CN103726056A - Method for preparing water-soluble molecular self-assembly film type metal protective agent - Google Patents
Method for preparing water-soluble molecular self-assembly film type metal protective agent Download PDFInfo
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Abstract
The invention discloses a method for preparing a water-soluble molecular self-assembly film type metal protective agent. The method comprises the following steps: A, mixing water and an organic solvent of which the mass ratio is (0.5-1.5);10, uniformly stirring, and preparing a mixed solvent; B, adding an emulsifier which accounts for 30-50 percent of the mass of the mixed solvent in the step A, uniformly stirring, and preparing a mixture; C, adding a film agent which accounts for 12-20 percent of the mass of the mixture in the step B, uniformly stirring, and further preparing a mixed solution; and D, adding a surfactant which accounts for 1.5-2.0 percent of the mass of the mixed solution and a reducing agent which accounts for 0.1-0.5 percent of the mass of the mixed solution in the step C, heating under water bath conditions at the temperature of 51-58 DEG C, controlling the temperature of the mixed solution, continuously stirring for 90-150 minutes, thereby obtaining the water-soluble molecular self-assembly film type metal protective agent. The method is simple in process, low in energy consumption and environmental friendly, a molecular self-assembly film can be formed on the metal surface through the protective agent, and the metal is effectively prevented from discoloring. The method is simple in process and large-scale production is easy to realize.
Description
Technical field
The present invention relates to metal protection agent field, be specifically related to the protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal.The prepared a kind of water soluble molecules self-assembled film shaped metal protective material of this technology can be used for the rust protection protection of various electroplating technology device metal coating, various metal historical relics etc.
Background technology
The resistivity of common platinum, gold and silver, nickel, copper, aluminium is respectively 10.6,2.4,1.58,6.8,1.67,2.66 μ Ω cm, and the thermal conductivity of these platinum, gold and silver, nickel, copper, aluminium is respectively 0.72,3.17,4.29,0.91,4.01,2.37 Wcm
-1k
-1, as can be seen here, comprehensive resistivity and thermal conductivity ratio, the conduction thermal resistance better performances of gold and silver.In addition, gold and silver also have many good characteristics, and as silver also has high reflective, its reflectivity is up to 95%, and gold and silver have higher chemical stability, and weldability and ductility are also splendid.Based on these good physics, the chemical property of gold and silver, gold and silver are in electronic industry, signal equipment, instrument, aircraft, opticinstrument, high-frequency component and waveguide, and the aspect such as ornament, decoration is widely applied.But gold and silver are as precious metal, and its application cost is higher, therefore generally take the surperficial plating one deck of the base metal good at conductivity (as copper) silver metal, so not only make its premium properties that has gold and silver, and save cost.In recent years, in space flight and aviation such as navigation, control, communications, with gold and silver electroplating device in electronic instrument and meter and equipment, obtained application widely.
Although with many metallographic phase ratios, the chemical stability of gold and silver, nickel is good, has stronger corrosion resistance, the variable color of all can getting rusty in use, storage and transportation.If silver features and silvering long-term exposure are in malaria, be subject in air various volatile sulfur compoundses (as H
2s, CS
2, OCS), oxide compound (SO
2, NO
xdeng), (airborne muriate is mainly derived from the atomization of burning of coal, waste incineration, volcanicity, sewage disposal, sea salt and seawater, and the photo-chemical smog of atmospheric polluting material etc. for oxygen, ozone and halogenide; Indoor muriate is mainly slowly to be decomposed and cause by industrial cleaning agent, refrigeration agent and plastics etc.) etc. corrosion, make silver features surface obfuscation variable color, the appearance luster that not only affects silverware or silver-plated goods reduces decorate properties, and more seriously affects welding property and the electrical specification of electronic product silver plate.Research shows that variable color makes silvered film surface resistivity increase approximately 20～80%, and electric energy loss increases, thereby the stability of electronics, reliability are greatly reduced, and even causes major accident.Therefore, no matter be as functional material, or the silver plate of decorative use, all must be through anti-variable color processing, to improve its corrosion resistance after plating.
