CN101705483A - Water soluble anti-discoloration after treating agent for noble metal, copper and copper alloy - Google Patents
Water soluble anti-discoloration after treating agent for noble metal, copper and copper alloy Download PDFInfo
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- CN101705483A CN101705483A CN200910154618A CN200910154618A CN101705483A CN 101705483 A CN101705483 A CN 101705483A CN 200910154618 A CN200910154618 A CN 200910154618A CN 200910154618 A CN200910154618 A CN 200910154618A CN 101705483 A CN101705483 A CN 101705483A
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- copper
- alkyl
- discoloration
- water soluble
- treating agent
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Abstract
The invention relates to a water soluble anti-discoloration after treating agent for noble metal, copper and a copper alloy, which comprises at least one compound of linear alkyl sulfhydryl, sulfydryl aromatics and derivatives thereof, phenyl sulfide and derivatives thereof, sulfydryl alkyl acetate, dialkylsulfide, alkyl dithiol and dialkylsulfide, and also comprises at least one amphoteric non-ionic surface active agent or organic solvent. The water soluble anti-discoloration after treating agent can form a self-assembled monomolecular film on the surface of the noble metal, the copper and the copper alloy, has excellent protective properties, and particularly has more obvious protection effect on gold, a gold -cobalt alloy, copper, a copper zinc alloy, a copper tin alloy, Jacksonalloy, and copper-nickel alloy.
Description
Technical field
The invention belongs to the anticorrosive metal technical field; belong to precious metal, copper and copper alloy anticorrosion technique field especially; especially the post-treatment agent that relates to a kind of water soluble anti-discoloration, it is applicable to protection and prevents the oxidized or variable color of precious metal, copper and copper alloy or be corroded.
Background technology
In most of electronic products protection against chemical product prescription, the anticorrosive metal agent is widely used, its objective is that to prevent precious metal, copper and copper alloy oxidized in environment for use, thereby prevent that the electronic product contact resistance from increasing, the generation of problems such as weldability can descend, reduction in work-ing life.
Self-assembled monolayer (SAMs) is a kind of novel organic superthin membrane technique that just grows up over nearly 20 years.The generation of self-assembled monolayer is a spontaneous process, metal or metal oxide immersion are contained in the dilute solution of bioactive molecule, by chemical bond spontaneous be adsorbed on the orientation that forms on the substrate regular, arrange closely unimolecular film in order, and have high stability.SAMs can be divided into three parts on structure, and the one, the head base of molecule, it combines with covalent linkage (as the Au-S key) with reflecting point on the substrate surface, and this reaction is thermopositive reaction, and bioactive molecule can occupy the reflecting point of substrate surface as far as possible; The 2nd, the alkyl chain of molecule, interchain makes bioactive molecule arrange in order and closely at solid surface by the Van der Waals force effect, can introduce special group by molecular designing in the middle of the molecular chain, therefore make SAMs have special physicochemical character, the surface physics chemical property that can obtain to expect by autonomous design molecular structure and surface tissue; The 3rd, the molecular end group, as-CH
3, COOH ,-OH ,-NH
2,-SH ,-CH
2-CH
3Be by selecting end group to construct multilayer film Deng, its meaning with the interface that obtains different physical and chemical performances or by its reactive behavior.Selectable molecule head base, tail based structures provide the research base material with the arrangement of molecule interfacial film and grow, adhere to, the good system of phenomenons such as wettability, corrosion.
In the electronic product, gold-plated, copper plate have good electrical conductivity, thermal conductivity, weldability, stability and with the reliable sticking power of matrix, therefore, electrogilding, electro-coppering are widely used in industries such as electronics, communication, electrician and decorations, particularly in the manufacturing processed of electronic connector, semi-conductor (LED), circuit lead frame (IC Load Frame), wave filter, often all to carry out gold-plated, copper plating treatment.Because price of gold lattice costliness, major part is only carried out flash during plating, coating as thin as a wafer, corrosion resistance is not enough, and the production of above-mentioned electronic devices and components, transportation, installation and between the usage period, with the H in the environment
2S, SO
2, CO
2, NO
XWhen contacting, even when being subjected to UV-irradiation, all very easily generate corresponding corrosion product, make its variable color blackout, can destroy the original electric property of coating widely like this at coating surface Deng gas.Adopt chemical passivation, electrolytic passivation, coating solvent-borne type protective material can improve the be corroded phenomenon of variable color of coating to some extent.But the chemical passivation method easily causes Cr
6+Pollute, the electrolytic passivation method has Cr equally
6+Pollution problems; And apply the solvent-borne type protective material, and solvent can polluted air, degradation manipulation environment, and most of solvent has carinogenicity, and also there be contact resistance and the weldability problem of influencing in above protective material.At above problem, CN101353800A has proposed to adopt linear saturated alkane mercaptan as silver protecting agent, but the protection of gold, copper and copper alloy is not made a search.
