CN101153405A - Composition for plating - Google Patents
Composition for plating Download PDFInfo
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- CN101153405A CN101153405A CNA2006101522451A CN200610152245A CN101153405A CN 101153405 A CN101153405 A CN 101153405A CN A2006101522451 A CNA2006101522451 A CN A2006101522451A CN 200610152245 A CN200610152245 A CN 200610152245A CN 101153405 A CN101153405 A CN 101153405A
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Abstract
A plating combination comprises pyrophosphate of alkali metal, compound containing plating coat metallic ion and lustre-coating agent, wherein, the lustre-coating agent is the reaction product of five membered nitrogen heterocyclic compound and 1-halogeno-group-2, 3-propylene oxide. The invention can substantially improve the surface glossiness and stability of plating coat; the plated piece made through adopting the invention has excellent glossiness, 3,600-revolution high wear resistance and 175-hour long corrosion resistant duration and can withstand cold shock and thermal shock. Compared with the plated piece made in proportion which has 1,500-revolution wear resistance and 140-hour corrosion resistant duration and can not withstand cold shock and thermal shock, the invention shows excellent performance in every index.
Description
Technical field
The invention relates to a kind of plating composition.
Background technology
Along with the appearance of the rules that limit the nickel use range, alloy plating is risen again as the plating that replaces the nickel plating.Contain plumbous tinsel and be widely used in the surface treatment of electronic component usually, but consider that wherein lead to the harm of human body and environment, released the gunmetal plating again in recent years.But the galvanized electroplate liquid great majority of gunmetal that are used for industry contain cryanide ion, and prussiate is highly toxic product, and the discharge meeting of the prussiate in the plating pollutes environment.
Therefore, CN 1665965A discloses a kind of no cyanogen gunmetal tetra-sodium electroplate liquid, the additive that this electroplate liquid contains alkali-metal pyrophosphate salt and is made up of sulfonamide derivatives, epihalohydrin and glycidyl ether compound, wherein, described sulfonamide derivatives can be ammonia, quadrol, diethylenetriamine, piperazine, Tri N-Propyl Amine, 1,2-propylene diamine, 1,3-propylene diamine, 1-(2-amino-ethyl) piperazine, 3 diethyl aminopropylamine, dimethylamine, vulkacit H, tetren, trolamine, hexamethylene-diamine and Yi Bingchunan.
Even by the formed coating surface of this electroplate liquid, and the defective goods production rate is lower, can use under the electric current application state that constantly changes between high current density state and the low current density state.But the coating surface glossiness of using above-mentioned electroplate liquid to obtain is not high, and the coating less stable.
Summary of the invention
To the objective of the invention is that the coating glossiness that electroplate liquid of the prior art obtains is not high, the shortcoming of less stable in order overcoming, a kind of plating composition that can obtain the coating of surface gloss height and good stability to be provided.
The invention provides a kind of plating composition, said composition contains alkali-metal pyrophosphate salt, contains the compound and the brightening agent of plated metal ion, wherein, described brightening agent is Five-membered Heterocyclic Compounds and 1-halogeno-group-2, the reaction product of 3-propylene oxide.
Owing to contain Five-membered Heterocyclic Compounds and 1-halogeno-group-2, the reaction product of 3-propylene oxide is as brightening agent with composition in plating provided by the invention, thereby can significantly improve the surface gloss and the stability of coating.For example, the plating piece by the embodiment of the invention makes all has tangible glossiness, and wear-resisting up to 3600 circles, corrosion-resistant for up to 175 hours, thermal shock all passes through.Wear-resisting 1500 circles of the plating piece that the ratio of comparing makes, 140 hours corrosion-resistant time and can't stand thermal shock test, the present invention all demonstrates superior performance on every index.
Embodiment
According to the present invention, described Five-membered Heterocyclic Compounds can be various saturated and/or undersaturated Five-membered Heterocyclic Compounds, nitrogen-atoms on the ring can be one or more, for example, described Five-membered Heterocyclic Compounds can be that the last hydrogen atom of pyrroles, pyrazoles, imidazoles and ring is substituted one or more in the basic pyrroles who replaces, pyrazoles, the imdazole derivatives.Described substituting group can be one or more in alkyl, halogen atom, nitro, the amino, and described alkyl is preferably positive structure or the isomery alkyl that carbonatoms is 1-6.
Described 1-halogeno-group-2, the 3-propylene oxide can be 1-chloro-2,3-propylene oxide and/or 1-bromo-2, the 3-propylene oxide is preferably 1-chloro-2, the 3-propylene oxide.