Under prior art condition, prevent that the major technique of burning variable color from having: anti-variable color alloy (as yellow gold, Stainless Steel Alloy etc.), employing plating or ion sputtering are at other metal of metallic surface plating (nickel layer, silvered film and platinum plating layer, Gold plated Layer etc.), chemical passivation (K
2cr
2o
7-Glacial acetic acid, two blunt method and K
2cr
2o
7-nitric acid Passivation Treatment), electrochemical passivation, galvanic couple passivation (negative electrode or anodic protection etc.), deposited oxide film, metallic surface rust protection coating treatment technology (as organic absorption passivation layer, resin coating, plasma polymerization film, self-assembled film etc.), compound organic anti-blushing agent etc. (Yang Changjiang. gold and silver coin Discoloration mechanism and anti-discolouring technology research [D]. Dalian University of Technology's doctorate paper, 2008).For the resist technology of silvering, the anti-variable color technique early adopting is electrophoresis beryllium hydroxide.Although the anti-silver-colored color changeable effect of this technology is better, because processing condition are comparatively harsh, be therefore difficult to apply in industrial production.Proposed again to be subsequently coated with the anti-variable color technique of organic oil film; the organism of coating comprises benzene wax silicon solution, paraffin-toluene solution, Vaseline-toluene solution; though this technique can protect silver not to be subject to the corrosion of Atmospheric Sulfur compound to a certain extent, this class oiliness film is easily stained with ash and space is many.Then adopt rosin-toluene proofing liquid, epoxy resin-polystyrene-ceresine-rosin to merge the inhibiter in organic solvent solution configurations such as toluene, the effect of the anti-silver-colored variable color of this type of film is better, but contact electricity performance, solderability decline (Li Hanye. copper base is electroplated the preapre for an unfavorable turn of events research [D] of look of silver layer. Northeastern University's master thesis, 2005).In addition, as previously mentioned, at the more metal of inertia of silvered film electroplating surface, as germanium, platinum or gold etc., inert metal alloy method prevents that silver-colored color changeable effect is better, little on impacts such as plating piece electric property, decoration and performances attractive in appearance, but the composition of alloy has very strict requirement, the manufacturing process of alloy is also very complicated, and raw materials cost and manufacturing technology cost are all higher, only on the key part of having relatively high expectations, just adopted, be difficult to adapt to large-scale industrial application.
Along with the development of related industries technology and the world, the domestic pay attention to day by day to environment protection, in following decades, comprise heavy metal ion (as Cr
3+, CrO
4 2-deng) surface treatment agent will progressively limit and use and be progressively eliminated, and the usage quantity of the environmentally friendly metal conditioner of new type water-solubility, protective material etc. will significantly increase.At present, the product in China's Mainland water-soluble metal protective material market is mainly main by the areas such as TaiWan, China, Singapore, Japan, Germany and national company.And the use of the water-soluble protective material product of American-European Main Developed Countries reaches more than 85%, China's Mainland electronics industry, metal protection field, electroplating industry field etc., the protectant ratio less than 40% of water-soluble metal of using.The anti-variable color protective material of visible China's Mainland water-soluble metal market potential is huge.
Correlative study and the disclosed patented technology of the resist technologies of domestic and international metal protective material, anti-silver-colored variable color and preventing metal corrosion etc. occur in a large number.The Chinese patent of patent No. ZL200710075422.5 discloses " a kind of water-soluble silver protecting agent and preparation method thereof ", the disclosed technology of this patent is silver protecting agent: the linear saturated alkane mercaptan that to utilize carbochain be 12-24, and carbochain is no more than oligopolymer wetting agent and the emulsifying agent composition of the hydroxyl functional group of 12; Its preparation method is, is being not less than at 60 ℃ of temperature, by linear saturated alkane mercaptan, wetting agent with emulsifying agent is fully emulsified, evenly mix.The Chinese patent of number of patent application 201010193567.7 also discloses a kind of " electric-contact metal protectant "; this invention technology relates to a kind of surface protectant that is mainly used in electronic devices and components and preparation method thereof; there are 3.0～8.0% filmogen, 2.5～5.0% organic inhibitor, 1.5～3.0% soldering flux, 2.5～5.0% lubricant; surplus is solvent, after mixing, heating, makes.The Chinese patent of number of patent application 201010535197.0 also discloses " a kind of anti-silver-colored off-color material and its preparation method and application ", and this material molecule structural formula is expressed as II, the R in molecular formula be on phenyl ring in ortho position, a position or contraposition, R is expressed as C
