CN1914359B - Sealing agent, method of sealing and printed circuit board treated with the sealing agent - Google Patents
Sealing agent, method of sealing and printed circuit board treated with the sealing agent Download PDFInfo
- Publication number
- CN1914359B CN1914359B CN2005800035457A CN200580003545A CN1914359B CN 1914359 B CN1914359 B CN 1914359B CN 2005800035457 A CN2005800035457 A CN 2005800035457A CN 200580003545 A CN200580003545 A CN 200580003545A CN 1914359 B CN1914359 B CN 1914359B
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- Prior art keywords
- sealing
- treatment agent
- hole
- sealing agent
- hole treatment
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- 238000007789 sealing Methods 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000013543 active substance Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 125000005842 heteroatom Chemical group 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000006174 pH buffer Substances 0.000 claims description 2
- 229910000679 solder Inorganic materials 0.000 abstract description 17
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 description 19
- 238000005260 corrosion Methods 0.000 description 19
- 238000009736 wetting Methods 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000007747 plating Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 10
- 239000010931 gold Substances 0.000 description 10
- 229910052737 gold Inorganic materials 0.000 description 10
- -1 amine compound Chemical class 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 230000006866 deterioration Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- XDVOLDOITVSJGL-UHFFFAOYSA-N 3,7-dihydroxy-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B(O)OB2OB(O)OB1O2 XDVOLDOITVSJGL-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 231100001010 corrosive Toxicity 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000007598 dipping method Methods 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
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229960002989 glutamic acid Drugs 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
Classifications
-
- 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
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/282—Applying non-metallic protective coatings for inhibiting the corrosion of the circuit, e.g. for preserving the solderability
-
- 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
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/12—Using specific substances
- H05K2203/122—Organic non-polymeric compounds, e.g. oil, wax or thiol
- H05K2203/124—Heterocyclic organic compounds, e.g. azole, furan
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention provides a sealing agent and method of sealing, in which there is no problem of environmental pollution and anticorrosion performance equivalent or superior to that of the prior art can be realized by treatment therewith without detriment to solder wettability; and a printed circuit board having been treated with the sealing agent. There is provided a sealing agent comprising 0.001 to 0.1 % by weight in total of at least one member selected from among mercapto-having heterocyclic compounds and salts thereof and 0.01 to 1 % by weight of surfactant, which sealing agent is in the form of a solution having a pH value adjusted to 10 or below. Further, there are provided a method of sealing with the use of the sealing agent and a printed circuit board having been treated with the sealing agent.
Description
Technical field
The printed base plate that the present invention relates to the sealing of hole treatment agent, particularly has the nickel coating of metallic substance or sealing of hole treatment agent that nickel-containing alloys coating is used as the gold or the au-alloy plating material of substrate, sealing of hole treatment process and handle with this treatment agent.
Background technology
All the time, in the electronic unit field, require the contact portions of electronics of the reliability of height at robot calculator, signal equipment etc., people use gold plate always.
Under the situation that requires miniaturization, densification and high reliability of in recent years electronics, on electronic unit (junctor, switch, printed base plate etc.), carry out gold-plated ratio, than increasing in the past.
In general, gold-plated is to implement nickel plating on the mother metal to carry out after as substrate coating at copper.
In recent years, a lot of to the requirement of the economy of electronics.With regard to above-mentioned gold-plated with regard to because gold is expensive,, seek to reduce cost so generally make the very thin thickness of gold plate.
But, if make gold plate very thin, then the pin hole exponentially ground in the tunicle increases, because the corrosives (moisture, sulfide, muriate etc.) in the atmosphere is immersed in the contact part of interior gold of this pin hole and nickel, so the formation local element, corrosion substrate, blank.Because this corrosion product precipitate into the gold plate surface, so cause the problem of contact resistance deterioration etc.