According to the present invention, described brightening agent is Five-membered Heterocyclic Compounds and 1-halogeno-group-2, the product that the 3-propylene oxide reaction obtains.Wherein, though the Five-membered Heterocyclic Compounds of arbitrary proportion and 1-halogeno-group-2, the 3-propylene oxide reaction all can obtain brightening agent of the present invention,, under the preferable case, at Five-membered Heterocyclic Compounds and 1-halogeno-group-2, in the reaction of 3-propylene oxide, Five-membered Heterocyclic Compounds and 1-halogeno-group-2, the mol ratio of 3-propylene oxide can be 1: 0.2-3, be preferably 1: 0.5-2.5, the temperature of reaction can be preferably 50-80 ℃ between 30-80 ℃.The time of reaction can be 0.1-5 hour, is preferably 0.5-2 hour
Though solid-state Five-membered Heterocyclic Compounds also can be directly and 1-halogeno-group-2, the 3-propylene oxide reaction obtains brightening agent, still since solid-state Five-membered Heterocyclic Compounds under solution state can with 1-halogeno-group-2, the 3-propylene oxide contacts more fully, make reaction more abundant, improve the speed of reaction, therefore, preferred earlier that Five-membered Heterocyclic Compounds is soluble in water, after obtaining the aqueous solution of Five-membered Heterocyclic Compounds, again with 1-halogeno-group-2, the 3-propylene oxide reaction.The amount of water is generally Five-membered Heterocyclic Compounds and 1-halogeno-group-2, and the 1-10 of 3-propylene oxide gross weight doubly is preferably 2-5 doubly.
Because Five-membered Heterocyclic Compounds and 1-halogeno-group-2, can emit a large amount of heat after the contact of 3-propylene oxide, therefore, the mode of preferred contact is earlier Five-membered Heterocyclic Compounds to be mixed with water, slowly add 1-halogeno-group-2 again after forming solution, 3-propylene oxide, each add-on make the temperature of reaction system be no more than 80 ℃.In order to make reaction more fully, evenly, described reaction is preferably carried out under agitation condition.Reacted product can remove and anhydrate, and also can not dewater and directly use as brightening agent.Among the present invention, all calculate during the weight of calculation composition, promptly do not comprise the content of water by its dry weight; The content of described brightening agent all refers to deduct the content of the surplus materials behind the content of water.
The present invention is not particularly limited the content of described brightening agent, for the conventional content of this area gets final product.Under the preferable case, with the dry weight basis of composition, the content of brightening agent is 0.5-50 weight %, is preferably 0.5-30 weight %.
Described kind and the content that contains the compound of plated metal ion can be the various conventional kind and the content that contain plating metal ionic compound that use, and specifically can select according to actual coating needs.For example, the described compound that contains plated metal ion can be one or more in water-soluble mantoquita, tin salt, molysite, zinc salt, the silver salt.Among the present invention, the preferred described compound that contains plated metal ion is water-soluble mantoquita and/or water-soluble tin salt.
Described water-soluble mantoquita can be one or more in copper sulfate, cupric nitrate, copper carbonate, copper methane sulfonate, thionamic acid copper, 2-ethylenehydrinsulfonic acid copper, 2-hydroxy-propanesulfonic acid copper, cupric chloride, the cupric pyrophosphate, is preferably cupric pyrophosphate.
Described water-soluble tin salt can be one or more in stannous pyrophosphate, tin protochloride, stannous sulfate, stannous acetate, the inferior tin of thionamic acid, the inferior tin of gluconic acid, stannous tartrate, tin protoxide, sodium stannate, potassium stannate, the inferior tin of methylsulfonic acid, the inferior tin of 2-ethylenehydrinsulfonic acid, the inferior tin of 2-hydroxy-propanesulfonic acid, the bromine tin protofluoride, is preferably stannous pyrophosphate.
In general, with the dry weight basis of composition, the described content that contains the compound of plated metal ion can be preferably 3-30% for 1-65 weight %.
Described alkali-metal pyrophosphate salt can be a field of electroplating various alkali-metal pyrophosphate salt commonly used, as potassium pyrophosphate and/or trisodium phosphate.With the dry weight basis of composition, the content of alkali-metal pyrophosphate salt can be 5-90 weight %, is preferably 40-85 weight %.In electroplating composition, it is generally acknowledged that alkali-metal pyrophosphate salt plays complexing agent, in order to make alkali-metal pyrophosphate salt bring into play its complexing agent effect better, make preferably that the weight ratio of pyrophosphate and plated metal ion is 2-80, more preferably 2-50 in the composition.Pyrophosphate described herein is meant pyrophosphates all in the composition, and for example, when the described compound that contains plated metal ion was cupric pyrophosphate and/or stannous pyrophosphate, described pyrophosphate comprised the pyrophosphate in cupric pyrophosphate and/or the stannous pyrophosphate.
