CN108950616A

CN108950616A - A kind of thiosulfate plating silver additive, preparation method and the electroplate liquid comprising it

Info

Publication number: CN108950616A
Application number: CN201811132657.8A
Authority: CN
Inventors: 王浩杰; 黄良平; 杨鹔; 张帆
Original assignee: Nanjing Product Quality Supervision and Inspection Institute
Current assignee: Nanjing Product Quality Supervision and Inspection Institute
Priority date: 2018-09-27
Filing date: 2018-09-27
Publication date: 2018-12-07
Anticipated expiration: 2038-09-27
Also published as: CN108950616B

Abstract

The invention discloses a kind of thiosulfate plating silver additive, preparation method and include its electroplate liquid, thiosulfate plates silver additive, water including lauryl sodium sulfate 12-18g/L, polyethylene glycol 3-5g/L, mustargen 10-13g/L, isopropylbenzene 5-10g/L, 1,10- Phen 250-350g/L, dimercaprol dimercaptopropanol 50-100g/L, mercaptoethylmaine 50-100g/L, EGTA 100-150g/L and surplus.Additive of the present invention makes the dispersibility of electroplate liquid, stability, plating resistance etc. have the promotion of highly significant, without going adjustment pH value repeatedly in the plating process, the performances such as the planarization, adhesive force, glossiness anti-discoloration of silvering are significantly improved simultaneously, also it is thinned the thickness of coating, and phenomena such as no cracking；Electroplate liquid of the present invention is free of cyanide, coating bright in mirror surface, brittleness are small, adhesive force is good, surfacing, light, anti-discoloration is good, heat resistance is strong, the multi-field application such as decorative electroplating and functional plating can be met, be not necessarily to preplating, binding force can also be guaranteed.

Description

A kind of thiosulfate plating silver additive, preparation method and the electroplate liquid comprising it

Technical field

The present invention relates to a kind of thiosulfate plating silver additive, preparation method and comprising its electroplate liquid, belong to plating Silver-colored field.

Background technique

Silver has unique silvery white gloss, with excellent electric conductivity and soldering property, chemically to organic bronsted lowry acids and bases bronsted lowry Matter is more stable, and price is relatively inexpensive compared to other noble metals, and silvering is widely used in tableware, jewellery, the art work, electrical With the fields such as contact material in electronics industry.

So far, plating silver process both domestic and external is most or silver-plated using cyanogen system, and reason is cyanogen system silver plating process Bath stability is good, and covering power and depth capability are preferable, and coating crystallization is careful.But cyanide is extremely toxic substance, to scene The Health cost of operator is big, requires have good ventilation equipment when production, while the sewage discharged is also unfavorable for environment Protection.

With the development of industry, environmental pollution is increasingly severe, countries in the world environmental protection consciousness also constantly reinforce and The appearance of relevant policies, cyanogen system is silver-plated to be gradually eliminated, however there are dull, silver coating are uneven for existing non-cyanide silver coating It is whole, anti-discoloration is poor, thickness of coating is thick, poor adhesive force, the defects of being easily cracked.

Summary of the invention

The defects of in order to solve the above-mentioned problems in the prior art, the present invention provide that a kind of thiosulfate is silver-plated to be added Add agent, preparation method and the electroplate liquid comprising it.

In order to solve the above technical problems, the technical solution adopted in the present invention is as follows:

A kind of thiosulfate plating silver additive, including lauryl sodium sulfate 12-18g/L, polyethylene glycol 3-5g/L, nitrogen Mustard 10-13g/L, isopropylbenzene 5-10g/L, 1,10- Phen 250-350g/L, dimercaprol dimercaptopropanol 50-100g/L, mercaptoethylmaine The water of 50-100g/L, EGTA (bis- (the 2- amino-ethyl ether) tetraacethyls of ethylene glycol) 100-150g/L and surplus.

Applicant it has been investigated that, by above-mentioned additive addition in plate silver plating solution so that electroplate liquid is dispersed, steady The promotion for having highly significant such as qualitative, plating resistance significantly improves simultaneously without going adjustment pH value repeatedly in the plating process The performances such as planarization, adhesive force, the glossiness anti-discoloration of silvering are also thinned the thickness of coating, and phenomena such as no cracking.

