of the outside lead terminal that improves electronic unit, mainly implement scolder plating (all the other are Pb 90%Sn-), therefore expect its countermeasure to unleaded transformation.Select as the candidate of lead-free solder plating, be divided into roughly that pure Sn, Sn-Ag (Cu) are, Sn-Zn system, Sn-Bi system, they respectively have relative merits, still fail to replace fully the Sn-Pb alloy so far.
Pure Sn plating from expense, plating operability etc. in general, is considered to best as unleaded plating.But, during plating Sn,, need be improved strongly because except that being easy to generate whisker, also there are the easy problem of deterioration in time of solder wettability in oxidation, the internal stress on surface.
Sn-Zn is an alloy because with existing Sn-Pb be that the fusing point of alloy is close, thereby need not to change present equipment, operation, it seems from this point, be favourable.In addition, the physical strength excellence of plated film, cost is also excellent.But Zn belongs to the active metal, oxidation easily, and Sn-Zn is the non-constant of the solder wettability of alloy, therefore currently comes, its practical feasibility is considered to minimum.
Solder paste is applied to electronic unit is assembled in the surface of substrate, and its usage quantity increases in recent years.Solder paste generally be with the welding flux alloy powder as main body, added the paste of the solder flux (flux) that contains tackiness agent, activator, thixotropic agent, tensio-active agent and solvent etc.Unleaded as solder paste, having studied Sn-Ag (Cu) is that alloy, Sn-Zn are that alloy, Sn-Bi are alloy, is alloy for Sn-Zn, as mentioned above, with existing Sn-Pb be that the eutectic temperature of scolder is close, therefore be considered to the most effective substitute scolder.But, as mentioned above, because Zn is oxidized easily, so to use Sn-Zn be alloy as the solder paste of solder powder can with the activator generation oxidizing reaction that contains in the solder flux, cause solder wettability, storage stability significantly to reduce, the shortcoming that must under inert atmosphere, carry out when in addition, also having soft heat.
At the problems referred to above, present inventors have proposed a kind of surface treatment agent in patent documentation 1 (special hope 2002-304554 number), it is characterized in that, contain a kind or 2 kinds acid phosphoric acid ester and the salt thereof with saturated or unsaturated alkyl.
In addition, in patent documentation 2 (spy opens flat 7-188942 number), propose a kind of antioxidant especially, it is characterized in that, contained di(2-ethylhexyl)phosphate phenylester and/or phosphorous acid diphenyl.
But, phosphoric acid ester in the above-mentioned technology or phosphorous acid ester, ester bond can decompose when the thermal treatment of higher temperature (more than 200 ℃), can not obtain sufficient antioxidant effect.Therefore, in above-mentioned technology, be difficult to prevent of the oxidation of general welding temperature than the Sn and the Sn alloy material of high in the past lead-free solder correspondence.
Patent documentation 1: special hope 2002-304554 number
Patent documentation 2: the spy opens flat 7-188942 communique
Summary of the invention
The objective of the invention is, provide a kind of and give oxidation-resistance and improve the surface treatment agent of solder wettability to metal, especially Sn and Sn alloy.And then, the object of the present invention is to provide a kind of Sn of inhibition and Sn alloy to produce the surface treatment agent of whisker.
Present inventors, oxidation at metal, especially Sn and Sn alloy surface suppresses to have carried out deep research, found that, use contains total and carries out surface treatment more than or equal to the surface treatment agent of the following substances of 0.01g/L, can give oxidation-resistance, improve solder wettability, wherein said material is: contain compound and/or its salt that phosphonate group more than 2 and intramolecularly do not contain ester bond at a part more than a kind or 2 kinds.In addition, can be observed, contain the solder paste of having implemented this surface-treated Sn solder powder, its storage stability significantly improves.Further, the generation of having carried out the whisker of this surface-treated Sn and Sn alloy is as can be known suppressed significantly.
That is, the present invention is as described below.
(1) a kind of metallic surface treatment agent is characterized in that, contains total and contains compound and/or its salt that phosphonate group 2 or more and intramolecularly do not contain ester bond at an intramolecularly more than or equal to 0.01g/L more than a kind or 2 kinds.