Under the identical situation of other condition, the color of coating is by the content decision of the plated metal ion of the compound that contains plated metal ion in the composition, and the content of plated metal ion is high more, and the color of coating is partial to the color of this plated metal ion more.For example, when the mol ratio of tin ion in the composition (and/or stannous ion) and cupric ion is Sn: Cu=(3-5): 1 and the content of Sn when surpassing 50 weight %, coating is silvery white in color; As Sn: Cu=(1.5-3): 1 and the content of Sn when being about 50 weight %, it is golden that coating is; As Sn: Cu=(0.5-1.5): 1 and the content of Sn when being about 20 weight %, coating is brassiness.
In order further to strengthen the glossiness of the coating that obtains with composition by this plating, under the preferable case, can also contain auxiliary brightener in the composition of the present invention.Wherein, described auxiliary brightener can be the reagent that the coating glossiness is increased of various routines, for example, can be oxoethanoic acid and/or Whitfield's ointment.The present inventor finds, oxoethanoic acid and/or Whitfield's ointment can with Five-membered Heterocyclic Compounds and the 1-halogeno-group-2 as brightening agent of the present invention, the reaction product of 3-propylene oxide acts synergistically, in the glossiness that improves the coating that obtains with composition by this plating greatly, can also improve the stability of coating and to the sticking power of base material, thus the wear resistance, erosion resistance, the cold-resistant thermal shocking that further improve coating.Therefore, preferably also contain oxoethanoic acid and/or Whitfield's ointment in the composition of the present invention.With the dry weight basis of composition, oxoethanoic acid and/or salicylic content can be 0-0.5 weight %, are preferably 0.03-0.5 weight %, more preferably 0.06-0.2 weight %.
In order to regulate the stress of electroplating the coating that obtains with composition by the present invention, improve the bonding force of coating and base material, under the preferable case, also contain the surface stress conditioning agent in the composition of the present invention, described surface stress conditioning agent can be asccharin, sulfonaphthol, 1, one or more in 5-naphthalene disulfonate, Sodium phenylsulfinate, the alkyl sulfinic acid.The present inventor finds, with alkyl sulfinic acid during as the surface stress conditioning agent, and the stress the when stress of electroplating the coating that obtains with composition by the present invention is significantly less than other surface stress conditioning agent.Therefore, the preferred described surface stress conditioning agent of the present invention contains alkyl sulfinic acid, and described alkyl can be straight chain or straight chained alkyl, also can be cycloaliphatic ring or aromatic nucleus alkyl, is preferably the straight chained alkyl that carbonatoms is 1-10.With the dry weight basis of composition, the content of described surface stress conditioning agent can be 0-0.1 weight %, is preferably 0.001-0.1 weight %, more preferably 0.005-0.02 weight %.In the surface stress conditioning agent, the content of alkylsulphonic acid preferably is not less than 50 weight %, more preferably 60-100 weight %.
Under the preferable case, the present composition can also contain conventional various other additives that use in this area, and described additive for example can be stablizer and/or tensio-active agent.
Because in solution, following reaction can take place in stannous ion in the composition and cupric ion:
Sn
2++Cu
2+→Sn
4++Cu
Make cupric ion in the composition solution be reduced and make copper powder be deposited in the solution, simultaneously, stannous ion is oxidized to tin ion, makes the electroplate liquid degradation.Therefore, described stablizer is preferably the various reagent that can prevent copper reduction or inferior tin oxidation, for example, described stablizer for example can be one or more in methanesulfonic, cresol sulfonic acid, sulfocarbolic acid, sulphosalicylic acid, hydrazine or the aniline, is preferably methanesulfonic.With the dry weight basis of composition, the content of stablizer can be 0-75 weight %, is preferably 5-75 weight %, more preferably 8-30 weight %.
Described tensio-active agent can be nonionic surface active agent and/or quaternary ammonium salt cationic surfactant.Nonionic surface active agent for example can be that carbonatoms is one or more in the Fatty Alcohol(C12-C14 and C12-C18), aliphatic amide, lipid acid, fatty amide of 10-18; Quaternary ammonium salt cationic surfactant can be that carbonatoms is the perfluoroalkyl quaternary ammonium iodide of 10-20, in the octadecyl dimethyl benzyl ammonia chloride one or more.With the dry weight basis of composition, the content of tensio-active agent can be 0-4 weight %, is preferably 0.02-4 weight %, more preferably 0.02-0.3 weight %.
The present invention electroplates with the preparation of compositions method simple, only said components need be mixed to get final product.