The application additive is specific to that thiosulfate is silver-plated to be researched and developed.

For performances such as the adhesive force and the planarizations that further increase coating, it is preferable that the above-mentioned silver-plated addition of thiosulfate Agent further includes alkyl glycosides 3-5g/L, nitromethane 2-4g/L, triphenylmenthane 1-2g/L and thiocarbamide 10-30g/L.

Under shock resistance in order to further increase coating and the performances such as temperature tolerance, it is preferable that above-mentioned thiosulfate is silver-plated to be added Add agent, further includes lauric acid amide of ethanol 1-3g/L, nitranilide 0.5-1g/L, tetrahydronaphthalene 1-2g/L and 8- hydroxyl quinoline Quinoline 5-15g/L.

In order to which further increase coating resists the performances such as color distortion and planarization, it is preferable that above-mentioned thiosulfate is silver-plated to be added Add agent, further includes lauric acid 0.5-0.8g/L, azobenzene 1-2g/L, phenanthrene 1-2g/L and vulcanized sodium 1-5g/L.

For performances such as the planarizations that further increases coating, it is preferable that above-mentioned thiosulfate plates silver additive, further includes Sorbitan ester 0.2-0.5g/L, formaldehyde semicarbazone 0.5-0.8g/L and citric acid 0.5-1g/L.

In order to which further increase coating resists the performances such as color distortion and temperature tolerance, it is preferable that above-mentioned thiosulfate is silver-plated to be added Add agent, further includes oxalic acid 0.2-0.5g/L.

Applicant it has been investigated that, above-mentioned mustargen, nitromethane, nitranilide, azobenzene, formaldehyde semicarbazone etc. are mentioning Effect in terms of liter coating glossiness is clearly；Isopropylbenzene, triphenylmenthane, tetrahydronaphthalene, phenanthrene etc. are improving coating planarization The effect of aspect is clearly；1,10- Phen, dimercaprol dimercaptopropanol, mercaptoethylmaine, thiocarbamide, 8-hydroxyquinoline, vulcanized sodium, Citric acid, oxalic acid, EGTA (bis- (the 2- amino-ethyl ether) tetraacethyls of ethylene glycol) etc. are conducive to improve the stability of electroplate liquid, reduce Plating solution dosage；Lauryl sodium sulfate, polyethylene glycol, alkyl glycosides, lauric acid amide of ethanol, lauric acid and anhydrous sorbitol Ester etc. is conducive to improve the stability of electroplate liquid and the anti-discoloration performance of coating；And applicant has been surprisingly found that, above-mentioned each substance it Between there is apparent collaboration to promote effect, the comprehensive performances such as color, planarization, anti-discoloration, the adhesive force of coating can not only be made It is obviously improved, and thickness of coating can obviously be thinned, reduce electroplating cost.

The preparation method of above-mentioned thiosulfate plating silver additive, includes the following steps:

1) heat the water to 70-80 DEG C, under the stirring of 1200-1400r/min, sequentially add lauryl sodium sulfate and After polyethylene glycol, continuation stirs 10-15min at 70-80 DEG C, 1200-1400r/min；

2) by 1,10- Phen, dimercaprol dimercaptopropanol, mercaptoethylmaine and EGTA (bis- (the 2- amino-ethyl ethers) four of ethylene glycol Acetic acid) it sequentially adds in the resulting material of step 1), then 15-20min is stirred at 70-80 DEG C, 1200-1400r/min；

3) mustargen and isopropylbenzene are sequentially added in the resulting material of step 2), then in 70-80 DEG C, 1200-1400r/ 20-30min is stirred under min, obtains thiosulfate plating silver additive.

The control of the order of addition, condition of material is very crucial in above-mentioned addictive preparation method, otherwise additive Stability, the stability of electroplate liquid and coating performance can obviously be deteriorated.