Summary of the invention
The present invention is directed to the defective that above-mentioned prior art exists; a kind of water soluble anti-discoloration after treating agent (or claiming protective material, oxidation inhibitor, passivator) that is used for precious metal, copper and copper alloy has been proposed; adopt this water soluble anti-discoloration after treating agent; can form self-assembled monolayer at precious metal, copper and copper alloy surface; have excellent barrier propterty, especially more remarkable for the protection effect of gold, gold cobalt alloy, copper and copper zinc alloy, gunmetal, Albaloy, cupronickel.
The technical scheme that technical solution problem of the present invention is taked is: a kind of precious metal that is used for, the water soluble anti-discoloration after treating agent of copper and copper alloy, it comprises at least a compound that is selected from straight chained alkyl mercaptan, sulfydryl aromatic hydrocarbon and derivative, diphenyl sulfide and derivative thereof, Thiovanic acid alkyl ester, dialkyl sulfide, alkyl two mercaptan or dialkyl group disulfide; It also comprises at least a both sexes, nonionogenic tenside or the organic solvent that can effectively dissolve described compound.
Described straight chained alkyl mercaptan, sulfydryl aromatic hydrocarbon and derivative thereof have the R1-SH structure, and wherein R1 is C
4～C
24Alkyl, aryl or polyaryl and derivative, C
1～C
12Alkaryl, C
1～C
12Cycloalkyl, C
4～C
24Alkoxyl group, C
4～C
24Many alkoxyl groups, C
4～C
24Alkyl carboxyl, C
4～C
24Alkylamino, C
4～C
24Haloalkyl, C
4～C
24Halogenated aryl.
Described Thiovanic acid alkyl ester has following structure:
Wherein R2 is C
12～C
24Alkyl or alkenyl.
Described dialkyl sulfide, dialkyl group disulfide and diphenyl sulfide and derivative thereof have R3-S-R3 and R3-S-S-R3 structure respectively, and wherein R3 is C
8～C
24Alkyl or alkenyl, phenyl or sulfydryl benzene.
Described alkyl two mercaptan have the HS-R4-SH structure, and wherein R4 is C
4～C
18Alkyl.
Described sulfydryl aromatic hydrocarbon and derivative thereof have following structure:
Wherein R5 and R6 are respectively C
1～C
12Alkyl, aryl, hydrogen, sulphur, sulfydryl, nitro or halogen.
Described phenyl or sulfydryl benzene have following structure:
Wherein R7 is hydrogen or sulfydryl.
Described precious metal, copper and copper alloy refer in particular to gold, gold cobalt alloy, copper and copper zinc alloy, gunmetal, Albaloy, cupronickel.
The inventor is through research trial repeatedly, employing self-assembled monolayer (SAMs) technology has been proposed, utilize one or more major ingredient of straight chained alkyl mercaptan, sulfydryl aromatic hydrocarbon and derivative thereof, Thiovanic acid alkyl ester, dialkyl sulfide or dialkyl group disulfide as the water soluble anti-discoloration after treating agent of precious metal, copper and copper alloy, show through the reality use, functional.
The major ingredient of water soluble anti-discoloration after treating agent of the present invention is a straight chained alkyl mercaptan, sulfydryl aromatic hydrocarbon and derivative thereof, diphenyl sulfide and derivative thereof, the Thiovanic acid alkyl ester, dialkyl sulfide, one or more of alkyl two mercaptan or dialkyl group disulfide, can dissolve or directly be dispersed in one or more both sexes, in the nonionic aqueous surfactant, gained solution or dispersion can further be diluted, certainly also can add components such as wetting agent. it is applicable to the processing precious metal, copper and copper alloy, be particularly useful for gold, gold cobalt alloy, copper and copper zinc alloy, gunmetal, Albaloy, cupronickel, protection effect is remarkable, and the preparation method is simple relatively.
The invention provides a kind of cost low, pollution-free and stable high water-soluble precious metal, copper and copper alloy protective material, and this protectant preparation method.In order to make purpose of the present invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.All any modifications of being done within the spirit and principles in the present invention, be equal to and replace and improvement etc., all should be included within protection scope of the present invention.
Embodiment
Embodiment 1
Getting weight is that 80 gram OP-10 emulsifying agents mix with the 20 linear saturated alkane mercaptan of gram (stearylmercaptan), and under 50 ℃～70 ℃ temperature, thorough mixing is even.
Embodiment 2
Getting weight is that 60 fatty alcohol-polyoxyethylene ether that restrain, 25 gram DOW wetting agent CF-10 and 10 gram linear saturated alkane mercaptan (stearylmercaptan), 5 gram Thiovanic acid alkyl esters mix fully emulsified under 60 ℃ of temperature, mixing.
Embodiment 3
Getting weight is the polyoxyethylene nonylphenol ether of 90 grams, 10 gram dipropyl disulfides, and under 50 ℃～70 ℃ temperature, thorough mixing is even.
Performance test: get 20 times of the foregoing descriptions 1, embodiment 2, embodiment 3 gained protective material dilute with waters, keep certain temperature, gold-plated, copper facing or copper alloy product were immersed wherein 2 minutes, it is clean to take out washing, tests after the drying.