nh
2n+1-group, n=0～8, n is integer.This disclosure of the invention preparation method and the application of this anti-silver-colored off-color material.This application specification sheets claims: the prepared material discoloration-resisting of this invention technology is good, can guarantee well again ag material pliability simultaneously, is applicable in application and pregnant woman's radioprotective clothes; Entirety synthesis technique is simple, only needs single step reaction and flash liberation; Coating processes can be various, can, by directly making from solution spin coating, also can spray.The Chinese patent of number of patent application 201210389716.0 discloses " a kind of iron and steel/cast iron metal protection agent and preparation method thereof ", and the disclosure technology adopts weight proportion to be respectively phytic acid 6-20%; Organic phosphates corrosion inhibiting and descaling agent 10-35%; High molecular polymer 0.5-2%; Aluminum orthophoshpate, zinc hydrate 2.5-6%; 5-nitro isophthalic ester zinc 0.1-0.5%; Water surplus; Preparation method is: water is added in reactor, add phytic acid, organic phosphates corrosion inhibiting and descaling agent, high molecular polymer to stir, under agitation add aluminum orthophoshpate, zinc hydrate and 5-nitro isophthalic ester zinc to stir and completely dissolve and form to material for 60-120 minute.The Chinese patent of number of patent application 201310212527.6 discloses " a kind of part aqueous metal protection agent and production technique thereof ", it comprises monomer, molecular weight adjusting agent and initiator, described monomer comprises that massfraction is the methyl methacrylate of 20%-40%, massfraction is the butyl acrylate of 20%-40%, massfraction is the vinylformic acid of 10%-18%, massfraction is the vinylbenzene of 5%-15% and the Hydroxyethyl acrylate that massfraction is 8%-15%, the amount that described molecular weight adjusting agent is added is the 0.1%-2% of described monomer total mass, the amount that described initiator adds is the 0.1%-5% of described monomer total mass.In addition, No. 4948523 patents of the U.S. disclose " a kind of composition without chlorine silver protecting lubricants ", and the disclosed silver protecting agent of this technology is by phosphorodithioic acid dialkyl ester salt compound, the C of zinc
5～C
60carboxylic acid and (1) guanidine, urea and thiourea compound; (2) to C
1～C
20alkyl or the alkyl monoamine that replaces of hydroxyl, at least one in polyalkylene polyamine and the N-alkyl glycine of Alkylenediamine and (3) is prepared from.
There is obvious defect in existing metal protection and silver protecting agent technology:
First; although alloy technology has good effect to metal protection and anti-variable color etc.; but the composition of alloy has very strict requirement; the manufacturing process of alloy is also very complicated; raw materials cost and manufacturing technology cost are all higher; only on the key part of having relatively high expectations, just adopted, difficulty is suitable for large-scale industrial application.
Second; electroplating technology is the same with alloy technology; although have and prevent preferably metal variable color and rust-proof effect; but electroplating technical conditions is comparatively harsh; Technology is had relatively high expectations, and in the application of the related fields such as metal historical relic's protection and decoration, jewel, is obviously restricted, and also needs additionally to use corresponding resist technology after plating; therefore, the practical application of electroplating technology is subject to larger restriction equally.
The 3rd, the chemical processing agent that the technology such as chemical passivation, galvanic couple passivation etc. are used or there is heavy metal ion (Cr
3+, CrO
4 2-deng) problem such as pollution to environment, have consumption to electric energy and the process technology limit of electrochemical techniques, use procedure always may produce more waste, pollutent and toxic product or consume the more energy or Technology itself requires the defects such as harshness.
The 4th; existing metallic surface rust protection coating treatment technology (as organic absorption passivation layer, resin coating, plasma polymerization film etc.); exist operation complexity or use range not extensive; manufacture protectant synthesis cycle longer; or complex process, produce starting material and production technology cost higher, or use procedure produces environmental pollution or the protection DeGrain to metal etc.; both be difficult to be widely used, and be also difficult to realize large-scale industrial and produce.