In order to further increase the comprehensive performance of coating, above-mentioned thiosulfate plates the preparation method of silver additive, including Following steps:

1) heat the water to 70-80 DEG C, under the stirring of 1200-1400r/min, sequentially add lauryl sodium sulfate, After polyethylene glycol, alkyl glycosides, lauric acid amide of ethanol, lauric acid and sorbitan ester, continue in 70-80 DEG C, 1200- 10-15min is stirred under 1400r/min；

2) by 1,10- Phen, dimercaprol dimercaptopropanol, mercaptoethylmaine, EGTA (bis- (the 2- amino-ethyl ether) tetrems of ethylene glycol Acid), thiocarbamide, 8-hydroxyquinoline, vulcanized sodium, citric acid and oxalic acid sequentially add in the resulting material of step 1), then in 70-80 DEG C, stir 15-20min under 1200-1400r/min；

3) by mustargen, nitromethane, nitranilide, azobenzene, formaldehyde semicarbazone, isopropylbenzene, triphenylmenthane, tetrahydro Naphthalene and phenanthrene sequentially add in the resulting material of step 2), then stir 20-30min at 70-80 DEG C, 1200-1400r/min, It obtains thiosulfate and plates silver additive.

Thiosulfate plate silver plating solution comprising above-mentioned thiosulfate plating silver additive, including thiosulfate are silver-plated Additive 300-400mL/L, silver nitrate 50-60g/L, sodium thiosulfate 250-300g/L, potassium metabisulfite 50-60g/L and remaining The water of amount.

The preparation method of above-mentioned thiosulfate plate silver plating solution, includes the following steps:

1) sodium thiosulfate is dissolved in water；

2) silver nitrate and potassium metabisulfite are dissolved in water respectively, then mixed under constant stirring；

3) under agitation, step 1) resulting material is added in the resulting material of step 2)；

4) under agitation, by thiosulfate plating silver additive be added the resulting material of step 3) in, add water to Aequum, 5) sulfosalicylic acid plating silver additive is added in solution four, it adds water to aequum, then adjusts pH to 6, obtain Thiosulfate plate silver plating solution.

The unmentioned technology of the present invention is referring to the prior art.

Thiosulfate of the present invention plates silver additive, so that the dispersibility of electroplate liquid, stability, plating resistance etc. have very It is obviously improved, without going adjustment pH value repeatedly in the plating process, while significantly improving the planarization of silvering, attachment The performances such as power, glossiness anti-discoloration are also thinned the thickness of coating, and phenomena such as no cracking；Electroplate liquid of the present invention is free of cyanogen Compound, coating bright in mirror surface, brittleness are small, adhesive force is good, surfacing, light, anti-discoloration is good, heat resistance is strong, can meet dress The multi-field application such as the plating of decorations property and functional plating, can be directly used for the workpiece such as brass, copper, chemical nickel, be not necessarily to preplating, knot Resultant force can also be guaranteed.

Specific embodiment

For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention Content is not limited solely to the following examples.

1 thiosulfate of table plates silver additive

In upper table, polyethylene glycol is polyethylene glycol 10000, alkyl glycosides model APG0810, lauric acid amide of ethanol Model 6501, sorbitan ester are anhydrous sorbitol laurate.

The preparation method of the thiosulfate plating silver additive of above-mentioned each example, includes the following steps:

1) 70-80 DEG C is heated the water to, under the stirring of 1300r/min, sequentially adds lauryl sodium sulfate, poly- second two After alcohol, alkyl glycosides, lauric acid amide of ethanol, lauric acid and sorbitan ester, continue in 70-80 DEG C, 1200-1400r/ 12min is stirred under min；

2) by 1,10- Phen, dimercaprol dimercaptopropanol, mercaptoethylmaine, ethylene glycol bis- (2- amino-ethyl ether) tetraacethyls, sulphur Urea, 8-hydroxyquinoline, vulcanized sodium, citric acid and oxalic acid sequentially add in the resulting material of step 1), then 70-80 DEG C, 18min is stirred under 1300r/min；

3) by mustargen, nitromethane, nitranilide, azobenzene, formaldehyde semicarbazone, isopropylbenzene, triphenylmenthane, tetrahydro Naphthalene and phenanthrene sequentially add in the resulting material of step 2), then stir 25min at 70-80 DEG C, 1300r/min, obtain thio sulphur Hydrochlorate plates silver additive.