(2) a kind of metallic surface treatment agent, it is characterized in that, contain total more than or equal to 0.01g/L contain compound and/or its salt that phosphonate group more than 2 and intramolecularly do not contain ester bond at an intramolecularly more than a kind or 2 kinds, the pH value of solution is adjusted into below 5.
(3) above-mentioned (2) described metallic surface treatment agent is characterized in that, further contains the tensio-active agent of 0.01～10g/L.
(4) the described metallic surface treatment agent of each of above-mentioned (1)～(3), it is characterized in that, above-mentioned have compound and/or its salt that phosphonate group more than 2 and intramolecularly do not contain ester bond at an intramolecularly, be following formula (I), (II) or (III) shown in compound and/or its an alkali metal salt, ammonium salt or the salt that forms with amine compound
(in the formula (I), X
1～X
3And Y
1～Y
3Respectively can identical, also can be different, the low alkyl group of expression hydrogen atom or carbonatoms 1～5),
(in the formula (II), R
1, R
2, R
4Respectively can identical, also can be different, expression following radicals (A), R
3The low alkyl group of expression following radicals (A) or carbonatoms 1～5, n represents 1～3 integer,
X in the group (A)
1And Y
1Identical with the definition in the general formula (I)),
(in the formula (III), X represents that hydrogen atom or carbonatoms are 1～5 low alkyl group, Y represents that hydrogen atom, carbonatoms are 1～5 low alkyl group, hydroxyl or amino).
As each described metallic surface treatment agent of above-mentioned (1)～(4), it is characterized in that (5) above-mentioned metal is Sn or Sn alloy.
(6) a kind of surface treatment method is to utilize each described metallic surface treatment agent of above-mentioned (1)～(5) to carry out.
(7) a kind of electronic unit or substrate is characterized in that, to the conductive surface of the splicing ear portion of electronic unit or substrate or after plating is carried out on its surface, utilize above-mentioned (6) described surface treatment method to carry out surface treatment.
(8) a kind of solder ball or solder powder is characterized in that, have used according to above-mentioned (6) described surface treatment method and have carried out surface-treated Sn alloy.
(9) a kind of ball grid array is characterized in that, has used above-mentioned (8) described solder ball as electric connecting part.
(10) a kind of assembling part is characterized in that, be above-mentioned (8) described solder ball is disposed at electronic unit, is connected to form on the circuit substrate.
(11) a kind of paste is characterized in that, has used above-mentioned (8) described solder powder.
(12) a kind of assembling part is characterized in that, has used above-mentioned (11) described solder paste.
Embodiment
Below surface treatment agent of the present invention is elaborated.
As the metal of handling with surface treatment agent of the present invention, can list Fe, Ni, Co, Cr, Cu, Zn, Sn, Al, Mg, Ti, Ag and Au etc., they also can be alloys.Preferred especially Sn and Sn alloy.As the Sn alloy, from the problem of environmental pollution etc., more preferably lead-free Sn alloy.As lead-free Sn alloy, can list any or the welding flux alloy more than 2 kinds of in Sn, containing among Zn, Bi, Cu, In, Ag and the Sb etc.
By containing compound that phosphonate group more than 2 and intramolecularly do not contain ester bond and/or the surface treatment agent of its salt carries out surface treatment at a part more than the 0.01g/L, can give oxidation-resistance to the surface of treated material, improve solder wettability with adding up to contain.
If a part contains the amount of compound that phosphonate group more than 2 and intramolecularly do not contain ester bond and/or its salt less than 0.01g/L, then its effect is very little.In addition, on the contrary, even addition is too much, characteristic can deterioration yet, so addition do not have the upper limit, but from the problem of cost, addition is preferably 0.01～500g/L, more preferably 0.1～100g/L.
In addition, surface treatment agent of the present invention owing to use intramolecularly not contain the compound of ester bond, so the decomposition of ester bond can not take place during thermal treatment, even heat-treat, also can obtain sufficient antioxidant effect under higher temperature.Therefore, though for welding temperature than pairing Sn of higher in the past lead-free solder and Sn alloy, also can give sufficient oxidation-resistance.