Plating of the present invention is easy to use with composition, only needs composition and solvent are prepared into after the solution, and the electro-plating method that re-uses routine is electroplated onto on the base material under the plating condition of routine and gets final product.Described solvent can be various can be with present composition dissolved solvent, comprehensive cost and environmental protection two aspects consider that preferred solvent is a water.The weight of solvent is preferably 1-10 times of composition weight, and more preferably 2-8 doubly.The plating condition comprises that temperature can be 20-55 ℃, is preferably 20-35 ℃, and current density can be 0.05-10 ampere/square decimeter, is preferably 0.1-8.0 ampere/square decimeter.Under the preferable case, before plating, also comprise and earlier solution is regulated pH to 7-10, be preferably 7.1-9.1.
Plating of the present invention is applicable to various base materials with composition, for example, can be metal base, various plastic basis material, composite material base.
Describe the present invention in detail below by embodiment.
Embodiment 1
Present embodiment is used to illustrate plating composition provided by the invention.
The preparation of brightening agent: 4 gram imidazoles and 15 ml waters are joined one be furnished with in the sealable container of thermometer, prolong and agitator, after the stirring and dissolving, solution is heated to 35 ℃, again with 6 gram 1-chloro-2, the 3-propylene oxide dropwise adds in the solution and stirs, and keeps temperature of reaction at 75-80 ℃.Treat all 1-chloro-2, after the 3-propylene oxide adds, under this temperature, stirred 2 hours again, make reaction product naturally cool to room temperature then, obtain mixture 25 grams.Because reaction is to carry out in encloses container, and the temperature of reaction is lower than the boiling point of water, can think that therefore the amount of gained brightening agent is the amount that the total amount of mixture is removed the water of adding, and also, the gained brightening agent is 10 grams in the present embodiment.Brightening agent Weight Calculation method in following examples is identical therewith.
Above-mentioned 25 gram mixtures are mixed with 750 gram potassium pyrophosphates, 6 gram cupric pyrophosphates, 36 gram stannous pyrophosphates; Gained solution mixes with 0.9 gram oxoethanoic acid, 196 gram methanesulfonics, 0.1 gram phenyl-sulfinic acid, 1 gram octadecyl dimethyl benzyl ammonia chloride again.Obtain plating of the present invention composition A1.A1 has following composition: brightening agent is that 1.00 weight %, alkali-metal pyrophosphate salt are 75.00 weight %, the compound that contains plated metal ion is that 4.20 weight %, auxiliary brightener are that 0.09 weight %, electroplate liquid stablizer are that 19.60 weight %, surface stress conditioning agent are that weight 0.01%, tensio-active agent are 0.1 weight %.
Embodiment 2
Present embodiment is used to illustrate plating composition provided by the invention.
The preparation of brightening agent: the pyrazoles and 40 ml waters of 7 grams are joined one and are furnished with in the sealable container of thermometer, prolong and agitator, after the stirring and dissolving, solution is heated to 35 ℃, again with the 13 1-chloro-2 that restrain, the 3-propylene oxide dropwise adds in the solution and stirs, and keeps temperature of reaction at 75-80 ℃.Treat all 1-chloro-2, after the 3-propylene oxide adds, under this temperature, stirred 2 hours again, make reaction product naturally cool to room temperature then, obtain mixture 60 grams.
Above-mentioned 60 gram mixtures are mixed with 700 gram potassium pyrophosphates, 19 gram cupric pyrophosphates, 81 gram stannous pyrophosphates; Gained solution mixes with 1 gram oxoethanoic acid, 177.9 gram methanesulfonics, 0.1 gram phenyl-sulfinic acid, 1 gram octadecyl dimethyl benzyl ammonia chloride again.Obtain plating of the present invention composition A2.A2 has following composition: brightening agent is that 2.00 weight %, alkali-metal pyrophosphate salt are 70.00 weight %, the compound that contains plated metal ion is that 10.00 weight %, auxiliary brightener are that 0.10 weight %, electroplate liquid stablizer are that 17.79 weight %, surface stress conditioning agent are that weight 0.01%, tensio-active agent are 0.06 weight %.
Embodiment 3
Present embodiment is used to illustrate plating composition provided by the invention.
The preparation of brightening agent: the pyrroles and 90 ml waters of 20 grams are joined one and are furnished with in the sealable container of thermometer, prolong and agitator, after the stirring and dissolving, solution is heated to 35 ℃, again with the 20 1-chloro-2 that restrain, the 3-propylene oxide dropwise adds in the solution and stirs, and keeps temperature of reaction at 75-80 ℃.Treat all 1-chloro-2, after the 3-propylene oxide adds, under this temperature, stirred 2 hours again, make reaction product naturally cool to room temperature then, obtain mixture 130 grams.