As the method that addresses this problem, generally carry out sealing of hole and handle.Sealing of hole is handled, and comprises organic system and inorganic system.Organic system generally use halogen be organic solvent as solvent, therefore, to the influence of human body, the viewpoint that damages the ozone layer etc., existing problems to the influence of environment.With regard to inorganic be with regard to sealing of hole is handled, the known chromate process of people, but except contact resistance rises,, therefore also exist to human body and the influential problem of environment owing in solution, contain sexavalent chrome.
In order to address these problems, proposed with tensio-active agent and emulsifying agent the organic system stopper is dissolved in the water and water system sealing of hole treatment agent.
For example, a kind of water system sealing of hole treatment agent is disclosed in patent documentation 1, its contain as in the specific benzotriazole based compound of being selected from of stopper, mercaptobenzothiazole based compound and the triazine based compound more than a kind and lubricant, emulsifying agent.
In addition, a kind of water system sealing of hole treatment agent is disclosed in patent documentation 2, its contain as stopper be selected from benzotriazole based compound, mercaptobenzothiazole based compound and the triazine based compound more than a kind and tensio-active agent, amine compound.
Comprise above-mentioned patent, existing sealing of hole treatment agent is mainly used in the contact purposes of junctor etc., therefore need give plug.This requires characteristic, assign to realize by the one-tenth that coating on tunicle has an oilness, and then this effective constituent becomes the obstruction of the corrosion composition in the atmosphere, also gives solidity to corrosion.
But under the situation of the pad portion that existing sealing of hole treatment agent is used for printed base plate, owing to will be hydrophobic for fusing assistant, solder alloy that the purpose that improves wettability be coated with, the solder wetting that therefore has a pad portion is the problem of deterioration greatly.
Patent documentation 1: No. 2804453 communiques of Japanese Patent
Patent documentation 2: the spy opens the 2003-129257 communique
Summary of the invention
Therefore, it is a kind of no problem aspect environmental pollution to need, and by handling, has corrosion resisting property equal with currently available products or on it, and can not make the sealing of hole treatment agent and the sealing of hole treatment process of solder wetting deterioration.The objective of the invention is to, the printed base plate that can satisfy sealing of hole treatment agent this requirement, that improved and sealing of hole treatment process and handle with this treatment agent is provided.
In order to address the above problem, present inventors further investigate, and the result has invented following sealing of hole treatment agent and used the sealing of hole treatment process of this sealing of hole treatment agent.That is, the present invention is as follows.
(1) a kind of sealing of hole treatment agent contains and adds up to the hetero ring type compound or its salt that contains sulfydryl more than a kind or a kind of 0.001～0.1 weight % and the tensio-active agent of 0.01～1 weight %, and the pH regulator of solution is to smaller or equal in 10 the scope.
(2) as above-mentioned (1) described sealing of hole treatment agent, it is characterized in that, in the scope of the pH regulator to 8 of above-mentioned solution～10.
(3) a kind of sealing of hole treatment process is characterized in that, uses the described sealing of hole treatment agent in above-mentioned (1) or (2) to carry out sealing of hole and handles.
(4) a kind of printed base plate is characterized in that, uses the described sealing of hole treatment agent in above-mentioned (1) or (2) to handle.
Embodiment
First neccessary composition of sealing of hole treatment agent of the present invention selects to contain more than a kind or a kind of hetero ring type compound or its salt of sulfydryl, adds up in treatment agent and contains 0.001～0.1 weight %.The base metal nickel reactant of the pin hole inside of these compounds and gold plate generates complex compound, because pin hole is by this complex compound landfill, so the solidity to corrosion of gold plate improves.
As the hetero ring type compound that contains sulfydryl that uses among the present invention, preferably have 5 yuan of heterocycles or 6 yuan of heterocyclic compounds of containing at least one nitrogen, also can with the aromatic nucleus condensation.More preferably can list the represented compound of following formula.In addition, also can use their salt (sodium salt, sylvite, ammonium salt, amine salt etc.).