In addition, though still indeterminate its detailed mechanism of action, can distinguish with the compound that in a part, only has 1 phosphonate group relatively, the antioxidant property of compound that has the phosphonyl group more than 2 in a part is more excellent.The number of an intramolecular phosphonate group, the angle from cost is preferably 2～6.
As having the phosphonyl group more than 2 at an intramolecularly and not containing compound and/or its salt of ester bond at intramolecularly, for example can list, following general formula (I), (II) and (III) shown in compound and/or its an alkali metal salt, ammonium salt and with the salt of amine compound.
(in the formula (I), X
1～X
3And Y
1～Y
3Respectively can identical, also can be different, expression hydrogen atom or carbonatoms are 1～5 low alkyl group),
(in the formula (II), R
1, R
2And R
4Respectively can identical, also can be different, expression following radicals (A), R
3Expression following radicals (A) or carbonatoms are 1～5 low alkyl group, and n represents 1～3 integer,
X in the group (A)
1And Y
1Identical with the definition in the general formula (I)),
(in the formula (III), X represents that hydrogen atom or carbonatoms are 1～5 low alkyl group, Y represents that hydrogen atom or carbonatoms are 1～5 low alkyl group, hydroxyl or amino).
As the compound shown in the above-mentioned general formula (I), for can industrialness ground obtain preferred nitrilo trimethylene phosphonic etc. especially.
Equally, as the compound shown in the above-mentioned general formula (II), preferred especially ethylene diamine tetramethylene phosphonic acid, diethylenetriamine pentamethylenophosphonic acid(DTPP) etc. are as the compound shown in the above-mentioned general formula (III), be preferably 1-hydroxyl ethane-1 especially, 1-di 2 ethylhexyl phosphonic acid etc.
As an alkali metal salt of above-claimed cpd, particular certain cancers, sylvite etc., as with the salt of amine compound, preferred triethyl amine salt, triethanolamine salt etc.
Surface treatment agent of the present invention can will have the phosphonyl group more than 2 and dissolve use at compound and/or its salt that intramolecularly does not contain ester bond in solvent in a part.As employed solvent,, just have no particular limits as long as solvable.For example, can make water, alcohol, ethylene glycol isopolarity solvent, from considerations such as solubleness, costs, preferably water.
In addition, under the situation of water system surface treatment agent, find further to improve the oxidation-resistance on processed surface by the pH value is adjusted to smaller or equal to 5.For the pH value of surface treatment agent, consider that more preferably the pH value is 1～5 to the influence of raw material etc.Adjust agent as pH, can use general obtainable acid, alkali.
Further,, the pH value is adjusted to below 5, can further improves the oxidation-resistance on processed surface by in the water system surface treatment agent, adding the tensio-active agent of 0.01～10g/L.If the addition of tensio-active agent is less than 0.01g/L, or addition then can not obtain antioxidant effect above 10g/L.The addition of tensio-active agent, preferred 0.1～10g/L.
As tensio-active agent, can suitably select to use in commercially available anionic, cationic, non-ionic type and the amphoterics more than a kind or 2 kinds.
As aniorfic surfactant, preferably sulfuric acid ester salt type, sulphonate salt type, the phosphate ester salt type, sulfosuccinate type etc., as cationic surfactant, preferred quaternary, amine salt type etc., as nonionic surface active agent, preferred higher alcohols ethylene oxide adduct, the alkylphenol ethylene oxide adduct, the polyoxyethylene polyoxypropylene block polymer, the polyoxyethylene polyoxypropylene block polymer of ethylene diamine, the ethylene oxide adduct of senior fatty amine and the ethylene oxide adduct of aliphatic amide etc., as amphoterics, the preferred amino acid type, betaine type etc.
When the pH value is used in smaller or equal to 5 scope, preferably suitably select to use anionic, more than a kind or 2 kinds of non-ionic type.Wherein, for nonionic surface active agent, preferred especially polyethylene glycol type, can especially preferably use higher alcohols ethylene oxide adduct, alkylphenol ethylene oxide adduct, polyoxyethylene polyoxypropylene block polymer etc., in addition, for aniorfic surfactant, special preferably sulfuric acid ester salt type, phosphate ester salt type.