Comparative example 3

It is substantially the same manner as Example 6, except that: in the preparation, 70-80 DEG C is heated the water to, 1300r/min's Under stirring, lauryl sodium sulfate, polyethylene glycol, alkyl glycosides, lauric acid amide of ethanol, lauric acid, dehydration are sequentially added Bis- (the 2- amino-ethyl ether) tetraacethyls of sorbitol ester, 1,10- Phen, dimercaprol dimercaptopropanol, mercaptoethylmaine, ethylene glycol, thiocarbamide, 8-hydroxyquinoline, vulcanized sodium, citric acid, oxalic acid, mustargen, nitromethane, nitranilide, azobenzene, formaldehyde semicarbazone, isopropyl Then benzene, triphenylmenthane, tetrahydronaphthalene and phenanthrene stir 55min at 70-80 DEG C, 1300r/min, it is silver-plated to obtain sulfosalicylic acid Additive.

Comparative example 4

It is substantially the same manner as Example 6, except that: in the preparation, at room temperature (25 DEG C or so), 1300r/min's Under stirring, successively by lauryl sodium sulfate, polyethylene glycol, alkyl glycosides, lauric acid amide of ethanol, lauric acid, dehydration mountain Pears alcohol ester, 1,10- Phen, dimercaprol dimercaptopropanol, mercaptoethylmaine, ethylene glycol bis- (2- amino-ethyl ether) tetraacethyls, thiocarbamide, 8- Oxyquinoline, vulcanized sodium, citric acid, oxalic acid, mustargen, nitromethane, nitranilide, azobenzene, formaldehyde semicarbazone, isopropyl Benzene, triphenylmenthane, tetrahydronaphthalene and phenanthrene are added to the water, and then stir 55min at 1300r/min, obtain sulfosalicylic acid plating Silver additive.

The preparation of electroplate liquid:

By above-described embodiment 1-6 and the resulting additive of comparative example 1-4 according to being prepared as electroplate liquid as following formula: thio sulphur Hydrochlorate plates silver additive 350mL/L, silver nitrate 55g/L, sodium thiosulfate 280g/L, the water of potassium metabisulfite 55g/L and surplus；

Electroplate liquid the preparation method comprises the following steps: including the following steps:

1) sodium thiosulfate is dissolved in water；

Comparative example 5

It is substantially the same manner as Example 6, except that: in electroplate liquid, silver nitrate 40g/L, sodium thiosulfate 200g/ L, potassium metabisulfite 40g/L.

Comparative example 6

It is substantially the same manner as Example 6, except that: in electroplate liquid, silver nitrate 70g/L, sodium thiosulfate 350g/ L, potassium metabisulfite 70g/L.

Comparative example 7

It is substantially the same manner as Example 6, except that: in the preparation of electroplate liquid, pH to 7 is adjusted in step 4).

The preparation of silvering:

Embodiment 1-6 and the resulting electroplate liquid of comparative example 1-7 are used respectively, prepares silvering, and test piece is through oil removing and polishing 5 × 5cm²Pure copper sheet, method particularly includes: in the plating process, plating solution is maintained 25-30 DEG C, then, test piece is accessed Circuit simultaneously immerses in electroplate liquid, cathode-current density 0.3A/dm², use plating mode for rack plating, electroplating time is 15 points Clock, obtains silver-plated sample, and thickness of coating is 5-8 μm.

The performance table of coating obtained by each example of table 2

In upper table, adhesive force is measured referring to GB/T9286；The test method of planarization is to measure coating surface with thickness gauge Maximum gauge it is poor；Impact strength measurement method is the steel ball with 64g in the height freely falling body of 1m, observes whether glass has Crackle, breakage, if intactly, passing through；Glossiness visually measures；Heat resistance is to toast 30 minutes discolorations at 200 DEG C and rise Skin phenomenon；Color visually measures；Room temperature anti-discoloration test method is lower 6 months discoloration situations of room temperature；High temperature anti-discoloration It is the discoloration situation of 2min at 300 DEG C.

Claims

1. a kind of thiosulfate plates silver additive, it is characterised in that: including lauryl sodium sulfate 12-18g/L, polyethylene glycol 3-5g/L, mustargen 10-13g/L, isopropylbenzene 5-10g/L, 1,10- Phen 250-350g/L, dimercaprol dimercaptopropanol 50-100g/ L, the water of mercaptoethylmaine 50-100g/L, ethylene glycol bis- (2- amino-ethyl ether) tetraacethyl 100-150g/L and surplus.