Above-mentioned 130 gram mixtures are mixed with 650 gram potassium pyrophosphates, 49 gram cupric pyrophosphates, 101 gram stannous pyrophosphates; Gained solution mixes with 0.8 gram oxoethanoic acid, 158.1 gram methanesulfonics, 0.1 gram phenyl-sulfinic acid, 1 gram octadecyl dimethyl benzyl ammonia chloride again.Obtain plating of the present invention composition A3.A3 has following composition: brightening agent is that 4.00 weight %, alkali-metal pyrophosphate salt are 65.00 weight %, the compound that contains plated metal ion is that 15.00 weight %, auxiliary brightener are that 0.08 weight %, electroplate liquid stablizer are that 15.81 weight %, surface stress conditioning agent are that weight 0.01%, tensio-active agent are 0.10 weight %.
Embodiment 4
Present embodiment is used to illustrate plating composition provided by the invention.
The preparation of brightening agent: the glyoxal ethylines and 200 ml waters of 100 grams are joined one and are furnished with in the sealable container of thermometer, prolong and agitator, after the stirring and dissolving, solution is heated to 35 ℃, again with the 180 1-chloro-2 that restrain, the 3-propylene oxide dropwise adds in the solution and stirs, and keeps temperature of reaction at 75-80 ℃.Treat all 1-chloro-2, after the 3-propylene oxide adds, under this temperature, stirred 2 hours again, make reaction product naturally cool to room temperature then, obtain mixture 480 grams.
Above-mentioned 480 gram mixtures are mixed with 400 gram potassium pyrophosphates, 45 gram cupric pyrophosphates, 155 gram stannous pyrophosphates; Gained solution mixes with 1 gram oxoethanoic acid, 117.9 gram methanesulfonics, 0.1 gram phenyl-sulfinic acid, 1 gram octadecyl dimethyl benzyl ammonia chloride again.Obtain plating of the present invention composition A4.A4 has following composition: brightening agent is that 28.00 weight %, alkali-metal pyrophosphate salt are 40.00 weight %, the compound that contains plated metal ion is that 20.00 weight %, auxiliary brightener are that 0.10 weight %, electroplate liquid stablizer are that 11.79 weight %, surface stress conditioning agent are that weight 0.01%, tensio-active agent are 0.10 weight %.
Embodiment 5
Present embodiment is used to illustrate plating composition provided by the invention.
The preparation of brightening agent: the 3-chlorine imidazoles and 210 ml waters of 60 grams are joined one and are furnished with in the sealable container of thermometer, prolong and agitator, after the stirring and dissolving, solution is heated to 35 ℃, again with the 60 1-chloro-2 that restrain, the 3-propylene oxide dropwise adds in the solution and stirs, and keeps temperature of reaction at 75-80 ℃.Treat all 1-chloro-2, after the 3-propylene oxide adds, under this temperature, stirred 2 hours again, make reaction product naturally cool to room temperature then, obtain mixture 330 grams.
Above-mentioned 330 gram mixtures are mixed with 500 gram potassium pyrophosphates, 80 gram cupric pyrophosphates, 190 gram stannous pyrophosphates; Gained solution mixes with 1.2 gram oxoethanoic acids, 107.7 gram methanesulfonics, 0.1 gram phenyl-sulfinic acid, 1 gram octadecyl dimethyl benzyl ammonia chloride again.Obtain plating of the present invention composition A5.A5 has following composition: brightening agent is that 12.00 weight %, alkali-metal pyrophosphate salt are 50.00 weight %, the compound that contains plated metal ion is that 27.00 weight %, auxiliary brightener are that 0.12 weight %, electroplate liquid stablizer are that 10.77 weight %, surface stress conditioning agent are weight 0.01%, table and promoting agent is 0.10 weight %.
Embodiment 6
Present embodiment is used to illustrate plating composition provided by the invention.
The preparation of brightening agent: the 2-nitro-pyrroles and 250 ml waters of 70 grams are joined one and are furnished with in the sealable container of thermometer, prolong and agitator, after the stirring and dissolving, solution is heated to 35 ℃, again with the 80 1-chloro-2 that restrain, the 3-propylene oxide dropwise adds in the solution and stirs, and keeps temperature of reaction at 75-80 ℃.Treat all 1-chloro-2, after the 3-propylene oxide adds, under this temperature, stirred 2 hours again, make reaction product naturally cool to room temperature then, obtain mixture 400 grams.
Above-mentioned 400 gram mixtures are mixed with 800 gram potassium pyrophosphates, 7 gram cupric pyrophosphates, 43 gram stannous pyrophosphates; Obtain plating of the present invention composition A6.A6 has following composition: brightening agent is that 15.00 weight %, alkali-metal pyrophosphate salt are 80.00 weight %, the compound that contains plated metal ion is 5.00 weight %.
Comparative Examples 1
This Comparative Examples is used to illustrate the performance of electroplate liquid of the prior art and coating.