The 5th, the protectant preparation of existing water-soluble metal and production technology process, owing to having adopted the large or higher starting material of fusing point of complicated chemical reaction or molecular weight, there is preparation, reaction process complexity or operation complexity (as the Chinese patent of application number 201310212527.6 comprises 7 ~ 8 or more more complicated preparation processes), temperature of reaction higher (the control temperature of Technology of preparing water-soluble silver protecting agent as the Chinese patent of patent No. ZL200710075422.5 is for being not less than 60 ℃ (referring to its specification digest) equally; The reaction reflux temperature of the Chinese patent technology of application number 201310212527.6 is 85～90 ℃, 100～103 ℃) etc. deficiency, directly making to prepare protective material equipment and processing requirement improves, energy consumption is high, directly raising of manufacturing cost, use cost undoubtedly.
The 6th, the scope that the protectant protection effect of existing water-soluble metal is undesirable, protective material is applicable is not extensive yet.Protective material prepared by the Chinese patent technology that the protective material of preparing as the Chinese patent technology of patent No. ZL200710075422.5 is 201010535197.0 for " a kind of water-soluble silver protecting agent " and application number is " a kind of anti-silver-colored off-color material and its preparation method and application ", namely only limits the use of in the anti-variable color of silver and protects; The Chinese patent of application number 201210389716.0 discloses " a kind of iron and steel/cast iron metal protection agent and preparation method thereof " prepared protective material and has been only applicable to the corrosion protection of iron and steel and cast iron.
In addition; the technology of the disclosed one of Chinese patent " electric-contact metal protectant " of number of patent application 201010193567.7; relate to a kind of surface protectant that is mainly used in electronic devices and components and preparation method thereof; there are 3.0～8.0% filmogen, 2.5～5.0% organic inhibitor, 1.5～3.0% soldering flux, 2.5～5.0% lubricant; surplus is solvent, after mixing, heating, makes.The obvious raw material type of this invention technology is more, technique is comparatively complicated, and production technology cost is obviously higher, and its protective material is also only applicable to the protection of electronic devices and components, and obviously the scope of application is not extensive, and its defect and deficiency are apparent.
Summary of the invention
In order to solve existing metal protection agent and the existing deficiency of technology of preparing thereof, the object of the invention is to be to provide a kind of water soluble molecules self-assembled film shaped metal protectant preparation method.Technical process of the present invention is simple, and because used raw material is the lower low polymerization degree organism of fusing point or more micromolecular organism, the consistency between raw material thing is good, the control of preparation process temperature is lower, without special equipment requirements, with short production cycle when energy consumption is low, production efficiency is high; The advantages of nontoxic raw materials that the prepared protective material of the technology of the present invention is used or low toxicity; The metal protection agent good water solubility of preparation, operation flow process is simple; Applied widely, applicable to the protection of various types of metal productss, metal plating and metal device.The technology of the present invention can be easy to accomplish scale production.
In order to realize above-mentioned object, the present invention is by being achieved with following technical proposals:
The protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal, the steps include:
A, the water that is 0.5～1.5:10 by mass ratio mix with organic solvent, stir, and make mixed solvent;
B, add 30～50% emulsifying agent of steps A mixed solvent quality, stir, make mixture;
C, add 12～20% film 8,14-dihydroxyl Stearyl mercaptan (D-SM) of step B gained mixture quality, stir, further obtain mixing solutions;
D, add 1.5～2.0% the tensio-active agent of mixing solutions quality of step C gained and 0.1～0.5% reductive agent technical pure vitamins C (or to claim xitix; be called for short: VC or AA); under 51～58 ℃ of water bath condition, heat; continue to stir 90～150 minutes, obtain water-soluble metal protective material.
Described organic solvent be α-phenyl methyl-ω-[(1,1,3,3-tetramethyl butyl) phenoxy group]-poly-(oxygen-ethylene) (TRITON);
Described emulsifying agent is hydroxyethyl lipid acid the third fat (HDP);
Described membrane-forming agent is 8,14-dihydroxyl Stearyl mercaptan (D-SM);
Described reductive agent is technical pure vitamins C (is xitix, is called for short: VC or AA);
Described tensio-active agent is dodecanol sodium sulfate (SDS).
Described water is the one in deionized water, distilled water, tap water or natural water.