In addition, surface treatment agent of the present invention in order to give desired performance, can contain additive with the amount of the scope that can not destroy itself performance.As additive, can list sanitas, pH buffer reagent etc., they can use present known additive.
When using surface treatment agent of the present invention that metal is carried out surface treatment, so long as the method that forms tunicle at metallic surface gets final product, for example, can list, metal only is immersed in method in the surface treatment agent; Surface treatment agent is sprayed or use Kohler coater, scrape coating machine, method that devices such as excellent coating machine, knife coater, grooved roll coating machine (gravure coater), contrary roll-coater, casting coating machine are coated with.
Carry out the shape of surface-treated metal with surface treatment agent of the present invention, can be wire, strip paper tinsel shape, granular, Powdered etc. any shape, surface treatment agent of the present invention can be handled electronic unit, substrate, solder ball, solder powder etc.
The surface treatment agent of the application of the invention, conductive surface to the splicing ear portion of electronic unit or substrate carries out surface treatment, or this conductive surface carried out carrying out surface treatment behind the plating, can make excellent in oxidation resistance, solder property improvement electronic unit or substrate.
Used the solder ball of the Sn alloy of handling with surface treatment agent of the present invention, excellent in oxidation resistance, can be well as the ball grid array of electric connecting part, in addition, also can be configured on the electronic unit, as the assembling part that itself and circuit substrate are formed by connecting and good use.
In addition, also can use surface treatment agent of the present invention that the Sn powdered alloy is handled, add the solder flux that contains tackiness agent, activator, thixotropic agent, tensio-active agent, solvent etc. therein, use as solder paste.Can be observed this solder paste the significant effect of improving is being arranged aspect its storage stability.As above-mentioned tackiness agent, activator, thixotropic agent, tensio-active agent and solvent, can use present known material.
Embodiment
Enumerate embodiment below, the present invention is described in detail.
Embodiment 1～14 and comparative example 1～5
Modulated 15 kinds and do not had the aqueous solution (embodiment 1～14, comparative example 1) of the compound or its salt of ester bond as effective constituent in a part, to have 2 above phosphonate groups and intramolecularly.Breaking down of solution is as shown in table 1.
On the other hand, for copper product (C1020P, 10mm * 25mm * 0.2
tMm), carry out following pre-treatment.
Alkali electrolytic degreasing (normal temperature, 15A/dm
2, handle about 30 seconds approximately) → washing → acid dipping (10% sulfuric acid, normal temperature, 5 seconds) → washing → chemical grinding (CPB-40, normal temperature, dipping 1 minute) → washing → acid dipping (10% sulfuric acid, normal temperature, 5 seconds) → washing
For this body material, carry out Sn plating (the plating bath: テ イ Application コ one ト K (day ore deposit メ Le プ レ one テ イ Application グ (strain) system), plating condition: cathode current density 2A/dm of the about 5 μ m of thickness
2, 20 ℃ of temperature, liquid-flow and negative electrode shake plating).
The body material (to call the Sn body material in the following text) of Sn plating will have been implemented, above-mentioned have in the solution of the compound or its salt that phosphonate group more than 2 and intramolecularly do not have ester bond containing, bathe under the temperature dipping after 10 seconds, washing at 60 ℃ at an intramolecularly, drying is as the test substrate.
For these test substrates, carry out following evaluation, test-results is as shown in table 1.
Heatproof oxidation performance
These test substrates are put into the electric furnace that remains on 220 ℃, heat treated utilized meniscus signature analysis (meniscograph) to measure the welding property (zero friendship time zero-cross time) of lead-free solder according to following condition determination after 1 hour under air atmosphere.
Device: welding tester SAT-2000 (レ ス カ system)
Solder bath: tin: silver: copper=96.5: 3: 0.5 (bathing 245 ℃ of temperature)
Solder flux: NA-200 (development of system ラization)
Impregnating depth: 2mm
Impregnating speed: 4 mm/second
Dipping time: 5 seconds
The moisture-proof oxidisability
To these test substrates, same after enforcement PCT handles (105 ℃ of temperature, placing 16 hours in the airtight still of humidity 100%) with meniscus signature analysis (meniscograph) and heatproof oxidation performance item, the weldability of lead-free solder is measured.