Electroplate liquid in this Comparative Examples is pressed embodiment 1 preparation among the CN 1665965A.
The preparation of brightening agent: the piperazines and 300 ml waters of 81.6 grams are joined one and are furnished with in the sealable container of thermometer, prolong and agitator stirring and dissolving.With the 1-chloro-2 of 92.5 grams, the mixture of the ethylene glycol diglycidylether of 3-propylene oxide and 150.2 grams dropwise adds in the solution and stirs again, keeps temperature of reaction at 65-80 ℃.Treat all 1-chlorine 2, after the 3-propylene oxide adds, under this temperature, stirred 2 hours again, make reaction product naturally cool to room temperature then, obtain brightening agent 324.3 grams.The weight of described brightening agent all refers to deduct the weight of the dry-matter behind the content of water, because water does not significantly reduce before and after reaction, therefore, the tare of water is generally the water add-on.
Above-mentioned 324.3 gram brightening agents are mixed with 600 gram potassium pyrophosphates, 2.6 gram cupric pyrophosphates, 14.2 gram stannous pyrophosphates, 120 gram methanesulfonics, 0.1 gram perfluor dodecyl trimethyl ammonium salt; Obtain plating of the present invention composition D1.D1 has following composition: brightening agent is that 30.60 weight %, alkali-metal pyrophosphate salt are 56.49 weight %, the compound that contains plated metal ion is that 1.60 weight %, electroplate liquid stablizer are that 11.30 weight %, tensio-active agent are 0.01 weight %.
Embodiment 7-12
These embodiment are used for illustrating by the electrolysis provided by the invention coating of preparation of compositions and the performance of coating.
The total amount of the composition A1 that the foregoing description 1 is obtained is a solvent with water respectively, is mixed with 2 premium on currency solution, and distinguishes regulator solution to the value of pH shown in the table 1 with the poly phosphoric acid solution of 0.5 mol, obtains electroplate liquid B1-B6.6 copper sheet base materials are polished to light with polishing machine earlier; With after soaking 3 minutes in the sodium hydroxide solution of 0.1 mol, take out the water flushing again; Afterwards, in the sulphuric acid soln of 0.05 mol, soaked 1 minute again, take out the water flushing; Then, put into above-mentioned electroplate liquid B1-B6 respectively, link to each other with galvanic positive pole as negative electrode, be that anode links to each other with galvanic negative pole and electroplates with the sheet tin, the temperature of electroplate liquid, as shown in table 1 by the current density of anode and negative electrode, in electrolyzer, electroplated 20 minutes, obtain plating piece C1-C6.
Table 1
| Numbering | B1 | B2 | B3 | B4 | B5 | B6 |
| pH | 7.1 | 7.5 | 7.9 | 8.3 | 8.7 | 9.1 |
| Current density (ampere/square decimeter) | 0.05 | 2 | 4 | 6 | 8 | 10 |
| Temperature of electroplating solution (℃) | 20 | 25 | 25 | 30 | 35 | 35 |
Embodiment 13-18
These embodiment are used for illustrating by the electrolysis provided by the invention coating of preparation of compositions and the performance of coating.
The total amount of the composition A1-A6 that the foregoing description 1-6 is obtained is a solvent with water respectively, is mixed with 2 premium on currency solution, and with the poly phosphoric acid solution of 0.5 mol the pH value of 6 kinds of solution is transferred to 8.0, acquisition electroplate liquid B7-B12.6 copper sheet base materials are polished to light with polishing machine earlier; In the sodium hydroxide solution of 0.1 mol, soak after 3 minutes, take out the water flushing; Afterwards, in the sulphuric acid soln of 0.05 mol, soaked 1 minute again, take out the water flushing; Then, put into above-mentioned electroplate liquid B7-B12 respectively, link to each other with galvanic positive pole as negative electrode, be that anode links to each other with galvanic negative pole and electroplates with the sheet tin, the temperature regulation of electroplate liquid is 25 ℃, current density by anode and negative electrode is adjusted to 0.8 ampere/square decimeter, electroplates 20 minutes in electrolyzer, obtains plating piece C7-C12.
Comparative Examples 2
This Comparative Examples is used for illustrating the electrolysis coating of preparation of compositions and the performance of coating that is provided by prior art.