The prepared protectant physico-chemical property of water soluble molecules self-assembled film shaped metal of the technology of the present invention is: under room temperature (25～28 ℃) condition, be semi-solid state liquid (paraffin shape), without definite melting point; It at 30～45 ℃, is light yellow or tea yellow liquid; Density is a bit larger tham water, is about 1.022g/mL; There is light thiol smell; Under 40 ℃ and above temperature condition, can with arbitrary proportion, mix with water.
Adopt technical scheme of the present invention, can obtain following significant effect:
First; water-soluble metal protective material prepared by the technology of the present invention method; due between membrane-forming agent in solution and surfactant molecule; form cryptomere molecular self-assembly; in the cryptomere molecular self-assembling body short period of time (several seconds), just can naturally open in metallic surface; and in metallic surface, again forming self-assembled monolayer, isolating metal contacts with the direct of oxidizing gas effectively, makes the metal variable color time be able to effective prolongation.The sulphide discoloration test in 2% potassium sulfide solution of the argent of protecting with protective material of the present invention and silver-plated testpieces shows; under room temperature (25～28 ℃) condition, the variable color time all exceedes 8 minutes, reaches 78 points 47 seconds (referring to the embodiment 3 of the embodiment of present specification) most.
The second, the present invention's membrane-forming agent used be 8,14-dihydroxyl Stearyl mercaptan; except the sulfydryl of mercaptan is isolated with metal formation coordinate bond and film forming protection metal and oxidizing gas; owing to also may forming hydrogen bond between hydroxyl; make molecular self-assembled monolayer more firm; further strengthened the protective value of self-assembled film to metal, the guard time (refer to following table 1) of significant prolongation to metal.
The present invention uses 8,14-dihydroxyl Stearyl mercaptan is t in the prepared a kind of water soluble molecules self-assembled film shaped metal protective material S1(table of film (being called for short " 8,14-mercaptan " in table 1)
s1) with a kind of water-soluble silver protecting agent S2(table that uses Stearyl mercaptan (in table 1 be called for short " mercaptan ") to prepare in t
s2referenced patent number is the method preparation that the Chinese patent of ZL200710075422.5 is prepared water-soluble silver protecting agent; refer to its specification sheets and embodiment); the two (S1, S2) protection measure of merit to the tested part metals of the present invention; the part preferred result contrast of i.e. sulfuration in 2% potassium sulfide solution test (under 25～28 ℃ of conditions of room temperature), as t in following table 1(table
s1and t
s2represent respectively with the metal after protective material S1 and the S2 difference conservation treatment of two kinds of simultaneous tests, the variable color time in potassium sulfide solution) shown in:
Table 1
The 3rd, due to the prepared water-soluble metal protective material of the present invention, adopted the good xitix reductive agent of reductibility, can reduce most metal ions (as Ag
+, Au
3+, Ni
2+deng), also can form water-soluble complexes with many heavy metal ion, make beavy metal impurity ion water-soluble, making shielded metal device variable color (is mainly metal ions M
n+with S
2-, Cl
-, O
2-deng in conjunction with producing ferrous metal sulfide, dark-coloured halogenide and oxide compound) possibility and variable color degree greatly reduce, further protect metal, make metal variable color be able to effective alleviation, effectively extend the variable color time (referring to following table 2).
It (is xitix that the present invention uses reductive agent vitamins C; VC or AA; test sample A) and not use reductive agent vitamins C (be xitix; VC or AA; test sample B) prepared a kind of water soluble molecules self-assembled film shaped metal protective material; to the tested metal protection effect of the present invention, i.e. the preferred comparing result of part of the test of the sulphide discoloration in 2% potassium sulfide solution (under 25～28 ℃ of conditions of room temperature), as the T in following table 2(table 2
aand T
b, represent respectively with the metal after protective material A, the B difference conservation treatment of two kinds of simultaneous tests, the variable color time in potassium sulfide solution) shown in:
Table 2
Four, due to the prepared water-soluble metal protective material of the present invention; main raw material used is water-soluble good organism; under general temperature condition, (more than 40 ℃) can almost mix with arbitrary proportion with water; be easy to make the aqueous solution of various concentration; use operational anomaly is simple; can be used for different shape, the metal products of size or the protection of device, applied widely.