In addition, and then as a comparative example, estimate following goods in the lump: above-mentioned Sn body material is used body material (but the not washing after the surface treatment that contains after 1g/L dodecyl phosphonic aqueous isopropanol carries out surface treatment, comparative example 2), the aqueous solution that use contains the 1g/L diethyl phosphonate carries out the body material (comparative example 3) after the surface treatment, untreated above-mentioned Sn body material (comparative example 4), the substrate (comparative example 5) that gets with above-mentioned Sn body material being used the spy open disclosed surface treatment agent in the flat 7-188942 communique (aqueous solution that contains 0.1g/L di(2-ethylhexyl)phosphate phenylester) processing.Test-results is shown in table 1 in the lump.
Table 1 surface treatment agent forms and evaluation result (plating Sn body material)
| # | Effective constituent and content thereof (g/L) | Tensio-active agent and content thereof (g/L) | pH | Heatproof oxidation performance | The moisture-proof oxidisability | |||
| Effective constituent | Content | Tensio-active agent | Content | |||||
| Embodiment | 1 | Nitrilo trimethylene phosphonic (formula (I)) | 1 | - | 0 | 2 | ○ | ○ |
| 2 | Diethylenetriamine pentamethylenophosphonic acid(DTPP) (formula (II)) | 1 | - | 0 | 2 | ○ | ○ | |
| 3 | 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid (formula (III)) | 1 | - | 0 | 2 | ○ | ○ | |
| 4 | Nitrilo trimethylene phosphonic sylvite | 1 | - | 0 | 6 | ○ | △ | |
| 5 | Diethylenetriamine pentamethylenophosphonic acid(DTPP) sylvite | 1 | - | 0 | 8 | △ | △ | |
| 6 | 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid sylvite | 1 | - | 0 | 7 | △ | △ | |
| 7 | The nitrilo trimethylene phosphonic | 1 | 12 moles of affixtures of natural lauryl alcohol propylene oxide | 1 | 2 | ◎ | ◎ | |
| 8 | Diethylenetriamine pentamethylenophosphonic acid(DTPP) | 1 | 12 moles of affixtures of nonylphenol oxyethane | 1 | 2 | ◎ | ◎ | |
| 9 | 1-hydroxyl ethane-1, the 1-di 2 ethylhexyl phosphonic acid | 1 | 9 moles of affixtures of natural lauryl alcohol oxyethane | 1 | 2 | ◎ | ◎ | |
| 10 | Nitrilo trimethylene phosphonic sylvite | 1 | 10 moles of affixtures of natural oleyl alcohol oxyethane | 1 | 6 | ○ | ○ | |
| 11 | Diethylenetriamine pentamethylenophosphonic acid(DTPP) sylvite | 1 | Polyoxyethylene polyoxypropylene block polymer (75 ℃ of cloud points) | 1 | 8 | ○ | △ | |
| 12 | 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid sylvite | 1 | 10 moles of affixtures of nonylphenol oxyethane | 1 | 7 | ○ | ○ | |
| 13 | The nitrilo trimethylene phosphonic | 1 | 12 moles of affixtures of natural lauryl alcohol propylene oxide | 20 | 2 | ○ | △ | |
| 14 | The nitrilo trimethylene phosphonic | 1 | 12 moles of affixtures of natural lauryl alcohol propylene oxide | 0.005 | 2 | ○ | ○ | |
| Comparative example | 1 | Diethylenetriamine pentamethylenophosphonic acid(DTPP) | 0.005 | - | 0 | 4 | × | × |
| 2 | The dodecyl phosphonic acids | 1 | - | 0 | - | △ | × | |
| 3 | Diethyl phosphonate | 1 | - | 0 | 4 | × | × | |
| 4 | Be untreated | - | - | - | - | × | × | |
| 5 | Te Kaiping 7-188942 | - | - | - | 2 | △ | △ | |
◎=zero friendship time is less than 1 second, and zero=zero friendship time is more than 1 second, less than 3 seconds, △=zero friendship time more than 3 seconds, less than 5 seconds, and *=zero friendship time is more than 5 seconds
Embodiment 15～28 and comparative example 6～11
To having carried out copper product (C1020P, 10mm * 25mm * 0.2 of the pre-treatment identical with the foregoing description 1～14, comparative example 1～5
tMm), carry out Sn-Zn plating (plating is bathed: day ore deposit メ Le プ レ one テ イ Application グ (strain) makes), plating condition: the cathode current density 3A/dm of the about 5 μ m of thickness
2, 35 ℃ of temperature, pH4.0, liquid-flow and negative electrode shake plating).