The total amount of the composition that above-mentioned Comparative Examples 1 is obtained is a solvent with water, is mixed with 2 premium on currency solution, and with the poly phosphoric acid solution regulator solution pH value to 7.3 of 0.5 mol, acquisition electroplate liquid B13.The copper sheet base material is polished to light with polishing machine earlier; With after soaking 3 minutes in the sodium hydroxide solution of 0.1 mol, take out the water flushing again; Afterwards, in the sulphuric acid soln of 0.05 mol, soaked 1 minute again, take out the water flushing; Then, put into above-mentioned electroplate liquid B13, link to each other with galvanic positive pole as negative electrode, be that anode links to each other with galvanic negative pole and electroplates with the sheet tin, the temperature regulation of electroplate liquid is 25 ℃, current density by anode and negative electrode is adjusted to 0.8 ampere/square decimeter, electroplates 20 minutes in electrolyzer, obtains plating piece E1.
Embodiment 19-30
These embodiment are used for illustrating by the electrolysis provided by the invention coating of preparation of compositions and the performance of coating.
The plated item E1 that obtains of plated item C1-C12 that embodiment 7-18 is obtained and Comparative Examples 2 carries out the test of tone, erosion resistance, wear resistance, cold-resistant thermal shocking respectively, and the result is as shown in table 2.
(1) with the naked eye estimate the gloss and the tone of coating, the result is as described in Table 2.
(2) erosion resistance is measured by saline fog method
The salt fog measuring method is for to place the plated item that makes in the salt fog cabinet, at 35 ℃ is that the sodium chloride aqueous solution of 5 weight % sprayed plated item after 2 hours with concentration down, plating piece being placed the another one temperature after the taking-up is that 40 ℃, relative humidity are 80% climatic chamber again, observe plated item, be recorded in how long plated item surface, back occurs unusually, the result is as described in Table 2.
(3) wearability test
Use the 7-IBB type RCA abrasion view of U.S. Nuo Man Instrument and Equipment Company production, mill plated item under the effect of 175 gram forces when show-through material, writes down the number of turns that rubber wheel rotates again, and the result is as described in Table 2.
(4) cold-resistant thermal shocking property testing
Method is for to be placed on plated item in the thermal shock test box, probe temperature is reduced to-40 ℃, placed 2 hours, in 3 minutes, probe temperature is risen to 85 ℃ then, placed 2 hours, repeat behind the aforesaid operations 5 times plating piece to be placed in the room temperature environment, whether observe the plating piece surface and occur unusually, the result represents that to pass through or to pass through the result is as described in Table 2.
Table 2
| Numbering | Tone | Wear resistance (circle) | Erosion resistance (hour) | Cold-resistant thermal shocking |
| C1 | The silvery white of light | 3600 | 160 | By |
| C2 | The silvery white of light | 3400 | 155 | By |
| C3 | The silvery white of light | 3400 | 155 | By |
| C4 | The silvery white of light | 3600 | 160 | By |
| C5 | The silvery white of light | 3200 | 160 | By |
| C6 | The silvery white of light | 3000 | 167 | By |
| C7 | The silvery white of light | 3200 | 170 | By |
| C8 | The silvery white of light | 2900 | 160 | By |
| C9 | The gold of light | 2700 | 165 | By |
| C10 | The gold of light | 2500 | 175 | By |
| C11 | The brassiness of light | 2600 | 170 | By |
| C12 | Silvery white, glossiness is higher | 3000 | 155 | By |
| E1 | Silvery white, glossiness is low | 1500 | 140 | Do not pass through |
From result shown in the table 2 as can be seen, the plating piece according to the method for embodiment 7-18 provided by the invention obtains all is better than the plating piece that Comparative Examples 2 obtains in wear resistance, erosion resistance, cold-resistant thermal shocking; The plating piece that makes from naked eyes electroplate liquid of the present invention will obviously be better than Comparative Examples on glossiness, even only added the embodiment 6 resulting plating piece C12 of brightening agent, every index also is better than Comparative Examples 2 resulting plating piece E1.
Claims (10)
1. plating composition, said composition contains alkali-metal pyrophosphate salt, contains the compound and the brightening agent of plated metal ion, it is characterized in that, and described brightening agent is Five-membered Heterocyclic Compounds and 1-halogeno-group-2, the reaction product of 3-propylene oxide.
2. composition according to claim 1, wherein, described Five-membered Heterocyclic Compounds is that pyrroles, pyrazoles, imidazoles and ring are gone up hydrogen atom and be substituted in pyrroles that base replaces, pyrazoles, the imdazole derivatives one or more, and described substituting group is that carbonatoms is one or more in the positive structure of 1-6 or isomery alkyl, halogen atom, nitro, the amino.
3. composition according to claim 1, wherein, at Five-membered Heterocyclic Compounds and 1-halogeno-group-2, in the reaction of 3-propylene oxide, Five-membered Heterocyclic Compounds and 1-halogeno-group-2, the mol ratio of 3-propylene oxide is 1: 0.2-3, and the temperature of reaction is 30-80 ℃, the time of reaction is 0.1-5 hour.