The 5th; a kind of water soluble molecules self-assembly shaped metal protective material of preparing due to the present invention; main raw material used is all fusing point lower than the organic substance (except water and reductive agent) of 55 ℃; preparation process and use procedure do not need higher temperature; produce and Energy in use is low, production unit is simple, be easier to realize efficiently, large-scale production.
Accompanying drawing explanation
Fig. 1 is the SEM photo of a kind of protective material of preparing at the molecular self-assembled monolayer of silvering surface formation.
Fig. 2 is the AFM photo of a kind of protective material of preparing at the molecular self-assembled monolayer of gold plate surface formation.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is done to further detailed description.
embodiment 1:
The protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal, the steps include:
A, by mass ratio, be that 0.5:10 is tap water and the 10kg organic solvent α-phenyl methyl-ω-[(1 of 0.5kg, 1,3,3-tetramethyl butyl) phenoxy group]-poly-(oxygen-1,2-ethylidene) (be called for short TRITON) mix in reactor, stir 2 minutes, make mixed solvent;
B, add 30% emulsifying agent of steps A gained mixed solvent quality, i.e. 3.15kg hydroxyethyl lipid acid the third fat (HDP), stirs 3 minutes, makes mixture;
C, add 12% membrane-forming agent of step B gained mixture quality, i.e. 1.638kg 8,14-dihydroxyl Stearyl mercaptan (D-SM), stirs 3 minutes, further obtains mixing solutions;
D, add 1.5% tensio-active agent of the mixing solutions quality of step C gained; it is the reductive agent of dodecanol sodium sulfate (SDS) 0.229kg and 0.1%; it is vitamins C (xitix; be called for short VC or AA) 15.3g; heating in water bath; control 51 ℃ of reactor mixing solutions temperature, continue to stir 150 minutes, obtain water-soluble metal protective material.
With SEM and AFM technical measurement the metal protection agent of preparation on silvering surface, form the shape characteristic of molecular self-assembled monolayer.The molecular self-assembled monolayer forming is orderly, fine and close, and thickness is about 20～35nm(and refers to accompanying drawing 1 and accompanying drawing 2).
With the metal protection agent of protective material of the present invention protection preparation, being made into mass percent concentration is 3% the aqueous solution; by argent and silver-plated testpieces 10～30 seconds of dynamic soaking in solution; distilled water embathes, air-dry or naturally dry; be immersed in again in 2% potassium sulfide solution; record sulphide discoloration test; result shows: under room temperature (25～28 ℃) condition, the variable color time exceedes 8 minutes, reach most 14 points 23 seconds.
embodiment 2:
The protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal, the steps include:
A, by mass ratio, be that 0.75:10 is deionized water and the 10kg organic solvent α-phenyl methyl-ω-[(1 of 0.75kg, 1,3,3-tetramethyl butyl) phenoxy group]-poly-(oxygen-1,2-ethylidene) (be called for short TRITON) mix in reactor, stir 3 minutes, make mixed solvent;
B, add 35% emulsifying agent of the mixed solvent quality of steps A gained, i.e. 3.76kg hydroxyethyl lipid acid the third fat (HDP), stirs 5 minutes, makes mixture;
C, add 15% membrane-forming agent of step B gained mixture quality, i.e. 2.18kg 8,14-dihydroxyl Stearyl mercaptan (D-SM), stirs 4 minutes, further obtains mixing solutions;
D, add 1.65% tensio-active agent of the mixing solutions quality of step C gained; it is the reductive agent of dodecanol sodium sulfate (SDS) 0.275kg and 0.2%; it is vitamins C (xitix; be called for short VC or AA) 33.9g; heating in water bath; control 54 ℃ of reactor mixing solutions temperature, continue to stir 140 minutes, obtain water-soluble metal protective material.
With SEM and AFM technical measurement the metal protection agent of preparation on silvering surface, form the shape characteristic of molecular self-assembled monolayer.The molecular self-assembled monolayer forming is orderly, fine and close, and thickness is about 20～35nm(and refers to accompanying drawing 1 and accompanying drawing 2).