The body material (to call the Sn-Zn body material in the following text) of this Sn-Zn plating will have been implemented, be placed in the foregoing description 1～14, comparative example 1～3 and the comparative example 5 in the synthetic solution, dipping was washed after 10 seconds under 60 ℃ of bath temperature, and dried substrate and untreated substrate are as the test substrate.
For these test substrates, same with the foregoing description 1～14 and comparative example 1～5, after the defining, measure weldability.Test-results is as shown in table 2.
In addition, and then as a comparative example, estimate to use in the lump special be willing to that the surface treatment agent shown in 2002-304554 number (aqueous isopropanol of the 1wt% of single two octadecyne base phosphoric acid ester) is handled untreated above-mentioned Sn-Zn body material and substrate (comparative example 11).Test-results is shown in table 2 in the lump.
Table 2 surface treatment agent is formed and evaluation result (Sn-Zn plating body material)
| # | Effective constituent and content thereof (g/L) | Tensio-active agent and content thereof (g/L) | pH | Heatproof oxidation performance | The moisture-proof oxidisability | |||
| Effective constituent | Content | Tensio-active agent | Content | |||||
| Embodiment | 15 | The nitrilo trimethylene phosphonic | 1 | - | 0 | 2 | ○ | ○ |
| 16 | Diethylenetriamine pentamethylenophosphonic acid(DTPP) | 1 | - | 0 | 2 | ○ | ○ | |
| 17 | 1-hydroxyl ethane-1, the 1-di 2 ethylhexyl phosphonic acid | 1 | - | 0 | 2 | ○ | ○ | |
| 18 | Nitrilo trimethylene phosphonic sylvite | 1 | - | 0 | 6 | △ | △ | |
| 19 | Diethylenetriamine pentamethylenophosphonic acid(DTPP) sylvite | 1 | - | 0 | 8 | △ | △ | |
| 20 | 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid sylvite | 1 | - | 0 | 7 | △ | △ | |
| 21 | The nitrilo trimethylene phosphonic | 1 | 12 moles of affixtures of natural lauryl alcohol propylene oxide | 1 | 2 | ◎ | ◎ | |
| 22 | Diethylenetriamine pentamethylenophosphonic acid(DTPP) | 1 | 12 moles of affixtures of nonylphenol oxyethane | 1 | 2 | ◎ | ◎ | |
| 23 | 1-hydroxyl ethane-1, the 1-di 2 ethylhexyl phosphonic acid | 1 | 9 moles of affixtures of natural lauryl alcohol oxyethane | 1 | 2 | ◎ | ◎ | |
| 24 | Nitrilo trimethylene phosphonic sylvite | 1 | 10 moles of affixtures of natural oleyl alcohol oxyethane | 1 | 6 | △ | ○ | |
| 25 | Diethylenetriamine pentamethylenophosphonic acid(DTPP) sylvite | 1 | Polyoxyethylene polyoxypropylene block polymer (75 ℃ of cloud points) | 1 | 8 | △ | △ | |
| 26 | 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid sylvite | 1 | 10 moles of affixtures of nonylphenol oxyethane | 1 | 7 | △ | ○ | |
| 27 | The nitrilo trimethylene phosphonic | 1 | 12 moles of affixtures of natural lauryl alcohol propylene oxide | 20 | 2 | △ | △ | |
| 28 | The nitrilo trimethylene phosphonic | 1 | 12 moles of affixtures of natural lauryl alcohol propylene oxide | 0.005 | 2 | ○ | ○ | |
| Comparative example | 6 | Diethylenetriamine pentamethylenophosphonic acid(DTPP) | 0.005 | --- | 0 | 4 | × | × |
| 7 | The dodecyl phosphonic acids | 1 | -- | 0 | - | △ | × | |
| 8 | Diethyl phosphonate | 1 | -- | 0 | 4 | × | × | |
| 9 | Be untreated | - | -- | - | - | × | × | |
| 10 | Te Kaiping 7-188942 | - | -- | - | 2 | △ | × | |
| 11 | Special hope 2002-304554 | - | - | - | - | × | ○ | |
◎=zero handed over deficiency of time 1 second, zero=zero friendship time more than 1 second, less than 3 seconds, and △=zero friendship time surpasses 3 seconds, less than 5 seconds, and *=zero friendship time is more than 5 seconds
Embodiment 29 and comparative example 12
In embodiment 29, the result shows: for Sn plating thing, carried out surface-treated and surface treated comparing not, the generation of the former whisker is suppressed significantly.