4. composition according to claim 1, wherein, with the dry weight basis of composition, the content of described alkali-metal pyrophosphate salt is 5-90 weight %, the described content that contains the compound of plated metal ion is 1-65 weight %, and the content of brightening agent is 0.5-50 weight %.
5. composition according to claim 4, wherein, alkali-metal pyrophosphate salt and the content that contains the compound of plated metal ion make that the mol ratio of pyrophosphate and plated metal ion is 2-80 in the composition.
6. composition according to claim 1, wherein, described composition also contains auxiliary brightener, and described auxiliary brightener is oxoethanoic acid and/or Whitfield's ointment; With the dry weight basis of composition, the content of described auxiliary brightener is 0.03-0.5 weight %.
7. composition according to claim 1, wherein, described composition also contains the surface stress conditioning agent, and described surface stress conditioning agent is an alkyl sulfinic acid; With the dry weight basis of composition, the content of described surface stress conditioning agent is 0.001-0.1 weight %.
8. according to claim 1,4 or 5 described compositions, wherein, described alkali-metal pyrophosphate salt is potassium pyrophosphate and/or trisodium phosphate.
9. according to claim 1,4 or 5 described compositions, wherein, the described compound that contains plated metal ion is one or more in water-soluble mantoquita, tin salt, molysite, zinc salt, the silver salt.
10. composition according to claim 9, wherein, the described compound that contains plated metal ion is water-soluble mantoquita and/or water-soluble tin salt.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101522451A CN101153405A (en) | 2006-09-25 | 2006-09-25 | Composition for plating |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101522451A CN101153405A (en) | 2006-09-25 | 2006-09-25 | Composition for plating |
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| CN101153405A true CN101153405A (en) | 2008-04-02 |
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| CNA2006101522451A Pending CN101153405A (en) | 2006-09-25 | 2006-09-25 | Composition for plating |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102303850A (en) * | 2011-06-28 | 2012-01-04 | 广东广试试剂科技有限公司 | Method for preparing stannous sulfamate solution and application thereof |
| KR20130021344A (en) * | 2011-08-22 | 2013-03-05 | 롬 앤드 하스 일렉트로닉 머트어리얼즈, 엘.엘.씨. | Plating bath and method |
| CN104988543A (en) * | 2015-08-06 | 2015-10-21 | 揭阳市比格莱化工有限公司 | Environment-friendly brightener for non-cyanide alkaline zinc plating and preparation method thereof |
| CN109989077A (en) * | 2017-12-29 | 2019-07-09 | 广东东硕科技有限公司 | A kind of copper electrolyte |
| CN111996562A (en) * | 2020-08-19 | 2020-11-27 | 苏州航林机械制造有限公司 | Electric brush plating solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102303850A (en) * | 2011-06-28 | 2012-01-04 | 广东广试试剂科技有限公司 | Method for preparing stannous sulfamate solution and application thereof |
| CN102303850B (en) * | 2011-06-28 | 2013-04-03 | 广东广试试剂科技有限公司 | Method for preparing stannous sulfamate solution and application thereof |
| KR20130021344A (en) * | 2011-08-22 | 2013-03-05 | 롬 앤드 하스 일렉트로닉 머트어리얼즈, 엘.엘.씨. | Plating bath and method |
| CN102953097A (en) * | 2011-08-22 | 2013-03-06 | 罗门哈斯电子材料有限公司 | Plating bath and method |
| JP2013049922A (en) * | 2011-08-22 | 2013-03-14 | Rohm & Haas Electronic Materials Llc | Plating bath and method |
| CN102953097B (en) * | 2011-08-22 | 2016-01-13 | 罗门哈斯电子材料有限公司 | Electroplate liquid and electro-plating method |
| EP2562294A3 (en) * | 2011-08-22 | 2017-04-12 | Rohm and Haas Electronic Materials LLC | Plating bath and method |
| KR102044180B1 (en) | 2011-08-22 | 2019-11-13 | 롬 앤드 하스 일렉트로닉 머트어리얼즈 엘엘씨 | Plating bath and method |
| CN104988543A (en) * | 2015-08-06 | 2015-10-21 | 揭阳市比格莱化工有限公司 | Environment-friendly brightener for non-cyanide alkaline zinc plating and preparation method thereof |
| CN104988543B (en) * | 2015-08-06 | 2018-01-12 | 广东比格莱科技有限公司 | A kind of environmental non-cyanide alkaline zinc plating brightener and preparation method thereof |
| CN109989077A (en) * | 2017-12-29 | 2019-07-09 | 广东东硕科技有限公司 | A kind of copper electrolyte |
| CN111996562A (en) * | 2020-08-19 | 2020-11-27 | 苏州航林机械制造有限公司 | Electric brush plating solution |
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