With the metal protection agent of protective material of the present invention protection preparation, being made into mass percent concentration is 3% the aqueous solution; by argent and silver-plated testpieces 10～30 seconds of dynamic soaking in solution; distilled water embathes, air-dry or naturally dry; be immersed in again in 4% potassium sulfide solution; record sulphide discoloration test; result shows: under room temperature (25～28 ℃) condition, the variable color time all exceedes 8 minutes, reach most 18 points 47 seconds.
embodiment 3:
The protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal, the steps include:
A, by mass ratio, be that 1.0:10 is distilled water and the 20kg organic solvent α-phenyl methyl-ω-[(1 of 2.0kg, 1,3,3-tetramethyl butyl) phenoxy group]-poly-(oxygen-1,2-ethylidene) (be called for short TRITON) mix in reactor, stir 3 minutes, make mixed solvent;
B, add 44.5% emulsifying agent of the mixed solvent quality of steps A gained, i.e. 9.79kg hydroxyethyl lipid acid the third fat (HDP), stirs 5 minutes, makes mixture;
C, add 15.5% membrane-forming agent of step B gained mixture quality, i.e. 4.93kg 8,14-dihydroxyl Stearyl mercaptan (D-SM), stirs 6 minutes, further obtains mixing solutions;
D, add 1.80% tensio-active agent of the mixing solutions quality of step C gained; it is the reductive agent of dodecanol sodium sulfate (SDS) 0.661kg and 0.3%; it is vitamins C (xitix; be called for short VC or AA) 112.1g; heating in water bath; control 55 ℃ of reactor mixing solutions temperature, continue to stir 120 minutes, obtain water-soluble metal protective material.
With SEM and AFM technical measurement the metal protection agent of preparation on silvering surface, form the shape characteristic of molecular self-assembled monolayer.The molecular self-assembled monolayer forming is orderly, fine and close, and thickness is about 20～35nm(and refers to accompanying drawing 1 and accompanying drawing 2).
With the metal protection agent of protective material of the present invention protection preparation, being made into mass percent concentration is 3% the aqueous solution; by argent and silver-plated testpieces 10～30 seconds of dynamic soaking in solution; distilled water embathes, air-dry or naturally dry; be immersed in again in 2% potassium sulfide solution; record sulphide discoloration test; result shows: under room temperature (25～28 ℃) condition, the variable color time exceedes 13 minutes, reach most 78 points 47 seconds.
embodiment 4:
The protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal, the steps include:
A, by mass ratio, be that 1.3:10 is distilled water and the 30kg organic solvent α-phenyl methyl-ω-[(1 of 3.9kg, 1,3,3-tetramethyl butyl) phenoxy group]-poly-(oxygen-1,2-ethylidene) (be called for short TRITON) mix in reactor, stir 4 minutes, make mixed solvent;
B, add 48% emulsifying agent of the mixed solvent quality of steps A gained, i.e. 16.27kg hydroxyethyl lipid acid the third fat (HDP), stirs 5 minutes, makes mixture;
C, add 17.5% membrane-forming agent of step B gained mixture quality, i.e. 8.78kg 8,14-dihydroxyl Stearyl mercaptan (D-SM), stirs 8 minutes, further obtains mixing solutions;
D, add 1.85% tensio-active agent of the mixing solutions quality of step C gained; it is the reductive agent of dodecanol sodium sulfate (SDS) 1.091kg and 0.4%; it is vitamins C (xitix; be called for short VC or AA) 240g; heating in water bath; control 57 ℃ of reactor mixing solutions temperature, continue to stir 130 minutes, obtain water-soluble metal protective material.
With SEM and AFM technical measurement the metal protection agent of preparation on silvering surface, form the shape characteristic of molecular self-assembled monolayer.The molecular self-assembled monolayer forming is orderly, fine and close, and thickness is about 20～35nm(and refers to accompanying drawing 1 and accompanying drawing 2).
With the metal protection agent of protective material of the present invention protection preparation, being made into mass percent concentration is 5% the aqueous solution; by argent and silver-plated testpieces 10～30 seconds of dynamic soaking in solution; distilled water embathes, air-dry or naturally dry; be immersed in again in 2% potassium sulfide solution; record sulphide discoloration test; result shows: under room temperature (25～28 ℃) condition, the variable color time exceedes 8 minutes, reach most 43 points 19 seconds.