To carry out the Sn plating substrate of the processing identical and be that 85 ℃, humidity are to place 24 hours under the atmosphere of 85% fixed temperature and humidity in temperature without surface-treated substrate with the foregoing description 7.Then with after the substrate thorough drying, utilize scanning electron microscope (SEM) to observe the surface, the result can be observed a lot of whiskers (comparative example 12), and do not observe whisker (embodiment 29) fully in surface treated substrate in not surface treated substrate.
The industry utilizability
Contain to add up in a part, to have in phosphonate group more than 2 and the molecule more than or equal to 0.01g/L one kind or two or more by utilization and do not contain the compound of ester bond and/or the surface conditioning agent of its salt, metal is carried out surface treatment, can give non-oxidizability, improve the wetability of scolder. PH value by adjusting this surface conditioning agent is for less than or equal to 5, and then by making its surfactant that contains 0.01～10g/L, can further improve non-oxidizability.
In addition, contain and used surface conditioning agent of the present invention to carry out the solder paste of surface-treated Sn Alloy soldering powder, its storage stability significantly improves. And then the surface conditioning agent of the application of the invention is processed Sn and Sn Alloy Plating application, the significantly generation of inhibition of whiskers.
Claims (12)
1. a metallic surface treatment agent is characterized in that, contain add up to 0.01g/L above have compound and/or its salt that phosphonate group more than 2 and intramolecularly do not contain ester bond at an intramolecularly more than a kind or 2 kinds.
2. metallic surface treatment agent, it is characterized in that, contain add up to 0.01g/L above have compound and/or its salt that phosphonate group more than 2 and intramolecularly do not contain ester bond at an intramolecularly more than a kind or 2 kinds, the pH value of solution is adjusted into smaller or equal to 5.
3. metallic surface treatment agent as claimed in claim 2 is characterized in that, further contains the tensio-active agent of 0.01g/L～10g/L.
4. as each described metallic surface treatment agent of claim 1～3, it is characterized in that, above-mentioned have compound and/or its salt that phosphonate group more than 2 and intramolecularly do not contain ester bond at an intramolecularly, be following formula (I), (II) or (III) shown in compound and/or its an alkali metal salt, ammonium salt or the salt that forms with amine compound
(in the formula (I), X
1～X
3And Y
1～Y
3Respectively can identical, also can be different, expression hydrogen atom or carbonatoms are 1～5 low alkyl group),
(in the formula (II), R
1, R
2, R
4Respectively can identical, also can be different, expression following radicals (A), R
3Expression following radicals (A) or carbonatoms are 1～5 low alkyl group, and n represents integer 1～3,
X in the group (A)
1And Y
1Identical with the definition in the general formula (I)),
(in the formula (III), X represents that hydrogen atom or carbonatoms are 1～5 low alkyl group, Y represents that hydrogen atom or carbonatoms are 1～5 low alkyl group, hydroxyl or amino).
5. as each described metallic surface treatment agent of claim 1～4, it is characterized in that above-mentioned metal is Sn or Sn alloy.
6. a surface treatment method is to utilize each described metallic surface treatment agent of claim 1～5 to carry out.