The addition of these compounds when less than 0.001 weight %, be can't see the sealing of hole treatment effect in the scope of 0.001～0.1 weight %, and when surpassing 0.1 weight %, finding has bad influence to contact resistance.Be preferably 0.005～0.05 weight %.
And then find that by adding the tensio-active agent of 0.01～1 weight %, solidity to corrosion improves.Can think that this is because tensio-active agent reduces the surface tension of water, contains the cause of the perviousness raising of hetero ring type compound or its salt in pin hole of sulfydryl.
When the addition of tensio-active agent during less than 0.1 weight %, can not obtain the above-mentioned sufficient perviousness in pin hole, can not obtain sufficient solidity to corrosion.In addition, when surpassing 1 weight %, the washing effect grow that tensio-active agent has, the absorption that contains the hetero ring type compound or its salt of sulfydryl is hindered, and therefore can not obtain effect of sufficient.
Tensio-active agent can suitably select to use commercially available negatively charged ion system, positively charged ion system, nonionic system and more than a kind or a kind of amphoterics.Particularly when using in the scope of the pH of solution 8～10, negatively charged ion system, nonionic system and more than a kind or a kind of amphoterics are used in preferred suitably selection.Wherein, in the anion surfactant, ethylene oxide adduct (number of moles of ethylene oxide 6～12), the medium alcohol ethylene oxide adduct (number of moles of ethylene oxide 6～12) of preferred especially nonylphenol.In addition, in anion surfactant, special preferably sulfuric acid salt type, phosphate type.
The sealing of hole treatment agent of putting down in writing in No. 2804453 communique of Japanese Patent by containing lubricant and emulsifying agent, forms the hydrophobicity tunicle, has given oilness, solidity to corrosion.In addition, the spy opens the sealing of hole treatment agent of putting down in writing in the 2003-129257 communique, by adding amine compound, makes the metallic surface demonstrate hydrophobicity, so solidity to corrosion improves.But if the metallic surface has hydrophobicity, it is hydrophobic then to use the fusing assistant, the solder alloy that are coated with in the purpose that improves wettability, so solder wetting deterioration greatly.
The present invention does not contain the above-mentioned composition to the metallic surface hydrophobic property, therefore can not make the solder wetting deterioration.
In addition, because hydrophobicity is little, so worry the solidity to corrosion deterioration, but, distinguish the osmosis of utilizing tensio-active agent to have in the present invention, promoted the complex compound of hetero ring type compound or its salt in pin hole, that contain sulfydryl to form, in addition, the pH by making solution also can obtain solidity to corrosion equal with existing sealing of hole treatment agent or on it smaller or equal to 10.
About the pH and the corrosion proof relation of solution, details is unclear, and still, pH tends to acidic side more from 10, and solidity to corrosion improves more.And then distinguish, when being when using in 8～10 the scope at pH, can give maximum solidity to corrosion.
In addition, the pH of solution is necessary for below 10, but when pH smaller or equal to 7 the time, under the high situation of the concentration of the hetero ring type compound or its salt that contains sulfydryl, sometimes produce the precipitation of the hetero ring type compound or its salt that contains sulfydryl through time ground, therefore from plating bath life-span and the consideration of process management aspect, also preferably in the scope of pH8～10, use.
Owing to the sealing of hole treatment trough, bring liquid into from former process, can envision in use, the pH of sealing of hole treatment soln fluctuates.In order to make this pH fluctuation be limited to inferior limit, preferably add the pH buffer reagent.As the material that in pH scope of the present invention, has the pH surge capability, can list an alkali metal salt, ammoniacal liquor, diethanolamine, diethylenetriamine of an alkali metal salt, the L-glutamic acid of an alkali metal salt, the tetraboric acid of an alkali metal salt, the boric acid of an alkali metal salt, the tripolyphosphate of tetra-sodium etc.