embodiment 5:
The protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal, the steps include:
A, by mass ratio, be that 1.5:10 is natural water and the 40kg organic solvent α-phenyl methyl-ω-[(1 of 6kg, 1,3,3-tetramethyl butyl) phenoxy group]-poly-(oxygen-1,2-ethylidene) (be called for short TRITON) mix in reactor, stir 6 minutes, make mixed solvent;
B, add 50% emulsifying agent of the mixed solvent quality of steps A gained, i.e. 23kg hydroxyethyl lipid acid the third fat (HDP), stirs 10 minutes, makes mixture;
C, add 20% membrane-forming agent of step B gained mixture quality, i.e. 13.8kg 8,14-dihydroxyl Stearyl mercaptan (D-SM), stirs 10 minutes, further obtains mixing solutions;
D, add the tensio-active agent of the mixing solutions quality 2.0% of step C gained; it is the reductive agent of dodecanol sodium sulfate (SDS) 1.656kg and 0.5%; it is vitamins C (xitix; being called for short VC or AA) 422.3g joins in C gained mixing solutions; heating in water bath; control 58 ℃ of reactor mixing solutions temperature, continue to stir 90 minutes, obtain water-soluble metal protective material.
With SEM and AFM technical measurement the metal protection agent of preparation on silvering surface, form the shape characteristic of molecular self-assembled monolayer.The molecular self-assembled monolayer forming is orderly, fine and close, and thickness is about 20～35nm(and refers to accompanying drawing 1 and accompanying drawing 2).
With the metal protection agent of protective material of the present invention protection preparation, being made into mass percent concentration is 3% the aqueous solution; by argent and silver-plated testpieces 10～30 seconds of dynamic soaking in solution; distilled water embathes, air-dry or naturally dry; be immersed in again in 2% potassium sulfide solution; record sulphide discoloration test; result shows: under room temperature (25～28 ℃) condition, the variable color time exceedes 8 minutes, reach most 29 points 57 seconds.
The foregoing is only the good embodiment of the present invention, not in order to limit the present invention, every any modification of making within the present invention spirit and principle, replace and improvement etc. on an equal basis, within all should being included in the scope of protection of the invention.
Claims (2)
1. the protectant preparation method of water soluble molecules self-assembled film shaped metal, the steps include:
A, the water that is 0.5～1.5:10 by mass ratio mix with organic solvent, stir, and make mixed solvent;
B, add 30～50% emulsifying agent of steps A mixed solvent quality, stir, make mixture;
C, add 12～20% film of step B gained mixture quality, stir, further obtain mixing solutions;
D, 1.5～2.0% the tensio-active agent that adds step C gained mixing solutions quality and 0.1～0.5% reductive agent heat under 51～58 ℃ of water bath condition, continue to stir 90～150 minutes, obtain water soluble molecules self-assembled film shaped metal protective material;
Described organic solvent is α-phenyl methyl-ω-[(1,1,3,3-tetramethyl butyl) phenoxy group]-poly-(oxygen-ethylene);
Described emulsifying agent is hydroxyethyl lipid acid the third fat;
Described film is 8,14-dihydroxyl Stearyl mercaptan;
Described tensio-active agent is dodecanol sodium sulfate;
Described reductive agent is technical pure vitamins C.
2. the protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal as claimed in claim 1, is characterized in that: described water is the one in deionized water, distilled water, tap water or natural water.
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| CN104593795A (en) * | 2015-01-08 | 2015-05-06 | 邯郸学院 | Brightness-retaining agent for silverware |
| CN105063705A (en) * | 2015-07-30 | 2015-11-18 | 柳州市旭平首饰有限公司 | Method for preventing color change of copper ornament plated with silver |
| CN109477226A (en) * | 2016-06-23 | 2019-03-15 | 德国艾托特克公司 | Aqueous composition for metal surface post-processing |
| CN111519219A (en) * | 2019-12-21 | 2020-08-11 | 东莞奕创表面处理科技有限公司 | Silver electroplating liquid composite additive and preparation method and application thereof |
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| CN102002696A (en) * | 2010-11-01 | 2011-04-06 | 李士法 | Silver tarnishing prevention material, and preparation method and application thereof |
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| CN111519219A (en) * | 2019-12-21 | 2020-08-11 | 东莞奕创表面处理科技有限公司 | Silver electroplating liquid composite additive and preparation method and application thereof |
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| CN103726056B (en) | 2015-10-21 |
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