2. thiosulfate as described in claim 1 plates silver additive, it is characterised in that: further include alkyl glycosides 3-5g/L, Nitromethane 2-4g/L, triphenylmenthane 1-2g/L and thiocarbamide 10-30g/L.

3. thiosulfate as claimed in claim 1 or 2 plates silver additive, it is characterised in that: further include coconut oil diethanol Amide 1-3g/L, nitranilide 0.5-1g/L, tetrahydronaphthalene 1-2g/L and 8-hydroxyquinoline 5-15g/L.

4. thiosulfate as claimed in claim 1 or 2 plates silver additive, it is characterised in that: further include lauric acid 0.5- 0.8g/L, azobenzene 1-2g/L, phenanthrene 1-2g/L and vulcanized sodium 1-5g/L.

5. thiosulfate as claimed in claim 1 or 2 plates silver additive, it is characterised in that: further include sorbitan ester 0.2-0.5g/L, formaldehyde semicarbazone 0.5-0.8g/L and citric acid 0.5-1g/L.

6. thiosulfate as claimed in claim 1 or 2 plates silver additive, it is characterised in that: further include oxalic acid 0.2-0.5g/ L。

7. the preparation method of thiosulfate plating silver additive as claimed in any one of claims 1 to 6, it is characterised in that:

Include the following steps:

1) 70-80 DEG C is heated the water to, under the stirring of 1200-1400r/min, sequentially adds lauryl sodium sulfate and poly- second After glycol, continuation stirs 10-15min at 70-80 DEG C, 1200-1400r/min；

2) 1,10- Phen, dimercaprol dimercaptopropanol, mercaptoethylmaine and bis- (the 2- amino-ethyl ether) tetraacethyls of ethylene glycol are successively added Enter in the resulting material of step 1), then stirs 15-20min at 70-80 DEG C, 1200-1400r/min；

3) mustargen and isopropylbenzene are sequentially added in the resulting material of step 2), then at 70-80 DEG C, 1200-1400r/min 20-30min is stirred, thiosulfate plating silver additive is obtained.

8. the method for claim 7, characterized by the following steps:

1) 70-80 DEG C is heated the water to, under the stirring of 1200-1400r/min, sequentially adds lauryl sodium sulfate, poly- second After glycol, alkyl glycosides, lauric acid amide of ethanol, lauric acid and sorbitan ester, continue in 70-80 DEG C, 1200- 10-15min is stirred under 1400r/min；

2) by bis- (the 2- amino-ethyl ether) tetraacethyls of 1,10- Phen, dimercaprol dimercaptopropanol, mercaptoethylmaine, ethylene glycol, thiocarbamide, 8-hydroxyquinoline, vulcanized sodium, citric acid and oxalic acid sequentially add in the resulting material of step 1), then in 70-80 DEG C, 1200- 15-20min is stirred under 1400r/min；

3) by mustargen, nitromethane, nitranilide, azobenzene, formaldehyde semicarbazone, isopropylbenzene, triphenylmenthane, tetrahydronaphthalene and Phenanthrene sequentially adds in the resulting material of step 2), then stirs 20-30min at 70-80 DEG C, 1200-1400r/min, obtains sulphur Thiosulfate plates silver additive.

9. the silver-plated plating of thiosulfate comprising thiosulfate as claimed in any one of claims 1 to 6 plating silver additive Liquid, it is characterised in that: plate silver additive 300-400mL/L, silver nitrate 50-60g/L, sodium thiosulfate including thiosulfate 250-300g/L, the water of potassium metabisulfite 50-60g/L and surplus.

10. the preparation method of thiosulfate plate silver plating solution as claimed in claim 9, characterized by the following steps:

1) sodium thiosulfate is dissolved in water；

4) under agitation, thiosulfate plating silver additive is added in the resulting material of step 3), is added water to required Amount, 5) sulfosalicylic acid plating silver additive is added in solution four, it adds water to aequum, then adjusts pH to 6, obtain thio Sulfate plate silver plating solution.