Each embodiment detected result
| Embodiment | Copper protection neutral salt spray test (hour) | Gold nitric acid sealing of hole test (branch) | Conclusion |
| Embodiment 1 | ??24h | ??30 | Qualified |
| Embodiment 2 | ??36h | ??40 | Qualified |
| Embodiment 3 | ??24h | ??30 | Qualified |
Claims (9)
1. water soluble anti-discoloration after treating agent that is used for precious metal, copper and copper alloy, it is characterized in that, comprise at least a compound that is selected from straight chained alkyl mercaptan, sulfydryl aromatic hydrocarbon and derivative, diphenyl sulfide and derivative thereof, Thiovanic acid alkyl ester, dialkyl sulfide, alkyl two mercaptan or dialkyl group disulfide.
2. water soluble anti-discoloration after treating agent as claimed in claim 1 is characterized in that, described straight chained alkyl mercaptan, sulfydryl aromatic hydrocarbon and derivative thereof have following structure:
R1-SH，
Wherein R1 is C
4～C
24Alkyl, aryl or polyaryl and derivative, C
1～C
12Alkaryl, C
1～C
12Cycloalkyl, C
4～C
24Alkoxyl group, C
4～C
24Many alkoxyl groups, C
4～C
24Alkyl carboxyl, C
4～C
24Alkylamino, C
4～C
24Haloalkyl, C
4～C
24Halogenated aryl.
3. water soluble anti-discoloration after treating agent as claimed in claim 1 is characterized in that, described Thiovanic acid alkyl ester has following structure:
Wherein R2 is C
12～C
24Alkyl or alkenyl.
4. water soluble anti-discoloration after treating agent as claimed in claim 1 is characterized in that, described dialkyl sulfide, dialkyl group disulfide and diphenyl sulfide and derivative thereof have following structure respectively:
R3-S-R3 and R3-S-S-R3,
Wherein R3 is C
8～C
24Alkyl or alkenyl, phenyl or sulfydryl benzene.
5. water soluble anti-discoloration after treating agent as claimed in claim 1 is characterized in that, described alkyl two mercaptan have following structure:
HS-R4-SH，
Wherein R4 is C
4～C
18Alkyl.
6. water soluble anti-discoloration after treating agent as claimed in claim 1 is characterized in that, described sulfydryl aromatic hydrocarbon and derivative thereof have following structure:
Wherein R5 and R6 are respectively C
1～C
12Alkyl, aryl, hydrogen, sulphur, sulfydryl, nitro or halogen.
7. phenyl as claimed in claim 4 or sulfydryl benzene have following structure:
Wherein R7 is hydrogen or sulfydryl.
8. water soluble anti-discoloration after treating agent as claimed in claim 1 is characterized in that described precious metal refers in particular to gold, gold cobalt alloy.
9. water soluble anti-discoloration after treating agent as claimed in claim 1 is characterized in that described copper and copper alloy refer in particular to copper, copper zinc alloy, gunmetal, Albaloy, cupronickel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910154618A CN101705483A (en) | 2009-11-16 | 2009-11-16 | Water soluble anti-discoloration after treating agent for noble metal, copper and copper alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910154618A CN101705483A (en) | 2009-11-16 | 2009-11-16 | Water soluble anti-discoloration after treating agent for noble metal, copper and copper alloy |
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| Publication Number | Publication Date |
|---|---|
| CN101705483A true CN101705483A (en) | 2010-05-12 |
Family
ID=42375733
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910154618A Pending CN101705483A (en) | 2009-11-16 | 2009-11-16 | Water soluble anti-discoloration after treating agent for noble metal, copper and copper alloy |
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|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109097759A (en) * | 2018-09-19 | 2018-12-28 | 深圳市傲新源科技有限公司 | A kind of gold and silver coating Anti- tarnishing protective agent and preparation method thereof and application method |
| US11365481B2 (en) | 2015-10-06 | 2022-06-21 | City University Of Hong Kong | Homogeneous and transparent protective coatings for precious metals and copper alloys |
| CN114959715A (en) * | 2022-05-17 | 2022-08-30 | 中北大学 | Preparation and corrosion inhibition application of thioether copper-based self-assembled film |
-
2009
- 2009-11-16 CN CN200910154618A patent/CN101705483A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11365481B2 (en) | 2015-10-06 | 2022-06-21 | City University Of Hong Kong | Homogeneous and transparent protective coatings for precious metals and copper alloys |
| CN109097759A (en) * | 2018-09-19 | 2018-12-28 | 深圳市傲新源科技有限公司 | A kind of gold and silver coating Anti- tarnishing protective agent and preparation method thereof and application method |
| CN109097759B (en) * | 2018-09-19 | 2019-07-26 | 深圳市傲新源科技有限公司 | A kind of gold and silver coating Anti- tarnishing protective agent and preparation method thereof and application method |
| CN114959715A (en) * | 2022-05-17 | 2022-08-30 | 中北大学 | Preparation and corrosion inhibition application of thioether copper-based self-assembled film |
| CN114959715B (en) * | 2022-05-17 | 2024-02-06 | 中北大学 | Preparation and corrosion inhibition application of thioether copper-based self-assembled film |
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Open date: 20100512 |