Sealing of hole treatment agent of the present invention has mentioned component, but as solvent, can suitably select from the not halogen-containing organic solvent of water or ethanol, acetone, n-paraffin etc.But, if consider economy, inflammableness etc., as solvent, water most preferably.At solvent is under the situation of water, if the temperature of solution is heated to 40～80 ℃, then the emulsification of composition in water becomes faster, and then it is easy that the drying of the material after the processing becomes.
As treatment process, also can use any method that the plating product is immersed in the treatment agent, sprays or is coated with cloth treating agent etc.But in the present invention, no matter the shape of plating product is lath, or pressed part, if behind plating just, promptly be tinuous production, then handles in this production line, so the effect height of the various functions of raising handled of sealing of hole.In addition, it also is effective the plating product being carried out sealing of hole processing with sealing of hole treatment agent of the present invention after the processing of compacting etc.Even carried out the metallic substance that sealing of hole is handled behind plating, in the operation of the compacting oil that washing is adhered in press process thereafter, sealing of hole is handled a lot of functions and is also lost.Under the sort of situation, it is effective that sealing of hole is once more handled.
In addition, using sealing of hole treatment agent of the present invention to handle under the situation of printed base plate, do not making the solder wetting deterioration and can obtain to have printed base plate equal with currently available products or the corrosion resisting property on it.
Embodiment
Enumerate embodiment below and describe the present invention in detail.
Embodiment 1～9 and comparative example 1～8
(C5210,25mm * 20mm * 0.4mm), carry out the nickel plating of 1 μ m by the watt plating bath carries out the gold-plated of 0.1 μ m thereon with the cyanogen plating bath with the phosphor bronze substrate to spring.
This gold-plated substrate is adopted the sealing of hole treatment agent of forming shown in the table 1, under 50 ℃ of bath temperature, 20 seconds condition of dipping time, handle,, on gold plate, formed sealing of hole and handled tunicle by carrying out washing and drying.In addition, the solvent of sealing of hole treatment agent has used ion exchanged water.
For having carried out the substrate that sealing of hole is handled, carry out following evaluation.The result is as shown in table 1.Salt spray testing
To these substrates, carry out 24 hours salt spray testing (according to JISZ2371), carried out the solidity to corrosion evaluation.
Metewand
Zero: basic not corrosion
△: can both see umbrinaceous hot spot everywhere
*: can both see green hot spot (bluish-green) solder wetting everywhere
In addition, to these substrates, whole coating fusing assistant (RM-26, the development of タ system ラization) is carried out the liquid that 2 times of dilutions are obtained with Virahol, place after 10 minutes, place 5 solder balls (ス バ ヘ ケ リ ニ ダ ボ ヘ Le S, Sn-37%Pb, Φ 0.6mm, thousand lives metal industry (strain) system), remaining on 150 ℃ the hot-plate after the heating 2 minutes (preheating), remaining on 230 ℃ the hot-plate heating 30 seconds.The evaluation of solder wetting is by measuring the wetting expanding area of the solder ball after the heating, is (n=5) that benchmark carries out with the wetting expanding area of the solder ball that do not carry out the substrate that sealing of hole handles.
The solder wetting metewand
Zero: the wetting expanding area of solder ball〉untreated wetting expanding area * 0.95
*: the wetting expanding area of solder ball＜untreated wetting expanding area * 0.7
In addition, as a comparative example, also in the lump disclosed substrate (comparative example 7) and the special disclosed substrate (comparative example 8) that has carried out handling of 2003-129257 communique of opening that has carried out handling of No. 2804453 communiques of Japanese Patent estimated.Composed as follows.In addition, the evaluation test result is shown in table 1 in the lump.