7. electronic unit or substrate is characterized in that, to the conductive surface of the splicing ear portion of electronic unit or substrate or after plating is carried out on its surface, utilize the described surface treatment method of claim 6 to carry out surface treatment.
8. solder ball or solder powder is characterized in that, have used and have utilized the described surface treatment method of claim 6 to carry out surface-treated Sn alloy.
9. a ball grid array is characterized in that, has used the described solder ball of claim 8 as electric connecting part.
10. an assembling part is characterized in that, be the described solder ball of claim 8 is disposed at electronic unit, is connected to form on the circuit substrate.
11. a paste is characterized in that, has used the described solder powder of claim 8.
12. an assembling part is characterized in that, has used the described solder paste of claim 11.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004061635 | 2004-03-05 | ||
| JP061635/2004 | 2004-03-05 | ||
| PCT/JP2005/002813 WO2005085498A1 (en) | 2004-03-05 | 2005-02-22 | Metal surface treating agent |
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| KR (1) | KR100802878B1 (en) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102282294A (en) * | 2009-01-14 | 2011-12-14 | 安美特德国有限公司 | Solution and process for increasing the solderability and corrosion resistance of a metal or metal alloy surface |
| CN102782189A (en) * | 2010-12-01 | 2012-11-14 | 吉坤日矿日石金属株式会社 | Surface treatment agent for pd or alloy mainly composed of pd, and surface coating layer structure of copper surface |
| CN103088333A (en) * | 2012-12-13 | 2013-05-08 | 苏州新区化工节能设备厂 | Water electrolysis pole plate surface treatment liquid |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007197791A (en) * | 2006-01-27 | 2007-08-09 | Daiwa Fine Chemicals Co Ltd (Laboratory) | Composition of post-treatment agent for plating |
| CN104894569B (en) * | 2015-06-30 | 2018-03-02 | 长沙理工大学 | Ni-Pd metal surface treatment agent |
| CN107326413A (en) * | 2017-07-04 | 2017-11-07 | 苏州道蒙恩电子科技有限公司 | A kind of electrotinning fastness inorganic agent and application method |
| 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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| JP2000332399A (en) * | 1999-05-24 | 2000-11-30 | Sumitomo Metal Mining Co Ltd | Solder ball and manufacture thereof |
| JP2003193255A (en) * | 2001-12-26 | 2003-07-09 | Kansai Paint Co Ltd | Surface treatment composition for metallic material |
-
2005
- 2005-02-22 CN CN2011103259870A patent/CN102424965A/en active Pending
- 2005-02-22 KR KR1020067019566A patent/KR100802878B1/en active IP Right Grant
- 2005-02-22 WO PCT/JP2005/002813 patent/WO2005085498A1/en active Application Filing
- 2005-02-22 JP JP2006510639A patent/JP4518507B2/en active Active
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102282294A (en) * | 2009-01-14 | 2011-12-14 | 安美特德国有限公司 | Solution and process for increasing the solderability and corrosion resistance of a metal or metal alloy surface |
| CN102282294B (en) * | 2009-01-14 | 2013-07-03 | 安美特德国有限公司 | Solution and process for increasing the solderability and corrosion resistance of a metal or metal alloy surface |
| CN102782189A (en) * | 2010-12-01 | 2012-11-14 | 吉坤日矿日石金属株式会社 | Surface treatment agent for pd or alloy mainly composed of pd, and surface coating layer structure of copper surface |
| CN103088333A (en) * | 2012-12-13 | 2013-05-08 | 苏州新区化工节能设备厂 | Water electrolysis pole plate surface treatment liquid |
Also Published As
| Publication number | Publication date |
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| KR20060122967A (en) | 2006-11-30 |
| CN1930323B (en) | 2012-06-27 |
| TWI301515B (en) | 2008-10-01 |
| CN102424965A (en) | 2012-04-25 |
| JPWO2005085498A1 (en) | 2008-04-24 |
| WO2005085498A1 (en) | 2005-09-15 |
| TW200533783A (en) | 2005-10-16 |
| KR100802878B1 (en) | 2008-02-13 |
| JP4518507B2 (en) | 2010-08-04 |
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