Comparative example 7 (the sealing of hole treatment agent of No. 2804453 communique record of Japanese Patent)
Stopper: benzotriazole 0.01 weight %
Lubricant: oleic acid 0.3 weight %
Emulsifying agent: lauryl acid phosphate monoester 0.3 weight %
Comparative example 8 (spy opens the sealing of hole treatment agent of 2003-129257 communique record)
Stopper: benzotriazole 0.05 weight %
Amine compound: trolamine 1 weight %
Phosphoric acid ester is a tensio-active agent: EN-2P (blue or green wooden oil industry system) 0.1 weight %
Show that by above result sealing of hole treatment agent of the present invention does not contain the material of contaminate environment, and, with the plating material that sealing of hole treatment agent of the present invention is handled, have corrosion resisting property equal with currently available products or on it, and can not make the solder wetting deterioration.
Claims (3)
1. sealing of hole treatment agent, it is the sealing of hole treatment agent that forms by the tensio-active agent of the hetero ring type compound or its salt that contains sulfydryl more than a kind that adds up to 0.001～0.1 weight %, 0.01～1 weight %, as the water and the pH buffer reagent of solvent in fact, the pH of the solution of described sealing of hole treatment agent is adjusted to 8～10 scope, and does not wherein contain lubricant.
2. a sealing of hole treatment process is characterized in that, uses the described sealing of hole treatment agent of claim 1 to carry out sealing of hole and handles.
3. a printed base plate is characterized in that, uses the described sealing of hole treatment agent of claim 1 to handle.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP023280/2004 | 2004-01-30 | ||
| JP2004023280 | 2004-01-30 | ||
| PCT/JP2005/000754 WO2005073435A1 (en) | 2004-01-30 | 2005-01-21 | Sealing agent, method of sealing and printed circuit board treated with the sealing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1914359A CN1914359A (en) | 2007-02-14 |
| CN1914359B true CN1914359B (en) | 2011-12-28 |
Family
ID=34823864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005800035457A Active CN1914359B (en) | 2004-01-30 | 2005-01-21 | Sealing agent, method of sealing and printed circuit board treated with the sealing agent |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4397376B2 (en) |
| CN (1) | CN1914359B (en) |
| TW (1) | TWI268967B (en) |
| WO (1) | WO2005073435A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7883738B2 (en) * | 2007-04-18 | 2011-02-08 | Enthone Inc. | Metallic surface enhancement |
| CN101580951B (en) * | 2008-05-12 | 2011-03-30 | 比亚迪股份有限公司 | Method for improving corrosion resistance of chromeplated product |
| JP5666940B2 (en) * | 2011-02-21 | 2015-02-12 | 株式会社大和化成研究所 | SEALING AGENT SOLUTION AND SEALING TREATMENT METHOD USING THE SAME |
| US20190112726A1 (en) * | 2016-03-28 | 2019-04-18 | Okuno Chemical Industries Co., Ltd. | Sealing liquid for anodic oxide coating films of aluminum alloy, concentrated liquid and sealing method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03215697A (en) * | 1990-01-19 | 1991-09-20 | Meidensha Corp | Method for sealing metallic material |
| JPH05311495A (en) * | 1991-12-25 | 1993-11-22 | Nikko Kinzoku Kk | Hole sealing treatment of noble metal plated material |
| JP3870225B2 (en) * | 2001-10-19 | 2007-01-17 | ユケン工業株式会社 | Gold plating sealing agent and method |
-
2005
- 2005-01-21 JP JP2005517426A patent/JP4397376B2/en active Active
- 2005-01-21 WO PCT/JP2005/000754 patent/WO2005073435A1/en active Application Filing
- 2005-01-21 CN CN2005800035457A patent/CN1914359B/en active Active
- 2005-01-27 TW TW094102439A patent/TWI268967B/en active
Non-Patent Citations (1)
| Title |
|---|
| JP特开平8-260194A 1996.10.08 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4397376B2 (en) | 2010-01-13 |
| CN1914359A (en) | 2007-02-14 |
| WO2005073435A1 (en) | 2005-08-11 |
| TWI268967B (en) | 2006-12-21 |
| JPWO2005073435A1 (en) | 2007-09-13 |
| TW200526817A (en) | 2005-08-16 |
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